M. Khare - Air Pollution - Monitoring, MDLG., Health and Control-Intech (2012)

AIR POLLUTION –
MONITORING,
MODELLING, HEALTH
AND CONTROL
Edited by Mukesh Khare

Air Pollution – Monitoring, Modelling, Health and Control
Edited by Mukesh Khare
Published by InTech
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Copyright © 2012 InTech

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First published March, 2012

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Air Pollution – Monitoring, Modelling, Health and Control, Edited by Mukesh Khare
p. cm.
ISBN 978-953-51-0381-3

Contents

Preface IX
Chapter 1 Pollution and Air Quality in Târgovişte

Municipality and Its Surroundings (Romania) 1
Pehoiu Gica and Murărescu Ovidiu
Chapter 2 Comprehensive Comparison of Trace Metal

Concentrations in Inhaled Air Samples 29
Mehmet Yaman
Chapter 3 Effect of Air Pollutants on Vegetation

in Tropical Climate: A Case Study of Delhi City 67
Sumanth Chinthala and Mukesh Khare
Chapter 4 Physico-Chemical Characterisation of Aerosol

Particles at Canopy Level in Urban Zone 75
S. Despiau
Chapter 5 Biomonitoring of Airborne Heavy Metal Contamination 97

Mehran Hoodaji, Mitra Ataabadi and Payam Najafi
Chapter 6 Air Quality Study, Comparison Between

the Proposed and Actual Scenarios of Generator Sets
in Havana, by Using CALPUFF Model 123
Yasser Antonio Fonseca Rodríguez, Leonor Turtós Carbonell,
Elieza Meneses Ruiz, Gil Capote Mastrapa
and José de Jesús Rivero Oliva
Chapter 7 On the Impact of Time-Resolved Boundary Conditions

on the Simulation of Surface Ozone and PM10 147
Gabriele Curci
Chapter 8 Recovery and Reuse of SO2

from Thermal Power Plant Emission 169
Arun Kumar Sharma, Shveta Acharya, Rashmi Sharma
and Meenakshi Saxena
VI Contents
Chapter 9 Design Efficiency of ESP 197

Maria Jędrusik and Arkadiusz Świerczok
Chapter 10 Allergens, Air Pollutants and Immune System

Function in the Era of Global Warming 221
Barbara Majkowska-Wojciechowska and Marek L. Kowalski

Preface

This book provides a comprehensive compilation of chapters in air quality modelling,

monitoring, exposure, health and control. The book consists of two volumes.
Air Pollution – Monitoring, Modelling and Health mainly consist of chapters describing
pioneering research findings in air quality monitoring, modelling, exposure and health;
Air Pollution – Monitoring, Modelling, Health and Control comprises research findings
on air quality monitoring, modelling, exposure, health and control. The book seeks to
provide environmental scientists, engineers, researchers and students with a
comprehensive and organised body of information in the area of air pollution.
I would like to express my sincere thanks to the chapter authors for their competence,
dedication and patience in the production of the book. Thanks are also due to the Ms.
Maja Bozicevic, Publishing Process Manager for her help and support in the
preparation of the entire book volume. Sincere appreciation is extended to Mr. Sunil
and Mr. Sumanth Chinthala who provided extremely valuable organizational
assistance throughout the book production cycle.

Dr. Mukesh Khare
IIT Delhi
Civil Engineering Department
India
1
Pollution and Air Quality in Târgovişte

Municipality and Its Surroundings (Romania)
Pehoiu Gica and Murărescu Ovidiu
“Valahia” University of Târgovişte
Romania
1. Introduction
Târgovişte Municipality is situated in the High Plain of Târgovişte, at an average absolute
altitude of 280 m. The town has an administrative area of 4,681 ha, in which the
constructible area includes 1,966 ha; within the latter, 100.7 ha represent green area (Fig.1).
Fig. 1. Geographical position of Târgovişte Plain (1) in Ialomiţa Plain (2) and Romania (3).
2 Air Pollution – Monitoring, Modelling, Health and Control
Târgovişte had a population of 88,119 inhabitants in the year 2010 - representing 54.06% of
the total urban population of Dâmboviţa County and 16.63% of the total population of the
county -, the density of the town’s population being of 1,882.4 inhabitants/km2 (Statistical
Yearbook of Dâmboviţa County, 2010).
This old industrial center has developed and diversified concomitantly to the general
development of the economy (after the year 1968, on the occasion of the new administrative-
territorial division, Târgovişte became political-administrative center of the county). It is
during this period that the industrial platform, with several economic units and new
branches appeared, completing the town’s industrial profile; this profile has undergone
significant changes after the year 1990. Here, at present, there are nationally important
industrial units, on the platform situated in the south-west of the town. They actually
represent the main sources with a potential impact on the air quality in Târgovişte
municipality and its neighborhood. Among these, one can mention: SC Mechel SA, in the
metallurgical domain, producing special steels, SC Upet SA (now being restructured), SC
Nemo SA, focused on machine building, SC Swarco - Vicas SA, producing paints and
varnish, SC Oţel Inox SA, laminating steels, SC Cromsteel SA, a company based on
chroming processes, SC Romlux SA, an industrial unit producing light fixtures and others
(Pehoiu, 2003; Pehoiu et al., 2005).
Doiceşti commune is situated near Târgovişte municipality; this commune also holds some
industrial units, of which Uzina Electrică (the Power Station), using black oil and brown coal
as fuels to generate electricity, SC Nubiola România SRL, a company producing whiteners
and green chrome oxide - SO2 and possibly a sulfuretted hydrogen source in the process of
sulphur combustion needed to obtain ultramarine -, SC Soceram SA, a company producing
bricks and ceramic materials.
Fieni Town, situated in the north of the political-administrative center of Dâmboviţa
County, is remarkable through its industrial units: SC Carpatcement Holding SA, a
producer of building materials (cement) and SC Carmeuse Holding SRL (lime producer),
which represent the main sources of environmental degradation for the locality of Fieni and
its surroundings (Pehoiu, 2008).
Târgovişte Town is a significant consumer of resources and at the same time a major
producer of polluting emissions, resulting mainly from: industrial activity, intensification of
road traffic and generation of high quantities of waste.
2. Working methodology
In order to analyze the air quality status and the effects of the air pollution in a mainly
industrial town that has gone through important structural modifications after 1990, when
we analyzed the pollutants’ dispersion, we took into account as well the role of the climatic
factors (wind – its speed and directions, atmospheric humidity, atmospheric calm,
hydrometeors - fog, air temperature).
The air analysis network component pertaining to Dâmboviţa County is managed by the
Departmental Agency for Environmental Protection - AEP (Agenţia Judeţeană pentru
Protecţia Mediului) and includes fixed monitoring stations in the localities Târgovişte (Fig.
2) and Fieni (an automatic station each), and one in Doiceşti, with manual sampling of the
pollutants and analysis in the laboratory, by means of which the specialists monitor the
Pollution and Air Quality in Târgovişte Municipality and Its Surroundings (Romania) 3
concentrations of the dusts in suspension and of the gaseous pollutants (ammonia, nitrogen
oxides, sulphur dioxide, sulphuretted hydrogen, formaldehyde).
Fig. 2. Map of the air monitoring locations in Târgovişte municipality (AEP Târgovişte).
At present, the monitoring of the air quality in these points supposes the continual
gathering of daily samples from the atmosphere (24 h), followed by the analysis of the
samples in the laboratory. This kind of analysis allows to highlight the dangerous
concentrations for the population’s health in due time. The data obtained following the
measurements serve to create databases and to elaborate reports or informative bulletins in
the aftermath of the occurrence of eventual pollution episodes.
Excepting the meteorological parameters, a series of polluting indicators were monitored,
such as: benzene, carbon monoxide, sulphur dioxide, nitrogen oxides, lead, heavy metals
etc. These pollutants were gathered from several manual sampling points distributed
around the town, including the residential and the industrial areas.
In order to determine the quantities of dusts and polluting emissions present in the
atmosphere and influencing the air quality status, the polluting agents were separated
depending on the area they influence (for instance, the dusts emitted in the atmosphere by a
series of metallurgical companies are carried over two residential quarters in the south-east
of the town.
Following the comparative analysis of the polluting components, during the last few years
one can notice a slight improvement of the air quality compared to the previous period in
point of dusts-caused pollution. In the areas in which they are monitored in the atmosphere,
gaseous pollutants (nitrogen dioxide, sulphur dioxide, ammonia, sulphuretted hydrogen,
formaldehyde, oxidant substances, and carbon monoxide) are not present in concentrations
over the limits allowed by the present legislation.
The pollutants to be monitored, the measurement methods, the limit values (LV), the alert
and information thresholds and the criteria for situating the monitoring points are
established by the national legislation concerning the atmospheric protection, being in
agreement with the demands of the European regulations.
The realizations concerning the development of the air quality monitoring network in
Dâmboviţa County during the period 2007-2010 consisted in:
- remodeling and adapting the environmental laboratories for the installation of new
laboratory equipments; installing these equipments; instructing the personnel;
- completing the endowment of the automated air quality monitoring stations from
Târgovişte and Fieni.
AEP Dâmboviţa monitored the level of the dusts in suspension in the area of Târgovişte, by
means of its four sampling stations. In the municipality, the indicator of breathable dusts
was monitored in the PM10 fraction in the quarter Micro XII (2 representative points for the
dusts resulted from SC Mechel SA Târgovişte) and the Civic Center – representative for the
dusts resulted from road traffic and other sources after dispersion (SC Mechel SA) – where
the indicator monitored was that of total dusts in suspension.
3. Air quality
The air is the environmental factor constituting the most rapid support favoring the pollutants’
transportation in the environment. Air pollution has many and significant negative effects on
the population’s health and may damage as well the flora and fauna in general.
Air quality depends on the emissions that end up in the air coming from stationary and
mobile sources (road traffic), mainly in big cities, as well as on the pollutants’ transport on
longer distances.
The automated stations and the manual sampling points are situated in representative areas
in point of pollution, in the localities mentioned, as follows:
 Automated station DB-1, situated in Târgovişte municipality, Vlad Ţepeş Str., no. 6 C (in the
courtyard of the Social Care Center “Sfânta Maria”), coordinates: 25028’41.6’’; 44054’58.39’’;
 Automated station DB-2, situated in Fieni Town, Teilor Str., no. 20 (in the town’s central
park), coordinates: 25025’18.30’’; 45007’52.98’’;
 Fixed manual sampling point in Târgovişte - PM10 fraction, in the Micro XII station, point
1, Constructorilor Str., no. 21 (Procor headquarters, industrial platform);
 Fixed manual sampling point in Doiceşti (CFR Station) – gaseous pollutants (sulphur
dioxide - SO2, nitrogen dioxide - NO2, sulphuretted hydrogen - H2S and hexavalent
chromium – expressed as CrO3) and total dusts in suspension (TSP). The gaseous
pollutants determinations in the point Doiceşti continue to be carried out in agreement
with the analysis methods mentioned by STAS 12574/1987.
Settleable dusts are monitored by means of measurements in six fixed points situated in the
following locations:
- Târgovişte - 3 sampling points – point 1 Micro XII, AEP headquarters, and Micro XI
(DB-1 station);
- Doiceşti - 1 sampling point - CFR Train Station;
- Fieni - 2 sampling points - point 1 (Fieni Park) and point 2, DB-2 station.
3.1 Atmospheric pollutants

 Benzene
General features:
- - Very light aromatic compound, volatile and water-soluble;

- - 90% of the benzene present in the air comes from road traffic;
- - The rest of 10% comes from fuel evaporation during its storage and distribution.
Effects on heath: carcinogenic substance, classified into the A1 toxicity class, known as
carcinogenic for man. It produces negative effects on the central nervous system.
Measurement methods: the method of reference for measuring benzene is that of sampling by
aspiration into an absorbing cartridge, followed by gas-chromatographic determination,
standardized at present by the European Committee for Standardization (CEN).
 Carbon monoxide
General features. At room temperature, carbon monoxide is a colorless, odorless, tasteless gas,
of both natural and anthropic origin. Carbon monoxide is formed mainly through the
incomplete burning of fossil fuels.
Natural sources: forest burning, volcanic emissions, electric discharges.
Anthropic sources: it is formed mainly through the incomplete burning of fossil fuels, steel
and pig iron production, oil refinement, and road, air and railroad traffic.
Carbon monoxide can accumulate up to a dangerous level especially during the period of
atmospheric calm during winter and spring (this gas being much more stable from a
chemical viewpoint at low temperatures), when the burning of fossil fuels attains a
maximum level. Produced by natural sources, it is very rapidly dispersed in a wide area,
and consequently does not affect human health.
Effects on people’s health. It is a toxic gas, being lethal in high concentrations (at concentrations
of about 100 mg/m3) through the reduction of the blood’s capacity to transport oxygen, with
consequences on the respiratory and cardiovascular system.
At relatively low concentrations, it affects the central nervous system, weakens the pulse
rate, diminishing the blood volume distributed in the organism, and at the same time it
reduces visual acuity and physical capacity. Being exposed for a short period of time, one
may experience acute fatigue. At the same time, it may trigger respiratory difficulties, chest
pains in people with cardiovascular diseases, determining as well irritability, migraines,
rapid respiration, lack of coordination, nausea, dizziness, confusion, and can reduce the
ability to concentrate.
The population segments most affected by the exposure to carbon monoxide are represented
by children, elderly, people with respiratory and cardiovascular diseases, anemic people
and smokers.
Effects on plants. At concentrations normally encountered when monitoring the atmosphere,
carbon monoxide does not affect the plants, the animals or the environment.
Measurement methods: the reference method for measuring carbon monoxide is the non-
dispersive infrared (NDIR) spectrometric method: ISO 4224.
 Sulphur dioxide
General features. Sulphur dioxide is a colorless, bitter, non-flammable gas, with a penetrating
odor that irritates the eyes and the respiratory system.
Natural sources: volcanic eruptions, marine phytoplankton, bacterial fermentation in the

marshy areas, oxidation of the gas containing sulphur resulted from biomass
decomposition.
Anthropic sources: population’s heating systems, when the fuel used is not methane,
thermoelectric power stations, industrial processes (siderurgy, refinery, sulfuric acid
production), cellulose industry and, to a lesser extent, the emissions coming from diesel
engines.
Effects on people’s health. Depending on its concentration and the period of exposure, sulphur
dioxide has different effects on human health. The exposure to a high concentration of
sulphur dioxide during a short period of time can cause severe respiratory difficulties.
Particularly affected are: people with asthma, children, elderly and people with chronic
respiratory diseases. The exposure to a low concentration of sulphur dioxide for a long lapse
of time can result in infections of the respiratory system. Sulphur dioxide can interfere with
the dangerous effects of the ozone.
Effects on plants. Sulphur dioxide clearly affects many plant species, the negative effect on
their structure and tissues being visible with the naked eye. Some of the most sensitive
plants are: pine, vegetables, red and black acorns, white ash, lucerne, blackberries.
Effects on the environment. In the atmosphere, it contributes to the acidification of the
precipitations, with toxic effects on the vegetation and on the soil. The increase of the
sulphur dioxide concentration accelerates metals’ corrosion, because of the formation of
acids. Sulphur oxides can erode: stones, brick-and-mortar, paints, fibers, paper, skin and
electric components.
Measurement methods: the standard sulphur dioxide analysis method is the one pointed out
in ISO/FDIS 10498 (standard project) named “Aer înconjurător - determinarea dioxidului de
sulf” (“Surrounding air – sulphur dioxide determination”) - UV fluorescence method.
 Ozone
General features: very oxidant, very reactive gas, with chocking smell. It is concentrated in the
stratosphere and assures our protection against the UV radiation, which is damaging for
life. The ozone present on the soil level acts as a component of the “photochemical smog”. It
appears following a reaction that involves mainly nitrogen oxides and volatile organic
compounds.
Effects on health. The ozone concentration at ground level causes respiratory system and
eye irritation. High ozone concentrations can trigger a reduction of the respiratory
function.
Effects on the environment: It is responsible for certain damages caused to the vegetation
through the atrophy of certain tree species in the urban areas.
Measurement methods. The standard methods for the ozone analysis and for the calibration of
the ozone-related tools are:
- analysis method: UV photometric method (ISO 13964);
- calibration method: UV reference photometer (ISO 13964, VDI 2468, B1.6).
 Nitrogen oxides
General features. Nitrogen oxides represent a group of very reactive gases, containing
nitrogen and oxygen in variable quantities. Most of these gases have no color and no smell.
The main nitrogen oxides are:
- nitrogen monoxide (NO), a colorless and odorless gas;
- nitrogen dioxide (NO2), a brown-reddish gas, with a strong, choking smell.
Combined with the air particles, nitrogen dioxide can form a brown-reddish layer. In the
presence of solar light, nitrogen oxides can react as well with hydrocarbons forming
photochemical oxidants. Nitrogen oxides are responsible for acid rains, which affect the
terrestrial surface and the aquatic ecosystem.
Anthropic sources: they appear in the combustion process, when fuels are burnt at high
temperatures, but most often they are the result of road traffic, industrial activities, and
electric energy production. Nitrogen oxides are responsible for: smog and acid rains
formation, water quality deterioration, greenhouse effect, and reduced visibility in the urban
areas.
Effects on people’s health. Nitrogen dioxide is known as a very toxic gas both for people and
for animals (its degree of toxicity is four times higher than that of the nitrogen monoxide).
Being exposed to high concentrations can be fatal, while low concentrations affect the
pulmonary tissue. The population exposed to this type of pollutants can experience
respiratory difficulties, respiratory irritations, and pulmonary dysfunction. A durable
exposure to a low concentration can destroy the pulmonary tissues, leading to pulmonary
emphysema. The most affected people through the exposure to this pollutant are children.
Effects on plants and animals. The exposure to this pollutant produces serious damage to the
vegetation, by whitening or destroying the plants’ tissues, and reducing their growth
rhythm. The exposure to nitrogen oxides can cause pulmonary diseases with animals
(resembling pulmonary emphysema), while the exposure to nitrogen dioxide can reduce the
animals’ immunity, causing diseases such as pneumonia and flu.
Other effects. Nitrogen oxides contribute to the formation of acid rains and favor nitrate
storage into the soil, which can alter the ecological balance of the environment. At the same
time, they can cause tissue deterioration, paints discoloring and metal degradation.
Measurement methods: the standard method for nitrogen dioxide and nitrogen oxides analysis
is mentioned in ISO 7996/1985 - “Aer înconjurător - determinarea concentraţiei masive de
oxizi de azot” (“Surrounding air – the determination of massive nitrogen oxides
concentration”), being chemiluminescence.
 Lead and other toxic metals: Pb, Cd, As and Hg
General features. Toxic metals come from coal, fuel, domestic waste combustion etc. and from
certain industrial procedures. They are generally found as particles (except for mercury
which is gaseous). Metals are stored in the body and trigger short and/or long term toxic
effects. In case of exposure to high concentrations they can affect the nervous system, and
the renal, hepatic and respiratory functions.
Measurement methods:
- the standard method for lead sampling is the same as the sampling method for PM10;
- the standard method for lead analysis is the one mentioned in ISO 9855/1993 “Aer
înconjurător - determinarea conţinutului de plumb din aerosolii colectaţi pe filter”
(“Surrounding air – determination of particulate lead content from aerosols collected on
filter”);
- method - atomic absorption spectroscopy.
- the standard method for measuring the concentrations of arsenic, cadmium and nickel
in the surrounding air is about to be standardized by the European Committee for
Standardization (CEN) and relies on manual sampling of the PM10 fraction (described
by the EN 12341 standard).
 Heavy metals
In Dâmboviţa County, including the area of Târgovişte municipality and its surroundings,
heavy metal emissions come from: combustion of gaseous fuels, road traffic (to a large
extent) (a special role going to the use of fuels with lead derivatives as additives),
metallurgical industry activities, building materials industry, and burning of dangerous
(hospital) wastes (to a lesser extent).
The determinations for lead, arsenic, cadmium and nickel were carried out starting from
breathable dusts - PM10 fraction -, and for chromium from total dusts in suspension. They
were carried out using the automated DB1 and DB2 stations and the manual sampling
station situated on the industrial platform in the southwest of Târgovişte municipality; for
chromium, other determinations were also carried out in the locality of Doiceşti (Table 1 and
Fig. 3-6).
0.6
0.5
0.4
0.3
0.2
0.1
0
Industrial platform DB 1 DB 2
Târgovişte
average year
LV/2009
2009
Fig. 3. Average annual concentrations: lead in the year 2009 (g/m3).

7
6
5
4
3
2
1
0
Târgovişte
average year
LV/2009
2009
Fig. 4. Average annual concentrations: arsenic in the year 2009 (ng/m3).
8
7
6
5
4
3
2
1
0
Târgovişte
average year
LV/2009
2009
Fig. 5. Average annual concentrations: cadmium in the year 2009 (ng/m3).
25
20
15
10
0
Târgovişte
average year LV/2009
2009
Fig. 6. Average annual concentrations: nickel in the year 2009 (ng/m3).
Station No. of valid data Data collecting (%) Average Maximum Median
LEAD (g/m3)
DB1 285 78.08 0.0246 0.1623 0.0115
Industrial
105 28.77 0.0916 0.5712 0.0628
platform
DB2 307 84.11 0.0205 0.0867 0.0140
ARSENIC (ng/m3)
DB1 232 63.56 0.6237 15.9719 0.0888
Industrial
89 24.38 5.5645 49.9795 1.7821
platform
DB2 251 68.77 1.7854 34.0692 0.0972
CADMIUM (ng/m3)
DB1 232 63.56 0.9870 10.2118 0.1801
Industrial
89 24.38 7.2788 83.9098 1.7728
platform
DB2 251 68.77 1.5757 9.7392 0.9380
NICKEL (ng/m3)
DB1 232 6356 3.2938 29.5864 0.2516
Industrial
89 24.38 10.5071 119.8768 0.0000
platform
DB2 235 64.38 5.4799 51.4799 2.2764
CHROMIUM (mg/m3)
0.00002
Doiceşti 193 52.88 0.000033 0.000091
9
Table 1. Values for heavy metals in the year 2009 (source: AEP Dâmboviţa).
One can notice an overpassing of the yearly limit value for the protection of human health at
the manual station situated on the industrial platform of Târgovişte municipality, for the
indicator cadmium, under the reserve that in the year 2009 the data collecting was of 24.4%
(89 measurements). The other indicators monitored did not go over the annual limit value
(lead, arsenic, zinc) or the maximum admitted daily concentration (chromium). The main
polluting units are: SC Cromsteel SA and SC Mechel SA from Târgovişte municipality.
 The tropospheric ozone and other photochemical oxidants
The inventory, according to the order 524/2000, of the sources and of the emissions
highlights the following pollutants accumulation concerning the category of volatile organic
compounds (VOCs) emitted in the atmosphere during the years 2007-2009 (Table 2):
Total emissions in Dâmboviţa County (t/year)

Year CH4
Total VOCs NMVOCs (non-methane volatile organic compounds)
(methane)
2007 89127.67 14919.671 74208
2008 19177.99 8451.86 10726.13
2009 15739.2 4075.69 11663.48
Table 2. Tropospheric ozone emissions and other photochemical oxidants (source: AEP
Dâmboviţa).
So, at present, one can notice a decrease of the non-methane volatile organic compounds,
more precisely by 72.7% in 2009 compared to 2007, while concerning methane, a quite
significant increase of the quantities emitted during the same periods was recorded,
especially because of the increase of the number of cars and of the road traffic
intensification, especially in the urban area (Murărescu & Pehoiu, 2009; Pehoiu, 2006).
3.2 Stationary air quality monitoring points

 Pollution with dusts in suspension
As we have mentioned before, in the area of Târgovişte municipality there are:
- the sampling point from Micro XII - point 1 (Constructorului Str., no. 21). Sampling
time: 24 h. Indicator – dusts in suspension: fraction PM10, Unit of measurement:
μg/m3; MAC – maximum allowable concentration (50 μg/m3);
- the sampling point from Micro XII - point 2 (High School no. 5). Sampling time: 24 h.
Indicator - total dusts in suspension (TSP), Unit of measurement: mg/m3; maximum
allowable concentration - MAC (0.15 mg/m3); AT - alert threshold (70% of the MAC =
0.105mg/m3) - Table 3.
Maximum value 0.058
Minimum value 0.026
Average value 0.049
Number of determinations 4
No. of situations in which the maximum
allowable concentration (MAC) was 0
exceeded
% MAC excess 0
Table 3. Concentrations for dusts in suspension: Târgovişte, Micro XII (source: AEP
Dâmboviţa.
One can notice that in point of the concentrations of dusts in suspension, at least on the
level of the quarter Micro XII of the municipality, no overpassing of the MAC was
determined.
- sampling point: AEP Dâmboviţa headquarters (Ialomiţei Str., no. 1); sampling time: 24
h. Indicators – total dusts in suspension (TSP), nitrogen dioxide (NO2), sulphur dioxide
(SO2), ammonia (NH3), formaldehyde (CH2O); MAC - maximum allowable
concentration (0.15 mg/m3); AT - alert threshold (70% of the MAC = 0.105mg/m3) -
Table 4.
Just as in the case of the pollution with dusts in suspension, following the four determi-
nations carried out, it was possible to notice that there was no MAC overpassing for dusts in
suspension, the values of the alert threshold overpassing being practically insignificant.
TSP NO2 SO2 NH3 CH2O

Measurement units mg/m3 mg/m3 mg/m3 mg/m3 mg/m3
Maximum value 0.054 0.0085 0.0016 0.0049 0.0020
Minimum value 0.026 0.0070 0.0009 0.0036 0.0007
Average value 0.040 0.0076 0.0014 0.0041 0.0011
No. of determinations 4 4 4 4 4
MAC 0.15 0.1 0.25 0.1 0.012
No. of MAC overpassing 0 0 0 0 0
% MAC overpassing 0 0 0 0 0
AT 0.105 0.07 0.175 0.07 0.0084
No. of AT overpassing 0 0 0 0 0
% AT overpasing 0 0 0 0 0
Table 4. Concentrations of dusts in suspension AEP Dâmboviţa (source: AEP Dâmboviţa).
- sampling point: Micro VI (Unirii Blvd., no. 6)

Sampling time: 24 h. Indicators - nitrogen dioxide (NO2), sulphur dioxide (SO2), ammonia
(NH3); MAC - maximum allowable concentration, AT - alert threshold (Table 5).
NO2 SO2 NH3

Measurement units mg/m3 mg/m3 mg/m3
Maximum value 0.0124 0.0025 0.0062
Minimum value 0.0090 0.0018 0.0029
Average value 0.0108 0.0021 0.0048
No. of determinations 4 4 4
MAC 0.1 0.25 0.1
No. of MAC
0 0 0
overpassing
% MAC overpassing 0 0 0
AT 0.07 0.175 0.07
No. of AT overpassing 0 0 0
% AT overpasing 0 0 0
Table 5. Concentrations presented by AEP Dâmboviţa.
The four determinations realized in the sampling point quarter Micro VI of Târgovişte
municipality highlight the overpassing of the maximum allowable concentrations for all the
pollutants, accompanied by the overpassing of the alert threshold, yet in very low
percentages.
AEP monitored the level of the dusts in suspension, in the area of Târgovişte, by means of
its three sampling stations: AEP Târgovişte (representative for road traffic), Micro XII
(representative for dusts resulted from SC Mechel Târgovişte), Civic Center (representative
for dusts resulted from road traffic and other sources after dispersion (SC Mechel SA, SC
UPET SA).
Following four determinations, we noticed that the values of the average concentrations in
24 hours went over the MAC (0.15 mg/m3) in all the three sampling points. The frequency
of the average overpassing in 24 h for the area of Târgovişte is of 13.94%, the maximum
overpassing being of 0.267 mg/m3 (in the point AEP headquarters) compared to 0.15 mg/m3
(MAC).
The values of the average yearly concentrations were above the annual MAC (0.075 mg/m3)
in all the three sampling points and globally in the area of Târgovişte (0.116 mg/m3). The
main reasons are the dust emissions containing iron oxides and ferrous metals (SC Mechel
SA), but also the intense road traffic.
In order to observe the air quality status and the pollution in the north of Târgovişte
municipality, the sampling points from the industrial area of Doiceşti were taken into
account as well, having as sampling point the locality’s train station, also because the wind
direction determines the transport of the dusts from this location to the municipality, along
the valley of Ialomiţa River. Sampling time: 24 h. Indicators - nitrogen dioxide (NO2),
sulphur dioxide (SO2), sulphuretted hydrogen (H2S), Cr6+, total dusts in suspension (TSP);
MAC - maximum allowable concentration; AT - alert threshold (70% of the MAC = 0.105
mg/m3) - Table 6 and Fig. 7.
TSP NO2 SO2 H2S CrO3
Measurement units mg/m3 mg/m3 mg/m3 mg/m3 mg/m3
Maximum value 0.057 0.0204 0.0033 0.0045 0.0001000
Minimum value 0.029 0.0087 0.0013 0.0017 0.0000840
Average value 0.037 0.0132 0.0020 0.0028 0.0000893
No. of determinations 4 4 4 4 4
MAC 0.15 0.1 0.25 0.008 0.0015

No. of MAC
0 0 0 0 0
overpassing
% MAC overpassing 0 0 0 0 0
AT 0.105 0.07 0.175 0.0056 0.0010
No. of AT overpassing 0 0 0 0 0
Table 6. Concentrations reported in the point Doiceşti Trains Station (source: AEP
Dâmboviţa).
0.16
0.14
0.12
0.1
0.08
0.06
0.04
0.02
0
2001 2002 2003 2004 2005 2006 2007 2008 2009
Târgovişte Doiceşti MAC/year
Fig. 7. Evolution of the concentrations of total dusts in suspension during the years 2001-
2009 (TSP) - mg/m3
In Doiceşti locality, one monitored the level of the pollution with settleable dusts, nitrogen
dioxide, sulphur dioxide, sulphuretted hydrogen, dusts in suspension, given the specific
emissions from the main polluting economic agents in the area: U.E. Doiceşti, which uses
black oil and brown coal as fuel to generate electricity and SC Nubiola România SRL (a
company producing whiteners and green chrome oxide) - the SO2 and possibly a sulfuretted
hydrogen source in the process of sulphur combustion needed to obtain ultramarine.
Other potential pollutants are SC. Soceram SA (producer of bricks, ceramic materials) and
road traffic. The evolution of the concentrations of total dusts in suspension, during the
period 2001 - 2009, clearly highlights the diminution in the atmosphere of these polluting
emissions, both for the municipality and for Doiceşti locality.
 Pollution with settleable dusts
AEP supervises the level of the settleable dusts in the areas of Târgovişte and Doiceşti.
Under exceptional conditions of air masses transportation along Ialomiţa River, settleable
dusts from the industrial area of Fieni can end up in Târgovişte and its surroundings. That is
why we consider it necessary to include Fieni locality as well in the present study. In these
areas, a characteristic feature is the pollution with dusts, the main polluting sources being:
- in Târgovişte: SC Mechel SA, SC Upet SA and to a lesser extent the road traffic; the
major impact is felt under the form of dusts in suspension;
- in Doicesti: UE Doiceşti, SC Soceram SA, road traffic; given the emissions’ features, the
major impact is felt under the form of settleable dusts. Dusts in suspension have been
monitored in the area starting with June 2002.
- in Fieni: SC Carpatcement Holding SA (producer of lime and cement); the major impact
is felt at the same time under the form of settleable dusts. Dusts in suspension have
been monitored in the area starting with March 2003.
Concerning each locality, the average annual quantities of settleable dusts did not go over
the annual MAC (204 t/km2/year) in none of them, yet in different sampling points the
annual average values have been exceeded, namely in the points situated in inhabited areas
in which the impact of the dusts emissions from the sources is high (Fig. 8).
18
16
14
12
10
8
0
MAC/month 2001 2002 2003 2004 2005 2006 2007 2008 2009
Târgovişte Doiceşti Fieni
Fig. 8. Evolution of the concentrations of settleable dusts during the years 2001-2009
(mg/m3).
3.3 Experimental results and syntheses concerning the automatic monitoring of the
emissions of atmospheric pollutants
 Târgovişte area
For the indicator dusts in suspension - the PM10 fraction - (Procor headquarters, industrial
platform), on 13 occasions one recorded values above the limit value (50 μg/m3) in 24
hours (out of the 15 measurements carried out). In the year 2009, the level of dusts in
suspension was analyzed in the localities Târgovişte (PM10 - manual station located on the
industrial platform and industrial automatic station - DB1), Doiceşti (total dusts in
suspension (TSP) - manual station) and Fieni (industrial automatic station - DB2) - Table 7
and Fig. 9-13.
Frequency
No. of Data No. of
of the Average Maximum Median Percentile
Station valid collecting data
overpassing (g/m3) (g/m3) (g/m3) 98 (g/m3)
data (%) >LV
(%)
TÂRGOVIŞTE
DB1,
272 74.52 6 2.21 19.665 55.373 15.634 48.942
automatic
DB1,
286 78.36 1 0.35 19.594 50.150 19.079 43.848
gravimetric
Industrial
platform, 142 38.90 87 61.27 57.629 118.387 57.364 106.567
gravimetric
DOICEŞTI
Train
194 53.15 0 0 0.063 0.148 0.059 0.136
Station
FIENI
DB2,
335 91.78 11 3.28 22.101 89.920 19.425 55.581
automatic
DB2,
307 84.11 8 2.61 18.739 75.043 15.808 53.060
gravimetric
Table 7. Indicators PM10 per 24 h in 2009 (source: AEP Dâmboviţa).
125
100
75
50
25
0
I II III IV V VI VII VIII IX X XI XII
DB1 DB2 Industrial platform
LV
Fig. 9. Maximums/24h of the PM10 indicator, measured gravimetrically (months) - year

2009, compared to LV/24h (g/m3).
100
90
80
70
60
50
40
30
20
10
0
Industrial
platform DB1 DB2
Fig. 10. Monthly frequencies of the exceeding of the LV/24h – dusts in suspension (PM10) in
the year 2009 (%).
70
60
50
40
30
20
10
0
Industrial platform DB1 DB2
average year
2009 LV/2009
Fig. 11. Average annual concentrations of the PM10 indicator, measured gravimetrically
(g/m3).
0.16
0.14
0.12
0.1
0.08
0.06
0.04
0.02
0
Months
Doiceşti MAC
Fig. 12. Maximums/24h of the TSP indicator in Doiceşti Commune - year 2009 (g/m3).
35
30
25
20
15
10
0
Months
Fig. 13. Monthly frequencies for the exceeding of the AT/24h, Doiceşti locality, TSP
indicator (%), year 2009.
According to the values recorded for the PM10 indicator, in April 2009, one can notice the
increase of the frequency for the exceeding of the limit value to 86.7% (compared to 37.5%,
the previous month), the average monthly concentration being of 68.7 μg/ m3, compared to
52.6 μg/ m3 in March the same year (Table 8).
Average of the Frequency of the

Maximum value of the Minimum value of the
values recorded overpassing of
concentration (μg/m3) concentration (μg/ m3)
(μg/ m3) the LV%
92.2 34.5 68.7 86.7%
Table 8. Average, maximum, minimum monthly quantities for settleable dusts and the
frequencies for the exceeding of the monthly MAC (Micro XII, point 1, Târgovişte).
At the Automatic station DB-1, Micro 11, Târgovişte, no exceeding of the limit value for the
indicator PM10 gravimetric, the average monthly value being of 20.73 μg/m3 (Fig. 14).
80
70
60
50
40
30
20
10
0
2005 2006 2007 2008 2009
Average
/year LV/year
Fig. 14. Evolution of the concentrations of breathable dusts - PM10 fraction, Târgovişte,
Micro XII, manual station (g/m3), years 2005-2009.
The dusts concentration in the atmosphere in the sampling area is influenced by the input
from nearby sources (activities in the domain of building materials) and of the nearby
sources from a distance of about 1 km (activities such as steel production, slag processing
etc.). At the same time, the PM10 concentration can have high values depending on the
evolution of the meteorological phenomena: high relative humidity (RH), atmospheric
pressure and wind intensity may lead to the appearance of “peaks” of the PM10
concentrations, because they can favor the agglomeration of the particles.
In Târgovişte municipality, the main sources generating dust emissions (with significant
impact in the area around their activity) are the activities of the economic agents from the
area of the industrial platform, which operate in the metallurgical domain, in the domain of
metallic ware, road transport, building materials, concrete production and road traffic.
In the case of gaseous pollutants, at the Automatic monitoring station DB-1 there was no
exceeding of the limit values or the information thresholds for the average hourly or daily
concentrations for the indicators monitored. The main sources emitting gaseous pollutants
in the area of Târgovişte, with a potential impact on the air quality are: metallurgical
companies, industrial companies that use solvents, economic agents operating in the
domain of metallic ware, road transport, building materials, fuel distribution stations and
road traffic.
4. Air quality status

In Târgovişte municipality one monitors daily concentrations (sampling time: 24 h) for the
indicators: breathable dusts, respectively the fraction with the diameter <10μm (PM10),
settleable dusts, highlighting the quantity of (settleable) dusts deposited during a 30-day
interval on a 1 m2 area, this being a characteristic indicator for highlighting the pollution
with heavy particles in suspension, which are later on deposited on the ground.
At the same time, the automatic station DB-1 Târgovişte, which continually monitors
meteorological parameters (temperature, wind speed, wind direction, solar radiation
intensity, precipitations quantity, atmospheric pressure), gaseous pollutants (nitrogen
oxides, sulphur dioxide, carbon monoxide, tropospheric ozone) and dusts in suspension
(breathable - PM10 fraction) transmits the data, in real time, to the panels dedicated to public
information (external panel - Prefecture Plateau of Târgovişte - and internal panel - AEP
Dâmboviţa headquarters) - Fig. 15.a-b.
In Doiceşti locality, air quality is monitored by supervising the indicators total dusts in
suspension, settleable dusts and gaseous pollutants (sampling point: manual/urban
station).
4.1 Examples of chronological series recorded during a day, (April 1-2 and 18, 2009),
3
at the automatic station DB-1 Târgovişte (concentration in g/m )
1.04.2009
SO2 de sulf
Dioxid NO2 de azot
Dioxid NOx de azot
Oxizi
PM10 authorized
PM10 - aut O3
Ozon NO
Monoxid de azot
14
12
10
8
6
4
2
0
0
0
:0
:0
:0
:0
:0
:0
:0
:0
:0
:0
:0
:0
01
03
05
07
09
11
13
15
17
19
21
23
2.04.2009
Dioxid
SO 2 de sulf Dioxid
NO2 de azot Oxizi
NOx de azot
PM10
PM - aut
10 authorized Ozon
O3 Monoxid
NO de azot
45
40
35
30
25
20
15
10
5
0
0
0
0
:0
:0
:0
:0
:0
:0
:0
:0
:0
:0
:0
:0
09
05
07
11
13
15
17
19
21
23
01
03
18.04.2009
Dioxid
SO 2
de sulf Dioxid
NO 2 de azot Oxizi
NO x de azot
PM10
PM - aut
10 authorized
Ozon
O3 NO
Monoxid de azot
80
70
60
50
40
30
20
10
0
0
0
:0
:0
:0
:0
:0
:0
:0
:0
:0
:0
:0
:0
01
03
05
07
09
11
13
15
17
19
21
23
1.04.2009
SO2 de sulf
Dioxid NO2 de azot
Dioxid NO
Oxizix de azot
PM10 authorized
PM10 - aut O3
Ozon NO
Monoxid de azot
14
12
10
8
6
4
2
0
2.04.2009
Dioxid
SO 2
de sulf NO
Dioxid
2 de azot NO
Oxizi
x de azot
PM10 authorized
PM10 - aut O3
Ozon NO
Monoxid de az ot
100
90
80
70
60
50
40
30
20
10
0
18.04.2009
Dioxid
SO 2
de sulf Dioxid
NO2 de azot NO
Oxizix de azot
PM 10 authorized
PM10 - aut O3
Ozon NO
Monoxid de azot
60
50
40
30
20
10
0
0
0
:0
:0
:0
:0
:0
:0
:0
:0
:0
:0
:0
:0
01
03
05
07
09
11
13
15
17
19
21
23
5. Air quality management
5.1 Goals and measures for air quality management
Air pollution represents a serious problem, with short, medium and long term effects. The
air, as environmental factor, is submitted to an intense local pollution, especially in the
urban area under analysis, because of the industrial activity, because of the intensification of
the road traffic and also because of the burning of domestic waste. The air pollution effects
can be direct, affecting the local population’s health condition, and also indirect, affecting
fauna, flora and building materials.
The goals and measures foreseen on the level of Dâmboviţa County and implicitly for all the
localities under analysis, in order to improve the air quality in the urban area, in agreement
with the quality standards, refer to: reducing the impact of the road traffic on the air quality,
reducing the emissions from individual heating systems, assuring the control of the
emissions from industrial sources and installing de-pollution equipments for all the sources
with a major impact.
There are priorities concerning volatile organic compounds (VOC) emissions control; they
aim to limit the emissions coming from the use of organic solvents in certain activities and
installations (protective cover, dry cleaning, fabrication of covering compounds and
varnishes; surface cleaning and degreasing; wood impregnation) and to meet the legal
regulations in this domain.
Considering the fact that industrial pollution represents the main source of pollution for all
the environmental factors (affecting the quality of the air, water, soil, generating different
types of waste and using natural resources and energy), the purpose of the integrated
environmental protection system is the implementation of preventive measures or the

emissions reduction with the purpose of protecting the environment as a whole.
The industrial branch with the highest impact on the environmental factors is metallurgical
industry, the air quality being affected by: emissions resulted from raw matter preparation
(iron melting), final products processing, raw matter and auxiliary products transport and
storage.
A significant impact on the environmental factors comes from the building materials
industry as well (through the existence of the previously mentioned economic agents); their
specific activities determine the elimination of large quantities of dusts and green house
effect gases in the atmosphere.
On the level of Dâmboviţa County, eleven environmental authorizations have been issued
concerning the emissions of green house effect gases, for installations under the regulations
of the EU-ETS (EU - Emission Trading System) Directive, for the period 2008-2012 (The
directive 87/2003/CE was adopted by the Romanian legislation through the governmental
decision H.G. no.780/2006)1.
The integrated authorizations contain demands and limit values regarding the emissions,
which try to make sure that all the adequate preventive measures for the environmental
protection have been taken. The limit values concerning emissions are established based on
the best available techniques. In order to support the EU member states in the application of
the IPPC (International Plant Protection Convention) Directive, among the member states
and the afferent industry, there has been an information exchange concerning the BAT - Best
Available Techniques. The purpose of this information exchange is to balance differences on
a technological level in the European Community and to promote universal limit values and
techniques.
In the areas affected by industrial pollution, through adjustment programs annexed to the
environmental authorizations emitted for the polluting economic agents, one established
measures for the reduction of the industrial activities’ impact on the environmental
quality. They are found as well in the Local Action Plan for the Environement of
Dâmboviţa County (Planul Local de Acţiune pentru Mediu al Judeţului Dâmboviţa),
reviewed even since the year 2007. Among the local economic agents concerned there are:
SC Mechel SA, SC Termica S.A, SC Oţelinox SA, all from Târgovişte, SC Termoelectrica
SA Bucureşti – the branch of Doiceşti, SC Soceram SA Bucureşti - the branch of Doiceşti,
SC Carmeuse Holding SRL – working point of Fieni, SC Carpatcement Holding SA - the
branch of Fieni.
Following the approval by the National Agency for Environmental Protection (Agenţia
Naţională pentru Protecţia Mediului - ANPM) of the Propositions of measure plans for
1A certificate concerning the green house effect gases emissions represents the title giving an installation
the right to emit a ton of carbon dioxide equivalent during a definite period; it is valid for meeting the
goal of the governmental decision H.G no. 780/2006 and transferable under the conditions foreseen by
this normative act.
green house effect gases emissions monitoring and reporting for the year 2010, the
environmental authorizations concerning this type of emissions were reviewed.
The joint implementation (JI), according to the Kyoto Protocol, concerning the advantages of
the project for Târgovişte municipality, considered the following aspects:
- producing non-polluting electric and thermal energy using modern, reliable
installations, with high energetic efficiency;
- assuring the necessary thermal energy for the municipality of Târgovişte from its own
source for the following 20 years;
- realizing 1,959,461 Euro worth investments in the infrastructure without using funds
from the state budget;
- creating new jobs;
- encouraging other foreign investments in the municipality.
The ERU 04/04 Contract was concluded between Senter Novem Agency from Holland,
from the part of the Government of Holland, and SC Nuon Energy Romania SRL Sibiu,
Romania - Project Developer, on September 28, 2004. In the year 2010 a transfer agreement
was concluded on the basis of the ERU 04/40 Contract from SC Nuon Energy Romania
SRL to SC Termica SA Târgovişte. The emission reductions generated by the project
beginning with January 1, 2010 are dealt with by SC Termica SA Târgovişte and the
above-mentioned Hollandese agency (Local Plan of Action for Environment of Dâmboviţa
County, 2010).
6. The air quality in relation to the population’s health condition

The environment in which people live is first of all defined by the quality of the air, of the
water, of the soil, of the dwellings, of the foods they eat, and of the environment in which
they deploy their activity. Closely connected to these factors, influenced or determined
immediately or after a certain period of time is the population’s health condition.
The evaluation of the population’s health condition consists in the identification of the
hazard factors that in the urban area have an influence on: air quality; potable water supply;
gathering and removing liquid and solid residues of any nature; urban noise; habitat –
improper conditions (noise, light, population agglomeration etc.); services quality (of all
types) provided to the population (Pehoiu et al., 2006).
Knowing and determining some environmental hazard factors is particularly important and
may constitute one of the most valuable activities related to the promotion and maintaining
of the population’s health condition (Pehoiu &n Murărescu, 2009).
The action of the environmental factors on human health is very diverse. When the pollution
intensity is higher, the action on organisms is immediate. However, more often than not,
their action has a low intensity, determining a chronic, long-term action, the quantification
of the effect becoming difficult to achieve. The atmospheric pollution in general and
especially the exposure to dusts in suspension produces diseases of the respiratory,
digestive, osteo-muscular and nervous systems and of the sensory organs, affecting all the
age groups; however, when it comes to children, it determines an early predisposition to
respiratory diseases and bronchial asthma. The irritating capacity of the dusts in suspension
increases when, in the air, there are other irritating respiratory pollutants, such as SO2 and
NO2, as a synergic effect comes into operation from the SO2 - dusts in suspension and NO2 -
dusts in suspension (Table 9).
Number of
Types of diseases
occurrences
1. Diseases of the respiratory system, of
which:
- acute bronchitis 1963
- chronic bronchitis 123
- bronchial asthma 110
2. Digestive diseases 8168
3. Cardiovascular diseases 4841
4. Endocrine and metabolic diseases 2966
5. Malignant tumors, of which:
- pulmonary cancer 21
6. Congenital malformations 16
7. Renal system diseases 7962
8. Flu 43
Table 9. Specific morbidity on the level of the year 2009 in the urban area of Dâmboviţa
County (source: Public Health Direction of Dâmboviţa County).
In the prevention of diseases caused by the exposure of the population to different

atmospheric pollutants, a special importance goes to their prophylaxis. In this sense, one
should have in view the maintaining of the concentration of the toxic substances from the
environment under the level of the maximum allowable concentrations (MAC) stipulated in
the norms (STAS).
7. Conclusions
In Dâmboviţa County and implicitly in Târgovişte municipality and its surroundings, the
distribution of the sampling equipments available and the organization of the air quality
monitoring network was carried out in the sense of assuring especially the monitoring of the
areas most likely to be affected by impact pollution.
The pollutants to be monitored, the methods of measurement, the limit values, the alert and
the information thresholds and the criteria for the location of the monitoring points are
established by the national legislation concerning the atmospheric protection and meet the
requirements foreseen by the European regulations.
The air quality has undergone a slight improvement compared to the previous years from
the viewpoint of the pollution with different dusts.
The gaseous pollutants (nitrogen dioxide, sulphur dioxide, ammonia, sulphuretted

hydrogen, formaldehyde, oxidant substances, and carbon monoxide) are not present in the
atmosphere in concentrations above the allowable limits in the areas in which they are
monitored.
The dominant pollution is represented by dusts in suspension (in the area of Târgovişte, in
Doiceşti and its surroundings), and by pollution with settleable dusts in Fieni area.
8. References
Agenţia Naţională pentru Protecţia Mediului (National Agency for Environment
Protection), statistical data, 2000-2010, Bucharest, Romania.
Anuarul statistic al judeţului Dâmboviţa (Statistical Yearbook of Dâmboviţa County), 2000-
2010, Târgovişte, Romania.
Direcţia de Sănătate Publică Dâmboviţa (Public Health Department Dâmboviţa), statistical
data, 2000-2010, Târgovişte, Romania.
Direcţia Judeţeană de Statistică Dâmboviţa (Statistical Department of Dâmboviţa County),
statistical data, 2000-2010, Târgovişte, Romania.
Ministerul Mediului şi Pădurilor (Ministry of Environment and Forestry), statistical data,
2000-2010, Târgovişte, Romania.
Murărescu, O.; Pehoiu, G. (2009). Integrated management of environmental pollution due tu
the County Dâmboviţa industrial activiy. Annals - Food Science and Technology, Vol.
10, Issue 2, 2009, pp. 681-686, ISSN 2065-2828, “Valahia” University, Târgovişte,
Romania.
Pehoiu, G. (2003). Câmpia Înaltă a Târgoviştei. Studiu de geografie umană şi economică
(Târgovişte High Plain. Study of Human and Economical Geography), Cetatea de
Scaun, ISBN 973-7925-01-7, Târgovişte, Romania.
Pehoiu, G. (2006). Actual aspects related to the quality of the air in the county Dâmboviţa, in
report with the status of health of the population. International Multidisciplinary
Symposium „Universitaira Sempro 2006”, Ingineria mediului (Environment
Engineering), ISSN: 1842-4449, Petroşani, 2006.
Pehoiu, G.; Muică, C.; Sencovici, M. (2006). Geografia mediului cu elemente de ecologie
(Environment Geography with Elements of Ecology), Transversal, ISBN (10) 973-
7798-32-5, ISBN: (13) 978-973-7798-32-9, Târgovişte, Romania.
Pehoiu G.; Murărescu O. (2009). Climate Change Impact on Environment and Health of
the Population in Dâmboviţa County, Romania, Proceedings of the 2nd WSEAS
International Conference on Climate Changes, Global Warming, Biological Problems
(CGB ’09), ISSN:1790-5095, ISBN: 978-960-474-136-6, Morgan State University,
Baltimore, USA, November 7-9, 2009.
Pehoiu G.; Simion T.; Murărescu O.M. (2005). Climat urbain, et la pollution de l’air dans les
villes industrielles. Etude de cas - La ville de Târgovişte (Roumanie). XVIIIe
Colloque Internationale de Climatologie, Genova, 7-11 septembrie 2005. In: Climat
urbain, ville et architecture, ed. Gerardo Brancucci, pp. 39-42, Laboratoire de
Géomorphologie Apliquée, Département Polis, Université de Gênes, Retrieved
from http://climato.ulg.ac.be/doc/AIC-table.pdf.
Pehoiu G. (2008). The impact of human activities on environmental quality in Dâmboviţa

county. In Present Environment and Sustainable Development, Vol. 2, pp. 283-296,
„Alexandru Ioan Cuza” University, ISSN 1843-5971, Iaşi, Romania.
Planul Local de Acţiune pentru Mediu al Judeţului Dâmboviţa (Local Plan of Action for
Environment of Dâmboviţa County), 2010, Târgovişte, Romania.
Agenţia pentru Protecţia Mediului - Dâmboviţa (Agency for Environmental Protection -
Dâmboviţa County), Raport privind starea mediului în judeţul Dâmboviţa (Report
regarding state of the environment in Dâmboviţa County), 2000-2010, Târgovişte,
Romania.
2
Comprehensive Comparison of Trace Metal

Concentrations in Inhaled Air Samples
Mehmet Yaman
Firat University, Science Faculty,
Department of Chemistry, Elazig
Turkey
1. Introduction
Because metals cannot be degraded or destroyed, the assessment of the health risks of
metals via ambient air and dietary intake is an issue of special interest. Trace metals in air
phase can be classified as metals or metalloids including the semi-metallic elements: boron,
arsenic, selenium, and tellurium. Both natural and anthropogenic processes and sources
emit metals and their compounds into the air. Anthropogenics; the processing of minerals,
incineration of metallic objects, motor vehicle combustion of fuel containing metal additives,
and the wearing out of motor vehicle tyres and brake pads result in the emission of metals
associated with particulate matter. Metals occur naturally in soil and in rocks rich with
minerals; thus weathering of the rocks, mining activities or even wind-blown dust can
release these metals into air as particulate matter. Trace metals are part of a large group of
air pollutants called air toxics, which upon inhalation or ingestion can be responsible for a
range of health effects such as cancer, neurotoxicity, immunotoxicity, cardiotoxicity,
reproductive toxicity, teratogenesis and genotoxicity (1-4).
When inhaled, very small particles containing metals or their compounds deposit beyond
the bronchial regions of the lungs into the alveoli region. Epidemiological studies have
established relationships between inhaled suspended particulate matter and morbidity/
mortality in populations (6-7). Studies in occupational or community settings have
established the health effects of exposure to trace metals, such as lead, cadmium, nickel and
their compounds (8-9). The accumulation of metals in human body can have middle and
long-term health risks and can adversely affect the physiological functions (1-4). Metals can
enter the human body mainly through inhalation and ingestion, with the diet being the
main route of human exposure for non-occupationally exposed individuals. To evaluate and
reduce the health and environmental effects of toxic metals in inhaled ambient air and food
matrices, it is vitally important to know their chemical compositions and the way they vary
in time and in space. Therefore, there are continuing efforts to determine particularly toxic
metals such as Pb, Cd and Ni in air phases and food samples (10-14). In considering lead
and cadmium in ambient air samples, this importance increases because the absorption rates
of those metals by inhalation are significantly higher (up to 50-60%) than those by ingestion
(between 3% and 10%) (10). The localized release of some heavy metals from inhaled
particulate matter has been hypothesized to be responsible for the lung tissue damage.
In spite of all these facts, there are fewer studies available on Pb and Cd determinations in
air samples compared to other food matrices due to, probably, the excessively lower
concentrations of those metals in aerial matrix than the sensitivities of analysis methods (7,
9-12). In order to overcome those difficulties except using analytical techniques with high
sensitivity such as electrothermal atomic absorption spectrometry (ETAAS), and inductively
coupled plasma-mass spectrometry (ICP-MS), there are increased attentions to the usage of
biomonitoring plants and plant parts such as leaves and shoots as biomonitoring (15-18).
2. Legislation
The emissions of three heavy metals, lead, mercury and cadmium, are being regulated in
Europe under the Convention on Long-range Transboundary Air Pollution (19). This
convention is the first international, legally binding instrument to deal with problems of air
pollution on a broad regional basis. It covers 42 countries in Europe and North America
and the European Union. Since entering into force in 1983, the Convention has been
extended by several protocols dealing with specific pollutants. The Aarhus Protocol (20),
the Protocol on Heavy Metals in June 1998, in Aarhus, Denmark (UN/ECE, 2000), targets
three particularly harmful metals: cadmium, lead and mercury, to set a framework for
national legislation that will lead to the substantial decrease in the emissions of the three
metals in Europe and North America. The protocol seeks to cut emissions of heavy metals
from industrial sources, combustion processes and waste incineration. The Protocol will
enter into force when ratified by sixteen signatory countries; as of 3 July 2000, only six
countries had ratified the Protocol (21).
Air toxics are not regulated under the National Environment Protection Measure (NEPM)
for Ambient Air Quality, which addresses criteria pollutants in ambient air (22). However, a
program initiated by the Commonwealth Government, the Living Cities-Air Toxics Program
(ATP) was aimed at addressing urban air quality issues by supporting the development of
national approaches to the management of 'air toxics'. For the purpose of the Living Cities
initiative, air toxics are defined as: “…gaseous, aerosol or particulate pollutants (other than the
six criteria pollutants) which are present in the air in low concentrations with characteristics such as
toxicity or persistence so as to be a hazard to human, plant or animal life…” (23). The terms 'air
toxics' and 'hazardous air pollutants' (HAPs) are used interchangeably (24). The Technical
Advisory Group (TAG) for the ATP included the metals cadmium, chromium (VI), mercury,
nickel and their compounds in the list of 28 priority air toxics identified in the ATP. Further,
lead is the most routinely monitored heavy metal in ambient air in some countries as a
result of its presence in motor vehicle fuel (25).
3. Speciation and toxicity

Compared to gaseous compounds, the assessment of metal and metalloid compounds in
inhaled ambient air is complicated by the fact that different species with considerably
differing toxicity and/or carcinogenic potency may be encountered. In order to fully
evaluate the health effects, it is important to know which species do occur in the
environment or at least which compounds form the main constituents. In ambient air,
metals, metalloids and their compounds are mainly encountered as part of particulate
matter. They may be present in the non soluble, non stoichiometric mixture phase such as
Comprehensive Comparison of Trace Metal Concentrations in Inhaled Air Samples 31
spinels or as soluble ionic compounds such as salts. In respect to their effects on the
environment and on human health, gaseous forms such as organometallic compounds can
be characterized by other parameters, such as water solubility (extended to solubility in
biological fluids), particle size distribution, morphology and specific surface area, and
chemical heterogeneity of the particles, or the concentration of metals and metalloids in the
particles ultimately contacting target tissues in the human body (26). For example, a metal
compound is encapsulated in another aerosol or surface enrichment of volatile species.
All parameters mentioned will influence the bioavailability and possible effects. In addition,
metal and metalloid containing substances can undergo various chemical and physical
transformations in the atmosphere on their way from the source to a possible receptor. For
example, As (III) compounds may be oxidized to As (V). Unfortunately, analytical methods
normally only identify the elements which are present in atmospheric particles, species
specific analysis being extremely difficult in the concentration range occurring in ambient
air (typically several ng/m³. In addition, the state of oxidation may change during
sampling. Consequently, information on the concentration of different species in ambient
air is very limited at present. Further, the limited knowledge available on the occurrence
of species is outlined.
Trace elements are found naturally in the environment and human exposure derives from a
variety of sources, including air, drinking water, and food. Concentrations of trace elements in
the air are generally low. Levels of As in the air range from approximately 1 to 2,000 ng/m3,
levels of Cd generally range from 1 to 40 ng/m3 but can reach up to 100 ng/m3 near emission
sources, and levels of Ni in cities and rural areas range from 7 to 12 ng/m3 (27-54). Workers in
the smelting and refining industries and those employed in the production of batteries,
coatings, and plastics can be exposed to much higher levels of airborne Cd and Ni (55).
3.1 Trace metal uses and their health effects

3.1.1 Arsenic
There are three major groups of arsenic (As) compounds: inorganic arsenic compounds,
organic arsenic compounds, arsine gas and substituted arsines.
Elemental arsenic is utilized in alloys in order to increase their hardness and heat resistance.
It is also used in the manufacture of certain types of glass, as a component of electrical
devices and as a doping agent in germanium and silicon solid-state products. The uses and
source of arsenic compounds are summarized in Table 1.
Organic arsenic compounds in marine organisms occur in concentrations corresponding to a
concentration of arsenic in the range 1 to 100 mg/kg in marine organisms such as shrimp
and fish. Such arsenic is mainly made up of arsenobetaine and arsenocholine, organic
arsenic compounds of low toxicity (56). The substituted arsines are trivalent organic
arsenical compounds which, depending on the number of alkyl or phenyl groups that they
have attached to the arsenic nucleus, are known as mono-, di- or tri-substituted arsines.
Dichloroethylarsine (C2H5AsCl2), or ethyldichloroarsine, is a colourless liquid with an
irritant odour. This compound was developed as a potential chemical warfare agent.
Dichloro(2-chlorovinyl-) arsine (ClCH:CHAsCl2), or chlorovinyldichloroarsine (lewisite), is
an olive-green liquid with a germanium-like odour. It was developed as a potential warfare

agent but never used according to our knowledge. Dimethyl-arsine (CH3)2AsH, or cacodyl
hydride and trimethylarsine (CH3)3As), or trimethylarsenic, are both colourless liquids.
These two compounds can be produced after metabolic transformation of arsenic
compounds by bacteria and fungi.
Compound Uses/Source
ceramics industry, manufacturing of chlorine-
Arsenic trichloride (AsCl3)
containing arsenicals
purification of synthesis gas, as a primary
material for all arsenic compounds, preservative
Arsenic trioxide (As2O3), or white arsenic for hides and wood, a textile mordant, a reagent
in mineral flotation, a decolourizing and refining
agent in glass manufacture
Calcium arsenite (Ca(As2H2O4), Calcium
insecticides
arsenate (Ca3(AsO4)2)
Cacodylic acid ((CH3)2AsOOH) herbicide and a defoliant
cupric acetoarsenite (usually considered
Insecticides, for painting ships and submarines
Cu(COOCH3)2 3Cu(AsO2)2)
herbicide, a corrosion inhibitor, as a drying agent
Sodium arsenite (NaAsO2)
in the textile industry
a component of infrared-transmitting glass, a
dehairing agent in the tanning industry, the
Arsenic trisulphide
manufacturing of pyrotechnics and
semiconductors
the manufacturing of arsenates, glass making,
Arsenic acid (H3AsO4·½H2O)
wood-treating processes
Herbicide, a wood preservative, in the
Arsenic pentoxide (As2O5)
manufacture of coloured glass
Arsanilic acid (NH2C6H4AsO(OH)2) as a grasshopper bait, as an additive in animal feeds
in organic syntheses, in the processing of solid-
state electronic components, inadvertently in
Arsine gas
industrial processes when nascent hydrogen is
formed and arsenic is present
Table 1. Arsenic compounds and their uses/source.
3.1.1.1 Toxicity
Although it is possible that very small amounts of certain arsenic compounds may have
beneficial effects, as indicated by some animal studies, arsenic compounds, particularly the
inorganic ones, are otherwise regarded as very potent poisons. Acute toxicity varies widely
among compounds, depending on their valency state and solubility in biological media. The
soluble trivalent compounds are the most toxic. Uptake of inorganic arsenic compounds
from the gastrointestinal tract is almost complete, but uptake may be delayed for less
soluble forms such as arsenic trioxide in particle form. Uptake after inhalation is also almost
complete, since even less soluble material deposited on the respiratory mucosa, will be
transferred to the gastrointestinal tract and subsequently taken up. The health effects of
arsenic were summarized in Table 2.
Metal-
Diagnosis/medical
Route of Health effects
monitoring
exposure
Inorganic - Acute exposure: nausea, diarrhea, Gastro intestinal Urinary arsenic level
and organic (GI ) bleeding, cardiovascular effects, shock, and is the most reliable
As- death. Liver, kidney damage and seizures have been indicator of recent
inhalation, reported. exposure to arsenic.
ingestion, - Chronic exposure: hyperpigmentation of skin, warts, Arsenic in hair and
skin corns, heart disease, neuropathy, liver damage, fingernails can
peripheral vascular disease (gangrene of lower indicate exposure to
limbs), and increased risk of skin, liver, lung and high levels in the
bladder cancer. Arsenic in drinking water can also past 6–12 months.
cause diabetes and hypertension.
- Anaemia, leucopenia and granulocytopenia
- The soluble trivalent compounds are the most toxic
- The fatal dose of ingested arsenic trioxide has been
reported to range from 70 to 180 mg. Death may
occur within 24 hours, but the usual course runs from
3 to 7 days.
- Cancer of the respiratory tract has been reported in
excess frequency among workers engaged in the
production of insecticides containing lead arsenate
and calcium arsenate, in vine-growers spraying
insecticides containing inorganic copper and arsenic
compounds, and in smelter workers exposed to
inorganic compounds of arsenic and a number of
other metals. The latency time between onset of
exposure and the appearance of cancer is long,
usually between 15 and 30 years.
- Arsine is one of the most powerful haemolytic agents
found in industry. Inhalation of 250 ppm of arsine
gas is instantly lethal. Exposure from 25 to 50 ppm
for 30 minutes is lethal, and 10 ppm may be lethal
after longer exposures.
Cd- - Cell proliferation, differentiation, apoptosis, and Cadmium levels in
inhalation, other cellular activities, numerous molecular lesions blood are mainly an
ingestion caused carcinogenesis. indication of the last
- Cadmium targets the lung, liver, kidney, and testes. few months
- In acute intoxication: nephrotoxicity, immunotoxicity, exposure, but can be
osteotoxicity, and tumors after prolonged exposures. used to assess body
- Prostate, lung, testicular, renal, and skeletal cancers. burden a few years
- In vivo: Generate O2•−, H2O2, and •OH accompanied after exposure has
by activation of redox-sensitive transcription factors. ceased.
- After inhalation above 1 mg Cd/m3 in air for 8 hours; The individual
chemical pneumonitis, and in severe cases critical
pulmonary oedema. concentrations of
Metal-
Diagnosis/medical
monitoring
exposure
- After ingestion of drinks exceeding 15 mg Cd/l; cadmium in urine
Cd- nausea, vomiting, abdominal pains and sometimes and/or in blood are
inhalation, diarrhoea. 50 nmol/l whole
ingestion - Prolonged exposure in air at concentrations blood or 3
exceeding 0.1 mg Cd/m3 ; Pulmonary emphysema nmol/mmol
- Exposure for more than 20 years to concentrations of creatinine.
about 0.02 mg Cd/m3 , certain pulmonary effects.
- Exceeding 200 µg Cd/g (this is critical concentration)
wet weight of renal cortex; tubular dysfunction with
decreased reabsorption of proteins from the urine,
tubular proteinuria with increased excretion of low-
molecular-weight proteins.
- The average cadmium concentration in workroom
air (8 hours per day) should not exceed 0.01 mg
Cd/m3.
Lead- - Hematologic: decreased heme synthesis enzymes, Lead in whole blood
Inhalation, anemia. is a reliable test.
ingestion, - Cardiovascular: elevated blood pressure. Erythrocyte
skin - Cognitive, neurobehavioral, and psychological protoporphyrin (EP)
effects. test can also be used
- Gastrointestinal: colic or abdominal cramps. but it is not sensitive
- Peripheral neuropathy; encephalopathy (at high to detect high levels
levels). of lead in children.
- Reduced fertility.
- Immune system: alterations in T cell, reduced IgG
serum levels.
- Children: lethargy, loss of appetite, anemia, colic,
neurological impairment, and impaired metabolism
of Vit D.
- Exposure in uterus and during childhood can result
in impaired neurological development, IQ deficits,
and growth retardation.
Mercury- - All forms of mercury are toxic to the central nervous Acute exposure is
Inhalation, system (CNS). best measured by
ingestion - Exposure to high levels can damage brain, kidneys, mercury in blood
and developing fetus. (methyl mercury is the most and chronic
toxic form). exposure
- Toxicity to brain results in irritability, tremors, visual by mercury in urine
changes, and memory problems.
- Mercury salts can cause abdominal cramps, diarrhea,
and kidney damage.
Metal-
Diagnosis/medical
monitoring
exposure
Nickel- - The National Maximum Workplace Concentration
Inhalation, Committee (NMWCC) of the Netherlands proposed
ingestion that urine nickel concentration 40 µg/g creatinine, or
serum nickel concentration 5 µg/l (both measured in
samples obtained at the end of a working week or a
work shift) be considered warning limits for further
investigation of workers exposed to nickel metal or
soluble nickel compounds.
- Exposures are classified as “mild” if the initial 8-h
specimen of urine has a nickel concentration less than
100 µg/l, “moderate” if the nickel concentration is
100 to 500 µg/l, and “severe” if the nickel
concentration exceeds 500 µg/l.
- Chronic exposure of workers to inhalation of low
atmospheric concentrations of nickel carbonyl (0.007
to 0.52 mg/m3) can cause neurological symptoms
such as insomnia, headache, dizziness, memory loss,
and other manifestations including chest tightness,
excessive sweating, alopecia.
Table 2. Reported metal toxicity and diagnosis/medical monitoring.
Occupational exposure to inorganic arsenic compounds through inhalation, ingestion or

skin contact with subsequent absorption may occur in industry. Acute effects at the point of
entry may occur if exposure is excessive. Dermatitis may occur as an acute symptom but is
more often the result of toxicity from long-term exposure, sometimes subsequent to
sensitization.
In occupational exposure to mainly airborne arsenic, skin lesions may result from local
irritation. Two types of dermatological disorders may occur:
1. an eczematous type with erythema (redness), swelling and papules or vesicles
2. a follicular type with erythema and follicular swelling or follicular pustules.
Dermatitis is primarily localized on the most heavily exposed areas, such as the face, back of
the neck, forearms, wrists and hands. Patch tests have demonstrated that the dermatitis is
due to arsenic, not to impurities present in the crude arsenic trioxide. Chronic dermal
lesions may follow this type of initial reaction, depending on the concentration and duration
of exposure. These chronic lesions may occur after many years of occupational or
environmental exposure. Hyperkeratosis, warts and melanosis of the skin are the
conspicuous signs (57).
3.1.1.2 Carcinogenic effects
Inorganic arsenic compounds are classified by the International Agency for Research on
Cancer (IARC) as lung and skin carcinogens (58). There is also some evidence to suggest that
persons exposed to inorganic arsenic compounds suffer a higher incidence of angiosarcoma

of the liver and possibly of stomach cancer. A synergistic action of tobacco smoking has
been demonstrated for lung cancer. Long-term exposure to inorganic arsenic via drinking
water has been associated with an increased incidence of skin cancer. This increase has been
shown to be related to concentration in drinking water.
3.1.1.3 Organic arsenic compounds
Organic arsenicals used as pesticides or as drugs may also give rise to toxicity, although
such adverse effects are incompletely documented in humans. Toxic effects on the nervous
system have been reported in experimental animals following feeding with high doses of
arsanilic acid, which is commonly used as a feed additive in poultry and swine.
The organic arsenic compounds that occur in foodstuffs of marine origin, such as shrimp,
crab and fish, are made up of arsinocholine and arsinobetaine. It is well known that the
amounts of organic arsenic that are present in fish and shellfish can be consumed without ill
effects because these compounds are quickly excreted, mainly via urine.
Many cases of acute arsine poisoning have been recorded, and there is a high fatality rate.
Arsine is one of the most powerful haemolytic agents found in industry. Its haemolytic
activity is due to its ability to cause a fall in erythrocyte-reduced glutathione content. Signs
and symptoms of arsine poisoning include haemolysis, which develops after a latent period
that is dependent on the intensity of exposure. Inhalation of 250 ppm of arsine gas is
instantly lethal. Exposure from 25 to 50 ppm for 30 minutes is lethal, and 10 ppm may be
lethal after longer exposures. The signs and symptoms of poisoning are those characteristic
of an acute and massive haemolysis. After acute and severe exposure, a peripheral
neuropathy may develop and can still be present several months after poisoning. Little is
known about repeated or chronic exposure to arsine, but since the arsine gas is metabolized
to inorganic arsenic in the body, it can be assumed that there is a risk for symptoms similar
to those in long-term exposure to inorganic arsenic compounds (59).
3.1.2 Cadmium
Cadmium (Cd) has many chemical and physical similarities to zinc and occurs together with
zinc in nature. In minerals and ores, cadmium and zinc generally have a ratio of 1:100 to
1:1,000. Cadmium is highly resistant to corrosion and has been widely used for
electroplating of other metals, mainly steel and iron. Screws, screw nuts, locks and various
parts for aircraft and motor vehicles are frequently treated with cadmium in order to
withstand corrosion. Nowadays, however, only 8% of all refined cadmium is used for
platings and coatings. It was established that Cd of used in developed and industrialized
countries is about 3% in certain alloys, 8% for platings and coatings, 30% for pigments and
stabilizers in plastics, 55% for rechargeable, small portable cadmium-containing batteries
used in mobile telephones and similars.
The most important Cd compound is cadmium stearate, which is used as a heat stabilizer
in polyvinyl chloride (PVC) plastics. Cadmium sulphide and cadmium sulphoselenide are
used as yellow and red pigments in plastics and colours. Cadmium sulphide is also used
in photo- and solar cells. Cadmium chloride acts as a fungicide, an ingredient in
elecroplating baths, a colourant for pyrotechnics, an additive to tinning solution and a
mordant in dyeing and printing textiles. It is also used in the production of certain
photographic films and in the manufacture of special mirrors and coatings for electronic
vacuum tubes. Cadmium oxide is an elecroplating agent, a starting material for PVC heat
stabilizers and a component of silver alloys, phosphors, semiconductors and glass and
ceramic glazes (60).
As a result, cadmium can represent an environmental hazard, and many countries have
introduced legislative actions aimed towards decreasing the use and subsequent
environmental spread of cadmium.
3.1.2.1 Toxicity
The health effects of cadmium were summarized in Table 2. Metallothioneins play a role in
the homeostasis of essential metals such as copper, detoxification of toxic metals such as
cadmium, and protection against oxidative stress. Gastrointestinal absorption of ingested
cadmium is about 2 to 6% under normal conditions. Individuals with low body iron stores,
reflected by low concentrations of serum ferritin, may have considerably higher absorption
of cadmium, up to 20% of a given dose of cadmium. Significant amounts of cadmium may
also be absorbed via the lung from the inhalation of tobacco smoke or from occupational
exposure to atmospheric cadmium dust. Pulmonary absorption of inhaled respirable
cadmium dust is estimated at 20 to 50%. After absorption via the gastrointestinal tract or the
lung, cadmium is transported to the liver, where production of a cadmium-binding low-
molecular-weight protein, metallothionein, is initiated (61).
About 80 to 90% of the total amount of cadmium in the body is considered to be bound to
metallothionein. This prevents the free cadmium ions from exerting their toxic effects. It is
likely that small amounts of metallothionein-bound cadmium are constantly leaving the
liver and being transported to the kidney via the blood. The metallothionein with the
cadmium bound to it is filtered through the glomeruli into the primary urine. Like other
low-molecular-weight proteins and amino acids, the metallothionein-cadmium complex is
subsequently reabsorbed from the primary urine into the proximal tubular cells, where
digestive enzymes degrade the engulfed proteins into smaller peptides and amino acids.
Free cadmium ions in the cells result from degradation of metallothionein and initiate a new
synthesis of metallothionein, binding the cadmium, and thus protecting the cell from the
highly toxic free cadmium ions. Kidney dysfunction is considered to occur when the
metallothionein-producing capacity of the tubular cells is exceeded. The kidney and liver
have the highest concentrations of cadmium, together containing about 50% of the body
burden of cadmium. The cadmium concentration in the kidney cortex, before cadmium-
induced kidney damage occurs, is generally about 15 times the concentration in liver.
Elimination of cadmium is very slow. As a result of this, cadmium accumulates in the body,
the concentrations increasing with age and length of exposure (62). Based on organ
concentration at different ages the biological half-life of cadmium in humans has been
estimated in the range of 7 to 30 years.
3.1.2.2 Acute toxicity
Inhalation of cadmium compounds at concentrations above 1 mg Cd/m3 in air for 8 hours,
or at higher concentrations for shorter periods, may lead to chemical pneumonitis, and in
severe cases pulmonary oedema. Symptoms generally occur within 1 to 8 hours after
exposure. They are influenza-like and similar to those in metal fume fever. The more severe
symptoms of chemical pneumonitis and pulmonary oedema may have a latency period up
to 24 hours. Death may occur after 4 to 7 days. Exposure to cadmium in the air at
concentrations exceeding 5 mg Cd/m3 is most likely to occur where cadmium alloys are
smelted, welded or soldered. Ingestion of drinks contaminated with cadmium at
concentrations exceeding 15 mg Cd/l gives rise to symptoms of food poisoning. Symptoms
are nausea, vomiting, abdominal pains and sometimes diarrhoea. Sources of food
contamination may be pots and pans with cadmium-containing glazing and cadmium
solderings used in vending machines for hot and cold drinks. In animals parenteral
administration of cadmium at doses exceeding 2 mg Cd/kg body weight causes necrosis of
the testis. No such effect has been reported in humans.
3.1.2.3 Chronic toxicity
Chronic cadmium poisoning has been reported after prolonged occupational exposure to
cadmium oxide fumes, cadmium oxide dust and cadmium stearates. Changes associated
with chronic cadmium poisoning may be local, in which case they involve the respiratory
tract, or they may be systemic, resulting from absorption of cadmium. Systemic changes
include kidney damage with proteinuria and anemia. Lung disease in the form of
emphysema is the main symptom at heavy exposure to cadmium in air, whereas kidney
dysfunction and damage are the most prominent findings after long-term exposure to lower
levels of cadmium in workroom air or via cadmium-contaminated food. Mild hypochromic
anemia is frequently found among workers exposed to high levels of cadmium. This may be
due to both increased destruction of red blood cells and to iron deficiency. Yellow
discolouration of the necks of teeth and loss of sense of smell (anosmia) may also be seen in
cases of exposure to very high cadmium concentrations.
Pulmonary emphysema is considered a possible effect of prolonged exposure to cadmium in
air at concentrations exceeding 0.1 mg Cd/m3. It has been reported that exposure to
concentrations of about 0.02 mg Cd/m3 for more than 20 years can cause certain pulmonary
effects. Cadmium-induced pulmonary emphysema can reduce working capacity and may
be the cause of invalidity and life shortening. With long-term low-level cadmium exposure
the kidney is the critical organ (i.e., the organ first affected). Cadmium accumulates in renal
cortex. Concentrations exceeding 200 µg Cd/g wet weight have previously been estimated
to cause tubular dysfunction with decreased reabsorption of proteins from the urine (63).
This causes tubular proteinuria with increased excretion of low-molecular-weight proteins
such as α,α-1-microglobulin (protein HC), β-2-microglobulin and retinol binding protein
(RTB). Recent research suggests, however, that tubular damage may occur at lower levels of
cadmium in kidney cortex. As the kidney dysfunction progresses, amino acids, glucose and
minerals, such as calcium and phosphorus, are also lost into the urine. Increased excretion of
calcium and phosphorous may disturb bone metabolism, and kidney stones are frequently
reported by cadmium workers. After long-term medium-to-high levels of exposure to
cadmium, the kidney’s glomeruli may also be affected, leading to a decreased glomerular
filtration rate. In severe cases uraemia may develop. Excessive cadmium exposure has
occurred in the general population through ingestion of contaminated rice and other
foodstuffs, and possibly drinking water. The itai-itai disease, a painful type of osteomalacia,
with multiple fractures appearing together with kidney dysfunction, has occurred in Japan
in areas with high cadmium exposure. Though the pathogenesis of itai-itai disease is still
under dispute, it is generally accepted that cadmium is a necessary aetiological factor. It
should be stressed that cadmium-induced kidney damage is irreversible and may grow
worse even after exposure has ceased.
3.1.2.4 Carcinogenic effects
Cd competes with Zn for binding sites and can therefore interfere with some of Zinc’s
essential functions. Thus, it may inhibit enzyme reactions and utilization of nutrients. Cd
can generate free radical tissue damage because it may be a catalyst to oxidation reactions.
Furthermore, excessive Cd exposure can cause renal damage, reproduction problems,
cardiovascular diseases and hypertension. There are several sources of human exposure to
Cd, including employment in primary metal industries, production of certain batteries,
some electroplating processes and consumption of tobacco products. Consequently, it was
reported by International Agency Research on Cancer (IARC) that through inhalation
cadmium could cause lung cancer in humans and animals (64). As a result, the World
Health Organization (WHO) (65) established provisional tolerable weekly intakes (PTWIs)
of Cd of 0.007 microgram/kg body weight, for all human groups.
There is strong evidence of dose-response relationships and an increased mortality from
lung cancer in several epidemiological studies on cadmium-exposed workers. The
interpretation is complicated by concurrent exposures to other metals which are known or
suspected carcinogens. Continuing observations of cadmium-exposed workers have,
however, failed to yield evidence of increased mortality from prostatic cancer, as initially
suspected. The IARC in 1993 (64) assessed the risk of cancer from exposure to cadmium and
concluded that it should be regarded as a human carcinogen. Since then additional
epidemiological evidence has come forth with somewhat contradictory results, and the
possible carcinogenicity of cadmium thus remains unclear. It is nevertheless clear that
cadmium possesses strong carcinogenic properties in animal experiments.
3.1.2.5 Limitations
The kidney cortex is the critical organ with long-term cadmium exposure via air or food.
The critical concentration is estimated at about 200 µg Cd/g wet weight, but may be lower,
as stated above. In order to keep the kidney cortex concentration below this level even after
lifelong exposure, the average cadmium concentration in workroom air (8 hours per day)
should not exceed 0.01 mg Cd/m3.
To ensure that excessive accumulation of cadmium in the kidney does not occur, cadmium
levels in blood and in urine should be checked regularly. Cadmium levels in blood are
mainly an indication of the last few months exposure, but can be used to assess body burden
a few years after exposure has ceased. A value of 100 nmol Cd/l whole blood is an
approximate critical level if exposure is regular for long periods. Cadmium values in urine
can be used to estimate the cadmium body burden, providing kidney damage has not
occurred. It has been estimated by the WHO that 10 nmol/mmol creatinine is the
concentration below which kidney dysfunction should not occur. Recent research has,
however, shown that kidney dysfunction may occur already at around 5 nmol/mmol
creatinine. Since the mentioned blood and urinary levels are at levels at which action of
cadmium on kidney has been observed, it is recommended that control measures should be
applied whenever the individual concentrations of cadmium in urine and/or in blood
exceed 50 nmol/l whole blood or 3 nmol/mmol creatinine respectively.
3.1.3 Chromium
In addition to chromic acid, the ferrous chromite (FeOCr2O3) ore contains variable quantities
of other substances. Only ores or concentrates containing more than 40% chromic oxide
(Cr2O3) are used commercially, and countries having the most suitable deposits are the
Russian Federation, South Africa, Zimbabwe, Turkey, the Philippines and India. The prime
consumers of chromites are the United States, the Russian Federation, Germany, Japan,
France and the United Kingdom.
The most significant usage of pure chromium is for electroplating of a wide range of
equipment, such as automobile parts and electric equipment. Chromium is used extensively
for alloying with iron and nickel to form stainless steel, and with nickel, titanium, niobium,
cobalt, copper and other metals to form special-purpose alloys.
Chromium forms a number of compounds in various oxidation states. Those of II
(chromous), III (chromic) and VI (chromate) states are most important; the II state is basic,
the III state is amphoteric and the VI state is acidic. Commercial applications mainly concern
compounds in the VI state, with some interest in III state chromium compounds.
The chromous state (CrII) is unstable and is readily oxidized to the chromic state (CrIII). This
instability limits the use of chromous compounds. The most important compounds
containing chromium in the CrVI state are dichromate compounds and chromium trioxide.
Compounds containing CrVI are used in many industrial operations: the manufacture of
important inorganic pigments such as lead chromes, molybdate-oranges, zinc chromate and
chromium-oxide green; wood preservation; corrosion inhibition; and coloured glasses and
glazes. Basic chromic sulphates are widely used for tanning. The dyeing of textiles, the
preparation of many important catalysts containing chromic oxide and the production of
light-sensitive dichromated colloids for use in lithography are also well-known industrial
uses of chromium-containing chemicals.
Chromic acid is used not only for “decorative” chromium plating but also for “hard”
chromium plating, where it is deposited in much thicker layers to give an extremely hard
surface with a low coefficient of friction.
Because of the strong oxidizing action of chromates in acid solution, there are many
industrial applications particularly involving organic materials, such as the oxidation of
trinitrotoluene (TNT) to give phloroglucinol and the oxidation of picoline to give nicotine
acid (66).
3.1.3.1 Toxicity
Compounds with CrIII oxidation states are considerably less hazardous than are CrVI
compounds. Compounds of CrIII are poorly absorbed from the digestive system. These CrIII
compounds may also combine with proteins in the superficial layers of the skin to form
stable complexes. Compounds of CrIII do not cause chrome ulcerations and do not generally
initiate allergic dermatitis without prior sensitization by CrVI compounds.
In the CrVI oxidation state, chromium compounds are readily absorbed after ingestion as well
as during inhalation. The uptake through intact skin is less well elucidated. The irritant and
corrosive effects caused by CrVI occur readily after uptake through mucous membranes, where
they are readily absorbed. Work-related exposure to CrVI compounds may induce skin and
mucous membrane irritation or corrosion, allergic skin reactions or skin ulcerations.
The untoward effects of chromium compounds generally occur among workers in
workplaces where CrVI is encountered, in particular during manufacture or use (67). The
effects frequently involve the skin or respiratory system. Typical industrial hazards are
inhalation of the dust or fumes arising during the manufacture of dichromate from chromite
ore and the manufacture of lead and zinc chromates, inhalation of chromic acid mists during
electroplating or surface treatment of metals, and skin contact with CrVI compounds in
manufacture or use. Exposure to CrVI-containing fumes may also occur during welding of
stainless steels.
Numerous sources of exposure to CrVI can be listed as contact with cement, plaster, leather,
graphic work, work in match factories, work in tanneries and various sources of metal work.
Workers employed in wet sandpapering of car bodies have also been reported with allergy.
Affected subjects react positively to patch testing with 0.5% dichromate.
It has been shown that CrVI penetrates the skin through the sweat glands and is reduced to
CrIII in the corium. It is shown that the CrIII then reacts with protein to form the antigen-
antibody complex. This explains the localization of lesions around sweat glands and why
very small amounts of dichromate can cause sensitization. The chronic character of the
dermatitis may be due to the fact that the antigen-antibody complex is removed more
slowly than would be the case if the reaction occurred in the epidermis.
Inhalation of dust or mist containing CrVI is irritating to mucous membranes. At high
concentrations of such dust, sneezing, rhinorrhoea, lesions of the nasal septum and redness of
the throat are documented effects. Sensitization has also been reported, resulting in typical
asthmatic attacks, which may recur on subsequent exposure. At exposure for several days to
chromic acid mist at concentrations of about 20 to 30 mg/m3, cough, headache, dyspnoea and
substernal pain have also been reported after exposure. The occurrence of bronchospasm in a
person working with chromates should suggest chemical irritation of the lungs.
In previous years, when the exposure levels to CrVI compounds could be high, ulcerations of
the nasal septum were frequently seen among exposed workers. This untoward effect
results from deposition of CrVI-containing particulates or mist droplets on the nasal septum,
resulting in ulceration of the cartilaginous portion followed, in many cases, by perforation at
the site of ulceration. Frequent nose-picking may enhance the formation of perforation.
Necrosis of the kidneys has also been reported, starting with tubular necrosis, leaving the
glomeruli undamaged. Diffuse necrosis of the liver and subsequent loss of architecture has
also been reported. Soon after the turn of the century there were a number of reports on
human ingestion of CrVI compounds resulting in major gastro-intestinal bleeding from
ulcerations of the intestinal mucosa. Sometimes such bleedings resulted in cardiovascular
shock as a possible complication. If the patient survived, tubular necrosis of the kidneys or
liver necrosis could occur.
Increased incidence of lung cancer among workers in manufacture and use of CrVI
compounds has been reported in a great number of studies from France, Germany, Italy,
Japan, Norway, the United States and the United Kingdom (68). Chromates of zinc and
calcium appear to be among the most potent carcinogenic chromates, as well as among the
most potent human carcinogens. Elevated incidence of lung cancer has also been reported
among subjects exposed to lead chromates, and to fumes of chromium trioxides. Heavy
exposures to CrVI compounds have resulted in very high incidence of lung cancer in
exposed workers 15 or more years after first exposure, as reported in both cohort studies
and case reports.
Thus, it is well established that an increase in the incidence of lung cancer of workers
employed in the manufacture of zinc chromate and the manufacture of mono- and
dichromates from chromite ore is a long-term effect of work-related heavy exposure to CrVI
compounds. Some of the cohort studies have reported measurements of exposure levels
among the exposed cohorts. Also, a small number of studies have indicated that exposure to
fumes generated from welding on Cr-alloyed steel may result in elevated incidence of lung
cancer among these welders.
There is no firmly established “safe” level of exposure. However, most of the reports on
association between CrVI exposure and cancer of the respiratory organs and exposure levels
report on air levels exceeding 50 mg CrVI/m3 air (69).
Water-soluble, acid soluble and water insoluble chromium is found in the lung tissues of
chromate workers in varying amounts.
Although it has not been firmly established, some studies have indicated that exposure to
chromates may result in increased risk of cancer in the nasal sinuses and the alimentary
tract. The studies that indicate excess cancer of the alimentary tract are case reports from the
1930s or cohort studies that reflect exposure at high levels than generally encountered today.
3.1.4 Iron
In addition to ferroalloys, the most important industrial iron compounds are the oxides and
the carbonate, which constitute the principal ores from which the metal is obtained. Of
lesser industrial importance are cyanides, nitrides, nitrates, phosphides, phosphates and
iron carbonyl.
3.1.4.1 Toxicity
Industrial dangers are present during the mining, transportation and preparation of the
ores, during the production and use of the metal and alloys in iron and steel works and in
foundries, and during the manufacture and use of certain compounds. Inhalation of iron
dust or fumes occurs in iron-ore mining; arc welding; metal grinding, polishing and
working; and in boiler scaling. If inhaled, iron is a local irritant to the lung and
gastrointestinal tract. Reports indicate that long-term exposure to a mixture of iron and
other metallic dusts may impair pulmonary function. Inhaling dust containing silica or iron
oxide can lead to pneumoconiosis, but there are no definite conclusions as to the role of iron
oxide particles in the development of lung cancer in humans. Based on animal experiments,
it is suspected that iron oxide dust may serve as a “co-carcinogenic” substance, thus
enhancing the development of cancer when combined simultaneously with exposure to
carcinogenic substances (70).
Mortality studies of haematite (Fe2O3) miners (containing up to 66% iron) have shown an
increased risk of lung cancer, generally among smokers, in several mining areas such as
Cumberland, Lorraine, Kiruna and Krivoi Rog. In experimental studies, ferric oxide has not
been found to be carcinogenic; however, the experiments were not carried out with
haematite (71). The presence of radon in the atmosphere of haematite mines has been
suggested to be an important carcinogenic factor. Epidemiological studies of iron and steel
foundry workers have typically noted risks of lung cancer elevated by 1.5- to 2.5-fold. The
International Agency for Research on Cancer (IARC) classifies iron and steel founding as a
carcinogenic process for humans. The specific chemical agents involved (e.g., polynuclear
aromatic hydrocarbons, silica, metal fumes) have not been identified. An increased
incidence of lung cancer has also been reported, but less significantly, among metal
grinders. The conclusions for lung cancer among welders are controversial. The dangerous
properties of the remaining iron compounds are usually due to the radical with which the
iron is associated. Thus ferric arsenate (FeAsO4) and ferric arsenite (FeAsO3·Fe2O3) possess
the poisonous properties of arsenical compounds. Iron carbonyl (FeCO5) is one of the more
dangerous of the metal carbonyls, having both toxic and flammable properties (71).
Ferrosilicon production can result in both aerosols and dusts of ferrosilicon. Animal studies
indicate that ferrosilicon dust can cause thickening of the alveolar walls with the occasional
disappearance of the alveolar structure. The raw materials used in alloy production may
also contain free silica, although in relatively low concentrations. There is some
disagreement as to whether classical silicosis may be a potential hazard in ferrosilicon
production. There is no doubt, however, that chronic pulmonary disease, whatever its
classification, can result from excessive exposure to the dust or aerosols encountered in
ferrosilicon plants.
3.1.5 Lead
About 40% of lead is used as a metal, 25% in alloys and 35% in chemical compounds.
Because populations in, at least, 100 countries are still exposed to air pollution with lead in
spite of banning the usage of lead in gasoline in many countries, usage of lead and lead
compounds will be detailed. Due to its malleability, low melting point, and ability to form
compounds, Pb has been used in hundreds of products such as pipes, solder, brass fixtures,
crystal, paint, cable, ceramics, and batteries (72). Metallic lead is used in the form of sheeting
or pipes where pliability and resistance to corrosion are required, such as in chemical plants
and the building industry; it is used also for cable sheathing, as an ingredient in solder and
as a filler in the automobile industry. It is a valuable shielding material for ionizing
radiations. It is used for metallizing to provide protective coatings, in the manufacture of
storage batteries and as a heat treatment bath in wire drawing. Lead is present in a variety
of alloys and its compounds are prepared and used in large quantities in many industries.
Lead oxides are used in the plates of electric batteries and accumulators (PbO and Pb3O4), as
compounding agents in rubber manufacture (PbO), as paint ingredients (Pb3O4) and as
constituents of glazes, enamels and glass.
Lead salts form the basis of many paints and pigments; lead carbonate and lead sulphate are
used as white pigments and the lead chromates provide chrome yellow, chrome orange,
chrome red and chrome green. Lead arsenate is an insecticide, lead sulphate is used in
rubber compounding, lead acetate has important uses in the chemical industry, lead
naphthenate is an extensively used dryer and tetraethyllead is an antiknock additive for
gasoline, where still permitted by law.
Other metals such as antimony, arsenic, tin and bismuth may be added to lead to improve
its mechanical or chemical properties, and lead itself may be added to alloys such as brass,
bronze and steel to obtain certain desirable characteristics. The very large numbers of
organic and inorganic lead compounds are encountered in industry.
3.1.5.1 Toxicity
The prime hazard of lead is its toxicity. For a long time, it is known that lead is toxic for
brain, kidney and reproductive system and can also cause impairment in intellectual
functioning, infertility, miscarriage and hypertension. Several studies have shown that lead
exposures in school-aged children can significantly reduce IQ and has been associated with
aggressive behavior, delinquency and attention disorders (73). The health effects of lead
were summarized in Table 2.
Clinical lead poisoning has always been one of the most important occupational diseases.
Industrial consumption of lead is increasing and traditional consumers are being
supplemented by new users such as the plastics industry. Hazardous exposure to lead,
therefore, occurs in many occupations. In lead mining, a considerable proportion of lead
absorption occurs through the alimentary tract and consequently the extent of the hazard in
this industry depends, to some extent, on the solubility of ores being worked. The lead
sulphide (PbS) in galena is insoluble and absorption from the lung is limited; however, in
the stomach, some lead sulphide may be converted to slightly soluble lead chloride which
may then be absorbed in moderate quantities. In lead smelting, the main hazards are the
lead dust produced during crushing and dry grinding operations, and lead fumes and lead
oxide encountered in sintering, blast-furnace reduction and refining.
Lead sheet and pipe are used principally for the construction of equipment for storing and
handling sulphuric acid. The use of lead for water and town gas pipes is limited nowadays.
The hazards of working with lead increase with temperature. If lead is worked at
temperatures below 500 °C, as in soldering, the risk of fume exposure is far less than in lead
welding, where higher flame temperatures are used and the danger is higher. The spray
coating of metals with molten lead is dangerous since it gives rise to dust and fumes at high
temperatures (74).
The demolition of steel structures such as bridges and ships that have been painted with
lead-based paints frequently gives rise to cases of lead poisoning. When metallic lead is
heated to 550 °C, lead vapour will be evolved and will become oxidized. This is a condition
that is liable to be present in metal refining, the melting of bronze and brass, the spraying of
metallic lead, lead burning, chemical plant plumbing, ship breaking and the burning,
cutting and welding of steel structures coated with paints containing lead tetroxide.
3.1.5.2 Absorption
The degree of absorption depends on the proportion of the dust accounted for by particles
less than 5 microns in size and the exposed worker’s respiratory minute volume. Since the
most important route of lead absorption is by the lungs, the particle size of industrial lead
dust is of considerable significance and this depends on the nature of the operation giving
rise to the dust. Fine dust of respirable particle size is produced by processes such as the
pulverizing and blending of lead colours, the abrasive working of lead-based fillers in
automobile bodies and the dry rubbing-down of lead paint. The exhaust gases of gasoline
engines yield lead chloride and lead bromide particles of 1 micron diameter. The larger
particles, however, may be ingested and be absorbed via the stomach. A more informative
picture of the hazard associated with a sample of lead dust might be given by including a
size distribution as well as a total lead determination.
In the human body, inorganic lead is not metabolized but is directly absorbed, distributed
and excreted. The rate at which lead is absorbed depends on its chemical and physical form
and on the physiological characteristics of the exposed person such as nutritional status and
age. Inhaled lead deposited in the lower respiratory tract is completely absorbed. The
amount of lead absorbed from the gastrointestinal tract of adults is typically 10 to 15% of the
ingested quantity; for pregnant women and children, the amount absorbed can increase to
as much as 50%. The quantity absorbed increases significantly under fasting conditions and
with iron or calcium deficiency (75).
Once in the blood, lead is distributed primarily among three compartments—blood, soft
tissue (kidney, bone marrow, liver, and brain), and mineralizing tissue (bones and teeth).
Mineralizing tissue contains about 95% of the total body burden of lead in adults.
The lead in mineralizing tissues accumulates in subcompartments that differ in the rate at
which lead is resorbed. In bone, there is both a labile component, which readily exchanges
lead with the blood, and an inert pool. The lead in the inert pool poses a special risk because
it is a potential endogenous source of lead. When the body is under physiological stress
such as pregnancy, lactation or chronic disease, this normally inert lead can be mobilized,
increasing the lead level in blood. Because of these mobile lead stores, significant drops in a
person’s blood lead level can take several months or sometimes years, even after complete
removal from the source of lead exposure.
Of the lead in the blood, 99% is associated with erythrocytes; the remaining 1% is in the
plasma, where it is available for transport to the tissues. The blood lead not retained is either
excreted by the kidneys or through biliary clearance into the gastrointestinal tract. In single-
exposure studies with adults, lead has a half-life, in blood, of approximately 25 days; in soft
tissue, about 40 days; and in the non-labile portion of bone, more than 25 years.
Consequently, after a single exposure a person’s blood lead level may begin to return to
normal; the total body burden, however, may still be elevated (76).
For lead poisoning to develop, major acute exposures to lead need not occur. The body
accumulates this metal over a lifetime and releases it slowly, so even small doses, over time,
can cause lead poisoning. It is the total body burden of lead that is related to the risk of
adverse effects.
3.1.5.3 Physiological effects
Whether lead enters the body through inhalation or ingestion, the biologic effects are the same;
there is interference with normal cell function and with a number of physiological processes.
Neurological effects: The most sensitive target of lead poisoning is the nervous system. In
children, neurological deficits have been documented at exposure levels once thought to
cause no harmful effects. In addition to the lack of a precise threshold, childhood lead
toxicity may have permanent effects. Some studies showed that damage to the central
nervous system (CNS) that occurred as a result of lead exposure at age 2 resulted in
continued deficits in neurological development, such as lower IQ scores and cognitive
deficits, at age 5 (77).
Adults also experience CNS effects at relatively low blood lead levels, manifested by subtle
behavioural changes, fatigue and impaired concentration. Peripheral nervous system
damage, primarily motor, is seen mainly in adults. Lead neuropathy is believed to be a
motor neuron, anterior horn cell disease with peripheral dying-back of the axons. Frank
wrist drop occurs only as a late sign of lead intoxication.
Lead inhibits the body’s ability to make hemoglobin by interfering with several enzymatic
steps in the heme pathway. A decrease in the activity of ferrochelatase enzyme results in an
increase of the substrate, erythrocyte protoporphyrin (EP), in the red blood cells. Recent
data indicate that the EP level, which has been used to screen for lead toxicity in the past, is
not sufficiently sensitive at lower levels of blood lead and is therefore not as useful a
screening test for lead poisoning as previously thought.
Lead can induce two types of anemia. Acute high-level lead poisoning has been associated
with hemolytic anemia. In chronic lead poisoning, lead induces anemia by both interfering
with erythropoiesis and by diminishing red blood cell survival. It should be emphasized,
however, that anemia is not an early manifestation of lead poisoning and is evident only
when the blood lead level is significantly elevated for prolonged periods.
A strong inverse correlation exists between blood lead levels and levels of vitamin D.
Because the vitamin D-endocrine system is responsible in large part for the maintenance of
extra- and intra-cellular calcium homeostasis, it is likely that lead impairs cell growth and
maturation and tooth and bone development.
A direct effect on the kidney of long-term lead exposure is nephropathy. There is also
evidence of an association between lead exposure and hypertension, an effect that may be
mediated through renal mechanisms. Maternal lead stores readily cross the placenta,
placing the foetus at risk. Increasing evidence indicates that lead not only affects the
viability of the foetus, but development as well. Developmental consequences of prenatal
exposure to low levels of lead include reduced birth weight and premature birth. Lead is an
animal teratogen; however, most studies in humans have failed to show a relationship
between lead levels and congenital malformations.
Inorganic lead and inorganic lead compounds have been classified as Group 2B, possible
human carcinogens, by the International Agency for Research on Cancer (IARC) (78).
3.1.5.4 Organic lead intoxication
The absorption of a sufficient quantity of tetraethyllead, whether briefly at a high rate or
for prolonged periods at a lower rate, induces acute intoxication of the CNS. The milder
manifestations are those of insomnia, lassitude and nervous excitation which reveal itself
in lurid dreams and dream-like waking states of anxiety, in association with tremor,
hyper-reflexia, spasmodic muscular contractions, bradycardia, vascular hypotension and
hypothermia. The more severe responses include recurrent (sometimes nearly continuous)
episodes of complete disorientation with hallucinations, facial contortions and intense
general somatic muscular activity with resistance to physical restraint. Such episodes may
be converted abruptly into maniacal or violent convulsive seizures which may terminate
in coma and death.
3.1.5.5 Legislation
Clinical lead poisoning has historically been one of the most important occupational
diseases, and it remains a major risk today. The considerable body of scientific knowledge
concerning the toxic effects of lead has been enriched since the 1980s by significant new
knowledge regarding the more subtle subclinical effects. Similarly, in a number of countries
it was felt necessary to redraft or modernize work protective measures enacted over the last
half-century and more (25).
Some regulation, such as the Occupational Safety and Health Administration (OSHA) lead
standard, specifies the permissible exposure limit (PEL) of lead in the workplace, the
frequency and extent of medical monitoring, and other responsibilities of the employer. As
of this writing, if blood monitoring reveals a blood lead level greater than 40 µg/dL, the
worker must be notified in writing and provided with medical examination. If a worker’s
blood lead level reaches 60 µg/dL (or averages 50 µg/dL or more), the employer is
obligated to remove the employee from excessive exposure, with maintenance of seniority
and pay, until the employee’s blood lead level falls below 40 µg/dL (79).
3.1.6 Nickel
Since nickel, copper and iron occur as distinct minerals in the sulphide ores, mechanical
methods of concentration, such as flotation and magnetic separation, are applied after the
ore has been crushed and ground. The nickel concentrate is converted to nickel sulphide
matte by roasting or sintering. The matte is refined by electrowinning or by the Mind
process. In the Mind process, the matte is ground, calcined and treated with carbon
monoxide at 50 °C to form gaseous nickel carbonyl (Ni(CO)4), which is then decomposed at
200 to 250 °C to deposit pure nickel powder. Worldwide production of nickel is
approximately 1.2 million ton/year (80).
More than 3,000 nickel alloys and compounds are commercially produced. Stainless steel
and other Ni-Cr-Fe alloys are widely used for corrosion-resistant equipment, architectural
applications and cooking utensils. Monel metal and other Ni-Cu alloys are used in
coinage, food-processing machinery and dairy equipment. Ni-Al alloys are used for
magnets and catalyst production. Ni-Cr alloys are used for heating elements, gas turbines
and jet engines. Alloys of nickel with precious metals are used in jewellery. Nickel metal,
its compounds and alloys have many other uses, including electroplating, magnetic tapes
and computer components, arc-welding rods, surgical and dental prostheses, nickel-
cadmium batteries, paint pigments (e.g., yellow nickel titanate), moulds for ceramic and
glass containers, and catalysts for hydrogenation reactions, organic syntheses and the
final methanation step of coal gasification. Occupational exposures to nickel also occur in
recycling operations, since nickel-bearing materials, especially from the steel industry, are
commonly melted, refined and used to prepare alloys similar in composition to those that
entered the recycling process.
3.1.6.1 Toxicity
Human health hazards from occupational exposures to nickel compounds generally fall into
three major categories: allergy, rhinitis, sinusitis and respiratory diseases, and cancers of the
nasal cavities, lungs and other organs. The health effects of nickel were summarized in Table 2.
Nickel and nickel compounds are among the most common causes of allergic contact
dermatitis. This problem is not limited to persons with occupational exposure to nickel
compounds; dermal sensitization occurs in the general population from exposures to
nickel-containing coins, jewellery, watch cases and clothing fasteners. In nickel-exposed
persons, nickel dermatitis usually begins as a papular erythema of the hands. The skin
gradually becomes eczematous, and, in the chronic stage, lichenification frequently
develops. Nickel sensitization sometimes causes conjunctivitis, eosinophilic pneumonitis,
and local or systemic reactions to nickel-containing implants (e.g., intraosseous pins,
dental inlays, cardiac valve prostheses and pacemaker wires). Ingestion of nickel-
contaminated tap water or nickel-rich foods can exacerbate hand eczema in nickel-
sensitive persons.
Workers in nickel refineries and nickel electroplating shops, who are heavily exposed to
inhalation of nickel dusts or aerosols of soluble nickel compounds, may develop chronic
diseases of the upper respiratory tract. Chronic diseases of the lower respiratory tract
including bronchitis, pulmonary fibrosis have also been reported, but such conditions are
infrequent (81).
Epidemiological studies of nickel-refinery workers in Canada, Wales, Germany, Norway
and Russia have documented increased mortality rates from cancers of the lung and nasal
cavities. Certain groups of nickel-refinery workers have also been reported to have
increased incidences of other malignant tumours, including carcinomas of the larynx,
kidney, prostate or stomach, and sarcomas of soft tissues, but the statistical significance of
these observations is questionable. The increased risks of cancers of the lungs and nasal
cavities have occurred primarily among workers in refinery operations that entail high
nickel exposures, including roasting, smelting and electrolysis. Although these cancer risks
have generally been associated with exposures to insoluble nickel compounds, such as
nickel subsulphide and nickel oxide, exposures to soluble nickel compounds have been
implicated in electrolysis workers.
Epidemiological studies of cancer risks among workers in nickel-using industries have
generally been negative, but recent evidence suggests slightly increased lung cancer risks
among welders, grinders, electroplaters and battery makers. Such workers are often exposed
to dusts and fumes that contain mixtures of carcinogenic metals (e.g., nickel and chromium,
or nickel and cadmium). Based on an evaluation of epidemiological studies, the
International Agency for Research on Cancer (IARC) concluded in 1990: “There is sufficient
evidence in humans for the carcinogenicity of nickel sulphate and of the combinations of
nickel sulphides and oxides encountered in the nickel refining industry. There is inadequate
evidence in humans for the carcinogenicity of nickel and nickel alloys”. Nickel compounds
have been classified as carcinogenic to humans (Group 1), and metallic nickel as possibly
carcinogenic to humans (Group 2B) (82).
3.1.6.2 Biological monitoring
Analyses of nickel concentrations in urine and serum samples may reflect the recent
exposures of workers to metallic nickel and soluble nickel compounds, but these assays do
not furnish reliable measures of the total body nickel burden. The uses and limitations of
biological monitoring of nickel-exposed workers have been summarized. A technical report
on analysis of nickel in body fluids was issued in 1994 by the Commission on Toxicology of
the International Union of Pure and Applied Chemistry (IUPAC) (83). The National
Maximum Workplace Concentration Committee (NMWCC) of the Netherlands proposed
that urine nickel concentration 40 µg/g creatinine, or serum nickel concentration 5 µg/l
(both measured in samples obtained at the end of a working week or a work shift) be
considered warning limits for further investigation of workers exposed to nickel metal or
soluble nickel compounds. If a biological monitoring programme is implemented, it should
augment an environmental monitoring programme, so that biological data are not used as a
surrogate for exposure estimates (83).
3.1.7 Mercury
3.1.7.1 Inorganic mercury
Mercury combines readily with sulphur and halogens at ordinary temperatures and forms
amalgams with all metals except iron, nickel, cadmium, aluminium, cobalt and platinum. It
reacts exothermically with alkaline metals, is attacked by nitric acid but not by hydrochloric
acid and, when hot, will combine with sulphuric acid. Inorganic mercury is found in nature
in the form of the sulphide (HgS) as cinnabar ore, which has an average mercury content of
0.1 to 4%. Mercury ore is extracted by underground mining, and mercury metal is separated
from the ore by roasting in a rotary kiln or shaft furnace, or by reduction with iron or
calcium oxide. The vapour is carried off in the combustion gases and is condensed in
vertical tubes.
The most important uses of metallic mercury and its inorganic compounds have included
the treatment of gold and silver ores; the manufacture of amalgams; the manufacture and
repair of measurement or laboratory apparatus; the manufacture of incandescent electric
bulbs, mercury vapour tubes, radio valves, x-ray tubes, switches, batteries, rectifiers, etc.; as
a catalyst for the production of chlorine and alkali and the production of acetic acid and
acetaldehyde from acetylene; chemical, physical and biological laboratory research; gold,
silver, bronze and tin plating; tanning and currying; feltmaking; taxidermy; textile
manufacture; photography and photogravure; mercury-based paints and pigments; and the
manufacture of artificial silk (84). Some of these uses have been discontinued because of the
toxic effects that the mercury exposure exerted upon workers.
3.1.7.2 Organic mercury compounds
Organic compounds of mercury may be considered as the organic compounds in which the
mercury is chemically linked directly to a carbon atom. Carbon-mercury bonds have a wide
range of stability; in general, the carbon-to-mercury bond in aliphatic compounds is more
stable than that in aromatic compounds. It was estimated that more than 400 phenyl
mercurials and at least that number of alkyl mercury compounds have been synthesized.
The three most important groups in common usage are the alkyls, the aromatic
hydrocarbons or aryls and the alkoxyalkyls. Examples of aryl mercury compounds are
phenylmercuric acetate (PMA), nitrate, oleate, propionate and benzoate. Most available
information is about PMA.
In medical practice, organic mercury compounds are used as antiseptics, germicides,
diuretics and contraceptives. In the field of pesticides, they serve as algicides, fungicides,
herbicides and slimacides, and as preservatives in paints, waxes and pastes; they are used
for mildew suppression, in antifouling paints, in latex paints and in the fungus-proofing of
fabrics, paper, cork, rubber and wood for use in humid climates. In the chemical industry,
they act as catalysts in a number of reactions and the mercury alkyls are used as alkylating
agents in organic syntheses.
3.1.7.3 Toxicity
Vapour inhalation is the main route for the entry of metallic mercury into the body.
Around 80% of inhaled mercury vapour is absorbed in the lung (alveoli). Digestive
absorption of metallic mercury is negligible (lower than 0.01% of the administered dose).
The main routes of entry of inorganic mercury compounds (mercury salts) are the lungs
(atomization of mercury salts) and the gastrointestinal tract. In the latter case, absorption
is often the result of accidental or voluntary ingestion. It is estimated that 2 to 10% of
ingested mercury salts are absorbed through the intestinal tract. The health effects of
mercury were summarized in Table 2.
Skin absorption of metallic mercury and certain of its compounds is possible, although the
rate of absorption is low. After entry into the body, metallic mercury continues to exist for a
short time in metallic form, which explains its penetration of the blood-brain barrier. In
blood and tissues metallic mercury is rapidly oxidized to Hg2+ mercury ion, which fixes to
proteins. In the blood, inorganic mercury is also distributed between plasma and red blood
cells. The kidney and brain are the sites of deposition following exposure to metallic
mercury vapours, and the kidney following exposure to inorganic mercury salts (85).
3.1.7.4 Acute poisoning
The symptoms of acute poisoning include pulmonary irritation (chemical pneumonia),
perhaps leading to acute pulmonary oedema. Renal involvement is also possible. Acute
poisoning is more often the result of accidental or voluntary ingestion of a mercury salt. This
leads to severe inflammation of the gastrointestinal tract followed rapidly by renal
insufficiency due to necrosis of the proximal convoluted tubules.
3.1.7.5 Chronic exposure
Chronic mercury poisoning usually starts insidiously, which makes the early detection of
incipient poisoning difficult. The main target organ is the nervous system. Initially,
suitable tests can be used to detect psychomotor and neuro-muscular changes and slight
tremor. Slight renal involvement (proteinuria, albuminuria, enzymuria) may be detectable
earlier than neurological involvement. If excessive exposure is not corrected, neurological
and other manifestations (e.g., tremor, sweating, dermatography) become more

pronounced, associated with changes in behaviour and personality disorders and,
perhaps, digestive disorders (stomatitis, diarrhoea) and a deterioration in general status
(anorexia, weight loss). Once this stage has been reached, termination of exposure may
not lead to total recovery.
In chronic mercury poisoning, digestive and nervous symptoms predominate and, although
the former are of earlier onset, the latter are more obvious; other significant but less intense
symptoms may be present. The duration of the period of mercury absorption preceding the
appearance of clinical symptoms depends on the level of absorption and individual factors.
The main early signs include slight digestive disorders, in particular, loss of appetite;
intermittent tremor, sometimes in specific muscle groups; and neurotic disorders varying in
intensity. The course of intoxication may vary considerably from case to case. If exposure is
terminated immediately upon the appearance of the first symptoms, full recovery usually
occurs; however, if exposure is not terminated and the intoxication becomes firmly
established, no more than an alleviation of symptoms can be expected in the majority of cases.
There have been studies over the years on the relationships between renal function and
urinary mercury levels. The effects of low-level exposures are still not well documented or
understood. At higher levels (above 50 µg/g (micrograms per gram) abnormal renal
function (as evidenced by N-acetyl-B-D-glucosaminidase (NAG), which is a sensitive
indicator of damage to the kidneys) have been observed. The NAG levels were correlated with
both the urinary mercury levels and the results of neurological and behavioural testing (86).
Chronic poisoning is accompanied by mild anemia sometimes preceded by polycythaemia
resulting from bone marrow irritation. Lymphocytosis and eosinophilia have also been
observed.
Absorption of phenylmercuric acetate (PMA) may occur through inhalation of aerosols
containing PMA, through skin absorption or by ingestion. The solubility of the mercurial
and the particle size of the aerosols are determining factors for the extent of absorption.
PMA is more efficiently absorbed by ingestion than are inorganic mercuric salts.
Phenylmercury is transported mainly in blood and distributed in the blood cells (90%),
accumulates in the liver and is there decomposed into inorganic mercury. Some
phenylmercury is excreted in the bile. The main portion absorbed in the body is distributed in
the tissues as inorganic mercury and accumulated in the kidney. On chronic exposure,
mercury distribution and excretion follow the pattern seen on exposure to inorganic mercury.
Occupational exposure to phenylmercury compounds occurs in the manufacture and
handling of products treated with fungicides containing phenylmercury compounds. Acute
inhalation of large amounts may cause lung damage. Exposure of the skin to a concentrated
solution of phenylmercury compounds may cause chemical burns with blistering. Ingestion
of large amounts of phenylmercury may cause renal and liver damage. Chronic poisoning
gives rise to renal damage due to accumulation of inorganic mercury in the renal tubules.
Available clinical data do not permit extensive conclusions about dose-response
relationships. They suggest, however, that phenylmercury compounds are less toxic than
inorganic mercury compounds or long-term exposure. There is some evidence of mild
adverse effects on the blood.
Alkyl mercury compounds. From a practical point of view, the short-chained alkyl mercury
compounds, like methylmercury and ethylmercury, are the most important, although some
exotic mercury compounds, generally used in laboratory research, have led to spectacular
rapid deaths from acute poisoning. These compounds have been extensively used in seed
treatment where they have been responsible for a number of fatalities. Methylmercuric
chloride forms white crystals with a characteristic odour, while ethylmercury chloride;
(chloroethylmercury) forms white flakes. Volatile methylmercury compounds, like
methylmercury chloride, are absorbed to about 80% upon inhalation of vapour. More than
95% of short-chained alkyl mercury compounds are absorbed by ingestion, although the
absorption of methylmercury compounds by the skin can be efficient, depending on their
solubility and concentration and the condition of the skin (87).
Methylmercury is transported in the red blood cells ( 95%), and a small fraction is bound to
plasma proteins. The distribution to the different tissues of the body is rather slow and it
takes about four days before equilibrium is obtained. Methylmercury is concentrated in the
central nervous system and especially in grey matter. About 10% of the body burden of
mercury is found in the brain. The highest concentration is found in the occipital cortex and
the cerebellum. In pregnant women methylmercury is transferred in the placenta to the
foetus and especially accumulated in the fetal brain.
3.1.7.6 Toxicity of organic mercury
Poisoning by alkyl mercury may occur on inhalation of vapour and dust containing alkyl
mercury and in the manufacture of the mercurial or in handling the final material. Skin
contact with concentrated solutions results in chemical burns and blistering. In small
agricultural operations there is a risk of exchange between treated seed and products
intended for food, followed by involuntary intake of large amounts of alkyl mercury. On
acute exposure the signs and symptoms of poisoning have an insidious onset and appear
with a latency period which may vary from one to several weeks.
On chronic exposure the onset is more insidious, but the symptoms and signs are essentially
the same, due to the accumulation of mercury in the central nervous system, causing neuron
damage in the sensory cortex, such as visual cortex, auditory cortex and the pre- and post-
central areas. The signs are characterized by sensory disturbances with paresthaesia in the
distal extremities, in the tongue and around the lips. With more severe intoxications ataxia,
concentric constrictions of the visual fields, impairment of hearing and extrapyramidal
symptoms may appear. In severe cases chronic seizures occur.
The period in life most sensitive to methylmercury poisoning is the time in utero; the foetus
seems to be between 2 and 5 times more sensitive than the adult. Exposure in utero results
in cerebral palsy, partly due to inhibition of the migration of neurons from central parts to
the peripheral cortical areas. In less severe cases retardation in the psychomotor
development has been observed.
The most common alkoxyalkyl compounds used are methoxyethyl mercury salts (e.g.,
methoxyethylmercury acetate), which have replaced the short-chain alkyl compounds in
seed treatment in many industrial countries, in which the alkyl compounds have been
banned due to their hazardousness. The available information is very limited. Alkoxyalkyl
compounds are absorbed by inhalation and by ingestion more efficiently than inorganic
mercury salts (88). The distribution and excretion patterns of absorbed mercury follow those
of inorganic mercury salts. Excretion occurs through the intestinal tract and the kidney. To
what extent unchanged alkoxyalkyl mercury is excreted in humans is unknown. Exposure
to alkoxyalkyl mercury compounds can occur in the manufacture of the compound and in
handling the final product(s) treated with the mercurial. Methoxyethyl mercury acetate is a
vesicant when applied in concentrated solutions to the skin. Inhalation of methoxyethyl
mercury salt dust may cause lung damage, and chronic poisoning due to long-term
exposure may give rise to renal damage.
Most exposure to organic mercury compounds involves mixed exposure to mercury vapour
and the organic compound, as the organic mercury compounds decompose and release
mercury vapour. All technical measures pertaining to exposure to mercury vapour should
be applied for exposure to organic mercury compounds. Thus, contamination of clothes
and/or parts of the body should be avoided, as it may be a dangerous source of mercury
vapour close to the breathing zone. Special protective work clothes should be used and
changed after the workshift. Spray painting with paint containing mercurials requires
respiratory protective equipment and adequate ventilation. The short-chained alkyl mercury
compounds should be eliminated and replaced whenever possible. If handling cannot be
avoided, an enclosed system should be used, combined with adequate ventilation, to limit
exposure to a minimum.
Great care must be exercised in preventing the contamination of water sources with mercury
effluent since the mercury can be incorporated into the food chain, leading to disasters such
as that which occurred in Minamata, Japan.
3.1.8 Metal carbonyls

Metal carbonyls have the general formula Mex(CO)y, and are formed by combination of the
metal (Me) with carbon monoxide (CO). Physical properties of some metal carbonyls are
listed in Table 3 (89). Most are solids at ordinary temperatures, but nickel carbonyl, iron
pentacarbonyl and ruthenium pentacarbonyl are liquids, and cobalt hydrocarbonyl is a gas.
Since iron pentacarbonyl and cobalt hydrocarbonyl also have high vapour pressures and
potential for inadvertant formation, they warrant serious consideration as possible
occupational toxicants. Most metal carbonyls react vigorously with oxygen and oxidizing
substances, and some ignite spontaneously. Upon exposure to air and light, nickel carbonyl
decomposes to carbon monoxide and particulate nickel metal, cobalt hydrocarbonyl
decomposes to cobalt octacarbonyl and hydrogen, and iron pentacarbonyl decomposes to
iron nonacarbonyl and carbon monoxide (90).
Metal carbonyls are used in isolating certain metals (e.g., nickel) from complex ores, for
producing carbon steel, and for metallizing by vapour deposition. They are also used as
catalysts in organic reactions (e.g., cobalt hydrocarbonyl or nickel carbonyl in olefin
oxidation; cobalt octacarbonyl for the synthesis of aldehydes; nickel carbonyl for the
synthesis of acrylic esters). Iron pentacarbonyl is used as a catalyst for various organic
reactions, and is decomposed to make finely powdered, ultra pure iron (so-called carbonyl
iron), which is used in the computer and electronics industries. Methycyclopentadienyl
manganese tricarbonyl (MMT) (CH3C5H4Mn(CO)3) is an antiknock additive to gasoline.
Metal carbonyl Mol. Wt. Sp. Gr. (20°C) M.P. (°C) B.P. (°C) V.P. (25°C) mm Hg
Ni(CO)4 170.75 1.31 –19 43 390

CoH(CO)4 171.99 – –26 – high
Co2(CO)8 341.95 1.87 51 52* 1.5
Co4(CO)12 571.86 – 60* – very low
Cr(CO)6 220.06 1.77 110* 151 0.4
Fe2(CO)9 363.79 2.08 80* – –
Fe(CO)5 195.90 1.46 –25 103 30.5
Fe(CO)4 167.89 2.00 approx. 140* – –
Mo(CO)6 264.00 1.96 150* 156 0.2
Ru(CO)5 241.12 – –22 – –
W(CO)6 351.91 2.65 approx. 150* 175 0.1
*Decomposition starts at temperature shown.

Table 3. Physical properties of some metal carbonyls.
3.1.8.1 Toxicity
The toxicity of a given metal carbonyl depends on the toxicity of carbon monoxide and of
the metal from which it is derived, as well as the volatility and instability of the carbonyl
itself. The principal route of exposure is inhalation, but skin absorption can occur with the
liquid carbonyls. The relative acute toxicity (LD50 for the rat) of nickel carbonyl, cobalt
hydrocarbonyl and iron pentacarbonyl may be expressed by the ratio 1:0.52:0.33.
Inhalation exposures of experimental animals to these substances induce acute interstitial
pneumonitis, with pulmonary oedema and capillary damage, as well as injury to the
brain, liver and kidneys (91).
Iron pentacarbonyl can be formed inadvertently when carbon monoxide, or a gas mixture
containing carbon monoxide, is stored under pressure in steel cylinders or fed through steel
pipes, when illuminating gas is produced by petroleum reforming, or when gas welding is
carried out. Presence of carbon monoxide in emission discharges from blast furnaces,
electric arc furnaces and cupola furnaces during steel-making can also lead to the formation
of iron pentacarbonyl.
3.1.8.2 Nickel carbonyl
Nickel carbonyl (Ni(CO)4) is mainly used as an intermediate in the Mind process for nickel
refining, but it is also used for vapour-plating in the metallurgical and electronics industries
and as a catalyst for synthesis of acrylic monomers in the plastics industry. Inadvertent
formation of nickel carbonyl can occur in industrial processes that use nickel catalysts, such
as coal gasification, petroleum refining and hydrogenation reactions, or during incineration
of nickel-coated papers that are used for pressure-sensitive business forms (92).
3.1.8.3 Toxicity
Acute, accidental exposure of workers to inhalation of nickel carbonyl usually produces
mild, non-specific, immediate symptoms, including nausea, vertigo, headache, dyspnoea
and chest pain. These initial symptoms usually disappear within a few hours. After 12 to 36
hours, and occasionally as long as 5 days after exposure, severe pulmonary symptoms
develop, with cough, dyspnoea, tachycardia, cyanosis, profound weakness and often
gastrointestinal symptoms. Human fatalities have occurred 4 to 13 days after exposure to
nickel carbonyl; deaths have resulted from diffuse interstitial pneumonitis, cerebral
hemorrhage or cerebral oedema. In addition to pathologic lesions in the lungs and brain,
lesions have been found in liver, kidneys, adrenals and spleen. In patients who survive
acute nickel carbonyl poisoning, pulmonary insufficiency often causes protracted
convalescence. Nickel carbonyl is carcinogenic and teratogenic in rats; the European Union
has classified nickel carbonyl as an animal teratogen. Processes that use nickel carbonyl
constitute disaster hazards, since fire and explosion can occur when nickel carbonyl is
exposed to air, heat, flames or oxidizers. Decomposition of nickel carbonyl is attended by
additional toxic hazards from inhalation of its decomposition products, carbon monoxide
and finely particulate nickel metal.
Chronic exposure of workers to inhalation of low atmospheric concentrations of nickel
carbonyl (0.007 to 0.52 mg/m3) can cause neurological symptoms such as insomnia,
headache, dizziness, memory loss, and other manifestations including chest tightness,
excessive sweating, alopecia. Electroencephalographic abnormalities and elevated serum
monoamine oxidase activity have been observed in workers with chronic exposures to
nickel carbonyl. A synergistic effect of cigarette smoking and nickel carbonyl exposure on
the frequency of sister-chromatid exchanges was noted in a cytogenetic evaluation of
workers with chronic exposure to nickel carbonyl.
Because of its flammability and tendency to explode, nickel carbonyl should be stored in
tightly closed containers in a cool, well-ventilated area, away from heat and oxidizers
such as nitric acid and chlorine. Flames and sources of ignition should be prohibited
wherever nickel carbonyl is handled, used or stored. Nickel carbonyl should be
transported in steel cylinders. Foam, dry chemical, or CO2 fire extinguishers should be
used to extinguish burning nickel carbonyl, rather than a stream of water, which might
scatter and spread the fire.
Exposures are classified as “mild” if the initial 8-h specimen of urine has a nickel
concentration less than 100 µg/l, “moderate” if the nickel concentration is 100 to 500 µg/l,
and “severe” if the nickel concentration exceeds 500 µg/l (93). Sodium
diethyldithiocarbamate is the drug of choice for chelation therapy of acute nickel carbonyl
poisoning. Ancillary therapeutic measures include bed rest, oxygen therapy, corticosteroids
and prophylactic antibiotics. Carbon monoxide poisoning may occur simultaneously and
requires treatment.
4. Comparison of metal concentrations in air samples

In literature, the most published articles on metal concentrations in air phases is related with
lead, nickel, cadmium and arsenic levels in airborne aerosol samples. Liang et al. (1990)
examined six metal levels in air taken from laboratory and clean room (32) Gucer et al.
(1992) determined six metal concentrations in ambient air taken from Malatya city
depending on month of year and distance from center of city (28). Jaradat and momani
(1999) analyzed soil, plant and air samples taken from both sides of the major highway
connecting for Cu, Pb, Cd and Zn (31). Fernandez et al. (2000) determined five metal
concentrations in four fractionation of particulate matters in air (94). Fuchtjohann et al.
(2000) used GFAAS and ICP-MS to determine soluble (NiCl2 and partly NiCO3) and
insoluble (NiO) nickel compounds in ambient air dusts (airborne particulate matters) taken
from locations close to two metallurgical plants (95). They found maximum concentrations
in total nickel at both sampling sites as 40 ng/m3 and 160 ng/m3 whereas the mean values
were 9 ng/m3 and 28 ng/m3 (95). Bolt et al. (2000) determined Ni levels in airborne dusts
collected from a metal factory processing nickel and nickel alloys (96). They found Ni
concentrations in range of 10.000-4.920.000 ng/m3. Hadad et al. (2003) found Pb, Cr and Fe
concentrations in Tehran air samples as 1.040.000, 56.000 and 2.720.000 ng/m3, respectively
(30). Wada et al. (2001) reported mean Pb, Ni and Mn concentrations in airborne samples
taken from Nagasaki as 8, 4 and 12 ng/m3 (37). Bhat and Pillai (1997) determined mean 0.42
ng Be /m3 in air sample taken from the vicinity of Be metal plant at New Bombay (97).
Gurjar and Mohan (2003) reported Cd, Cr and Ni concentrations in atmospheric
environment at fourten cities of India in ranges of 1-21, 16-207 and 23-257 ng/m3,
respectively (34). Pekney and Davidson (2005) determined 28 metal concentrations in
ambient particulate matter by ICP-MS (33). Vijayanand et al. (2008) assessed seven trace
metals in the ambient air of Coimbatore city in India (29). They found Ni, Pb and Cr
concentrations in range of BDL-310, 210-620 and 5-880 ng/m3, respectively (29). Limbeck et
al. (2009) found Ni, Pb and Cr concentrations in ranges of 6-10, 9-11 and 4-6 ng/m3,
respectively (27). Canepari et al. (2009) compared XRF, and ICP-OES results for
multielement concentrations in ambient air suspended particulate matter (98). Chen and
Lippmann (2009) reviewed effect of metal concentrations in ambient air particulate matter
on human health (35). They reported that Ni, Pb and Cr levels in PM2.5 for 13 city in USA
were in ranges of 1-2, 2-14 and 1-3 ng/m3, respectively. Morishita et al. (2006) attempted to
determine source of pollution by using concentrations of trace metals including Pb, Zn, Cd
and Fe in PM2.5 (99). Odabasi et al. (2002) determined 11 trace metals in ambient air
samples taken from Izmir city center and compared their results with other values reported
in literature (36). Newhook et al. (2003) reviewed trace metal concentrations in ambient air
(PM10) samples near copper smelter and refineries, and zinc plants in Canada (40).
Mohanraj et al. (2004) determined six trace metals in airborne samples from India (38). They
found 2.147 ng Pb /m3 in particulate matter taken from industrial location. Pierre et al.
(2002) attempted to determine relationship between blood lead concentration of workers
employed in crystal industry and ambient air lead (100). Vanhoof et al. (2003) determined
Pb, Cu and Zn concentrations in ambient air from nonferrous metal industry (39). Fang et al.
reviewed 7 metal concentrations in particulate matter (PM2.5 and PM10) taken fro Asia
countries between 2000-2004 (101). Krzemińska-Flowers et al. (2006) determined 15 trace
metals in urban air particulate matter by ICP-MS (102). They compared the results taking
into consideration summer and winter season. They found that winter-Ag, As and Hg
concentrations in both PM3 and PM10 taken from all three locations having different
pollution were higher than in summer season whereas other trace metals changed
depending on season and locations. These results reveal the difficulties in comparison of
trace metal concentrations in air samples due to many factors affected the values. The
detailed concentrations and information about those studies were given in Table 4.
Location Character Size Cd Pb Ni Cu As Fe Cr Ref.

PM2.5=16.5
Boston-USA 240 9 11 62
µg/m3
PM2.5=19.2
St. Louis-USA 213 2 30 144
µg/m3
PM2.5=21.1
Knoxville-USA 109 1 13 117
µg/m3
PM2.5 7
PM2.5=11.3
Madison-USA 33 0.5 6 44
µg/m3
PM2.5=30.5
Steubenville-USA 185 4 12 542
µg/m3
PM2.5=12.2
Topeka-USA 72 0.6 7 72
µg/m3
Out of City-
Schafberg 0.4 8.9 7.0 7.2 0.7 250 3.8
Viena
City Suburb-
Kendlerstrabe Moderate 0.5 11 5.7 21 0.9 780 5.5
PM10 27
Traffic
Iner-City-
Rinnböckstrabe Density 0.5 11 9.9 20 1.2 740 5.0
Traffic
3630- 1080- 4280-
Malatya-Turkey City Center ND 28
27270 1760 6030
Residential
Coimbatore-India and Traffic BDL 340 120 660 2850 BDL
Area
Residential
Coimbatore-India and Traffic BDL 560 150 610 3150 470
Area
Industrial
Coimbatore-India BDL 280 90 880 1850 630
Area
Industrial
Area
Industrial
Area SPM 29
Industrial and
Coimbatore-India BDL 520 BDL 290 2200 40
Traffic Area
Industrial and
Traffic Area
Residential
Coimbatore-India and Traffic BDL 170 120 730 2200 280
Area
Industrial and
Traffic Area
Industrial and
Traffic Area
Traffic-
1.040.0 2720.
Tehran Industrial SPM 56 30
00 000
Summer

Traffic-
1.000.0 1740.
Industrial 40
00 000
Winter
Traffic-
3252.
Industrial 410 15
000
Summer
Shiraz
Traffic-
1891.
Industrial 669 15
000
Winter
Highweigh- 260- 260-
Amman-Jordan 31
Roadside 1370 600
Connecticut- Nov. 1988 1.25 1.89 6.65
laboratory June 1989 1.24 1.43 16.9
32
Connecticut- Nov 1988 0.19 0.31 1.54
Clean room June 1989 0.18 0.41 4.13
Ambient
Pitsburgh particulate PM2.5 20 20 200 33
matter
Andhra Pradesh –
14 68 32
India
Bihar 11 208 133
Chandigarh (UT) -
5 257 207
India
Gujarat-India 16 45 51
Haryana-India 8 134 90
Himachal
8 66 64
Pradesh-India Ambient air 34
Karnataka-India 1 43 17
Kerala-India 6 23 18
Orissa-India 8 78 144
Punjab-India 4 107 82
Rajasthan-India 20 63 16
Tamil Nadu-India 6 28 17
Uttar Pradesh-
21 222 71
India
Burlington-USA - - 2 2 - - 2
Philadelphia-USA - 5 6 4 - - 2
Atlanta-USA - 3 - 2 1 1 -
Detroit-USA - 6 2 6 2 - 2
Chicago-USA - 6 1 4 1 1 1
ST.Louis-USA Air particulate - 14 2 14 2 1 2
PM2.5 35
Houston-USA matter - 2 2 3 1 1 1
Minneapolis-USA - 5 2 3 2 - 2
Boulder-USA - 5 1 4 - - 2
Phoenix-USA - - 3 6 2 3 2
Seattle-USA - 4 2 3 1 1 2
Sacramento-USA - - 10 6 2 - 2

Riverside-
- 6 2 6 2 - 3
Rubidojx-USA
Izmir, Turkey City suburb TSP 8 111 39 154 11 36
Nagasaki City High Traffic 7.95 3.78 37
Urban
India, (6 sampling residential,
2.8 143.5 31.37 388.6 14.2 38
station) industrial,
highway,
Southern side
Location 1 Rural 29 20
the road
Eastern side
Location 2 PM10 17 12 39
the road
Northern side
Location 3 TSP 26 17
the road
Copper
Canada PM 1 197 28
smelters
Noranda- 33-
Canada PM 2 18 40
horne 255
Copper
Canada PM 0 34 8
refineries
Canada Zinc plants PM 19
Japon, Sapporo TSP 43.9 3.81 20.9 625 2.61
Urban City 41
Japon, Tokyo 125 5.63 30.2 677 6.09
Airborne TSP 79 - 88 1421 -
China, Hong
PM10 98740 8620 35380 860 6850 42
Kong Traffic
PM2.5 76860 5340 17320 250 2430
PM10 100520 9580 63530 790 5750
Industry
China, Hong PM2.5 91620 6000 36780 480 4510
43
Kong PM10 62750 8270 15330 620 4970
Urban
PM2.5 60130 6330 9710 190 4190
University PM2.5 270 - - 820 -
China, Shanghai 44
Urban PM2.5 280 - - 900 -
PM2 73 - 3 1222 -
Vietnam, Ho Chi
Urban PM2-10 79 - 2 261 - 45
Minh
TSP 146 - - 2904 -
India,Sakinaka, 1655
SPM 1060 - 370 -
Mumbai Traffic 00
46
India, Junction 2655
SPM 820 - 1550 -
Gandhinagar 00
Indonesia, Bukit Tropical PM2.5 1.22 - <0.14 2.6 -
Tinggi Jungle PM2.5-10 <0.3 - <0.16 14.8 -
PM2.5 8.7 - 0.22 4.7 - 47
Indonesia,
Rural PM2.5-10 4.2 - 0.56 53 -
Pontianak
PM2.5 26 11 - 581 -
PM2.5-10 3 2 - 1479 -
Indonesia Rural TSP 39 18 - 2700 - 48
<2.5 88 54 32 994 360

Indonesia Temple PM2.5-10 120 73 14 568 147 49
Traffic
Junction TSP 180 - 240 1710 -
(daytime)
Taiwan Traffic 50
Junction TSP 180 - 230 1660 -
(nighttime)
Inland Urban PM10 150 30 - 1730 -
Inland
PM10 80 90 - 2090 -
Industrial
Taiwan,
Coastal 51
Kaoshiung PM10 190 40 2140 -
Industrial
Coastal Urban PM10 340 30 - 1740 -
TSP 269 33.6 54.9 1839 31.8
Korea, Taejon Industrial 52
PM10 195 42.6 32.4 1577 39.3
PM2.5 96.4 19.6 27.8 743 13.7
Korea, Seoul Urban 53
PM10 124 47.8 50.1 2321 18.8
0.03- 0.1- 0.19-
Rural
0.7 3.5 4.2
0.11- 1.6- 0.8-
Urban 54
Annual means- 1.2 13 3.1
TSP
Sites in Europe 0.21- 2.4- 0.05-
Traffic
2.4 21 4.1
0.2- 2.2- 1.2-
Industrial
23.7 102 97
PM: particulate matter; TSP: Total Suspended Particles; SPM: Suspected Particule Matter
ND: Not detection; BDL: Below detection limit
Table 4. Reported metal concentrations and information related with air particules in
literature. The metal concenttrations are ng/m3.
5. Conclusion
Exposure to chemicals is a serious public health problems that affect wildlife, soils, water,
and air and can have very harmful human health effects. Exposures to chemicals including
metals must be identified promptly, and individuals exposed to them must be evaluated
and managed without delay. Major sources of metal emissions into environment can be able
to change due to the updating in industrial activities and legislations. Before forbidding
tetraethyl Pb in gasoline, automobile emissions were the primary source of Pb emissions
while, nowadays, piston engine aircraft and industrial sources seem the two largest sources,
depending on developing of countries (25).
As it is seen from Table 4, the reported toxic metal concentrations in air phases are significantly
difference even if taking consideration their character such as rural, urban, traffic and industry.
It was found that metal concentrations (ng/m3) were in the ranges of 0.03-21 for Cd, 0.18-
1.040.000 for Pb, 0.1-9.580 for Ni, 0.14-63.530 for Cu, 0.7-255 for As, 1-3.252.000 for Fe and 1-
6.850 for Cr. Particularly, the observed metal concentrations in air of industry area in China are
extremely higher. As a result, there are a greet need for determinations of metal concentrations
in air phases, to obtain reliable and considerable values.
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3
Effect of Air Pollutants on Vegetation in

Tropical Climate: A Case Study of Delhi City
Sumanth Chinthala and Mukesh Khare
Indian Institute of Technology Delhi
India
1. Introduction
Urban air pollution is a serious problem in both developed and developing countries (Li,
2003). As a rapidly expanding centre of government, trade, commerce and industry,
Delhi, the Indian capital, has been facing many air pollution related problems. The
vehicular exhaust contributes significantly to the pollution load in Delhi. The plant
species are severely affected by various pollutants emitted from different sources e.g. SOx,
NOx and particulates. To maintain ecological balance in this fastly developing capital,
there is an immediate necessity to assess the effect of the air pollutants on the plant
speices so that the strategies can be formulated and implemented to protect the species.
Plants remove air pollutants by three mechanisms: absorption by the leaves, deposition of
particulates and aerosols over leaf surfaces, and fallout of particulates on the leeward side
of the vegetation (Tewari, 1994; Rawat and Banerjee, 1996). As a result, the chlorophyll
concentrations in the leaf which is responsible for the photosynthetic activity may
decrease (Seyyednejad et al, 2011). Hence, the ability of the plant to tolerate the air
pollution gets affected. Plantation of tolerant tree species will have a marked effect on
varied aspects of the quality of the urban environment and the cleanliness of life in a city
(Bamnia et al, 2011). The Anticipated Performance Index (API) has been used as an
indicator to assess the capability of some of the predominant species present in Delhi.
Further, the air pollution tolerance index (APTI) of the plants needs to be monitored and
checked for the predominant species that are located in the city.
2. Topography of Delhi
Delhi is positioned with the Great Indian Desert (Thar Desert) of Rajasthan to the west and
southwest, central hot plains to the south and gangetic plains of Uttar Pradesh/Uttaranchal
to the east while cooler hilly regions to the north. It is situated at latitude 28º24’17” and
28º53’00” North; Longitude 76º45’30” and 77º21’30” (East) at elevation of 216 m above the
mean sea level (msl). Delhi's climate is very hot in summer (April - July) and cold in winter
(December - January). The average temperature can vary from 25º C to 45º C during the
summer and 22º C to 5º C during the winter respectively. The topography of the city is
manly urban plain having two main features - the Ridge and the river Yamuna. The Ridge
refers to an area inhabited by extraordinary plants and fierce animals.
3. Air quality status in Delhi

The Air quality in Delhi is primarily affected by the vehicular exhausts, small scale
industries, power plants and biomass burning. The relative contribution of various sources
for the air pollution in Delhi has been shown (Table 1&2). It can be found that the vehicular
exhausts contribute a significant amount to the air pollution in the city. The pollutants
include SPM, RSPM, SOx, NOx and Benzene. It has also been reported that the benzene
concentration has exceeded seven times that of the permissible limit during the winter
season. In summers, the concentration of the pollutant has been below the permissible
standards prescribed. A Source apportionment study to identify the sources of the benzene
is to be carried out (DPCC, 2011).
Sl No Sector Percentage of emissions

1 Roads (Paved and Unpaved) 52-53
2 Area sources 18-20
3 Vehicles 3-5%
4 Industrial 20-22
Table 1. Prominence of Sources of PM10 for Delhi city (Source: CPCB, 2010).
NOx SOx
Sl No
Sector Percentage of emissions Sector Percentage of emissions
1 Industrial 78-80 Industrial 98
2 Vehicular 18-20 Vehicular 1
3 Area Sources 2-3 Area Sources 1
Table 2. Prominence of Sources of NOx and SOx for Delhi city (Source: CPCB,2010).
4. Vegetation covers in the city

The landscape of Delhi consists of a broad spectrum of environments ranging from the
city forests to highly modified artificial landscapes in certain parks (Khera et al, 2009).
Among the 260 different varaities of species present in delhi, only 42 species are native
species. The most dominant speicies is Prosporis Juliflora, a tree from central America that
was introduced around 1915 in order to afforest the central ridge forests. The other
commonly found tree species in Delhi include, Eucalyptus sp., Ficus benghalensis, Ficus
religiosa, Mangifera indica, Melia azedarach, and Syzygium jambolanum, Alstonia
scholaris, Azadirachta indica, and Cassia fistula. Since the majority of the tree species are
not a native varaities, their ability to sustain and sequestrate the air pollutants needs to be
evaluated at regular intervals. The features of the predominant tree species has been
shown in the table 3.
The effect of air pollutants is showing a significant effect on the vegetation in the city. The
predominant species, Prosporis Juliflora in the capital’s central ridge has been considered as
most sensitive to air pollution (Seyyednjad et al, 2011). With the presence of the most
sensitive species in a vast area in the heart of a city, the amount of pollutants absorbed by
the vegetation may get reduced. Further, some of the tree species may emit VOC’s which
play an important role in the atmospheric chemistry affecting the local air quality.
Effect of Air Pollutants on Vegetation in Tropical Climate: A Case Study of Delhi City 69
Sl no Name Scientific name Family

1 Shoe Babool Leacena leucophloea Mimoseae
2 Gulmohar Delonix regiosa Caesalpiniaceae
3 Neem Azardirachta indica Meliaceae
4 Vilayati kikkar Acacia farnesiana Mimoseae
5 Bankayan Melia azedarch Meliaceae
6 Bottle brush Calistemon citrinus Myrtaceae
7 Torch Tree Ixora parviflora Rubiaceae
8 Chikkoo Archise sapota Sapotaceae
9 Arjun Terminalia arjuna Combrataceae
10 Babool Accacia nelotica Mimoseae
11 Shesham Delbergia sisso Papilionaceae
12 Jangal Badam Terminalia catappal Combrataceae
13 Ashoka Polyalthia longifolia Annoniaceae
14 Kanju, Papadi Holiptelia integrifolia Ulmaceae
15 Amrood Psidium guyaua Myrtaceae
16 Mahua Madhuca indica Sapotaceae
17 Mulberry Morus alba Moraceae
18 Semal Bombax ceiba Bombaceae
19 Popular Populus trimuloides Siliaceae
20 Plums Prunus Comminis Rosaceae
21 Lemon Citrus lemon Rutaceae
Sl no Name Scientific name Family
22 Kanchnar Bauhinia Variegata Caesalpiniaceae
23 Bel Aegle marmelos Rubiaceae
24 Satni Alstonia Scholaris Apocynaceae
25 Mango Magnifera Indica Anacardiaceae
26 Blue gum Eucalyptus globulus Myrtaceae
27 Jamun Syzygium cuminii Myrtaceae
28 Peepal Ficus religiosa Moraceae
29 Teak Tectona grandis Verbenaceae
30 Kadam Anthosephalus cadamba Rubiaceae
31 Wolly Mopming Glorry Argyreia roxburghira Caesalpiniaceae
32 Amaltas Cassia fistula Caesalpiniaceae
33 Banyan tree Ficus bengalensis Moraceae
34 Indian rubber Ficus elastica Moraceae
Table 3. Predominant Tree species in Delhi (CPCB, 2007).
Regional as well as global scale VOC emission, from vegetation, may dominate over
anthropogenic sources of emission (Guenther et al., 1995). Out of the nine commonly
occurring tree species in Delhi, VOC emissions were found in six species, namely, Eucalyptus
sp., Ficus benghalensis, Ficus religiosa, Mangifera indica, Melia azedarach, and Syzygium
jambolanum, at higher concentrations. Further it has also been observed that that these
emissions are dependent up on sunlight and temperature (Tingey et al., 1979; Lamb et al.,
1987; Padhy and Varsheney, 2005).
5. Quantifying the effects of air pollution using APTI and API

The effect of air pollution on the plants can be quantified using a parameter, air pollution
tolerence index (APTI) (Singh and Rao, 1993). The APTI is a function of total chlorophyll
content of the leaf, pH, relative water content and the ascorbic acid content. The APTI for a
particular tree species is given in eq (1)
APTI = (A (T+ P) + R)/10 (1)

Where A= Ascorbic acid content in mg/g dry weight,
T= Total Chlorophyll content in mg/g dry weight,
P= pH of the Leaf extract,
R = Relative water content (%)
The plant species can be convinently grouped based on the APTI values (Table 4).
Sl no APTI Response
1 30 -100 Tolerant
2 29-17 Intermediate
3 16-1 Sensitive
4 <1 Very sensitive
Table 4. Grouping of plants using APTI (Source: Lakshmi et al, 2006).
Further, the parameters of the APTI have been correlated with the increasing concentration
of the pollutants. It has been found that the relative water content , total chlorophyll are
negatively correlated and ascorbic acid is positively correlated with all the pollutants. The
pH values are negatively correlated in the case of NOx (Table 5).
Relative water content pH Total chlorophyll Ascorbic acid

SPM Negative Positive Negative Positive
RSPM Negative Positive Negative Positive
SO2 Negative Positive Negative Positive
NO2 Negative Negative Negative Positive
Table 5. Correlation between Air pollutants and Biochemical parameters (Govindaraju et al,
2011).
The APTI index shows the effect of the pollutants only on the biochemical parameters. In
order to combat air pollution by planning the green belt development in a particular area,
many socio-economic factors are to be considered. Hence the anticipated performance index
has been used to determine the same (Govindaraju et al, 2011). The method contains a
grading system where a tree species is graded based on various parameters. The API has
been calculated for predominant tree species in Delhi. The table 6 shows the parameters
used to grade the performance of a particular tree species. It includes the parameters like
APTI along with the socio-economic parameters. Based on the current grading system, a tree
can secure a maximum of 16 positive points. These points were scaled to a percentage
system and based on the score obtained, the category has been assessed. Table 7 shows the
assessment categories along with the scores.
Grading Character Parameter Pattern of assessment Grade alloted

9.0-12.0 +
12.1-15.0 ++
Tolerence APTI 15.1-18.0 +++
18.1-21.0 ++++
21.1 -24.0 +++++
Small -
Plant habit Medium +
Large ++
Biological and Sparse /Irregular/ Globular -
Canopy
Socio -economic Spreading crown/open/ semi dense +
Structure
Spreading dense ++
Decidious -
Type of Plant
Evergreen +
Small -
Leaf Size Medium +
Large ++
Smooth -
Texture
Coriacious +
Laminar structure
Delineate -
Hardness
Hardy +
Less than Three uses -
Economic
Three or Four uses +
Value
Five or more uses ++
Table 6. Gradation of plant species based on APTI as well as morphological parameters and
socio – economic importance (Govindaraju et al, 2011).
Grade Score (%) Assesment category

0 Up to 30 Not recommended
1 31-40 Very poor
2 41-50 Poor
3 51-60 Moderate
4 61-70 Good
5 71-80 Very good
6 81-90 Excellent
7 91-100 Best
Table 7. Anticipated performance Index (API) for species (Govindaraju et al, 2011).
To determine the effect of air pollutants on the tree species in Delhi, the API values have
been calculated. Since the data on the APTI values of the tree species considered are not
available, the analysis is performed for both the extreme cases i.e for maximum APTI and
for the minimum APTI. Table 8 and 9 shows the maximum and minimum values of the API
obtained.
It can be shown from the table 9 that even though the APTI of a species is negligible (less
than 9) , but still the API of a plant species are securing a reasonable grades. Out of the eight
species, three are good, two are moderate, two are poor and one is very poor.
Sl Species a b c d e f g h Total (%) Category

Prosporis
1 + + + - - ++ + +++++ 11 68.7 Good
juliflora
Eucalyptus
2 ++ + + ++ + ++ + +++++ 15 93.7 Best
sp
Ficus
3 ++ + + ++ + ++ + +++++ 15 93.7 Best
benghalensis
Ficus
4 ++ + + ++ + + + +++++ 14 87.5 Excellent
religiosa
Mangifera
5 ++ + + ++ + ++ + +++++ 15 93.7 Best
indica
Alstonia
6 ++ - + ++ + + + +++++ 13 81.2 Excellent
scholaris
Azadirachta
7 ++ ++ - - - ++ + +++++ 12 75 Very good
indica
8 Cassia fistula ++ ++ - ++ + + + +++++ 14 87.5 Excellent
Table 8. Maximum API for the predominant plant species in Delhi.
Sl Species a b c d e f g Total (%) Category

Prosporis
1 + + + - - ++ + 6 37.5 Very poor
juliflora
2 Eucalyptus sp ++ + + ++ + ++ + 10 62.5 Good
Ficus
3 ++ + + ++ + ++ + 10 62.5 Good
benghalensis
4 Ficus religiosa ++ + + ++ + + + 9 56.2 Moderate
Mangifera
5 ++ + + ++ + ++ + 10 62.5 Good
indica
Alstonia
6 ++ - + ++ + + + 8 50 Poor
scholaris
Azadirachta
7 ++ ++ - - - ++ + 7 43.7 Poor
indica
8 Cassia fistula ++ ++ - ++ + + + 9 56.2 Moderate
where a= plant habitat; b= canopy structure; c= type of plant; d=leaf size; e= texture; f= economic
importance; g= hardiness ; h = APTI.
Table 9. Minimum API for the plant species in Delhi.
Since the Delhi’s most predominant species is showing very poor performance, it can be said
that if the APTI value decreases, the API may not indicate the performance of a plant
species. Since the reduction in the APTI values may also affect the other biochemical and
socio-economic parameters, a modified index is proposed by adding a negative weightage.
For every unit reduction in the positive value of the APTI, a negative weightage is proposed.
Further, it has been found that among all the pollutants, SPM has the maximum effect on the
biochemical parameters; and NOx has the least effect. The pollutants can be arranged in the
following order. SPM> RSPM> SOx> NOx (Govindaraju et al, 2011). To incorporate the effect
of increase of the concentrations of these pollutants, an additional weightage of 1, 0.75, 0.5
and 0.25 may be added to the negative weightage, respectively. This additional weightage
will be added only when the concentration of the polluants exceed the specified standards.
Sl APTI Weightage SPM RSPM SOx NOx

1 +++++ 0 1 0.75 0.5 0.25
2 ++++ 1 1 0.75 0.5 0.25
3 +++ 2 1 0.75 0.5 0.25
4 ++ 3 1 0.75 0.5 0.25
5 + 4 1 0.75 0.5 0.25
Table 10. Proposed negative weightage allocation for varying APTI values and under
different environmental conditions.
Thus, the incorporation of the negative weightage in the calculation of the API for existing
plant species can make it more practical if applied for the city like Delhi.
6. Conclusions
It can be concluded that due to the increasing pollution load on the plants, the vegetation in
the city is under extreme stress. To ensure that the generated pollutant load is removed from
the atmosphere, the quantification of the effect of the pollutants on the tree species should
be made at regular intervals to ensure that they perform well under pollutant stresses.
Further, the source apportionment studies have to be conducted to identify the pollutants
like benzene which are exceeding the permissible standards during winter. Aditionally, the
effect of the water contamination and other miscellaneous factors may add additional stress
to the vegetation which needs to be considered to ensure that the species sustain in a
polluted environment.
7. References
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pollution on physiological activites of Pongamia pinnita (L.) Pierre”, Clean
technology environmental policy, Springer. DOI 10.1007/s10098-011-0383-z.
CPCB (2007) “Phytoremediation of particulate matter from ambient environment through
dust capturing plant species”, Abstracted from www.cpcb.nic.in on January 2nd ,
2012.
CPCB (2010) “Air quality monitoring, emission inventory and source apportionment study
for Indian cities”, National Summary Report, Abstracted from www.moef.nic.in on
January 5th , 2011.
DPCC (2011) “A Background note on status of PM10, PM2.5, NOx and Benzene”, Unpublished
Report.
Govindaraju, M., Ganeshkumar, R.S., Muthukumaran, V.R and Visvanathan, P (2011)

“Identification and evaluation of air-pollution-tolerant plants around lignite-based
thermal power station for greenbelt development”, Environmental Science
Pollution Research,DOI 10.1007/s11356-011-0637-7.
Guenther, A., Hewitt, C.N., Erickson, D., Fall, R., Geron, C., Graedel, T., Harley, P., Klinger,
L., Lerdan, M., Mckay, W.A., Pierce, T., Scholes, B., Steinbrecher, R., Tallamraju, R.,
Taylor, J. and Zimmerman, P (1995) “A global model of natural volatile organic
emissions”, Journal of Geophysical Research, 100, 8873–8892.
Khere, N., Mehta, V and Sabata, B.C (2009) “Interrelationships of birds and habitat features
in urban green spaces in Delhi, India”, Urban Foresty and Urban greeining,
Volume 8, Issue 3, 2009, 187-196.
Lakshmi, P.S., K.L. Sravanti and N. Srinivas, (2009) Air pollution tolerance index of various
plant species growing in industrial areas. The Ecoscan., 2: 203-206.
Lamb, B., Guenther, A., Gay, D., Westberg, H., (1987) “A nationalinventory of biogenic
hydrocarbon emissions”. Atmospheric Environment, 21, 1695–1705.
Li, M.H. (2003) “Peroxidase and superoxide dismutase activities in fig leaves in response to
ambient air pollution in a subtropical city” Arch. Environ. Contamination
toxicology, 45: 168-176.
Padhy and Varsheney (2005) “Isoprene emission from tropical tree species”, Environ Pollut.
2005 May;135(1):101-9.
Rawat, J.S., Banerjee, S.P., (1996) “Urban forestry for improvement of environment’ Journal
of Energy Environment Monitoring 12 (2),109–116.
S.M. Seyyednjad, K. Majdian, H. Koochak and M. Niknejad, (2011) “Air Pollution Tolerance
Indices of Some Plants Around Industrial Zone in South of Iran”. Asian Journal of
Biological Sciences, 4: 300-305.
Singh, S. K. and Rao, D. N. (1983). Evaluation of plants for their tolerance to air pollution. In
Proceedings of the Symposium on Air Pollution Control, November, pp. 218-224.
Tewari, D.N., (1974) Urban forestry. Indian Forester 120 (8), 647–657.
Tingey, D.T., Manning, M., Grothaus, L.C., Burns, W.F., (1979) The influence of light and
temperature on isoprene emission rates from live oak. Plant Physiology 47, 112–
118.
4
Physico-Chemical Characterisation of Aerosol

Particles at Canopy Level in Urban Zone
S. Despiau
LSEET-LEPI / UMR 6017/ Université du Sud Toulon-Var
France
1. Introduction
For many years, national and/or international research programs devoted to understand the
effects of aerosol particles on health (COST action 633, ..) and/or climate (ACE experiments,
INDOEX, TARFOX, NAMBLEX …) have been carried out in various regions of the world
and at various scale of time and space and more and more papers are published in
connection with these two effects, health (Dockery et al., 1993; Dockery and Pope, 1994;
Oberdörster, 2000; Pekanen et al., 1997 ; Pope and Dockery, 1999; Pope et al., 2002;
Wichmann and Peters, 2000; …) and climate (Charlson et al., 1992; Jacobson, M.Z., 2001;
Kaufman et al., 2002; Penner et al., 2004; …).
These effects are mainly the consequence of the physico-chemical characteristics of the
aerosol particles that depend first on the mode (natural, anthropogenic, primary, secondary)
and place (urban, industrial, rural, marine, coastal zones …) of production. They depend
also on their transformation during transport, which is mainly depending on the
meteorological conditions prevailing in the region where the experiments are carried out,
the occurrence of possible and specific sources and sinks all along the pathway of the air
mass. Whatever the scale considered, a global watch of these effects and their possible
future changes requires the availability of adequately emission inventories (François et al.,
2005) and the use of numerical models which improvement assumes accurate comparisons
with experimental data (Builtjes et al., 2003, Cousin et al., 2005).
The two main objectives of the regional ESCOMPTE experimental campaign (Cros et al.,
2004) which took place in the south of France in the “Fos-Berre-Marseille” region in June-
July 2001, were to study the numerous photochemical pollution events that occur in that
region and to produce a relevant set of data for testing and evaluating regional pollution
models. Among the various data sets recorded during the campaign, the one concerning the
aerosol particles resulted from the measurements realised in 7 sites representative of
industrial, urban, suburban and rural areas (Cachier et al., 2005). It is well known that urban
zones are a strong and complex source of aerosol particles but an “urban source” is difficult
to characterize precisely. In order to try to provide data characterising better one urban
zone, it was decided to realise the measurements at a height representative of a mean urban
“canopy level”. The measurements were then carried out on the roof of a public building
localized in Marseille downtown.
The main results obtained during the campaign are presented here and are considered with
respect to two main questions:
Have the particles particular physico-chemical characteristics at canopy level and are these
characteristics useful for modelling purposes or for emission inventories validation ?
Are IOP situations (described hereafter) leading to a specific signature in terms of particle
characteristics ?
2. Experimental campaign and methodology

The experimental zone of the ESCOMPTE program covered an area of 120x120 km centred
on the “Marseille-Berre” region, including an important coastal zone (Fig. 1).
Fig. 1. Left: view of the ESCOMPTE domain (small black square), Marseille city (red ellipse);
The arrows in the small square indicate the dominant wind directions. Right: Location of the
measurement stations: canopy level (red ellipse) and details (above) of the sensors installed
on the roof and street level (black square).
This region is characterised by the presence of numerous industrial and urban sources of
primary and secondary pollutants and by specific summer meteorological conditions,
mainly anticyclonic with strong solar radiation, both aspects leading to a high probability of
photochemical pollution events (Cros et al., 2004). The study of these photochemical events
was one of the two main objectives of the campaign and, when favourable conditions for
photochemical processes were forecasted, Intensive Observation Period (IOP) was decided.
Four situations: 14-15 June (IOP 1), 21-26 June [IOP 2a (21-23) and 2b (24-26)], 2-4 July (IOP
3) and 10-12 July (IOP 4), corresponded to these conditions.
2.1 Experimental set up

The building where the urban measurement station was installed is located along a one-way
street canyon (Rue St Sebastien) and nearby (100 m) a two-way road (Prado avenue), both
Physico-Chemical Characterisation of Aerosol Particles at Canopy Level in Urban Zone 77
with intense traffic (Fig.1). The measurement station was installed on the roof of the
building, 30 m above street level, and composed of one Scanning Mobility Particle Sizer
(SMPS TSI : 3071 classifier and 3022 CPC) measuring between 14 and 720 nm, one optical
counter (Royco) between 0.5 and 15 µm, two TEOMS (Rupprecht and Patachnick) with 1
and 10 µm cut-off inlets (heated at 50°C) and one aethalometer (Magee Scientific AE 14) for
quasi-real time BC concentration measurements. A total filter and two cascade impactors (a
6 stages “High Vol Sierra” between 0.5 and 10 µm and 13 stages low pressure “Dekati”
between 0.03 and 10 µm) were used to collect particles on filters for chemical analyse.
Meteorological parameters were locally measured with an automatic station while radiative
measurements were provided by a specific system located on the roof of a neighbouring
building. One Aeronet station was also installed during the experimental period. Gas
measurements (CO, NOx) were taken at street level on the Prado avenue, by AIRMARAIX
(now ATMOPACA), the local air pollution network.
2.2 Data acquisition

All these systems were systematically run during IOPs but also outside these specific
periods, except the Dekati low pressure impactor. The SMPS and the optical counter provide
number concentrations and size distributions in their specific size domains. Each one was
set up to give one concentration and one distribution every 15 minutes, resulting from the
average of 3 successive scans lasting 4 minutes each. Every 30 minutes, two mass
concentrations (µgm-3) were available with the two TEOM. The aethalometer provided one
BC concentration (ngm-3) every 3 minutes and five successive values were averaged to
obtain one measurement every 15 minutes. In order to obtain enough material for the
chemical characterization and according to their respective flow rates, the total filter, High
Vol and Dekati impactors sampled 3, 6 and 10 hours, respectively. The black and organic
carbon contents were determined by the 2-step thermal analysis method (Cachier et al.,
1989) of the total filters, generally two, daily sampled (Cachier et al., 2005). The ionic
composition was determined by chromatographic analysis (Putaud et al., 2004) of the filters
impacted with the “Dekati” low pressure cascade impactor.
3. Results and discussion

3.1 PM mass concentrations
PM10 and PM1 concentration measurements started the 16/06 and 18/06, respectively, and
were then monitored during the whole campaign. Over the 16/06 – 13/07 period, the
average PM10 concentration (Fig. 2a) is (28  5) µgm-3, a value of the same order as those
obtained in various European urban zones, generally comprised between 20 and 45 µgm-3
(Harrison et al., 2001; Perez et al., 2008; Pey et al., 2010; Putaud et al., 2004; 2010; Schwarz et
al., 2008), according to the site (kerbside, downtown, suburbs), the season or to specific
meteorological conditions. Averaged over 24 h only, the concentration varies between 11
µgm-3 the 18/06 and 61 µgm-3 the 06/07. During the campaign, PM10 concentration passed
once only (06/07) beyond the EU standard 24-hour limit value of 50 µgm-3, but reached,
punctually, higher values : 131 µgm-3 at 16:00 and (91,5  19,2) µgm-3 between 10:00 and
19:00, on July 6, a “non–IOP” day.
80 day (05:00-20:00)
70 night (20:30-04:30)
60
PM10 (µg/m3)
50
40
30
20
10
0
15.6 20.6 25.6 30.6 5.7 10.7 15.7
Fig. 2a. PM10 mean concentrations recorded during the campaign.
35 day (05:00-20:00)
30 night (20:30-04:30)
25
PM1 (µg/m3)
20
15
10
0
15.6 20.6 25.6 30.6 5.7 10.7 15.7
Fig. 2b. PM1 mean concentrations recorded during the campaign.
The PM1 mean concentration (fig. 2b) over the 18/06 – 13/07 period is (17.5  2.1) µgm-3 and
varies between 7 and 26 µgm-3 when averaged over 24 hours. These values are comparable
with those obtained in Barcelona and reported by Viana et al. (2005), Pey et al. (2010)
between 7 and 20 µgm-3, or by Gugliano et al. (2005) in Milano, around 15.3 µgm-3 in
summer. Nevertheless, as for PM10, PM1 punctually reached higher values: 56 µgm-3 at
06:00 on June 22 or (35.6  3.7)µgm-3 between 7:00 and 13:00 on June, 30. It must be noted
that the higher concentrations were not recorded the same day than those of PM10 but, as
for PM10, during non “IOP days”. This shows that the IOP conditions do not correspond to
a systematic enhancement of PM10 and PM1 concentration, and that PM10 and PM1 may
evolve differently.
Analysed over 24 hours, PM10 and PM1 present both a strong increase (around 50 % to 60 %
of the background values) in the morning, around 7:00 to 8:00, linked to the traffic rush. But
both are also characterised by large daily variations, during and outside IOP periods. For
PM10 the standard deviation represents, in average, 47% of the mean daily value and reach
67% on July, 4. The corresponding values for PM1 are 36% and 54% on June, 22. Despite the
fact that PM10 includes PM1, sometimes PM10 increases while PM1 decreases and
conversely (Fig. 3). In the first case this means that coarse particles (> 1µm) are mainly
generated and, conversely, that fine particles (<1 µm) are generated in excess, in the second
case. This simply confirms that the main PM10 and PM1 sources are different.
70,0
60,0
50,0
concentration (µg/m3)
40,0
PM1
PM10
30,0
20,0
10,0
0,0
18/6
20/6
22/6
24/6
26/6
28/6
30/6
2/7
4/7
6/7
8/7
10/7
12/7
Fig. 3. Day to day comparison of PM10 and PM1 evolutions. The red arrows indicate the
cases where PM1 increase while PM10 decrease, the blue arrows indicate the reverse
situation.
The PM10 and PM1 concentrations depend also highly on various other factors, of which the
meteorological conditions. Indeed, both wind and humidity affect differently the fine and
coarse particles.
The daily comparison between the mean values of concentration and wind velocity (V), (Fig.
4.a) shows that PM10 and V are not correlated (R2 = 0.01), that PM1 decreases slightly when
V increases (R2 = 0.41) whereas the coarse fraction (PM10 – PM1) tends to increase with V
(R2 = 0.58). This indicates that the wind velocity tends to disperse the fine particles (< 1µm)
more efficiently than it generates or raises up to the canopy coarse particles, leading to the
non-correlation PM10-wind velocity.
On the other hand, the PM-humidity relationship shows (Fig. 4b) that the fine particles are
more humidity dependent (R2 = 0.54) than the coarse (R2 = 0.10 only), indicating a less
hygroscopic character of the larger particles.
PM10 = 1,25 V + 25,77 PM1= -2,81 V+ 23,96 (PM10-PM1)= 7,48V - 1,16

R2 = 0,01 R2 = 0,41 R2 = 0,58
70.0 PM10
60.0 PM1
50.0 PM10 - PM1
PM (µg/m3)
40.0
30.0
20.0
10.0
0.0
0 1 2 3 4 5
Wind speed (m/s)
Fig. 4a. PM10, PM1 and (PM10-PM1) versus wind speed.
45.0 PM10
40.0 PM1
35.0
(PM10 - PM1)
30.0
PM (µg/m3)
PM10 = 0,51 H+ 0,51

25.0 R2 = 0,45
20.0
PM1 = 0,34 H + 0,44
15.0 R2 = 0,53
10.0
(PM10-PM1) = 0,12 H + 3,63
5.0 R2 = 0,10
0.0
0 10 20 30 40 50 60 70 80
Humidity (%)
Fig. 4b. PM10, PM1 and (PM10-PM1) versus humidity.

The comparison between the fine and coarse fractions is generally made through the study
of PM2.5/PM10 ratio (Harrison et al., 2001; Keywood et al., 1999; Putaud et al, 2010; Querol
et al., 2004; Van Dingenen et al., 2004) and more rarely through the PM1/PM10 ratio. In our
case, the PM1/PM10 ratio varies mainly between 0.5 and 0.7 leading to an average value
over the whole campaign of (0.60  0.12). These values are in accordance with those of
Gugliano et al. (2005) in Milano, around 0.60, but slightly greater than those of Keywood et
al. (1999) for six cities in Australia (0.50  0.08) or those by Viana et al. (2005), between 0.33
and 0.54 and Perez et al. (2008) between 0.42 and 0.48, both in Barcelona. However, this ratio
reached during the campaign higher (0.85 the 20/06) or lower values, (0.3 the 06/07) and
increased slightly (0.69  0.06) during IOPs 2 and 3, indicating a tendency for IOP periods to
produce more fine particles.
By comparison, the average PM2.5/PM10 ratio calculated by Putaud et al. (2004) from
measurements in various European regions including rural and urban sites is (0.73  0.02),
but it is précised (Putaud et al, 2010) that this ratio may vary between 0.4 and 0.9. These
large variations make the comparisons difficult but our PM1/PM10 values are not very
different of the PM2.5/PM10 ratio, showing that the (PM2.5-PM1) may be estimated around
10% only of PM10 in our situation. This estimation is comparable with the Pey et al (2009)
value (15% in urban background in Barcelona) and Querol et al. (2004) values who found
that the PM2.5-1 contributed between 9 and 21 % to PM10 in their study in different
locations of Spain.
Nevertheless, in order to better compare the relative importance of the fine and coarse
modes, we calculated the ratio PM1 / (PM10 - PM1) for each of the 24 days with available
data.
PM1 / (PM10-PM1)
6,0
5,0
4,0
3,0
2,0
1,0
0,0
19/6 20/6 21/6 22/6 23/6 24/6 25/6 26/6 27/6 28/6 29/6 30/6 1/7 2/7 3/7 4/7 5/7 6/7
Fig. 5. Ratio PM1/(PM10-PM1) calculated for each day of the campaign.

The results plotted in Fig. 5 indicate clearly that, in our situation, the fine mode dominates
largely, in mass, the coarse mode. Averaged over the whole campaign the ratio is (1.9  0.8)
but it may reach in some cases higher values (3.3 the 21/06 or 5.1 the 20/06), while it is < 1
for only three days. The fact that the measurements are realised at the canopy level may
partially explain this result since the coarse particles are more efficiently deposited and/or
less efficiently raised up than the fine particles, in particular during the night and periods of
weak winds.
3.2 Chemical composition

3.2.1 Carbon compounds
Elemental or black carbon (EC or BC) measurements were everyday available through the
use of the aethalometer. In parallel with the aethalometer measurements, EC and total
carbon (TC) were also daily available through total filters analysed by the thermal method
(Cachier et al., 1989). We dispose also of one set of “Dekati filters” sampled during the 23-24
June, in the middle of IOP2, allowing in that case the study of EC and TC mass distribution.
Organic carbon (OC) was deduced from the previous values (OC = TC – EC).
Over the whole campaign, the average EC concentrations measured by the aethalometer and
deduced from the filter analyse are comparable, (2.93  0.73) and (2.75  0.92) µgm-3,
respectively. The TC concentration obtained from the filter analyse is (9.11  2.38) µgm-3, the
corresponding OC value is thus evaluated at (6.37  1.95) µgm-3. As for PM1 or PM10, to
compare our TC and/or EC measurement results with the large number of those realised in
various places in the world is quite difficult because of the specific conditions
(meteorological, season, site, duration) that characterise each measurement.
Our TC values are nevertheless comprised in the wide range of those obtained in similar
sites (urban or urban background) and summer season, which vary between 4 to 5 µgm-3 in
Aveiro (Castro et al., 1999), Helsinki (Viidanoja et al., 2002), Belfast (Jones and Harisson,
2005) or in Oporto (Duarte et al., 2008) and higher values around 19 µgm-3 in Seoul (Kim et
al., 1999) or Hong Kong (Ho et al., 2002). The EC/TC ratio is equal to (0.31  0.08). This ratio
is higher than the one (0.17) reported by Pey et al. (2009) for regional background sites in the
west coast of Spain but equivalent to those reported by Viana et al. (2007) concerning
measurements in Amsterdam and Barcelona, or by Jones and Harrison (2005) in the centre
of Belfast and of the same order than those generally found in measurements carried out in
similar urban zones, comprised between 0.22 and 0.38, and reported in Ruellan and Cachier,
(2001), Yttri et al. (2007) or Harrison and Yin (2008). For the IOP days only, the results are
slightly different. The EC, TC and OC concentrations are respectively (2.72  0.94) µgm-3,
(10.37  2.59) µgm-3 and (7.65  1.97) µgm-3, while the EC/TC value is 0.26  0.07. The
tendency for IOP days is thus an increase of the OC concentrations and, consequently, a
decrease of the EC/TC ratio. This tendency is logical since the IOP days are favourable to
photochemical processes that favour secondary organic aerosol formation and thus the
increase of the OC concentration that is partly composed of secondary organic aerosols.
3.2.2 Water Soluble Compounds (WSC)

Seven sets (6 days and 1 night) of 13 filters sampled with the Dekati impactor during IOP1
(14 and 15/06), IOP2 (22, 25d, 25n, and 26/06) and IOP3 (02/07) periods, were analysed by
ionic chromatography. The amount of the different water soluble compounds in PM10 and
PM1 was obtained by summing, for each set of 13 filters, the concentrations measured on
each one. Averaged over the 7 samples, nss sulphate (nssSO4) is the most abundant (5.7  2.3
µgm-3), followed by sea salt (3.81  1.19 µgm-3), ammonium and nitrates in equivalent
amount, (2.9  0.4 µgm-3) and (2.8  1.1 µgm-3), respectively, then by the main crustal
elements [nss(Ca + Mg + K)  1.4 µgm-3]. These values are of the same order than those
obtained in Barcelona (Viana et al., 2005; Perez et al., 2008) or in other coastal sites in Spain
(Querol et al., 2004). These average values hide however the large variations observed on
some occasions. The 25 June (IOP 2b) the nssSO4 and NH4 concentrations reach respectively
8.7 and 4.22 µgm-3, while they are of 1.91 and 1.09 µgm-3 only the 22 June (IOP 2a). Inversely,
the sea salt concentration is maximum (5.5 µgm-3) the 22 June and of 3.8 µgm-3 only the 25
June. These variations result mainly from the very different meteorological conditions of
these two days. The 22, the average humidity during the sampling time is 41.8% only while
it is 78.5% the 25. The wind velocity is 5.5 ms-1 in average between 11:30 and 17:30 the 22,
and of 2.7 ms-1 only the 25 for the same period. Moreover, the mean wind direction the 22
corresponds to a situation of sea breeze leading to an enhanced production of coarse marine
aerosol while the direction is more continental the 25, coming mainly from the industrial
Fos-Berre zone.
3.2.3 Mass chemical distribution

The use of the cascade impactor allows the study of the mass distribution of the water
soluble compounds for the 7 samples available and of the carbon compounds for the 23-24
July set of filters. 80% of EC and 69% of OC are found on the fine mode (<1µm).
Carbon
1.40
1.20
1.00
C (µg/m3)
TC
0.80
0.60 EC
0.40 OC
0.20
0.00
0.01 0.1 1 10 100
diameter (µm)
Fig. 6. TC, EC and OC mass size distributions.
Our results (Fig. 6) show that the EC distribution is monomodal and centred on the
accumulation mode on particles of diameter comprised between 0.25 and 0.4 µm, while the
OC distribution tends to be bimodal with two relative maximum at 0.25 and 2.5 µm,
respectively. Nevertheless, that distribution must be considered as indicative because they
are deduced from the analysis of one set of filters only.
For the water soluble compounds, the analyse shows that 100 % of ammonium and 94 % of
nss-sulphate are found in the fine mode and for the major part on particles of diameter 0.3-
0.4 µm. Sea salt and crustals are classically found on the coarse mode, both at 80 %, on
particles of diameter 1 and 5 µm, while nitrate is spread over the whole range but mainly, at
64 %, on the coarse mode (Fig.7). Concerning NO3 it must be noted the fine particle amount
is mainly due to the distribution obtained during the night (25/06) and that its distribution
in the coarse mode tends to be bimodal with two maximum around 2.5 and 7 µm.
12.00 16.00
14.00
10.00
NH4 12.00
nssSO4
dC/dLogDp (µg.m -3)
dC/dLogDp (µg.m -3)

8.00
10.00
6.00 8.00
6.00
4.00
4.00
2.00
2.00
0.00 0.00
0.01 0.10 Dp (µm) 1.00 10.00 0.01 0.10 Dp (µm) 1.00 10.00
14/6 15/6 22/6 25/6 25/6night 26/6 2/7 14/6 15/6 22/6 25/6 25/6night 26/6 2/7
4.00
7.00
3.50
6.00
dC/dLogDp
3.00 (µg,m-3)
5.00
dC/dLogDp (µg.m-3)
Sea Salt 2.50

NO3
4.00
2.00
3.00
1.50
2.00 1.00
1.00 0.50
0.00 0.00
0.01 0.10 Dp (µm) 1.00 10.00 0.01 0.10 Dp (µm) 1.00 10.00
14/6 15/6 22/6 25/6 25/6night 26/6 2/7 14/6 15/6 22/6 25/6 25/6n 26/6 2/7
Fig. 7. Mass size distribution of 4 WSC corresponding to the seven sets of filters.
In Fig. 8 are reported the relative percentages of the compounds analysed for PM10, PM1
and PM1-10.
PM 1-10 (Coarse)
5% BC
OC
30% 23% NO3
nssSO4
Cl
NH4
1% Na
dust
18%
12% Oxa
4%0%4% 3% s.salt
4% PM1 (fine)
2%
1%
12% BC
1% OC
15% NO3
nssSO4
1% Cl
29% NH4
Na
dust
29% Oxa
6% s.salt
PM10
9% BC
14%
1% OC
NO3
5%
nssSO4
2% 27% Cl
NH4
10%
Na
2% dust
Oxa
10%
20% s.salt
Fig. 8. relative percentages, averaged over the seven sets of filters, of the different
compounds in PM10, PM1 (Fine) and PM(1-10) (coarse).
It can be seen that for PM10 (36%) as for PM1 (41%), TC (OC + EC) is by far the major
contributor, followed by nssSO4, 20% and 29%, respectively. For PM1-10, sea salt becomes
the major contributor (30%), followed by TC (28%). Compound by compound, the four
more important are OC (27%), nssSO4 (20%), seasalt (14%) and NH4+ and NO3 (10%) for
PM10, OC (29%), nssSO4 (29%), NH4 (15%) and EC (12%) for PM1, seasalt,(30%), OC
(23%), NO3 (18%) and crustals (14%) for PM1-10. The comparison between the three
distributions shows that, for PM1, the relative parts of carbon (EC and OC), nss SO4 and
NH4 increase, while NO3 and sea salt decrease, confirming simply that the first
compounds are mainly distributed on the fine particles and conversely for NO3 and sea
salt.
3.2.4 Correlation between WSCs

We calculated (Table 1) the coefficient of correlation between different WSCs for each set of
filters (the 13 filters are considered together) and for each day. When R2 is very high (> 0.8),
this means that the two compounds are found on the same size category, fine or coarse, and
more precisely on the same narrow size range.
R2 14/06 15/06 22/06 25/06D 25/06N 26/06 02/07

NH4 - nssSO4 0.99 0.98 0.98 0.98 0.99 0.44 0.98
NH4 - NO3 0.05 0.07 0.32 --- 0.56 0.18 0.30
Na - NO3 0.84 0.86 0.45 0.48 --- 0.34 0.73
Na - Cl 0.58 0.55 O.97 0.35 0.35 0.06 0.40
Table 1. Coefficient of correlation between different WSCs.
It is clearly the case for NH4 and nss SO4 that are, except the 26/06, both localised on
particles of diameter comprised between 0.3 and O.5 µm and classically linked as
(NH4)2SO4. It is also the case for Na and NO3 the 14 and 15 June, associated as NaNO3 in
coarse particles or Na and Cl (NaCl) the 22 June, also on the coarse mode. On the contrary,
when R2 is weak, the two compounds are distributed differently (coarse and fine). However,
even when R2 calculated over the whole size range is weak, it is possible that the
corresponding compounds be associated only in the fine or in the coarse mode. For example,
R2 calculated for NH4 and NO3 over the fine mode only, reach values > 0.90 the 14/06, 15/06
or 25/06 of June, indicating the presence of ammonium nitrate in the fine mode. The 26/06
is characterised by a weak ammonium-nss-sulphate correlation (R2 = 0.44) and no
ammonium-nitrate correlation. According to wind direction and back-trajectories, the air
masses on that day were exclusively of marine origin that could explain the weak
correlations, as it was previously noticed in the same region and under similar conditions by
Sellegri et al. (2001).
3.3 Particle concentrations and size distributions

During the campaign, the SMPS system was set up to provide one average Size Distribution
(SD) every 15 minutes, derived from 3 SD lasting 4 minutes each. From these SD, other
parameters were deduced (total concentrations, day average SD,…), according to the
analysis conducted. Total dN or dN/dLogD concentrations were obtained by summing the
concentrations measured for each size range. In Fig. 9 are plotted the day and night average
of the dN concentrations obtained at the canopy level for 17 days and 10 nights during the
campaign.
2.50E+04
2.00E+04
1.50E+04
dN (#/cm3)
1.00E+04
5.00E+03
0.00E+00
12.6 14.6 16.6 18.6 20.6 22.6 24.6 26.6 28.6 30.6 2.7 4.7
Dates
Fig. 9. Plot of the day (black stars) and night dN average concentrations (with standard
deviation) recorded during the campaign.
These concentrations vary mainly between 0.75.104 and 1.4.104 cm-3, except in two occasions.
The 18/6 and 19/6 the concentrations are lower because these two days are characterised by
strong winds [(8  1) ms-1 in average against  2 ms-1 for the other days] that disperse very
efficiently the fine particles, as already noted for the PM1 concentration. The 21/6 and 22/6,
which are the first days of the IOP2, the concentrations are on the contrary higher. Averaged
over the whole campaign the concentration is (1.3  0.5)104 cm-3 including the 4 specific
situations mentioned before or (1.3  0.2 ).104 cm-3, without. This value, that may be
considered as the background value at the canopy level for the corresponding period and
site, is of the same order than those measured in Prague (1.18 104 cm-3) by Salma et al. (2011),
in Augsburg (1.22 104 cm-3) by Birmili et al. (2010) or in other urban sites (London, Leipzig or
Milano), comprised between 0.7.104 and 2.4.104 cm-3) and reported in Putaud et al., (2004,
2010). Our value is however largely lower than those measured at kerbside, which vary
between 4.0.104 and 6.0.104 cm-3, Putaud et al., (2004, 2010) or by Yue et al., (2010), 2.9104 cm-3
in average in Ghangzoua, during summer pollution episodes. This simply shows that, in
urban zone and in summer season, the particles produced by the traffic at street level are
partially dispersed before reaching the canopy and that measurements made at canopy level
are likely more representative, as input values for regional models, than results obtained at
street level. It must also be noted that IOP days, as it was already the case for the PM
measurements, do not correspond systematically to the higher concentration values. Indeed,
the concentrations obtained during the IOP1, 2b and 3 are of the same order than those of
“non-IOP” days.
If these daily average values give a quite good indication of what is expected at the canopy
level of a great coastal urban area in summer and may be considered as useful input values
for modelling purpose at local and regional scale, or for comparison with particle emission
inventories in urban zone, they hide nevertheless the large variations that occur generally
during a day.
In Fig. 10 are plotted the background estimated value ((1.3  0.5)104 cm-3 - dot point line)
and the variations recorded, as an example, the 21 June. Two parts, marked by ellipse on the
figure, are typical and detected every day. The part 1 corresponds to the morning traffic
rush characterised by a strong increase in concentration detected at roof level between 7:00
and 8:00. The part 2 corresponds to the period of lowest concentration due to the conjugate
effect of wind speed increase (from  2 ms-1 in the morning to  4 -5 ms-1 in the afternoon),
often linked to the afternoon sea breeze regime, and the vertical development of the
boundary layer that disperse very efficiently the particles.
4,00E+04
3,50E+04
3,00E+04
Concentration (cm-3)
2,50E+04
2,00E+04 21 June
1,50E+04
1,00E+04
5,00E+03
0,00E+00
00:00 04:48 09:36 14:24 19:12 00:00
Time
Fig. 10. Example of 24 hours evolution of the fine particles concentration. Ellipses blue and
pink mark the maximum and minimum daily observed. The black rectangle mark a specific
case of secondary aerosol production.
The peak around 12:00, discussed in detail in Despiau and Croci (2007), is more specific. It is
independent of any traffic rush but corresponds to the signature of secondary aerosol
production process that occurs in special conditions of wind direction, humidity and
radiation. For the six days where that specific peak was detected (hereafter “SPD”,
Secondary Production Day), the dN average concentration is (1.12  0.7)104 cm-3 while it is of
(1.05 0.4)104 cm-3 for “normal” days (hereafter “ND”). These values remain of the same
order than those indicated in the previous paragraph. This means that the diurnal average
values remain practically constant, even when a specific process occur, and then do not
allow to consider short time variations. Indeed, during the morning rush, the mean of the
concentration maximum is around 3 times the previous value: (3.3  1.7)104 cm-3 while
during the afternoon the concentration is only one half of the mean diurnal value.
The dN or dN/dLogD shape of the particle size distributions gives also useful indications
about the characteristics of the particles. In Fig. 11 are reported the averaged size
distributions obtained during the night (9 nights between 20:00 and 06:45), during the 6 days
with secondary production (SPD) and during the “normal” 10 days (ND). The normal and
secondary production days differ mainly by their diameter mode, (93.0  15.5) nm for ND,
(40  4) nm only for SPD. On the contrary, the mode concentrations are of the same order
(1.24  0.5) 104 cm-3 for ND, and (1.46  0.94) 104 cm-3, for SPD. In-between (ND) and (SPD) is
the average night distribution with a mode diameter about 55 nm and a concentration
around 1.3 104 cm-3.
The size distributions corresponding to the specific periods illustrated by the Fig. 10 are also
characteristic and largely different from the mean size distributions of Fig. 11.
Night "SPD" "ND"

1,60E+04
1,40E+04
1,20E+04
dN/dLogDp
1,00E+04
8,00E+03
6,00E+03
4,00E+03
2,00E+03
0,00E+00
10 100 1000
Dp (µm)
Fig. 11. Plot of the mean size distribution corresponding to “normal” days (ND), “secondary
production day” (SPD) and night.
Since they have been presented in details in Despiau and Croci (2007) we just summarize
here their main characteristics. The size distribution of the morning traffic rush are
characterized by an increase (factor 3 to 4 with respect to the background values) in
concentration of the whole size range of fine particles leading to a monomodal SD with a
diameter mode around 100 nm. For those corresponding to the secondary production
process, only the concentration of the particles smaller than 70 nm increases (factor 4 in 30 to
45 minutes) leading to a peak around 35 nm in average, Fig. 12.
2106
9,00E+04
11:10:15
8,00E+04 11:25:15
7,00E+04 11:40:14
dN/dLogDp (cm-3)
11:55:14
6,00E+04
12:10:14
5,00E+04
12:25:13
4,00E+04 12:40:13
3,00E+04 12:55:13
2,00E+04
1,00E+04
0,00E+00
10 100 1000
Dp (nm)
Fig. 12. Evolution of the size distribution in one case (21/06) of secondary aerosol
production.
3.4 Discussion with regard to an “urban signature”

All the previous results come from measurements realised at the canopy level. They are
obviously a mixing of local urban sources and conditions, and of regional transport from
the surroundings, that may be, in our situation, as different as marine or anthropogenic
origin. It is then difficult to separate precisely the relative influence of the different
sources but we estimate that the results obtained reflect quite accurately the main
physico-chemical characteristics of the particles at that level and under the specific
conditions described.
So, considering the two main questions asked in the introduction, the results obtained show
clearly that there is not a specific physical signature corresponding to the local IOP
conditions. Nor the PM10 and PM1 mean concentrations are significantly different (larger or
smaller for example) for IOP or non-IOP days. The mean number concentrations or size
distributions are not either different. We detected a normal tendency for enhanced
concentration in OC during IOP days but without conduct to mean concentrations
significantly different (7.67  1.97 µgm-3 against 6.37  1.95µgm-3). We cannot conclude about
the WSC chemical composition since we measured only during IOP days but it seems
unlikely that the chemical composition be very different, except perhaps for compounds that
would mainly result, as OC, from strong photochemical processes.
It is nevertheless possible to describe the main physico-chemical characteristics of the
aerosol particles at the canopy level of a great Mediterranean conurbation, in summer. These
local conditions may appear restrictive but we believe that similar conditions may be found
at least in the Mediterranean area where various great cities are coastal cities (Barcelona,
Valencia, Genoa, Roma, Athens or north African cities, …) and probably in other coastal
regions in the world where conditions leading to photochemical processes would be
fulfilled. For modelling at large scale and over long periods and probably to compare with
emission inventories at urban zone scale, the order of magnitude of the mean values
obtained should be useful. They may be summarized in terms of PM10 and PM1
concentrations around 28 and 17 µgm-3, respectively, number concentration around 1.3 104
cm-3 and a unimodal size distribution with a diameter mode around 100 nm. Always in
terms of order of magnitude, the concentrations of the main elements may be estimated at
10 µgm-3 for carbon compounds (7 µgm-3 for OC and 3µgm-3 for EC), 6 µgm-3 for nss SO4, 4
µgm-3 for sea salt and 3 µgm-3 for ammonium and nitrate. Ammonium and nssSO4 are
distributed over the fine particles, sea salt mainly over coarse particles while nitrate and
carbon compounds are spread over the whole size range.
However, if more precise information are needed for modelling at local scale and/or short
time period for example, or to verify estimations of inventory emissions at short time
scale, the previous average data become unreliable. It is then necessary to take into
account specific characteristics like those linked to the morning traffic rush, the afternoon
decrease, the secondary aerosol processes or very particular meteorological conditions.
All those particular situations last about 2 to 3 hours and are characterized by very
different values of PM or dN concentrations, shape of size distribution or mode diameter.
Inversely, a significant modification of the chemical composition over the same time scale
is quite unlikely since this would suppose a change in the sources that supply the
particles and because the chemical modification of the particles is a process much more
slow than dN or PM concentration variations. During the morning traffic rush or the SPD
events, the dN and PM concentrations will increase strongly while the corresponding
sources do not change.
Nevertheless, the meteorological conditions play a crucial role that must be accounted for,
especially at local scale. The wind velocity and the vertical development of the boundary
layer will influence the afternoon decrease. The wind velocity and direction will
contribute to the transport over the city of particles from different origin (marine or
industrial in our situation). The amount of radiation will influence the production of
secondary aerosols while the humidity will influence the mass concentration or the
chemical composition. So, except for the morning traffic rush that is well characterized
whatever the meteorological conditions, most of the other situations must be envisaged
only after considering the main meteorological conditions: wind velocity and direction,
radiation and humidity.
4. Conclusion
The measurements carried out in urban zone during the ESCOMPTE campaign allowed us
to study, at roof level and summer season, the physico-chemical characteristics of aerosol
particles.
Most of the number or mass concentrations, chemical composition or size distributions
results obtained during this campaign, are in agreement with those recorded in large urban
zones and reviewed in the papers by Putaud et al. (2004, 2010). Nevertheless, the PM1 and
PM10 mass concentrations are characterized by strong daily variations, they may sometimes
evolve in opposite sense and the fine mode (Dp < 1µm) is largely dominant in mass
compared to the coarse mode. The fine particles are more dispersed by the wind and are
more humidity dependent than those of the coarse mode.
During the campaign, the OC concentration was the higher, followed by nss sulphate, sea
salt, ammonium nitrates and EC in equivalent concentration and finally by the main crustal
elements. EC, nss sulphate and ammonium are found on the fine mode, sea salt and crustal
elements on the coarse mode while nitrates and OC are spread over the two modes. The OC
concentration tends to increase in the fine mode during the periods of strong
photochemistry conditions that produce secondary aerosols.
The background number concentration at the canopy level has been estimated around (1.3 
0.5) 104 cm-3. This value is significantly lower than concentrations measured at kerbsite but
do not vary significantly according to the environmental conditions, except when the day
average wind velocity go beyond 4 to 5 ms-1.
That background value hide however the large variations observed daily and characterized
by a strong increase in the morning, linked to the morning traffic rush, and by a minimum
in the afternoon explained by the double dispersion effect of wind and boundary layer
dynamics.
On some occasions a peak in concentration resulting from secondary aerosol production has
been detected and lead to a size distribution with a mode around 40 nm while on “normal”
days the mode is around 100 nm.
The results obtained also show that it does not exist, at canopy level in urban zone, a typical
or characteristic “aerosol particle signature” corresponding to the specific conditions leading
to photochemical events. Nevertheless, it is possible to describe a set of average
characteristics that might be useful for modelling purposes at large spatial or time scale and
to be compared with emission inventories.
For similar considerations at shorter time or spatial scales, it becomes necessary to take into
account specific characteristics like the increase in concentration linked to the morning
traffic rush, the afternoon decrease linked to the wind velocity and the development of the
boundary layer, both every day detected, or, in some particular circumstances, the effect of
secondary aerosol production.
For those situations, except for the morning rush, the meteorological conditions influence is
obvious. The wind velocity determines the dispersion process, thus the mass and number
distributions measured at roof level. The chemical composition may be modified according
to wind direction. The relative humidity modify the mass distribution, while the radiation
level may contribute to photochemical phenomenon and secondary aerosol production.
5. Acknowledgements
This work has been funded by two French national research programmes : PNCA and
PRIMEQUAL-PREDIT and by the ADEME agency. The author would thanks very specially
H. Cachier and J.P. Putaud for their help in chemical analyse.
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5
Biomonitoring of Airborne
Heavy Metal Contamination
Mehran Hoodaji, Mitra Ataabadi and Payam Najafi
Islamic Azad University, Khorasgan Branch (Isfahan)
Iran
1. Introduction
During the last few decades, heavy metal contamination of biotic component of
environment has attracted the attention of many investigators. The main reason of these
researches based on the heavy metal concentration may have a potential hazard in our
food chain after a long period of procrastination. Using biological materials in the
determination of environmental pollution as indicators is a cheap and reliable method.
Various types of plant such as lichens, mosses, bark and leaves of higher plants, have been
used to detect the deposition, accumulation and distribution of metal pollution (Akosy,
2008), Because of plants greatly affected by physical and chemical environmental
conditions. If conditions become altered, the exposed plant community can accurately
reflect these changes (Nash, 1988).
This chapter discusses the possibility of various types of plant usage as biomonitors for
detection atmospheric heavy metal pollution in different conditions and factors that affect
their accumulative potential.
1.1 Heavy metals

Over the past two decades, “heavy metals” has been used increasingly in various
publications and in legislation related to chemical hazards and the safe use of chemicals. It is
often used as a group name for metals and semimetals (metalloids) that have been
associated with contamination and potential toxicity or ecotoxicity (Duffus, 2002).
Now, it is known that heavy metals represent a large group of chemical elements (> 40) with
atomic mass > 50 carbon units (Fig 1.) Most of heavy metals may be important trace
elements in the nutrition of plants, animals or humans (e.g. Zn, Cu, Mn, Cr, Ni, V), while
others are not known to have positive nutritional effects (e.g. Pb, Cd, Hg). However all of
these may cause toxic effects (some of them at a very low content level) if they occur
excessively (Spiegel, 2002). The toxicity of heavy metal depends a great deal on their
chemical form, concentration, residence time, etc (Mielke & Reagan, 1988). Because of these
elements do not decay with time, their emission to the environment is a serious problem
which is increasing worldwide due to the rapid growth of population, increasing
combustion of fossil fuels, and the expansion of industrial activities (Smodis & Bleise, 2000).
Fig. 1. Heavy metal position in Periodic Table.
1.1.1 Origin of heavy metals in the environment

There are two different sources for heavy metals in the environment. These sources can be
both of natural or anthropogenic origin.
1.1.1.1 Natural
The principal natural source of heavy metals in the environment is from crustal material that
is either weathered on (dissolved) and eroded from (particulate) the Earth’s surface or
injected into the Earth’s atmosphere by volcanic activity. These two sources account for 80%
of all the natural sources; forest fires and biogenic sources, account for 10% each. Particles
released by erosion appear in the atmosphere as windblown dust. In addition, some
particles are released by vegetation. The natural emissions of the some heavy metals are
12,000 (Pb); 45,000 (Zn); 1,400 (Cd); 43,000 (Cr); 28,000 (Cu); and 29,000 (Ni) metric tons per
year, respectively (Nriagu, 1990).
1.1.1.2 Anthropogenic
There are a multitude of anthropogenic emissions in the environment. Generally heavy
metals enter into the environment mainly via three routes: (I) deposition of atmospheric
particulates (e.g. Mining, Smelting, Fossil fuel combustion, municipal waste incineration,
cement production and phosphate mining). (II) disposal of metal enriched sewage sludge
and sewage effluents, commercial Fertilizers and pesticides and animal waste specially to
the terrestrial and aquatic environment (III) by-product from metal mining processes
(Shrivastav, 2001; Smodis & Bleise, 2000). Among them, the major source of metals is from
mining and smelting. Mining releases metals to the fluvial environment as tailings and to
the atmosphere as metal-enriched dust whereas smelting releases metals to the atmosphere
as a result of high-temperature refining processes (Adriano, 1986). The estimation of metal
input into environment from the two latter sources (II & III) is relatively easy to measure,
but atmospheric input is difficult to quantify accurately because of after emission, the
Biomonitoring of Airborne Heavy Metal Contamination 99
pollutants are subjected to physical, chemical and photochemical transformations, which

ultimately decide their fate depending upon the atmospheric concentrations (Shrivastav,
2001; Smodis & Bleise, 2000). Air pollutants do not remain confined near the source of
emission, but spread over distances, transcending natural and political boundaries
depending upon topography and meteorological conditions, especially wind direction, wind
speed and vertical and horizontal thermal gradients (Smodis & Bleise, 2000). Among the
various species present in the particulate matter, a great attention has been devoted since
many years to the study of the elements with elevated toxicity and great diffusion in the
environment (As, Cd, Cr, Hg, Ni, Pb, etc.) because of both anthropogenic and natural
pollutant emissions (Beijer & Jernelöv, 1986). The contributions of natural and
anthropogenic sources in atmospheric heavy metal pollution are shown in table 1.
Fluxes Fluxes Fluxes in PM

Element Atmospheric
from from gas of emission of Total
Element flux from Alteration
crustal volcanic volcanic industrial Emission
fossil fuel Factor
origin origin origin origin
Ag 0.5 0.1 0.0006 40 16 50 8333
Al 356,500 132,750 8.4 40,000 32,000 72,000 15
As 25 3 0.1 620 160 780 2786
Cd 2.5 0.4 0.001 40 15 55 1897
Co 40 30 0.04 24 20 44 63
Cr 500 84 0.005 650 290 940 161
Cu 100 93 0.012 2200 430 2630 1363
Fe 190,000 87,750 3.7 75,000 32,000 107,000 39
Hg 0.3 0.1 0.001 50 60 110 27,500
Mn 4250 1800 2.1 3000 160 3160 52
Mo 10 1.4 0.02 100 410 510 4474
Ni 200 83 0.0009 600 380 980 348
Pb 30 8.7 0.012 16,000 4300 20,300 34583
Sb 9.5 0.3 0.013 200 180 380 3878
Se 3 1 0.13 50 90 140 3390
Sm 32 9 - 7 5 12 29
Sn 50 2.4 0.005 400 30 430 821
Ti 23000 12,000 - 3600 1600 5200 15
V 500 150 0.05 1000 1100 2100 323
Zn 250 108 0.14 7000 1400 8400 2346
Table 1. Natural and anthropogenic element fluxes (value ×108 g y−1)
Atmospheric Alteration Factor (%) = Total Emission/ (Fluxes from crustal origin+Fluxes
from volcanic origin)×100 (from Avino et al., 2008).
1.1.2 Fate and transport of atmospheric heavy metals in the environment

The environmental and human health effects of heavy metals depend on the mobility of
each metal through environmental compartments and the pathways by which metals reach
humans and the environment. The free ion is generally the most bioavailable form of a
metal, and the free ion concentration if often the best indicator of toxicity. However, there
are exceptions, such as the well known case of mercury, where the organic form, (methyl
mercury) is more toxic than the inorganic ion. Metals exert toxic effects if they enter into
biochemical reactions in the organism and typical responses are inhibition of growth,
suppression of oxygen consumption and impairment of reproduction and tissue repair
(Long et al., 1995). The World Health Organization (WHO) estimates that more than 2
million premature deaths occur annually worldwide, and these can be attributed to the
effects of outdoor and indoor air pollution (WHO, 2002). The main outdoor air pollutants
are as follows: particulate matter (PM), carbon monoxide, nitrogen oxides, sulfur oxides,
ozone, and volatile organic compounds. Most of the mortality/morbidity caused by
atmospheric pollution in urban areas is caused by PM with aerodynamic diameters less than
10 μm, known as the inhalable fraction (MacNee & Donaldson, 2000). Heavy metals occur, in
atmosphere, basically in particulate form. PM-containing heavy metals may induce the
oxidative stress mediated by reactive oxygen, with potential mutagenic effects as a strong
correlation between the high elemental concentrations in aerosol particles and high mortality
and morbidity has been found in several epidemiological studies (Manoli et al., 2002).
1.1.2.1 Mechanisms of heavy metal deposition
The aerosols, which have a very small falling velocity, are easily transferred by the wind and it
is possible to be deposited through the rain at long distances from the point of their emission
(Smirnioudi et al., 1998). Therefore, it is expected that chemical components in the rainwater
(acid components, anions, cations and heavy metals) damage significantly the environment
(surface waters, plants, animals, human beings). These metals even if deposited constantly in
small rates over long periods of time, accumulate in the environment and will probably pose
an increasing major environmental and human health hazard in future.
The transfer of airborne particles to land or water surfaces by dry, wet and occult deposition
constitutes the first stage of accumulation of atmospheric heavy metals. The predominant
path depends upon the type of chemical species and upon meteorological factors such as the
intensity and distribution of rain fall.
1.1.2.1.1 Dry deposition
Dry deposition involves four distinct processes: gravitational settling, impaction, turbulent
transfer and transfer by Brownian motion. The relative importance of these processes
depends primarily on the size of particles (Shrivastav, 2001). Dry deposition is more likely to
remove particulate forms. Two major categories of particulate matter are fine particles and
coarse particles. Fine particulate matter (FPM) comprises particles with aerodynamic
diameters of 2.5 µm or less. They are emitted from fossil fuel combustion, motor vehicle
exhausts (including diesel) and wood burning. Several toxic metals, including arsenic,
cadmium, lead, zinc, antimony and their compounds are associated with FPM in ambient
air. This is important from a public health perspective since these fine particles are
respirable and can be transported over very long distances. Coarse particulate matter or
PM10 is the mass concentration of particulate matter having aerodynamic diameters less
than 10 µm (USEPA, 1996). Anthropogenically added particulates and aerosols in
atmosphere show a broad size distribution from 0.001 μm to 50 μm and are strongly
influenced by atmospheric transport processes. In rural regions anthropogenic particles > 5
μm are absent (Ward et al., 1975) and in Polar Regions heavy metals are mostly associated
with small aggregated particles in the range of 0.1-10 μm. Dry deposition of heavy metals in
rural and remote regions is therefore, through impaction and turbulent transfer (Barrie &
Schemenauer, 1986). Dry deposition represents a major removal pathway for many
pollutants from the atmosphere, and it is especially important in arid and semiarid regions
where removal by wet deposition (i.e., rainfall scavenging) is greatly diminished because of
limited precipitation (Seinfeld & Pandis 1998).
1.1.2.1.2 Wet deposition
In wet deposition, there are always some atmospheric hydrometeors which scavenge
aerosol particles. This means that wet deposition is gravitational, Brownian and/or
turbulent coagulation with water droplets. Wet deposition involves two major processes:
nucleation and within and below cloud scavenging, whereby the wet aerosol particles are
collected by falling raindrops (Barrie & Schemenauer, 1986). Wet deposition (via rain and
other types of precipitation) is most efficient at removing soluble form of heavy metals from
the air. A great percentage of metals fall through the rain at the place of their production
(Nurnberg et al., 1984).
For example, dry deposition can remove gaseous mercury forms (particulate forms), while
wet deposition is responsible for removing divalent mercury form (soluble form)
(Nurnberg et al., 1984).
1.1.2.1.3 Occult deposition
Generally, this route is considered as one of the wet deposition processes. In occult
deposition, wetted particles (fog and mist) are deposited by impaction or turbulent transfer
(Barrie & Schemenauer, 1986).
However, heavy metals are principally dispersed by atmospheric transportation
(Dobrovolsky, 1980), but it is necessary to consider that most atmospherically dispersed
heavy metals enter the soil surface and the aboveground plant tissues very rapidly. In the
soil, they are sorbed by the absorption complex and redistributed through the soil profile. A
proportion of heavy metals is taken up by plants and leached by surface and subterranean
runoff. The need to control atmospheric contamination of soils by heavy metals and take
preventive and remediation measures is dictated by the serious ecological consequences of
this contamination, as observed in different regions of the world (Galiulin et al., 2002).
2. Urgency of monitoring air contamination

The degree and extent of environmental changes over the last decades has given a new
urgency and relevance to the detection and understanding of environmental change, due to
human activities, which have altered global biogeochemical cycling of heavy metals and
other pollutants. Approximately 5 million chemicals are presently known and 80,000 in use;
500 - 1,000 are added per year resulting in a progressive increase in the flux of bioavailable
chemical forms to the atmosphere. Therefore air pollution has been one of the major threats
to human health and the environment since the last century (Obbard et al., 2005; Batzias &
Siontorou, 2006; Dmuchowski & Bytnerowicz, 2009).
2.1 Approaches for monitoring air contamination

There are two conceptual approaches for collecting samples relevant to air and atmospheric
deposition related pollution studies. The first approach involves the direct collection of
airborne particulate matter, precipitation and total deposit whereas the second approach
uses air pollution biomonitors. The first approach is aimed at quantitative surveys at local,
short-range, medium-range or global transport of pollutants, including health-related
studies when collecting size fractionated airborne particulate matter. It requires continuous
sampling on a long-term basis at a large number of sites, in order to ensure the temporal and
spatial representativeness of measurements. The application of such direct measurements
on a large scale is extremely costly and person-power intensive. Furthermore, it is not
possible, due to logistic problems, to install instrumental equipment at all needed locations.
Therefore, the second approach is considered as a non-expensive, yet reliable means of air
quality status assessment in a country or a region. Certain types of biological organisms
provide a measure of integrated exposure over a certain amount of time and enrich the
substance to be determined so that the analytical accessibility is improved and the
measurement uncertainty reduced. Sampling is relatively simple (even in remote areas and
areas with difficult access) because of no expensive technical equipment is needed (Bagla et
al., 2009). Furthermore, the sample treatment and analysis steps in the laboratory are
facilitated (Wolterbeek, 2002) Also, this method avoids the need for deploying large
numbers of precipitation collectors with an associated long-term program of routine sample
collection and analysis (Harmens et al., 2008). Therefore, a much higher sampling density
can be achieved than with conventional precipitation analysis and increases the possibility
of monitoring many sites simultaneously (Wannaz et al., 2006). Also Bioindicators may be
very useful due to their high sensitivity towards a broad spectrum of substances or because
of their tolerance to high levels of a substance, accumulated in their tissues over an extended
period of time or to integrate its influence in an area of known and relevant size (De
Temmerman, 2004). Biomonitoring data are being compared with precipitation, particulate
matter fractionation, and speciation data and also with medical statistics to evaluate the
correlation between the amount of pollutants in the atmosphere and the human reaction to
it (Szczepaniak & Biziuk, 2003).
2.2 Definition of biomonitoring and related terms

The term bioindicator/biomonitor is used to refer to an organism, or a part of it, that
depicts the occurrence of pollutants on the basis of specific symptoms, reactions,
morphological changes or concentrations (Markert et al., 1997). There is considerable
variation in the use of the terms bioindicator and biomonitor: A bioindicator is an
organism (or part of an organism or a community of organisms) that contains information
on the quality of the environment (or a part of the environment). A biomonitor, on the
other hand, is an organism (or part of an organism or a community of organisms) that
contains information on the quantitative aspects of the quality of the environment. The
clear differentiation between bioindication and biomonitoring using the
qualitative/quantitative approach makes it comparable to instrumental measuring
systems (Markert, 2007). Therefore biomonitoring, in the general sense, may be defined as
the use of organisms and biomaterials to obtain information on certain characteristics of
the biosphere. With proper selection of organisms, the general advantage of the
biomonitoring approach is related primarily to the permanent and common occurrence of
the organism in the field, even in remote areas, the ease of sampling, and the absence of
any necessary expensive technical equipment (Wolterbeek, 2002).
2.3 Classification of biomonitors

Organisms can be classified according to the way in which the reaction is manifested: (1)
reaction indicators, which have a sensitive reaction to air pollutants and which are used
especially in studying the effects of pollutants on species composition, and on physiological
and ecological functioning, and (2) accumulation indicators that readily accumulate a range
of pollutants and are therefore used especially when monitoring the amount of pollutants
and their distribution (Markert et al., 1997). Bioaccumulation monitoring methods can be
divided into two groups: (Fig 2.)
Biomonitoring
Based on origin Based on reaction
Active Passive Reaction Acumulative
Test
Transplantation Test plant
chamber
Fig. 2. General scheme of heavy metal biomonitoring using different materials and sampling
techniques.
2.3.1 Active biomonitoring

Active biomonitoring includes the exposure of well-defined species under controlled
conditions and can be divided into transplantation, test plant, and test chamber methods (Cˇ
eburnis & Valiulis, 1999). In the transplantation procedure, suitable organisms (mainly
mosses and lichens) are transplanted from unpolluted areas to the polluted site under
consideration. The exposure time thus is well defined, but the change in uptake efficiency
due to climatic change is usually applied to testing either synergistic or single species effects
of pollutants on sensitive biomonitors. Transplant techniques appear to be useful, in
particular at relatively high pollutant levels. One distinct advantage, compared to the use of
indigenous species, is that of well-defined exposure time, but the reproducibility of this
technique appears not to be very satisfactory for parameters such as air concentration and
deposition rate (Cˇ eburnis and Valiulis, 1999).
2.3.2 Passive biomonitoring

Passive biomonitoring refers to the observation or chemical analysis of indigenous plants. In
general, the passive biomonitoring method has one major disadvantage; all processes and
all sources act at the same time and there is no possibility of separating them and looking for
a particular one (Cˇ eburnis and Valiulis, 1999). Natural variabilities in ambient macro and
microclimate conditions, such as acidity, temperature, humidity, light, and altitude (Gerdol
et al., 2002), or ambient elemental (nutritional) occurrences may cause the biomonitors to
exhibit variable behavior. Part of this variance is local (Wolterbeek & Verburg, 2002), but it
may be clear that this variable behavior becomes a problem when it seriously affects the
biomonitors in its accumulative exposure (Wolterbeek, 2002).
2.4 Principles of bioaccumulation monitoring

Biomonitoring is regarded as a means to assess trace element concentrations in aerosols and
deposition. This implies that the monitor should concentrate the element of interest and
quantitatively reflect its ambient conditions (Wolterbeek, 2002). In general, a good
accumulation indicator of air pollutants should:
1. Accumulate pollutants from the air in the same way and to the same degree under
different conditions (Wittig, 1993; Conti & Cecchetti, 2001).
2. The pollutants should be easily measured and the measurements should provide
information about the level of pollutant deposition.
3. It should also indicate the risk limits caused by increasing levels of pollutants.
4. The species of organism used should be common enough and be available for collection
throughout the year in the same area.
5. Its use should be based on standard sampling and analysis methods.
6. In order to determine the state of the ecosystem in relation to the pollutant under study,
the state of the ecosystem in the background area should also be known (Seaward 1995).
The background level is usually considered to be the “natural” level at which emissions
have as small an effect as possible (Conti & Cecchetti, 2001). The background level of
different pollutants varies between plant species.
2.5 Type of biomonitors

As plants are immobile and more sensitive in terms of physiological reaction to the most
prevalent air pollutants than humans and animals, they better reflect local conditions (Nali
and Lorenzini 2007). For these reasons, plants are the most common used bioindicators in
air quality biomonitoring studies (Balasooriya et al. 2009). Types of plant and their different
parts have been applied in trace element air monitoring programs, such as lichens, mosses,
ferns, grass, tree bark, tree rings, tree leaves and pine needles (Szczepaniak & Biziuk, 2003;
Morselli et al., 2004). For all biomonitors used, the mechanisms of trace element uptake and
retention are still not sufficiently known. For grass, tree rings, and ferns, substantial element
contributions from other sources than atmospheric, such as the soil or the tree bole, have to
be taken into account (Szczepaniak & Biziuk, 2003). Rossini Oliva and Mingorance (2006)
reported that the accumulation pattern in the different parts of Pinus pinea L. and Nerium
oleander L. was the following: wood < bark ≤ leaves, because of metals are taken up by wood
stem from the soil and soil water, while the outer part (leaves and bark) intercept metals
also by deposition from the atmosphere (Rossini Oliva & Mingorance, 2006).
It is important to note that a unique species that can be a suitable bioindicator for
biomonitoring of toxic metal pollution all over the world has not been found yet. But lower
and higher plants use as suitable biomonitors world-wide.
Plants accumulate metals due to many factors, such as element availability, the
characteristics of the plants (such as species, age), state of health, and type of reproduction,
temperature, available moisture, substratum characteristics, etc (Conti & Cecchetti, 2001)
2.5.1 Biomonitoring by lower plants

Lower plants are resistant to many substances which are highly toxic for other plants
species. They are able to survive in such diverse and often extreme environment; these
sedentary organisms possess an equally diverse set of physiological adaptations (Cenci et
al., 2003; Fernandez et al., 2006; Dragovič & Mihailovič, 2009). Of all biological species used
in biomonitoring, lichens and mosses have the most common occurrence. The morphology
of lichens and mosses does not vary with seasons; thus accumulation can occur throughout
the year. Lichens and mosses usually have considerable longevity, which led to their use as
long-term integrators of atmospheric deposition (Szczepaniak & Biziuk, 2003).
2.5.1.1 Mosses as biomonitor
Botanically, mosses are bryophytes1. About 15,000 species of mosses are known world-wide
(Richardson, 1981), most of which are abundantly distributed amongst the different
ecosystems, growing on a variety of substrates (Onianwa, 2000). Two Swedish scientists Åke
Rühling and Germund Tyler (1960) have discovered that mosses are good bioindicator of
heavy metal pollution in the atmosphere, after this successful discovery many European
countries have used mosses in national and multinational surveys of atmospheric-metal
deposition. Mosses are cryptogams that thrive in a humid climate. Ectohydric mosses have
been used as biomonitors – in most cases terricolous bryophytes. They possess many
properties that make them suitable for monitoring air pollutants (Onianwa, 2000). These
species obtain nutrients from wet and dry deposition because of they do not have real roots
so there is no uptake of mineral substrates from other sources than the atmosphere. Nutrient
uptake from the atmosphere is promoted by their weakly developed cuticle (so metal ions
easily penetrate the cell wall), large surface to weight ratio, and their habit of growing in
groups. Other suitable properties include a slow growth rate, small size and easy to handle,
undeveloped vascular bundles (so transport of minerals between segments is limited),
minimal morphological changes during the mosses’ lifetime, perenniality, wide distribution
(even in industrial and urban areas), an ability to survive in highly polluted environment,
ease of sampling and the possibility to determine concentrations in the annual growth
segments (Poikolainen, 2004; Dragovič and Mihailovič, 2009).
Air pollutants are deposited on mosses in aqueous solution, in gaseous form or attached to
particles. The accumulation of pollutants in mosses occurs through a number of different
mechanisms:
 As layers of particles or entrapment on the surface of the cells.

 Incorporation into the outer walls of the cells through ion exchange processes
 Metabolically controlled passage into the cells (Poikolaonen, 2004).
The attachment of particles is affected e.g., by the size of the particles and the surface
structure of the mosses.
1 Contains Mosses and Liverworts

Ion exchange is a fast physiological-chemical process that is affected e.g., by the number and
type of free cation exchange sites, the age of the cells and their reaction to desiccation, growing
conditions, temperature, precipitation pH, composition of the pollutants and leaching (Brown
& Brûmelis 1996). In the ion exchange process, cations and anions become attached to
functional organic groups in the cell walls among other things through chelation (Rao, 1984).
The cell wall has a high polyuronic acid content which makes moss a very good natural ion
exchanger. The cell walls of bryophytes possess many negatively charged anionic sites to
which cations are bound in exchangeable form. Studies of electron microscope have shown
that the sorbed metal may be held either in the extracellular region outside of the cytoplasm,
bound to the cell wall, and due to the highly reduced presence or absence of cuticle in the
moss, ions have a direct access to the cell wall, mosses surfaces and rhizoids do not perform
any active heavy metal ion discrimination (Shakya et al., 2008; Reimann et al., 2006;
Onianwa, 2000).
Results of previous studies have shown that the degree of metal uptake efficiency retention
proved to decrease in the order Cu > Pb > Ni > Co > Cd > Zn, Mn. Lead is very strongly
fixed in the moss, and for this reason the correlation between concentration in moss and
bulk deposition is particularly high (Szczepaniak & Biziuk, 2003; Rosman, et al., 1998).
Mosses have been used for monitoring atmospheric heavy metal levels in various forms,
these include indigenous naturally-occurring epiphytic forms, moss transplants, moss-bags,
and Sphagnum mosses. The majority of investigations have utilised epiphytic mosses
growing naturally at a given location. Such mosses may be found growing on rocks, tree
barks, walls or forest floors, and may be of the acrocarpous or pleurocarpous types. Many
species of mosses have been so used, but perhaps the most commonly reported in the
literature are the species Hypnum cupressiforme, Hylocomium splendens, and Pleurozium
schreberi, particularly in parts of Europe where they are largely abundant (Onianwa, 2000).
The comparisons between indigenous and transplanted mosses are summarized in table 2.
Factors affecting on uptake efficiency by mosses
The chemical composition of deposition has a large effect on the accumulation of pollutants,
because the uptake efficiency of mosses for individual elements varies considerably (Berg et
al., 1995). A high proportion of the pollutant load accumulates in mosses through wet
deposition. The amount, duration and intensity of precipitation affect accumulation and
leaching (Berg et al. 1995). Ross (1990) and Berg et al (1995) found the best correlation
between the concentrations in mosses and in wet deposition for elements such as Pb, Cd, Co
and Cu that have high uptake efficiency from wet deposition. The contribution of dry
deposition increases on moving from humid to arid climates (Couto et al., 2004). Uptake
efficiency is also affected by competition for free cation exchange sites; for instance, the
presence of sea salts and acidic deposition has been found to have an effect on the
absorbtion of metals by mosses (Gjengedal & Steinnes, 1990). The types of vegetation and
soil dust have also been reported to cause regional differences in uptake efficiency
(Szczepaniak & Biziuk, 2003). Other factors affecting the concentrations include stand
throughfall and leaching from vegetation layers located above the mosses (Steinnes, 1993),
the nutrient status of the site (Pakarinen & Rinne 1979; Økland et al., 1999) and snowmelt
water (Ford et al. 1995). The altitude may also have an effect (Gerdol et al. 2002), due e.g., to
changes in the amount of precipitation, dust or biomass production. The sampling and
measuring methods employed can also have a considerable influence on the analytical
results in biomonitoring studies (Steinnes et al. 1993; Wolterbeek & Bode 1999).
Indigenous Transplants
Results of pollution patterns can be obtained A survey period of a year is required to allow
within a few days. for effects of seasonal variation.
Results demonstrate pollution in previous Results illustrate pollution only over the
years. sampling period.
Accumulation levels are usually above Concentrations of accumulated levels may be
detectable levels due to longer exposure time. undetectable over shorter sampling period.
Minimal supervision and risk from
Potential risk from vandalism.
vandalism.
Costs acquired from transport to sites and Additional costs from materials, increased
chemical analyses. transport and more sampler preparation.
Density of sampling sites, samplers and their
Potential shortage of indigenous samples.
position under the control of investigators.
Deposition rates calculated from controlled
Pollution deposition rates difficult to estimate.
exposure time.
Metal concentrations reflect influences from
Pollutant concentrations in plants can be
other factors such as age of plant, metal
more directly related to airborne pollution.
content of substrate and local contamination.
Plants may be stressed or undergo
morphological/physiological changes, which
affect uptake, by long-term exposure to
certain pollutants.
Table 2. Comparisons of indigenous samplers and transplants in heavy metal deposition
monitoring (from Gailey and Lloyd, 1993).
It must be noted that the high concentrations of atmospheric pollutants such as sulphur
dioxide and heavy metal particulates are harmful to the full development of mosses, and
mosses do not thrive well around locations of such very high pollution levels (Onianwa, 2000).
2.5.1.2 Lichens as biomonitor
Lichens are the most studied biomonitors of air quality, since in 1866 a study was published
on use of epiphytic lichens as bioindicators. They have been defined as “permanent control
systems” for air pollution assessment (Conti & Cecchetti, 2001). Because of their high
sensitivity toward specific pollutants and ability to store contaminants in their biological
tissues, lichens are defined as bioindicators and/or bioaccumulators, respectively. Lichen
form conspicuous gray, green, orange, or red patches on trees or rockes (Blasco et al., 2008).
Lichens are perennial cryptogams. They live on different types of substrate, usually on dry
or nutrient-poor sites in boreal and sub-arctic regions (Nash 1996). The lichen species best
suited as biomonitors are foliose2 and fruticose3 epiphytic lichens. Lichens consist of a
symbiotic association of two organisms: the fungal component is usually an Ascomycetes
2. Some lichens have the aspect of leaves

3. Some lichens adopt shrubby forms
fungus (mycobiont), and the algal component (photobiont), a green alga (Chlorophyceae)
and/or blue-green alga (Cyanobacteriae). The fungal component is responsible for taking
up water and minerals, and the algal component, which grows amidst the fungal mycelia,
for photosynthesis. Most lichen species obtain their nutrients from wet and dry deposition
(Martin & Coughtrey 1982; Garty 1993). The lichen surface, structure, and roughness
facilitate the interception and retention particles (Szczepaniak & Biziuk, 2003). They possess
many of the same properties as mosses that make them suitable for monitoring purposes:
the cuticle and vascular bundles are weakly developed, (means that the different pollutants
are absorbed over the entire tallus surface of the organism), they do not have any real roots,
they are slow-growing and long-lived, and they have an extremely broad distribution
(Wolterbeek et al., 2003).
In general, three mechanisms have been reported with regard to the absorption of metals in
lichens:
 Intercellular absorption through an exchange process
 Intercellular accumulation
 Entrapment of particles that contain metals (Szczepaniak & Biziuk, 2003).
Lichens may be used as bioindicators and/or biomonitors in two different ways: (1) By
mapping all species present in a specific area; entitled "mapping lichen diversity" that
consists recording changes in arboreal species diversity in fixed plots over time, either
through the use of grid or transects samples, using a standardized method develop by
lichenologists and (2) Through the individual sampling of lichen species and measurement
of the pollutants that accumulate in the thallus, or by transplanting lichens from an
uncontaminated area to a contaminated one and then measuring the morphological changes
in the lichen thallus and/or evaluating the physiological parameters and/or evaluating the
bioaccumulation of the pollutants (Conti & Cecchetti, 2001).
It was found that concentrations of Pb, Fe, Cu, Cr and Zn in Hypogymnia physodes correlated
strongly with annual average atmospheric deposition (Sloof, 1995).
In the context of pollution monitoring which uses naturally occurring lichens at monitoring
sites as well as lichen transplants, changes in lichen morphology, cytology, metabolism and
physiological processes, all provide environmental insight. Normal Hypogymnia physodes
(L.) Nyl., for example, has a smooth, grey thallus with large lobes but when exposed to air
pollution, the surface becomes cracked and the coloration brown or black (Richardson &
Nieboer, 1981)
Factors affecting on uptake efficiency by lichen
There are a considerable number of factors, associated with the site where lichens are
growing, which may change the concentrations of pollutants in lichens (Brown, 1991; Garty,
2000). These factors are, in most cases, the same as those affecting mosses including quality
of the deposition (form of occurrence, composition, pH), climate (composition of
precipitation, temperature, wind, drought, length of the growing period) and local
environmental factors (vegetation, quality of the substrate, stand throughfall and stemflow,
dust derived from soil, altitude of area). On the other hand, throughfall and stemflow,
which vary according to the type of canopy cover, have a greater effect on epiphytic lichens
than on terricolous mosses (Poikolainen, 2004; Rasmussen, 1978).
Most species are especially sensitive to SO2, nitrogen and fluoride compounds and to ozone.
These compounds affect the condition of lichens and thus reduce the capacity of lichens to
accumulate and absorb elements from the atmosphere (Poikolainen, 2004).
Air pollutants have a different effect on the fungal and on the algal partner. The algal
partner has been reported to react more sensitively e.g., to acidic deposition and heavy
metals, and to show varying accumulation of metals depending on the acidity of
precipitation. Sporadic desiccation of lichens may also have an effect on the accumulation
and absorption of elements (Poikolainen, 2004). After a dry period, rainfall may result in
appreciable washing off particles and the exchange of cations bound on negatively charged
exchange sites on the cell walls and plasma membranes of the cells (Bargagli, 1998).
Results of different studies about heavy metal concentrations in various lichen species are
summarized in table 3. There are clear differences in the accumulation of elements between
different lichen species (even in the same studies) as a result of morphological and
physiological differences.
Pseudevernia Foliose (e.g. Evernia Dirinaria Pyxine Phaeophyscia

Lichens C.rangiformis
furfuracea Parmelia, prunastri picta cocoes hispidula
(Bowen, (Cayir et al.,
(Adamo, Hypogymnia) (Conti, (NG et al., (Rajesh et (Rajesh et
1979) 2007)
2003) (Adamo, 2003) 2004) 2006) al., 2011) al., 2011)
Cd - 0.46 (<0.1-0.3) (0.05-0.09) (0.14-0.28) (0.14-0.69) (0.9-6.3) (0.8-6.8)
Cr (0.6-7.3) 2.23 (1-4) (1.04-2.81) - (2.24-13.0) (0.8-26.2) (3.4-35.2)
Cu (9-24) 5.42 (4-10) (1.94-4.45) (11.75-45.13) (1.06-5.29) - -
Pb (1-78) 23 (1-8) (1.05-3.62) (2.83-16.59) (1.35-33.8) (0.1-13.3) (4.4-11.7)
Zn (20-60) 99 (20-90) (20.3-53.2) (44.17-83.15) (9.15-47.6) (57.3-194.4) (103.1-214.6)
Table 3. Heavy metal concentrations in lichen species from different studies (mg/kg),
(ranges in brackets).
2.5.1.3 Moss to lichens comparison

As above mentioned mosses and lichens do not have root systems like higher plants
therefore their contaminant content depend on surface absorption. These organisms have
been shown to concentrate particulates and dissolve chemical species from dry and wet
deposition. Differences in substrata result in differences in lichen metal content. For mosses,
relatively high contribution of crustal elements such as Al, Sc, La and lanthanides is
observed. The increase in cation exchange capacity from moss apex to base is apart of its
natural balance of elements, which in turn is affected by the proximity of the soil.
Lichen identification and collecting turns out to be very complicated, whereas for mosses it is
much easier. The annual growth increment is easier to distinguish for mosses than for lichens;
therefore they are considered superior to lichens, if any time resolution in the measurement is
required. Older parts of lichens carry fruiting bodies rich in metals. Mosses build carpets
during a period of 3–5 years, and their metal content is generally considered to reflect the
atmospheric deposition during that period (Szczepaniak & Biziuk, 2003). Loppi and Bonini
showed that lichens and mosses can be used indifferently as accumulators of As, Cd, Cu, Mo,
and S. Differences in concentrations between lichens and mosses were statistically significant
(P<0.05) for Al, B, Fe, Hg, Pb, Sb and Zn, with mosses retaining higher values than lichens
except for Hg and Zn. The elements found in higher concentrations in mosses were associated
with particulate matter (Szczepaniak & Biziuk, 2003). Bargagli et al. found higher
concentrations of lithophile elements (Al, Cr, Fe, Mn, Ni, and Ti) in moss and atmophile
elements (Hg, Cd, Pb, Cu, V, and Zn) in lichen (Bargagli et al., 2002). According to studies of
Kansanen and Venetvaara (1991) mosses and lichens as the most effective indicators for low
and moderate level of metal deposition in polluted areas.
2.5.2 Biomonitoring by higher plants

However mosses and lichens most frequently used for monitoring metal pollution, but these
lower plants are characterized by irregular and patchy distribution and their sampling should
be done by specialists who can differentiate between similar-looking species. These limitations
become more pronounced in industrial and densely populated areas, where sever
anthropogenic pressure may cause scarcity or even lack of indicator species at some sampling
points. For instance lichens are characterized by slow regeneration and relatively weak
tolerance to the complex influence of mycophytotoxic pollutants, Therefore intensive sampling
may lead to their reduced availability and even disappearance (Berlizov et al., 2007).
The use of higher plants, especially different parts of trees (leaves and barks), for air
monitoring purposes is becoming more and more widespread. The main advantages are
greater availability of the biological material, simplicity of species identification, sampling
and treatment, harmless sampling and ubiquity of some genera, which makes it possible to
cover large areas. Higher plants also exhibit greater tolerance to environmental changes
which is especially important for monitoring areas with elevated anthropogenic influence
(Berlizov et al., 2007), therefore higher plants have appeal as indicators in air pollution
monitoring in highly polluted areas where lichens and mosses are often absent.
Higher plants not only intercept pollutants from atmospheric deposition but also
accumulate aerial metals from the soil. Aerial heavy metal depositions are taken up from the
soil by plants via their root system and translocated them to other parts of the plant
(Mulgrew & Williams, 2000). An otherwise in the industrial and urban areas, higher plants
can give better quantifications for pollutant concentrations and atmospheric deposition than
non-biological samples (Markert, 1993).
Some plant species are sensitive to single pollutants or to mixtures of pollutants. Those
species or cultivars are likely to be used in order to monitor the effects of air pollutants as
bioindicator plants (DeTemmerman et al., 2005).
In general, it can be assumed two separated groups of higher plants for biomonitoring
purposes including herbs/grasses and trees/shrubs on both groups, aboveground plant
tissues (leaf and bark) contribute in airborne heavy metal accumulation.
2.5.2.1 Herbs and grasses as biomonitor
Kovács (1992a) recommended the use of ruderal plants as bioaccumulative indicators due to
their ability to accumulate metals in high quantities without visible injury (Kovács, 1992a).
Some plant species may be more efficient in retaining atmospheric metal particles than
others. A measure of this efficiency can be resolved by calculating air accumulation factors
(AAF) according to the following equation:
AAF (m3.g-1) = PAc (mg. g-1 dry weight)/CA (mg. m-3) (1)
PAc = atmospheric contribution of the metal in plants and CA = concentration of the metal
in the atmosphere (Mulgrew & Williams, 2000).
2.5.2.2 Trees and shrubs as biomonitor
Both coniferous and deciduous trees can be used in the detection of aerial heavy metal
pollution, but Coniferous trees indicate pollution over a longer time period such as, Pinus
eldarica, Cupressus arizonica (Ataabadi et al., 2010a), Pinus brutia (Baslar et al., 2009), Cupressus
semervirens (El-Hasan et al., 2002). Broad-leaved tree species regarded as sensitive to metal
contamination include Betula pendula, Fraxinus excelsior, Sorbus aucuparia, Tilia cordata and
Malus domestica (Mulgrew & Williams, 2000). Numerous bioaccumulative indicators exist;
some tree examples include Ailanthus glandulosa, Celtis occidentalis, Salix alba, Tilia tomentosa,
Sambucus nigra, Quercus robur, Fagus silvatica (Mulgrew & Williams, 2000) and Elaeagnus
angustifolia (Akosy and Sahin, 1999). Also results of studies indicate that Robinia pseudoacacia
(black locust tree) is appropriate species because of this tree is genetically homogeneous,
easily identifiable and ubiquitously distributed (Kovács, 1992b).
However, there are limited studies about biomonitoring by shrub species, but it could
numbered some shrub species such as Nerium oleander (Ataabadi et al., 2010a; Rossini Oliva
& Mingorance, 2006), Lantana Camara (Fernandez Espinoza & Rossini Oliva, 2005) Ligustrum
vulgare, Photinia serrulata, Berberis vulgaris and Thuja orientalis (Ataabadi et al., 2010a,b;
Ataabadi et al., 2011).
For comparative studies, it is important that sampling is undertaken at the same time of the
year to reduce variability. Chemical composition of foliage varies with season and rainfall
(Taylor et al., 1990). For most deciduous species, suitable time is period of year when metal
content in leaves will be highest. For instance standard sampling of heavy metal
accumulation in Populus nigra in central Europe is carried out in August.
Metal content will vary depending on which part of the plant is sampled. The extent of
accumulation in different plant parts will vary with species and the nature of the element.
It should be noted that using transplantation exercises are not common for higher plants
(Mulgrew & Williams, 2000).
2.5.2.2.1 Plant leaves as biomonitor
Leaves of higher plants have been used for heavy metals biomonitoring since 1950s (Al-
Shayeb eta l., 1995). The use of leaves as bioindicators of environmental pollution has been
studied, more and more, to assess their suitability, to assess effect of a specific pollution
source, to differentiate between background (unpolluted) and polluted sites and to monitor
or assess the level of pollution in an area (Turan et al., 2011).
Rossini Oliva & Mingorance (2006) and Ataabadi et al (2010a), reported that pine needles
can be considered suitable biomonitor for atmospheric heavy metal contamination
(e.g. Fe, Al, Pb).
Factors that affect efficiency of heavy metal accumulation on leaf surface
Particle (containing heavy metals) deposition on leaf surfaces may be affected by two
different factors including plant-dependent factors such as morphological and structural
properties of leaves contain orientation and size (Mulgrew & Williams, 2000) of leaves,
cuticle thickness, cork existence, roughness, existence of surface waxy layer, specific leaf
area (SLA), stomatal density (SD) and stomatal pore surface (SPS) (Ataabadi et al., 2011;
Rossini Oliva & Mingorance, 2006; Balasooriya et al. 2008) and plant-free factors such as
particle size and wind velocity (Mulgrew & Williams, 2000). Also the accumulation of heavy
metals by higher plants depends on the binding and solubility of particles deposited on leaf
surfaces (Mankovska et al., 2004).
The deposited particles may be washed by rain into the soil, resuspended or retained on
plant foliage. The degree of retention is influenced by weather conditions, nature of
pollutant, plant surface characteristics and particle size (Harrison and Chirgawi, 1989).
Leaves of evergreen species are considered to be better traps because of higher accumulation
on a longer period of time (Turan et al., 2011).
2.5.2.2.2 Plant bark as biomonitor
The physiological function of bark is to protect the tree from mechanical injury, damaging
agents and excessive evaporation. Bark quality varies considerably in different tree species
and at different stages in the lifetime of a tree species. The outer bark of trees consists of the
inner layer (phloem), the cork-forming layer (phellogen), and the outer layer (rhytidom or
phellem) composed of dead cork cells (Prance et al., 1993). This dead cork layer has usually
been employed in biomonitor studies. The chemical composition of the bark is specific to
each tree species. For instance, the pH, electrical conductivity and ash content of the bark of
coniferous trees are usually lower than those of broad-leaved species (Barkman, 1958).
When bark is exposed to air pollutants either directly from the atmosphere or from the
rainwater running down the stem, the chemical composition of the surface layers of the bark
changes, such changes can be utilised in investigating the extent of the area subjected to air
pollutants. In this respect tree bark is a good bioindicator because it remains in place for an
extended period of time, it is easily accessible and sampling does not damage the tree
(Berlizov eta al., 2007). Retention of suspended particles is promoted by a moist, porous,
rough, or electrically charged surface, making bark a highly effective collector (Panichev et
al., 2004). Therefore bark has been widely employed as a passive monitor for airborne metal
contaminations. The accumulation of atmospheric pollutants in bark is purely a
physiological-chemical process. The pollutants either accumulate passively on the bark
surface or become absorbed through ion exchange processes in the outer parts of the dead
cork layer (Poikolainen, 2004). Although a number of air pollution biomonitoring studies
have been performed using bark of different tree species include oak, elm, willow, poplar,
pine, olive, cedar, eucalyptus etc. (Berlizov et al., 2007).
Metal accumulation in bark and plant foliage in urban and industrial areas can be
considerable, with the greatest amount of the heavy metal burden located in the bark
(Ceˆburnis & Steinnes, 2000; Watmough & Hutchinson, 2003).
Factors that affect efficiency of heavy metal accumulation on bark surface
Factors, in addition to atmospheric pollutants, that affect the chemical composition of tree
bark are mainly the same as those for mosses and lichen, although the chemical reactions
that occur in bark are somewhat different because bark is a non-living plant material. The
concentrations in bark are mainly affected by bark quality, stand throughfall and stem flow.
The concentrations are highest in the surface layers of the outer bark, and decrease rapidly
on moving towards the inner layers. Many different factors have an effect on the collecting
of heavy metals in bark surface, such as heavy metal quantities in air, physiological and
chemical properties of the bark, through fall, soil factors, contamination of other plants,
climate factors, etc. A coarse and rough surface more readily accumulates atmospheric
pollutants than a smooth surface (Poikolainen, 2004), As Barnes et al., (1976) showed that
rough barks accumulate metals more than smooth barks. Other factors include the bark
texture and thickness (Poikolainen, 2004), the presence of epiphytic organisms, the time of
exposure to the atmosphere and the depth of sampling (Bellis et al., 2001). Also bark acidity
has an effect on the concentrations of some heavy metals. For instance, Bates and Brown
(1981) found a clear negative correlation between bark pH and the Fe concentration in a
study on the occurrence of epiphytic lichens on oak and ash. They concluded that this is due
to the increased mobility of Fe with decreasing bark pH. There is no significant migration of
elements from the bark surface through the cork tissue into the underlying wood, or vice
versa. The migration of heavy metals from the soil via the roots into the bark as it is being
formed is also usually insignificant. On the other hand, heavy metals and other compounds
may be carried by the wind from the soil to the bark surface (Poikolainen, 2004).
The study carried out by Szopa et al (1973) on lead concentrations along highways in the US
indicated that the lead concentration in bark reacts rapidly to marked changes in lead
concentrations in the atmosphere (Poikolainen, 2004).
2.6 Analytical method

Finally, the choice of analytical method for heavy metal detection in all plant materials
depends on the purpose of the respective survey. Some analytical methods are non-
destructive (e.g. Neutron Activation Analysis: N.A.A.) and are useful for repetitive surveys
such as baseline studies. Samples can also be archived and used at a later date for additional
analysis. Destructive techniques include atomic absorption spectrometry (AAS) and
inductively coupled plasma (ICP) analysis (Mulgrew & Williams, 2000).
On consideration of the methods available for moss monitoring in Norway, Steinnes et al.
(1993) concluded that ICP-ES works well for Fe, Zn, Pb and Cu, to a lesser extent for V
and Ni and but is not satisfactory for Cr, Cd and As. ICP-MS analysis proves a good
method for all of the above except As and Cd where less satisfactory results were
observed (Steinnes, 1993).
2.7 Some atmospheric heavy metal contamination indices

Several integrated environmental indices reflecting the quality of environment and life have
begun to appear in recent years. On the other hand, quantitative information can be
obtained by calculating different indices to estimate air quality (Calvelo & Liberatore, 2004).
2.7.1 Index of Atmospheric Purity (IAP)

DeSloover(1964) and DeSloover and LeBlanc (1968) suggested the IAP method for mapping
air pollution on the basis of epiphytic lichen and bryophyte sensitivity for mapping aerial
pollution (Moore, 1974). This method is based on the fact that the epiphytic lichen and
mosses diversity is impaired by air pollution and environmental stress. Therefore the
frequency of occurrence of species on a defined portion of a tree trunk is used as a
parameter to estimate the degree of environmental stress. This index gives an evaluation of
the level of atmospheric pollution, which is based on the number, frequency, and tolerance
of the epiphytic species present in an area.
IAP ∑ Q f (2)
n, the number of epiphytic species per site; Qi, the resistance factor or ecological index of each
species, thus representing the sensibility of a species against pollutants; fi, the frequency or
coverage score of each species per site (Max. 10; 1≤f ≤ 10). The IAP-index was calculated
separately for each sampling site (Blasco et al., 2008; Zechmeister & Hohenwallner, 2006).
The frequency method makes it possible to predict pollution levels with a certainty of over
97% (Conti & Cecchetti, 2001). After calculation of IAP, pollution intensity will be
determined by IAP classification is shown in Table 4.
Level A 0≤ IAP≤ 12.5 Very high level of pollution

Level B 12.5≤ IAP≤ 25 High level of pollution
Level C 25≤ IAP≤ 37.5 Moderate level of pollution
Level D 37.5≤ IAP≤ 50 Low level of pollution
Level E IAP> 50 Very low level of pollution
Table 4. Quality levels of index of atmospheric purity (IAP) (from Szczepaniak & Biziuk, 2003).
Quality levels may somewhat differ in various studies. As Dymytrova (2009) studied a total
of 1730 trees and 272 sampling plots in different parts of Kyiv (Ukraine) including industrial
areas, residential areas, roads and inner parks and investigated epiphytic bryophytes and
lichens on isolated trees. Results showed the highest and lowest epiphytic richness in the
inner parks and industrial area respectively. Consequently based on IAP, four zones with
different air pollution were distinguished: highly polluted (0-8.5), moderately polluted (8.6-
20.2), slightly polluted (20.3-31.9) and unpolluted (32-88.8). In these studies, heavy metal
concentrations in epiphytic vegetation and quality levels of IAP are correlated.
2.7.2 Enrichment factor

One approach used to characterize airborne particulate matter in terms of chemical
composition is to calculate so called ‘enrichment factors’ (EF), relating the concentration
of an anthropogenic ‘pollutant’ element (X), such as Pb, to that of a crustal element
(typically Al, Ti, Sc or Fe) in air, normalized to the ratio of these elements in the average
continental crust:
EF= (Xair/Alair) / (Xcrust/Alcrust) (3)

Enrichment factors close to unity thus indicate that windblown dusts are the dominant
airborne source, whilst values in excess of unity indicate that analyte concentrations have
been elevated as a result of anthropogenic inputs. The calculation assumes that the
anthropogenic contribution of the normalizing element (i.e. Al) is insignificant (Zoller et al.,
1974; Puxbaum, 1991).
Pacheco et al. (2002) evaluated olive-tree bark for the biological monitoring of airborne trace
elements and found significant enrichment of Cu in olive bark relative to Parmelia spp.
lichen was reported (Pacheo et al., 2002).
3. Conclusion
Application of lower and higher plants as biomonitors seams to be a good way to monitor
airborne heavy metal contamination, but the choice of proper phytomonitor for
environmental studies depends on many factors such as availability of the biological
material, contamination extent, study scale and etc. However lichen and moss due to have
superior ability to accumulate elements and indicate them without interference with soil are
reported the best bioindicators for the atmospheric heavy metal contamination, but in the
urban and industrial areas, using aboveground parts of indigenous higher plants is
recommended. Simplicity of species identification, sampling and treatment and ubiquity of
some genera makes it possible to cover large areas. For the comprehensive conclusion, both
of lower and higher plants should be studied simultaneously in the specific area and
manifested with respect to their limitations and advantages.
4. Acknowledgment
The authors would like to thank Dr. Ahmad Ali Foroughi, the chancellor of Islamic Azad
University Khorasganan branch (Isfahan) and Research Center of this University.
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6
Air Quality Study, Comparison Between the

Proposed and Actual Scenarios of Generator
Sets in Havana, by Using CALPUFF Model
Yasser Antonio Fonseca Rodríguez1, Leonor Turtós Carbonell2,
Elieza Meneses Ruiz1, Gil Capote Mastrapa1 and José de Jesús Rivero Oliva2
1CUBAENERGIA
2Universidade Federal do Rio de Janeiro
1Cuba
2Brazil
1. Introduction
"Air Pollution" means the introduction by man, directly or indirectly, of substances or
energy into the air resulting in deleterious effects of such a nature as to endanger human
health, harm living resources and ecosystems and material property and impair or interfere
with amenities and other legitimate uses of the environment, and "air pollutants" shall be
construed accordingly (18 ILM 1442, 19791).
Among the main reasons of increased air pollution is the expanding use of fossil energy
sources, particularly in energy facilities, like the present case. Under the distributed power
generation program that is currently being implemented in the country, generator sets (GS)
have been installed and are still being installed in urban and sub-urban areas, to generate
electricity using fossil fuels, such as in base-load as in emergency cases. During the
operation of this equipment pollutants are released to the atmosphere, primarily nitrogen
oxides (NOx), sulphur dioxide (SO2) and particulate matter (PM), which increase the
concentrations of these pollutants in the atmosphere, affecting air quality.
It is essential to control these emissions so that concentrations achieved by each of the
released pollutants be below their regulated values; therefore it is necessary to know to what
extent air concentrations resulting from emissions from each facility could change. To this
end, direct measurements and estimates of their concentrations by using Air Quality Models
could be made. The measurements require specialized instrumentation and trained
personnel, which increases the cost of the task; however, the use of models is much cheaper.
They present algorithms to simulate physical and chemical processes for each pollutant in
the atmosphere, allowing us to evaluate their behaviour after them being released. Despite
this fact, none of the two methods is self-sufficient; so, it is necessary them be
complemented. In many countries, particularly in developing countries, there are
insufficient resources to carry out measurements of air quality with the necessary temporal
and spatial extent, thus the computational modelling using the Air Quality Models carries
the most importance. Moreover, the use of models for assessing air quality, and possible
mitigation measures considering the results, often fall on simplified models due to their few
requirements of input data.
The implementation of sophisticated models enables a more accurate assessment, however,
their requirements and data complexity grow, and they are not always available in such
countries. To this end, solutions to overcome the disadvantage of lack of data were taken.
The Environmental Protection Agency (US EPA) established on October 21st, 2005 the
AERMOD modelling system as the model recommended to be used for the dispersion of local
pollutants, replacing ISCST3 (Industrial Source Complex Short Term version 3), hitherto used.
AERMOD is a steady state, Gaussian local model, which includes the treatment of surface
and elevated sources, both in simple and complex field (Fonseca, 2010)2. It is fed with
surface hourly meteorological data and upper air. It is used in many countries in accordance
with the regulations. The solutions taken in Cuba allow the use of the model even when the
upper air data are not available, based only on surface data (Turtós et al., 2010)3.
CALMET-CALPUFF Modelling System was developed by Earth Tech (Concord, MA) and it
is the model proposed since 2003 by the U.S. EPA as the regulatory model to be used to
perform detailed modelling of air pollution dispersion processes, in regional domains (at
distances between 50 and 200 km from the source, with acceptable values up to 300 km)
using three-dimensional wind fields. It is also proposed to be used at local level (from 0 to
50 km away from the source) in case of complex meteorological conditions such as those
arising from the presence of hills and large bodies of water within the study area.
CALPUFF is a multi-layer, multi-species, non-steady state puff dispersion model which can
simulate the effects of time- and space-varying meteorological conditions on pollutant
transport, transformation, and removal. CALPUFF can use the three-dimensional
meteorological fields modelled by the CALMET model, or simple, single station winds in a
format consistent with the meteorological files used to drive the ISCST3, AUSPLUME or the
CTDMPLUS steady-state Gaussian models. However single-station ISCST3, CTDMPLUS or
AUSPLUME winds do not allow CALPUFF to take advantages of its capabilities to treat
spatially-variable meteorological fields. CALPUFF contains algorithms for near-source
effects such as building downwash, transitional plume rise, partial plume penetration, and
subgrid scale terrain interactions as well as longer range effects such as pollutant removal
(wet scavenging or dry deposition), chemical transformation, visibility effects (Scire et al.,
2000)4. As the AERMOD, CALMET also requires upper air meteorological data, although
the solutions taken in Cuba for AERMOD have not been introduced in CALMET given the
complexity in introducing the meteorological data grid. Therefore, it is proposed to feed
CALMET with results from the pre-processors of mesoscale meteorological and geophysical
data, such as WRF and MM5.
The present chapter assesses the ability of the CALPUFF modelling system to simulate the
dispersion of pollutants at local level, instead of using AERMOD, and predict the maximum
concentrations each pollutant could achieve. CALPUFF was selected for the local domain as
it provides more accurate results under complex meteorological conditions resulting from
Cuban modelling domain, since it uses a three-dimensional meteorological grid, thus
obtaining a better approximation for each variable as the resolution of each cell is higher.
However, the AERMOD (EPA-454/B-03-001)5 - the most advanced of those used in Cuba
and regulatory EPA for local domains – assumes meteorological conditions to be uniform
Air Quality Study, Comparison Between the Proposed and
Actual Scenarios of Generator Sets in Havana, by Using CALPUFF Model 125
throughout the domain, what is a potential source of error in the model’s input data. Other
advantages of the CALPUFF is that it takes into account, although not at the same level of
complexity as photochemical models do, the reactions occurring among pollutants in the
atmosphere, making it possible to obtain the values of concentrations and deposition of
sulphate and nitrate aerosols.
2. Background
As a result of the decision to install GS fed with fuel oil in Havana, a study of the related
impacts to air quality that would produce the operation of the 11 planned GS by using the
ISCST3 model (Turtós et al, 2006)6 was carried out. This study concluded that significant
amounts of oxides of sulphur and nitrogen will be released into the atmosphere with the
simultaneous operation of these devices in a densely populated area, according to data
provided by the manufacturer. In the selected modelling domain of 50 x 37 km, average
population density is approximately 1240 inhabitants per km2, according to the data of the
year 2000 from Population Study Center.
The work showed concentration levels of SO2 and NO2 to be achieved in 1850 points of
Havana as a result of simultaneous operation of all the generator sets, which exceeds in an
appreciable number of receptors the regulated values in the country for one-hour and one-
day periods, and even permissible values from the World Health Organization (WHO).
As a result, it was decided to install only five GS with higher stack (from 15 to 37.5 m) and to
carry out several studies (INEL, 20087; CUBAENERGIA, 20098 and CUBAENERGIA, 20109).
The 2009 study was divided into two parts; the first was a comparative study between
ISCST3 and AERMOD, and the second one, the modelling of different scenarios by using
AERMOD. The 2010 study included measurement of emissions in different sites and
modelling with AERMOD. Although five sites were built, only four are finally in operation.
The use of the AERMOD has been questioned since it is a domain that includes a coastline,
which is not properly reflected by the uniform meteorology used by the model. Despite its
high computational cost, the use of CALPUFF in this case is justified.
3. Methodology
CALPUFF calculates the pollutant dispersion in the receptor sites, taking into account
complex three-dimensional wind fields, obtained with CALMET, which is particularly
important for emission sources located in coastal areas and near high elevations. CALMET
calculates wind structures in the study area from surface and upper air data. WRF outputs -
model for calculating and forecasting the meteorological variables- was used as an
alternative due to the unavailability of upper-air meteorological data in Cuba.
This system calculates the concentrations in the receptors distributed in the domain of
study, at different times, for example, PM10, sulphur dioxide (SO2) and the species of the
nitrogen family (NOx). It also includes a simple model of chemical transformation to study
and calculate some minor species such as sulphates (SO4-2) and nitrates (NO3-), which have a
lot of relevance because of their potential effects on human health. Therefore, the system has
been used in studies as a conceptual basis for these tests (Fonseca, 2010).
Fig. 1. Flowchart of the modelling with CALPUFF.
3.1 Reference values

The maximum permissible concentrations according to the Cuban Standard (NC) (NC
39:199910 and NC 111-200211) and the reference values of the World Health Organization
(WHO, 2005)12 are used as reference for the analysis of results. These concentration values
should not be higher than those of the pollutant (in the atmosphere) in the established time
interval.
Maximum permissible concentrations (µg/m3)

Pollutant 1 hour 24 hours
SO2 500 50
NOx 85 40
PM10 100 50
Table 1. Maximum permissible concentrations (µg/m3) according to the Cuban Standard
(NC) and the World Health Organization (WHO).
4. Case study: Modelling scenarios

In this chapter, we used the Air Quality Model CALPUFF in the evaluation of measures
related to the design and location of the GS in order to mitigate the possible effects caused
by these technologies on air quality.
Two scenarios were defined, which underwent a thorough analysis. The influence of
meteorological conditions was assessed in detail, as well as the effective height of emission
and power of each facility from a scenario to another.
Scenarios:
 Scenario 1 or proposed scenario (an initial project with 11 GS to be installed).
 Scenario 2 or real scenario (with 4 GS actually installed).
4.1 Modelling period

The modelling period (approximately two months of calculation) was that between January
2nd, 2009 at 00:00 pm and March 7th, 2009 at 23:00 pm.
4.2 Geophysical and meteorological data required for meteorological processing by

using CALMET
The characteristics of geophysical and meteorological data used by CALMET for
meteorological processing are set out below.
4.2.1 Topography and land use

In order to get information on the relief Digital Elevation Models (DEM) were used while
land uses were obtained from the Global Database of Soil Coverage features, both available
on the Internet.
4.2.2 Surface meteorological data

Hourly meteorological data of the entire modelling period were processed. They were
collected in the seven surface stations located within the meteorological domain. See Table 2.
Coordinates
Station Code Name
Latitude Longitude
78322 Batabano 22.717◦ N 82.267◦ W
78318 Bahia Honda 22.92◦ N 83.17◦ W
78325 Casablanca 23.167◦ N 82.350◦ W
78373 Santiago de las Vegas 22.967◦ N 82,367◦ W
78320 Güira de Melena 22.78◦ N 82.52◦ W
78375 Melena del Sur 22.767◦ N 82.117◦ W
78376 Bauta 22.967◦ N 82.517◦ W
Table 2. Location of surface stations.
(Source: INSMET, 2008)
4.2.3 Upper air data – WRF configuration

WRF outputs are used in order to feed CALMET with upper air data. The WRF model was
implemented with the configuration shown in the following tables.
Main Data Domain 1 Domain 2 Domain 3

Cells 45 * 30 34 * 34 34 * 34
Cell Size 27km 9km 3km
Center location 22.19ºN 23.1ºN 23.1ºN
(Lambert Conformal Conic) 79.52ºW 82.35ºW 82.35ºW
Table 3. Modelling domain.
Physical Data Domain 1 Domain 2 Domain 3

WSM5
(A more sophisticated version of
Microphysics WSM3, allows for mixed-phase WSM3 WSM3
processes and super-cooled
water) (mp_physics=4)
Kain-Fritsch
(Not
Kain-Fritsch scheme (Deep and scheme
necessary for
Cumulus shallow convection sub-grid (Deep and shallow
domains with
Parameterization scheme) convection sub-
cells lower
(cu_physics=1) grid scheme)
than 4 km)
(cu_physics=1)
RRTMG
(a shortwave scheme with
Montecarlo Integrated Column
Shortwave Dudhia
Approach (MCICA) method of Dudhia Scheme
Radiation Scheme
random
cloud overlap)
(ra_sw_physics=4)
RRTM
RRTMG
RRTM (Rapid
Longwave (new RRTM scheme that includes
(Rapid Radiative Radiative
Radiation MCICA method of random cloud
Transfer Model) Transfer
overlap) (ra_sw_physics=4)
Model)
MM5
Surface Layer MM5 similarity MM5 similarity
similarity
5-layer
5-layer thermal
Land Surface 5-layer thermal diffusion thermal
diffusion
diffusion
Yonsei
Planetary Yonsei University
Yonsei University scheme University
Boundary layer scheme
scheme
Table 4. Physical parameters.
The domains 1, 2 and 3, mentioned in the previous tables, in which the WRF model was
implemented, are shown below.
Fig. 2. Domains for WRF modelling.

(Source: Capote et al. n.d.)13
4.3 Structuring the CALMET meteorological grid

A rectangular grid of 90 x 95 km with a 1 km resolution and centered in X = 340500 Y =
340800 m was set up.
The following values collected by the surface stations within the meteorological domain
were used: values of speed and prevailing wind direction, temperature, cloud coverage,
height of the cloud base, pressure, relative humidity and precipitation rate. Upper air data
obtained from processing WRF and adapted to the needs of CALMET by CALWRF
(CALWRF, 2008)14 pre-processor were added to these data. The description of these
meteorological variables used by CALMET was obtained for 10 intervals of different heights
(0 to 20, 20 to 40, 40 to 80, 80 to 160, 160 to 320, 320 to 640, 640-1200, 1200 to 2000, 2000 to
3000 and 3000 to 4000 m above ground level), thus obtaining the three-dimensional
meteorological grid.
The CALMET meteorological field was simulated for a 1-hour time scale and was obtained
by intelligent interpolation mechanisms applied to all the above variables.
Fig. 3 shows a sub-domain of the wind field obtained from CALMET. Examples of the wind
direction and speed variability in an area of the modelled domain are given.
Fig. 3. Speed and direction of winds to 240 m above ground level.

(Source: Base Map Google Earth)
The arrows illustrate the wind direction (coinciding with that of the arrows) and speed
(color scale) in a study sub-domain.
4.4 Processing by CALPUFF

For processing with CALPUFF two more grids were defined - the calculation and receptor
grids - which are made to coincide with the meteorological grid, so that the puff modelling
cover a larger area in order to obtain the values of the concentrations and deposition or
removal flow of released pollutants. In the calculation grid, puffs are released and
transported, allowing their dispersion modelling, and it is in the receptors where the final
values of each study are obtained. A total of 8550 receptors, arranged in the shape of a
rectangular grid at a distance of 1 km from receptor to receptor, resulted from this
configuration.
Calculations were made using a pseudo-first order chemical reaction mechanism for the
conversion of SO2 to SO4-2 and NOx to nitrate aerosols. This mechanism is based on the
chemical transformation scheme used in the MESOPUFF II model (Scire et al., 1984)15, which
introduces the most significant dependencies of transformation rates over varying
environmental conditions, in time and space. This scheme models 5 species (SO2, SO4-2, NOx,
HNO3 y NO3-1) to which the modelling of suspended particles with diameter less than 10
micrometers (PM10) was added.
5. Proposed scenario
Behold the initial project for the installation of 11 in Havana. See Fig. 4.
Fig. 4. Proposed location of the 11 generator sets to be initially installed in Havana.

The following tables show the composition of each of the GS to be installed, their technical
features and emission rates.
Emission values for the study were those provided by the manufacturer. A fuel with a
sulphur content of 2% was assumed to be used.
Number of Engine
Composition Number
Nu. Name of GS engines making power
of the GS of stack
them up unit (MW)
Guanabacoa
1 16 4x4 4 1.7
(GUA)
Apolo
2 16 4x4 4 1.7
(APOLO)
Naranjito
3 16 4x4 4 1.7
(NAR)
Victoria de Giron
4 16 4x4 4 1.7
(GIRON)
Diezmero
5 16 4x4 4 1.7
(DIEZ)
San Agustin
6 16 4x4 4 1.7
(SANAG)
Regla
7 28 7x4 7 1.7
(REGLA)
Cotorro
8 24 6x4 6 2.5
(COTO)
Parque Metropolitano
9 24 6x4 6 2.5
(PMA)
Berroa
10 24 6x4 6 2.5
(BERROA)
CUJAE
11 24 6x4 6 2.5
(CUJAE)
Total 220 55 450.8
Table 5. Composition of GS to be installed.
Stack Stack Output Output

Nu. Name of GS
Height (m) Diameter (m) Speed (m/s) Temperature (°K)
1 NAR 15 1.27 14.98-11.23* 520
2 SANAG 15 1.27 14.98-11.23* 520
3 APOLO 15 1.27 14.98-11.23* 520
4 CUJAE 15 1.27 23.1-17.32* 553.5
5 REGLA 15 1.27 14.98-11.23* 520
6 BERROA 15 1.27 27.7 504.15
7 COTO 15 1.27 27.7 504.15
8 DIEZ 15 1.27 18.1 477.15
9 GIRON 15 1.27 18.1 477.7
10 GUA 15 1.27 18.1 477.7
11 PMA 15 1.27 27.7 504.15
* In these cases, it was considered that the output speeds change with variations in emission rates.
Table 6. Specifications of the stacks of the GS to be installed.
LCC North Cuba geographic projection (LCC-CN) was used, since it meets the study’s
needs. The LCC-CN projection parameters are:
 Projection Origin (22.35° of north latitude and 81° of west longitude)
 Standard Parallels (21.7 ° and 23 ° North)
 False North and False East (X = 500000 Y = 280296.016 m)
Nu. Name of GS SO2(g/s) NOx(g/s) PM10(g/s)

1 NAR 12.8 13.84 0.1932
2 SANAG 12.8 13.84 0.1932
3 APOLO 12.8 13.84 0.1932
4 CUJAE 18.84 19.44 0.6906
5 REGLA 12.8 13.84 0.1932
6 BERROA 18.84 19.44 0.6906
7 COTO 18.84 19.44 0.6906
8 DIEZ 12.8 13.84 0.1932
9 GIRON 12.8 13.84 0.1932
10 GUA 12.8 13.84 0.1932
11 PMA 18.84 19.44 0.6906
Table 7. Emission values for each source (g/s).
Maximum emissions for each engine (by its power) are showed, though it is considered that
each set worked with 87.5% availability.
5.1 Analysis of results and comparison with those of the reference values
Table 8 shows the maximum modelled concentrations by each pollutant species in the
atmosphere for each of the intervals of importance in the study.
Maximum concentrations
Pollutant 1 hour 24 hours the whole period (1559 hours)
SO2 558 168 53
SO4-2 8.1 2.4 0.1
NOx 567 180 56
NO3-1 27 3.5 0.2
PM10 21 5.4 0.9
HNO3 23 3.8 0.6
Table 8. Maximum modelled concentrations (µg/m3) for each pollutant for each time
interval.
It is possible to check if the standardized values are exceeded by comparing the maximum
modelled concentrations by each species in 1-hour and 24-hour periods with the maximum
permissible concentrations (for 1 and 24 hours respectively) according to Cuban standards.
It should be noted that there are species for which the standards do not provide maximum
permissible concentrations.
Table 9 below shows a ratio between reached maximum concentrations and maximum
permissible (for each species and time interval). When this value is greater than 100, then
this species exceeds its maximum permissible for that interval of time.
MC / MPC (%)
SO2 112 336
NOx 667 450
PM10 21 11
Table 9. Ratio of the maximum Modelled Concentrations (MC) and the Maximum
Permissible Concentrations (MPC) according to the NC and WHO, for different time
intervals.
Taking into account the above criteria it can be confirmed that both SO2 and NOx (values
highlighted in red) go over the MPC in both evaluation periods.
The following table shows the maximum average concentrations reached by the two "critical
species".
Maximum average concentrations

SO2 66.2 11.9
NOx 68.8 11.6
Table 10. Maximum average concentrations of SO2 and NOx (µg/m3).
5.1.1 Critical receptors

The following tables show the receptors, in which the maximum concentrations of SO2 and
NOx are obtained and at the same time exceed the MPC:
Evaluation Period NuO Number of Receptors

1 hour 1 3
1 31
2 13
3 9
4 3
5 3
24 hours
8 1
9 1
10 1
15 1
32 1
Table 11. Number of receptors in which SO2 exceeds the MPC and number of opportunities
(NuO) this occurs.
Table 11 shows the number of opportunities SO2 exceeds its MPC (middle column), as well
as the amount of receptors in which this occurs (right column).
Analyzing the maximum hourly concentrations of NOx, it is observed that exceeds its MPC
for 1-hour and for 24-hour periods in many receptors, therefore only the most critical
receptors are shown in Table 12. It is worth noting that 687 receptors go over the MPC for 1-
hour period, while the most critical receptor exceeds this MPC for 315 hours out of the 1559
modelled hours, which represents approximately 20% of the modelling period.

112 2
132 2
138 1
149 1
1 hour
155 1
185 1
188 1
315 1
Table 12. Number of receptors that NOx exceeds the MPC for 1-hour period (middle
column) and the NuO it occurs (right column).

1 68
2 20
3 13
4 5
5 6
6 6
24 hours
7 2
8 2
10 3
12 3
13 1
18 1
Table 13. Number of receptors that NOx exceeds the MPC for 24-hour period (middle
column) and the NuO it occurs (right column).
The following figures show the isolines of the maximum daily and hourly concentration of
NOx and SO2 respectively.
The sources are identified by red crosses and all locations where the NOx exceeds its MPC
by red areas.
Fig. 5. Isolines of the maximum daily concentration of NOx.

Source: Base Map Google Earth)
Fig. 6. Isolines of the maximum hourly concentration of SO2.

5.1.2 Depositions
There is general consensus that the deposition of sulphur compounds and nitrogen causes
acidification on aquatic and terrestrial ecosystems, which means, among other impacts, less
fertile soils and impacts to aquatic organisms which can not tolerate the acidity conditions.
In general, these effects appear when the threshold of the critical load is exceeded. The
critical load has been defined as "the maximum deposition of acidifying compounds that
will not cause chemical changes leading to long term harmful effects on ecosystem structure
and function" (Sverdrup et al., 1995)16.
As there are not critical load values for Cuban conditions, a comparison could be made with
the values set in the Air Quality Guide for Europe, WHO, 2000, shown in Table 14.
Compound Guide values of critical loads Evaluation Period
S 250–1500 eq/ha/year* annual
N 5–35 kg N/ha/year* annual
* Depending on soil type and ecosystem

Table 14. Values set in the Air Quality Guide for Europe.
Table 15 shows the maximum and average deposition values of sulphur and nitrogen,
which are considered valid in practice, expressed in µg/m2 for each evaluated period, and
their respective conversions to eq / ha and to kg N / ha, depending on the species that
identify the critical loads for each compound.
N S
Evaluation
(µg/m2) (Kg_N/ha) (µg/m2) (eq/ha)
Period
Maximum 2490 --- 5190 ---
1 hour
Average 77 6.7 355 1944
Maximum 11600 --- 23000 ---

24 hours
Average 327 1.2 1520 347
Maximum 111000 6.2 203000 713

1559 hours
Average 2830 0.2 11900 42
Table 15. Maximum and average deposition values of sulphur and nitrogen.
The table above shows that nitrogen does not exceed critical load values, while the average
sulphur for 1-hour period does exceed them.
6. Real scenario
It is the one that takes into account the four GS currently installed in Havana.
Fig. 7. Location of the four generator sets currently installed in Havana.

The following table shows the composition of each of the currently installed GS.
Number of engines Composition Number Engine power

Nu. Name of GS
making them up of the GS of Stack unit (MW)
1 APOLO 16 4x4 4 1.7
2 SANAG 16 4x4 4 1.7
3 REGLA 28 7x4 7 1.7
4 CUJAE 24 6x4 6 2.5
Total 84 21 162
Table 16. Composition of the 4 GS currently installed in Havana.
The technical data of each of the stacks of these 4 GS match those assumed in the initial
project, except for the height, since they are 37.5 m. See Table 6.
The emission values of each of these sources are the same as those used in the proposed
scenario, since the values provided by the manufacturer were used in both studies. See
Table 7.
6.1 Analysis of results and comparison with the reference values

Table 17 shows the maximum concentrations modelled in the atmosphere for each pollutant
species for each of the intervals of importance in the study.
Maximum concentrations
Pollutant 1 hour 24 hours All Period (1559 hours)
SO2 435 105 38
SO4-2 4.5 1.11 0.045
NOx 441 112 40
NO3-1 12.6 1.9 0.068
PM10 16 3.4 0.57
HNO3 18.7 2.14 0.3
Table 17. Maximum concentrations reached (µg/m3) by each pollutant for each time interval.
It is possible to check if the standardized values are exceeded by comparing MC with their
respective MPC according to Cuban standards.
Table 18 below shows a ratio between MC and the MPC (for each species and time interval),
following the same criteria as in the previous scenario, where this value is greater than 100,
then this species exceeds its MPC for that time interval.
MC / MPC (%)
SO2 87 210
NOx 519 280
PM10 16 6.8
Table 18. Ratio between MC and MPC according to NC and WHO, for different time intervals.
Given the above criteria, it can be confirmed that both SO2 for 24-hour periods and NOx for
1-hour and for 24-hour periods exceed their MPC (values in red).
The following table shows maximum average concentrations modelled in the entire domain
compared to the previous scenario.
Maximum average concentrations

SO2 33.9 4.5
NOx 35.5 4.39
Table 19. Maximum average concentrations of SO2 y NOx (µg/m3).
6.1.1 Critical receptors

The following tables show the receptors in which NOx and SO2 exceed the MPC and the
number of opportunities it happens.
Table 20 shows the number of opportunities the SO2 exceeds its MPC daily (middle column)
and the amount of receptors in which this happens (right column).

1 6
2 2
24 hours 3 2
6 1
25 1
Table 20. Number of receptors in which SO2 exceeds the MPC and the number of
opportunities (NuO) it occurs.
After analyzing the maximum hourly concentrations of NOx, it can be observed that it
exceeds its MPC in many receptors, therefore only the most critical ones will be showed,
although it is worth noting that 207 receptors go above MPC for 1-hour period, while the
most critical receptor exceeds this MPC for 251 hours out of the total modelled, representing
approximately 16% of the modelling period.

42 1
49 1
59 1
64 1
1h 77 1
90 1
92 1
105 1
251 1
Table 21. The most critical receptors where NOx exceeds for 1-hour period maximum
permissible concentrations and the number of opportunities this happens.
The following table shows the days in which MPC are exceeded by NOx

1 13
2 1
3 7
24 hours 5 1
6 1
7 1
32 1
Table 22. The most critical receptors where NOx exceeds in 24 hours maximum permissible
concentrations and the number of opportunities this happens.
The following figures show the isolines of the maximum daily and hourly concentration of
NOx and SO2 respectively.
The sources are identified by red crosses and all locations where the NOx exceeds its MPC
by red areas.
Fig. 8. Isolines of the maximum daily concentration of NOx.

Fig. 9. Isolines of the maximum hourly concentration of SO2.

6.1.2 Deposition
Table 23 shows the maximum and average deposition values of sulphur and nitrogen,
which are considered valid in practice, expressed in µg/m2 for each evaluated period, and
their respective conversions to eq / ha and to kg N / ha, depending on the species that
identify the critical loads for each compound.
N S
Evaluation Period (µg/m2) (Kg_N/ha) (µg/m2) (eq/ha)
Maximum 1500 --- 3180 ---
1 hour
Average 40 3.5 185 1013
Maximum 8680 --- 17500 ---
24 hours
Average 131 0.5 568 130
Maximum 83200 4.7 154000 541
1559 hours (All period)
Average 884 0.05 3500 12.3
Table 23. Maximum and average deposition values of sulphur and nitrogen.
The above table shows that neither nitrogen nor sulphur exceeds their critical load values.
7. Comparison between scenarios

The following table shows a ratio between the maximum modelled concentrations by each
species in the Scenario 1 (MC1) and the Scenario 2 (MC2).
MC1/MC2
Pollutant 1 hour 24 hours the whole period (1559 hours)
SO2 1.28 1.6 1.39
SO4-2 1.8 2.16 2.22
NOx 1.29 1.61 1.4
NO3-1 2.14 1.84 2.94
PM10 1.31 1.59 1.58
HNO3 1.23 1.78 2
Table 24. Ratio between MC1 and MC2.
The above table shows that all the MC decrease between 1.23 and 2.94 times.
If the ratio between MC1 and MC2 with respect to MPC (see Table 9 y Table 18) is analyzed,
it can be observed that SO2 and NOx exceed their MPC for 1-hour and for 24-hour periods in
the scenario 1, while in the scenario 2, NOx exceeds their MPC for 1-hour and for 24-hour
periods, but SO2 only exceeds its MPC for a 24-hour period.
As the MC only show the behaviour in the most critical receptor and there is not a complete
analysis of the entire domain, the ratio between MC1 and MC2 really does not show the
variation from one scenario to another. Therefore, maximum average concentrations were
calculated to qualitatively get a better idea of the critical pollutant dispersion in every scenario
(see Table 10 y Table 19). As a result there was a decrease of about half in the concentrations.
The decrease in absolute maximum hourly concentrations of the 2 critical species is mainly
due to the elimination of the GS responsible for them, since they are caused by the action of
individual sites and not by overlapping plumes of several sites, for example: the maximum
hourly concentration of SO2 and NOx in the scenario 1 is reached in the vicinity of the
COTO site, while it is achieved near CUJAE in the scenario 2. However, the overall decrease
in maximum average concentrations is due to the increase of 22.5m in the height of the
stacks in the four currently installed GS. For example, the maximum daily concentration of
SO2 reached in the vicinity of the REGLA site in the scenario 1 is 168 µg/m3, while in the
scenario 2 decreases to 105 µg/m3.
Analyses carried out to deposition levels showed that only the average sulphur for 1 hour in
the scenario 1 is the one which exceeds the critical load values for Europe. See Table 15 y
Table 23.
As the critical load depends on the past and present management, of the type of
ecosystem and soil conditions, to what extent these critical load values proposed for
Europe can be applied in other regions is not known. The information required to
properly analyze these results and turn them into physical impacts and external costs is
difficult to obtain.
In order to qualitatively compare how much the level of deposition from one scenario to
another decrease, ratio of the maximum and average deposition of sulphur and nitrogen in
each evaluation period was analyzed.
Period N S
Maximum 1.7 1.6
1 hour
Average 1.9 1.9
Maximum 1.3 1.3
24 hours
Average 2.5 2.7
Maximum 1.3 1.3
1559 hours
Average 3.2 3.4
Table 25. Ratio of the maximum and average deposition of sulphur and nitrogen in each
evaluation period from one scenario to another.
The table above shows that maximum deposition levels decreases between 1.3 and 1.7 times,
while average deposition levels decreased between 1.9 and 3.4 times.
As with maximum concentrations, the highest hourly deposition in the scenario 1 is
observed near COTO site and in the scenario 2 - in the vicinity of CUJAE site. This is also
due to the elimination of the site where the maximum emissions occur.
8. Comparison between AERMOD and CALPUFF

The real scenario was modelled using the AERMOD (the same period, the same sources,
emission rates, etc.). Results, very similar to those obtained with CALPUFF for the same
scenario, were obtained. Because of the similarities in the results, we will analyze only the
behaviour of SO2 in the REGLA site.
Table 26 shows the behaviour of some of the maximum concentrations in the vicinity of the
REGLA.
Period Model Concentration of SO2 (µg/m3)

CALPUFF 339
1 hour
AERMOD 312
CALPUFF 93
24 hours
AERMOD 141
Table 26. Maximum concentrations of SO2 (µg/m3) in the vicinity of REGLA.
The above table shows that the results are comparable.

This is only a preliminary analysis due to the short temporal modelled interval, but it shows
the possibility of using the AERMOD in the evaluation of local pollutant dispersion in
Havana despite the existence of the extensive coastline. In order to obtain a final result, an
assessment of air quality for a longer modelling period (at least for a year) is recommended
to be carried out since this makes it more likely to show all possible synoptic conditions,
which does not occur in two-month period.
9. Conclusions
 A refined modelling was performed using the CALPUFF model, following the
recommendations for using it at the local level under complex weather conditions. This
is considered a significant progress because the AERMOD was the model used for
national studies so far.
 The WRF-CALMET-CALPUFF methodology was first used in a real case.
 Significant reductions in air pollution were obtained by replacing the initial project
(proposed scenario) with the end project (real scenario) for the installation of generator
sets, regarding the following aspects:
1. Decrease in maximum concentrations with the elimination of the site that produced
them, i.e. decrease in absolute maximum hourly concentrations of SO2 and NOx by
removing the COTO.
2. Decrease in maximum concentrations by increasing height of the stacks, i.e.
decrease in absolute maximum daily concentrations of SO2 of COTO.
3. Decrease in maximum concentrations by increasing height of the stacks, i.e.
decrease in absolute maximum daily concentrations of SO2 of GS COTO.
 Despite the improvements in air quality when using the scenario 2, actions must be
taken and new alternatives should be developed to continue reducing emissions so that
the maximum concentrations of these pollutants do not exceed their maximum
permissible concentrations.
 It was found that the results obtained with CALPUFF and AERMOD, despite the
differences between the models and short modelling period, provide comparable
results in assessing the dispersion of pollutants at local scale for scenarios in Havana,
what makes it possible the use of the AERMOD instead of the CALPUFF model in such
scenarios.
 It is recommended to carry out a future local study in Havana (at least one-year
assessment) in order to obtain conclusive results about the similarities by using one or
the other model in these scenarios.
10. References
1 18 ILM 1442 (1979). Convention on Long-Range Transboundary Air Pollution, Article 1(a).
2 Fonseca,Y. (2010). Implementación y aplicación del sistema de modelación CALMET-CALPUFF-
CALPOST a escala local. Trabajo de Diploma. Instituto Superior de Tecnologías y
Ciencias Aplicadas (INSTEC), Departamento de Ingeniería Nuclear.
3 Turtós L., J. Rivero, L. Curbelo, M. S. Gácita, E. Meneses & N. Díaz, 2010. Methodological
guide for implementation of the AERMOD system with incomplete local data. Atmospheric
Pollution Research, ISSN: 1309-1042, Vol 1, Issue 2, pp 102-111.
4 Scire, J. (2000). User's guide for the CALPUFF Dispersion Model, July 2011, Available from:
www.src.com/calpuff/download/CALPUFF_UsersGuide.pdf.
5 EPA-454/B-03-001, September 2004. User's guide for the ams/epa regulatory model –
AERMOD. U.S. Environmental Protection Agency, Office of Air Quality Planning

and Standards Emissions, Monitoring, and Analysis Division Research Triangle
Park, North Carolina 27711
6 Turtós L, N. Díaz, M. Padrón & E. Molina, 2006, Estudio de calidad del aire por la instalación de
los Grupos Electrógenos en Ciudad de la Habana. Informe de Servicio Científico Técnico

entre CUBAENERGIA y la Empresa de Ingeniería para la Electricidad, INEL.
7 INEL, 2008. Datos usados en el estudio global pronostico 2008. Informe Técnico.
8 CUBAENERGIA, 2009. Estudios ambientales vinculados a las emisiones de gases y material
partículado total de los grupos electrógenos de fuel oil en Ciudad Habana. Informe de
Servicio Científico Técnico CUBAENERGIA-INEL.
9 CUBAENERGIA, 2010. Informe de servicio de medición y modelación de dispersión de
contaminantes atmosféricos emitidos por los grupos electrógenos de régimen base en La

Habana.
10 NC 39:1999, NORMA CUBANA. Sistema de Normas para la protección del Medio Ambiente,
Atmósfera, Requisitos higiénicos sanitarios: Concentraciones máximas admisibles,

alturas mínimas de expulsión y zonas de protección sanitaria. Comité Estatal de
Normalización.
11 NC 111: 2002, NORMA CUBANA. Calidad del aire, Reglas para la vigilancia de la calidad del
aire en asentamientos humanos. La Habana, Oficina Nacional de Normalización.

12 WHO, 2005, WHO/SDE/PHE/OEH/06.02. Air quality guidelines for particulate matter,
ozone, nitrogen dioxide and sulfur dioxide Global update 2005. Summary of risk
assessment.
13 Capote G., L. Turtós, L. Alvarez, A. Bezanilla & I. Borrajero, (n.d.).Implementación del
modelo meteorológico WRF en Cuba para su uso en modelos de dispersión de contaminantes

atmosféricos.
14 CALWRF, 2008. Version 1.1. Level 080429. Atmospheric Study Group in TRC Environmental
Corporation.
15 Scire et al., 1984. User’ Guide to the MESOPUFF II dispersion Model and related processor
programs. EPA-600/8-84-013. US Environmental Protection Agency. Research
Triangle Park. NC.
16 Air Quality Guidelines for Europe, 2000. World Health Organization. Regional Office for
Europe, Copenhagen. WHO Regional Publications. European Series. No. 91.
Second Edition.
7
On the Impact of Time-Resolved

Boundary Conditions on the
Simulation of Surface Ozone and PM10
Gabriele Curci
Dept. Physics, CETEMPS, University of L’Aquila
Italy
1. Introduction
The grid-spacing of chemistry-transport models (CTM) is always limited by computational
resources and ranges from 100-200 km of global scale models, to 25-50 km of continental
scale models, to 1-10 km of regional and local scale models. We push to higher resolution in
hope of better reproducing small scale processes that affect our ability to assess the
environmental and health impacts of emissions. Running simulations at a resolution less
than 50 km is often feasible only using a limited area model, which uses a domain ascribed
to the region of interest. However, even the air quality of a single city is in principle affected
by all the emission sources at global level: we thus account for such long-range transport of
pollutants and oxidants specifying the chemical state of the atmosphere outside the domain
through boundary conditions (BC). BC concentrations are usually taken from typical
profiles or from larger-scale simulations with a procedure called “nesting”. In this chapter,
we focus on the latter technique, exploring in particular the effect of different BC time-
resolutions (monthly to hourly) on the simulation of ozone and particulate matter on a
nested domain at European scale. For the sake of completeness, we point out here that even
very high-resolution models cannot explicitly simulate processes at all possible spatial-
temporal scales and thus a certain degree of parameterization is always required. For further
insights on the “subgrid” issues we refer the reader to the literature (e.g. Galmarini et al.,
2008; Qian et al., 2010; Denby et al., 2011; Paoli et al., 2011).
In addition to boundary conditions, chemistry-transport model simulations also require
initial conditions (IC) for chemical species. The general aspects of the influences of IC and
BC on the simulation may be understood in the simplified framework presented by Liu et al.
(2001). The authors consider an Eulerian box model with one chemical species, whose
evolution of concentration C is regulated by the species continuity equation:
dC C C
 P  LC  BC (1)
dt r
where P and L are the production and loss rates, respectively, CBC is the background
concentration, which represent the boundary condition in this case, and τr is the residence
time into the box. The third term on the right-hand side isolates the source term attributable
to the BC. The analytical solution of the equation is as follows (eq. 4 in Liu et al., 2001):
P r
C (t )  C IC e ( L  1/ r )t 
L r  1
 
1  e ( L  1/ r )t 
C BC
L r  1

1  e ( L  1/ r )t  (2)
where CIC is the initial condition. The influence of CIC exponentially decreases with time, due
both to photochemical loss and deposition (L) and outward-transport (1/τr), thus it vanishes
if a sufficient “spin-up” time is allowed. On the other hand, the importance of local sources
(second term on the r.h.s.) and boundary conditions (third term on the r.h.s.) grow with time
and drive the evolution of C after the “spin-up“ time. The importance of BC is to be
evaluated comparing the relative magnitudes of the local production term Pτr
(photochemical plus emission) against CBC. If the local sources are much larger than CBC, the
influence of BC might be ignored. It is expected that boundary influence decreases during
downwind transport and that it reaches a maximum when the arrival time is short and the
species lifetime is long.
The simple considerations about the influence of IC and BC obtained from the solution in
equation (2) of the box model, was demonstrated to be valid also for full three-dimensional
Eulerian chemistry-transport models. Regarding IC, Berge et al. (2001) found that their
influence a 3-D model decreases more slowly with time with respect to a box model, but still
is reduced to <10% in the planetary boundary layer (PBL) after 3 days in a 400 km × 480 km
domain covering Southern California. However, the same authors pointed out that the
influence of IC might be >10% after 3 days for long lived grouped species (e.g. sum of
reservoir species of ozone) and in the free troposphere. A similar spin-up time of 2 days for
ozone in the PBL was reported by Jiménez et al. (2007) for a 272 km × 272 km covering
North-Eastern Iberian Peninsula. On a larger domain covering Europe, Langmann & Bauer
(2002) found that 5 days are needed by ozone in the PBL to “forget” its initial condition.
More recently, a further sensitivity test at the North American continental scale, confirmed
that a week is the minimum spin-up time recommended for a 3-D simulation of ozone and
particulate matter (Samaali et al., 2009).
Liu et al. (2001) analyzed the influence of BC on their 3-D ozone simulation over California
using the difference of concentrations between a reference run and another with zeroed
boundary concentrations. They found that the percentage of ozone concentration
attributable to BC is mostly determined by the distance from the domain edges, the
influence being inversely proportional to the distance. The influence at a specific location
and time is modulated by the characteristics of the local and upwind sources. During night
the impact of BC on ozone is less than daytime, because of a less active photochemistry. It
was calculated that BC may contribute 30-40% of ozone formation in polluted PBL, while
stratospheric BC dominated ozone values in the free troposphere (Langmann & Bauer, 2002;
Song et al., 2008). Barna & Knipping (2006) pointed out that a different representation of BC
has a great impact on source-apportionment analysis.
While Liu et al. (2001) helped clarifying the general concepts of the influence of BC on
chemistry-transport model simulations, several other studies focused on the impact of
improved boundary conditions on simulations. Many studies found that increasing both
temporal and spatial resolution of BC benefit the ozone (Langmann et al., 2003; Appel et al.,
2007; Song et al., 2008; Szopa et al., 2009), carbon monoxide (Tang et al., 2007; Tombrou et
On the Impact of Time-Resolved Boundary
Conditions on the Simulation of Surface Ozone and PM10 149
al., 2009) and particulate matter simulation (Barna & Knipping, 2006; Borge et al., 2010). On
the continental scale, BC have a significant impact on ozone background levels, while
having much less impact on the variability and peak values (Tang et al., 2007; Szopa et al.,
2009). In the free troposphere, a careful treatment of the variable tropopause is critical for a
real advantage in using improved stratospheric ozone BC on model top (Lam and Fu, 2009;
Makar et al., 2010).
The chapter is organized as follows. We first briefly describe the models used in the study in
section 2. Then we study the impact and time scales of IC and BC on simulated ozone in
section 3.1. In the same section, we analyse the difference among surface ozone simulations
with the use of boundary conditions alternatively with monthly, daily or hourly update rate.
In section 3.2 we analyse the effect of alternative BC on surface PM10, in particular during a
Saharan dust event in July 2005. The scientific questions we shall try to address are:
 How long should be the spin-up time for simulated surface concentrations to be
unaffected by initial conditions?
 How much is the contribution of boundary conditions to local ozone and PM10 levels?
 Is there any improvement in simulations of ozone and PM10 if the boundary conditions
are provided at an higher frequency (up to the model time-step)?
In final section 4 we draw conclusions on these questions.
2. Models description
In this section we give a brief description of chemistry-transport models used in this study.
We use the CHIMERE regional model (Bessagnet et al., 2008) to simulate lower atmosphere
composition over continental Europe and the GEOS-Chem global model (Bey et al., 2001) to
provide CHIMERE with gases and dust boundary conditions.
2.1 CHIMERE regional model

CHIMERE is a regional chemistry-transport model developed by a community of French
institutions primarily designed to produce daily forecasts of ozone, aerosols and other
pollutants and make long-term simulations for emissions control scenarios (Bessagnet et al.,
2008; CHIMERE, 2011). In this study, The model is setup on a 0.5°×0.5° horizontal grid
covering Europe (35°-58°N; 15°W-25°E) and 8 hybrid-sigma vertical layers extending to 500
hPa. Meteorological input is provided by PSU/NCAR MM5 model (Dudhia, 1993) run at
36×36 km2 horizontal resolution and 29 vertical sigma layers extending up to 100 hPa, and
regridded on the 0.5° × 0.5° CHIMERE grid. The model is forced by NCEP analyses using
the grid nudging (grid FDDA) option implemented in MM5.
Anthropogenic emissions are derived from the Co-operative Programme for Monitoring and
Evaluation of the Long-range Transmission of Air pollutants in Europe (EMEP) annual
totals (Vestreng, 2003) for NOx, CO, VOC, SOx, NH3 and primary PM species, while
carbonaceous aerosol emissions are taken from Junker & Liousse (2008). Biogenic emissions
of isoprene and monoterpenes are calculated with the MEGAN model (Guenther et al.,
2006). Dust and sea-salt emissions are also simulated on-line (CHIMERE, 2011).
The gas-phase chemical mechanism MELCHIOR (Latuatti, 1997) includes about 50 species
and 120 reactions. The aerosol phase is simulated with a sectional approach with 8 size bins
from 0.04 to 10 µm of diameter. The main processes governing the production and loss of
main inorganic (sulphate, nitrate, ammonium) and organic secondary species are included.
Boundary conditions are implemented in a classical one-way approach. Species
concentrations at the boundaries are introduced in the simulation through an outer
envelope of model cells having the same resolution of the actual simulation grid. The
boundary concentrations are transported inside the domain by the transport operator, i.e.
the part of the model that simulates advection (Fig. 1). Regardless of the particular scheme
choice (CHIMERE, 2011), the model uses information only from one upwind cells to solve
for advection. Numerical stability is warranted by the adaptive time-step adjusted in order
to have a Courant number always less than 1, e.g. for the zonal direction:
C x  U t x (3)
where Cx is the Courant number for the x-direction, U is the maximum zonal wind speed, Δt
is the time step, and Δx is the grid spacing. By definition, the Courant number measures the
influence that upwind concentrations may have on a given grid-cell in a single time-step in
units of the grid size. If this number is less than one it means that information from only one
upwind cell is needed. In CHIMERE, the time-step is adapted throughout the simulation to
ensure this condition always holds. For some more details on the relationship among
advection schemes and boundary conditions the reader is referred to the nice discussion
given by Wang et al. (2004).
Fig. 1. Schematic of boundary conditions (BC) of a regional chemistry-transport model. The

domain of simulation is denoted by the black cube, the 2-D map at the bottom is a sample of
an output surface ozone field. Boundary concentrations of gases and aerosol species are
passed to the model through an envelope of cells that wraps the domain around its edges.
The transport operator of the model will use those cells for advection calculations and it will
transport BC information into the domain.
In the default configuration, the boundary conditions for CHIMERE regional simulations
are taken from monthly mean simulations of the global model LMDz-INCA (Hauglustaine
et al., 2004) for species listed in Tab. 1. For aerosol species, size-resolved mass concentrations
of global model are redistributed onto regional model size bins, using a simple linear
interpolation in logarithmic bin diameters space. In Fig. 2 we show a sample of the monthly
static ozone boundary conditions for the month of June.
CHIMERE species Species long name GEOS-Chem species

Gases
O3 Ozone O3
NO2 Nitrogen dioxide NO2
HNO3 Nitric acid HNO3
PAN Peroxyacetylnitrate PAN
H2O2 Hydrogen peroxide H2O2
CO Carbon monoxide CO
CH4 Methane -
HCHO Formaldehyde CH2O
C2H6 Ethane C2H6
NC4H10 Butane and higher alkanes ALK4
C2H4 Ethene -
C3H6 Propene PRPE
OXYL Xylenes -
Aerosol
H2SO4 Sulfates -
OC Organic Carbon -
BC Black Carbon -
DUST Dust DST1-4
SS Sea Salts -
Table 1. List of species for which boundary conditions are provided to CHIMERE regional
chemistry-transport model. In the third column, the GEOS-Chem global model species used
in this study to test sensitivity of CHIMERE to different boundary conditions.
Fig. 2. Sample default ozone boundary conditions of CHIMERE model for the month of
June. Ozone concentrations are taken from the monthly average of a simulation of the
LMDz-INCA global model (Hauglustaine et al., 2004) and interpolated upon the CHIMERE
horizontal and vertical grids. The panels show the resulting concentrations at the sides and
top lid of the domain, as if the “box” of Fig. 1 has been open on a table.
2.2 GEOS-Chem global model

GEOS-Chem is a global chemistry model developed by a large international users
community, originally stemming from the Harvard’s Atmospheric Chemistry Modelling
group (Bey et al., 2001; GEOS-Chem, 2011). The meteorological input is provided by the
Goddard Earth Observing System (GEOS) of the NASA Global Modeling and Assimilation
Office (GMAO). Mostly relevant to this study is the emission module developed by Fairlie et
al. (2007), used here to include a more detailed contribution of Saharan dust emissions into
the simulations. Desert dust emissions are lowered by a factor of three according to the
study of Generoso et al. (2008).
GEOS-Chem simulations will be used in this study to produce alternative boundary
conditions for the CHIMERE regional model at different time scales, from hourly to
monthly.
3. Results
3.1 Ozone
3.1.1 Time-scales and impact of IC and BC
In order to study the effect of initial and boundary conditions on the CHIMERE ozone
simulation at the European scale we use the simulations listed in Tab. 2. Basically, we
alternatively zero IC and BC to isolate their effect through the difference with a reference
simulation (Stein & Alpert, 1993). We choose a one month in summer (June 2005) in order to
allow enough time to study the effect of IC and to ensure an active ozone photochemistry.
Simulation Label Description

CTRL Control simulation (reference)
NIC No Initial Conditions (IC = 0)
NBC No Boundary Conditions (BC = 0)
Table 2. List of simulations performed to study the effect of initial and boundary conditions
on ozone.
The reference ozone simulation of CHIMERE is quickly evaluated against ground based
measurements available from the EMEP network (www.emep.int). Let Obsij and Modij be
the observed and modeled values at time i and station j, respectively. Let N be the number
of stations, and Nobs j the number of observations at station j.
 Pearson’s Correlation (r) and coefficient of determination (R2):
j
1 N 1 Nobs
r  j  Zij ( Mod )  Zij (Obs)
N j  1 Nobs  1 i  1
(4)
X X
Z( X ) 
X
where X is a generic vector and Z(X) is its standard score, also defined above. R2 is defined
as the square of r and denotes the fraction of variability of observations explained by the
model.
 Mean Bias (MB):
1 N 1 Nobs j 
MB  
N j  1  Nobs j
 Modij  Obsij 

(5)
i 1 
 Mean Normalized Bias Error (MNBE):
1 N 1 Nobs j
Modij  Obsij 
MNBE       100 (6)
N j  1  Nobs j i 1 Obsij 

 Mean Normalized Gross Error (MNGE):
 Nobs j Modij  Obsij 

1 N 1   100
MNGE  
N j  1  Nobs j
 Obsij 
(7)
i 1
 
Results for current simulation are presented in Tab. 3 and Fig. 3. The model captures the
central part of the observed distribution, but overestimates its low end and underestimates
the upper end. This is a quite typical behaviour of regional chemistry-transport models (e.g.
Appel et al., 2007). The average MNBE and MNGE for ozone hourly timeseries is slightly
above the quality thresholds recommended by EPA (15% and 35% respectively), but the
indices are well within the suggested limits for the daily maxima timeseries.
Observed Modelled
Variable MB MNBE MNGE r
mean mean
Units µg/m3 µg/m3 µg/m3 % %
O3 hourly 78.6 82.7 4.0 22.5 36.5 0.53
O3 daily max 103.4 98.7 -4.7 -0.4 15.8 0.69
Table 3. Comparison of observed and modelled ozone timeseries at EMEP monitoring
stations. Values are averaged over all times and stations available for June 2005.
Fig. 3. Comparison of hourly ozone observed and modelled at EMEP stations. Left panel:
scatter plot of 5th, 25th, 50th, 75th and 95th percentiles at all available stations. Right panel:
boxplot of statistical indices shown in Tab. 3. Horizontal reference lines denote the quality
level suggested by EPA (1991).
The impact of IC on ozone is studied through the difference between CTRL and NIC runs.
We arbitrarily define the influence of ΨIC as the relative difference between CTRL and NIC
simulations and the spin-up time τIC as the time needed to reduce ΨIC to less than 1%. In Fig.
4 we show the average ozone timeseries as measured and modelled at EMEP stations. After
about 4 days of simulations the average ΨIC becomes negligible. According to our definition
the average τIC is 3.9 days, but ranges from 0.5 to 8.1 days. In Fig. 5 we may appreciate the
spatial distribution of τIC. We find a clear positive gradient from the North-West to the
South-East of the domain. The reason may be found in the ozone distribution itself. In Fig. 6
we show the average ozone concentrations simulated by the model and we note that τIC
gradients follows closely ozone gradients: the model just takes more time to build up ozone
from the zero concentration starting point when the ozone level to be reached is higher.
While this may pose questions on the method we used to estimate the “lifetime” of IC, this
test is useful to verify that the model is essentially able to completely forget a whatever
“wrong” initial condition after about 9 days of run.
Fig. 4. Simulated influence of initial (IC) and boundary conditions (BC) in CHIMERE ozone
at the European scale. The average timeseries at EMEP monitoring stations are shown. For
explanation of simulation labels please refer to Tab. 2. The definition of ΨIC, ΨBC, τIC, and τBC
is given in main text.
The influence of boundary conditions is studied in an analogous way. We define ΨBC as the
difference between CTRL and NBC runs and the time of arrival of BC τBC as the first time
when ΨBC is larger than 1%. In Fig. 4 we see that the behaviour of ΨBC mirrors that of ΨIC.
As expected, the influence of BC grows as that of IC decreases. According to our definition,
the average τBC is 16 hours, and ranges from 1 to 29 hours. As shown in Fig. 5, shortest times
are found near the domain edges, while longest times are found in the interior of the
domain. The variability inside the domain is attributable to the specific meteorological
situations, since the time of arrival of BC at a specific location is determined by the winds
encountered along the travel from the edges.
Until the spin-up time (τIC) is elapsed, ΨBC continues to ramp until a plateau is reached: the
model is “warmed-up”, and the ozone production at certain place is determined by the
equilibrium between the sources inside the domain and the boundary conditions (eq. 2). For
any time and location, ΨBC quantifies the relative influence of BC with respect to local
production. The periods with higher values of ΨBC in timeseries of Fig. 4, thus indicate
periods of less intense photochemical activity.
Fig. 5. Spatial distribution of the influence time of IC and BC on ozone.
Fig. 6. Average surface ozone simulated with CHIMERE in June 2005.
The spatial distribution of the average ΨBC at the surface calculated from 10 to 30 June 2005
with CHIMERE is shown in Fig. 7. As also noted above, we find that the maximum
influence of BC is around the borders, and it is striking to see that it is higher than 80-90%
even in the polluted North-Western Europe. ΨBC reaches a minimum of less than 50% over
Po Valley where the local production is invigorated by the elevated precursors emissions
and very active photochemistry. This result imply that an error in BC may be effectively
propagated into the simulation domain. For example, an error of 1 in the BC becomes 0.7 in
a place where ΨBC = 0.7.
Liu et al. (2001) found that 3-D model results are consistent with analytical solution of a
simple one-dimensional model, where the influence of BC may be written as:
 BC  C BC e Lx /uSx /u (t ) (8)

where x is the distance to boundary and u is the wind speed, so that x/u is the time of BC
arrival. S is a step function which is 0 for t < x/u (before BC arrival) and 1 for t ≥ x/u (after BC
arrival). If the ozone lifetime τ = 1/L is known, equation (8) can be applied directly to
estimate ΨBC. Since the lifetime is generally unknown, but the BC arrival time τBC can be
easily estimated, equation (8) can be inverted to roughly estimate the local averaged ozone
lifetime. Inserting our definition of relative influence of BC on ozone ΨBC we obtain:
   BC log  BC  (9)
The result is shown in Fig. 7. Ozone lifetime estimated with this simple method ranges 1-3
days in the continental boundary layer and is longer than 5 days over the ocean, which is
quite consistent with our expectations.
Fig. 7. Left: average influence of BC on ozone simulated in June 2005 (excluding first 9 days
of spin-up). Right: ozone lifetime estimated with eq. 9.
3.1.2 Effect of alternative BC on surface ozone

We analyse the effect of different BC on simulated surface ozone using four simulations as
listed in Tab. 4. We choose a longer summer period of two months, June and July 2005, to
have a more robust statistics. Consistently with what found in previous section, we spin-up
the model for 10 days.
Simulation Label Description

CTRL Control simulation (w/ reference LMDz-INCA BC)
BCGM BC from GEOS-Chem monthly output
BCGD BC from GEOS-Chem daily output
BCGH BC from GEOS-Chem hourly output
Table 4. List of simulations performed to study the effect of alternative boundary conditions
on ozone.
In Fig. 8 we compare the timeseries of ozone BC in the simulations averaged over the western
border (leftmost rectangle in Fig. 2). The GEOS-Chem model simulates lower (higher) ozone
values with respect to LMDz-INCA in June (July). One important reason, apart the many
differences in models’ formulation, is that the latter simulation is an average over five years of
run, while GEOS-Chem simulates the “actual” (i.e. assimilated) meteorology of the CHIMERE
simulation. The introduction of more detailed in time BC introduces much more variability,
with differences up to ±30% with respect to the fixed monthly BC.
Fig. 8. Timeseries of the ozone boundary condition averaged over the west side of the
European domain (left side of the box in Fig. 2). For explanation of the simulation labels
please refer to Tab. 4.
In Tab. 5 we report the statistical summary, i.e. the average indices over all available EMEP
stations, of the four simulations. The comparison with reference simulation over the two-
month period is consistent with the one month simulation without spin-up (Tab. 3). The
introduction of GEOS-Chem BC benefits the high CHIMERE model bias, reducing both the
normalized bias and the gross error, probably because they are more specific of the
simulation period than the LMDz-INCA climatology. The introduction of time resolution
into the BC produces further reduction of model error and also significantly increases the
correlation with the measurements.
Simulation Observed mean Modelled mean MB MNBE MNGE r

CTRL 77.6 81.5 3.9 28.0 42.3 0.55
BCGM 77.6 77.2 -0.3 20.8 38.9 0.56
BCGD 77.6 75.4 -2.2 16.9 36.8 0.59
BCGH 77.6 75.3 -2.6 13.1 33.4 0.58
Table 5. Statistical indices of sensitivity simulations against EMEP hourly ozone
measurements for June-July 2005. Values are averaged over all times and stations available.
In Fig. 9 we compare the simulated ozone with measurements at two selected EMEP
stations, one near the border and very sensitive to BC (Mace Head, Ireland), the other about
the centre of the domain and much less sensitive to BC (Heidenreichstein, Austria). For the
Irish site we note interesting differences among the runs. During the first week of
simulation, the monthly GEOS-Chem alternative BC enhances model underestimation with
respect to reference, while the time-resolved GEOS-Chem BC slightly alleviates the bias with
respect to reference. In the days around June 17th the time-resolved BC allow the model to
capture a low ozone episode, but the subsequent week GEOS-Chem values are even too
low. Also in other periods, the time-resolved BC allow the model to go closer to
observations (July 7-10, 20-23). The correlation with measurements goes from 0.38 of the
CTRL run, to 0.29 of the BCGM, to 0.44 of BCGD and BCGH. The gross error is reduced
from 26% to 22% from CTRL to BCGD and BCGH runs. We also point out that the difference
of the impact of hourly and daily BC is minimal.
The effect of alternative BC on the Austrian site, as expected is much less evident. However,
the statistical indices of comparison with observation constantly get better as we introduce
more resolution in time. The correlation increases from 0.56 to 0.61, the bias decreases from
23% to 14%, and the gross error decreases from 39% to 35%. Again, we note that using
hourly or daily resolved BC does not significantly impact the simulation.
These results point out that the time resolution of BC may greatly affect the simulation, but
an higher resolution may episodically worsen model skills. The big step is between monthly
and daily resolved BC, while going down to hourly resolved BC, at the expense of more disk
space and pre-processing time, does not yield further significant improvements..
Fig. 9. Ozone timeseries in June-July 2005 as observed at two EMEP stations and simulated
with CHIMERE with four sensitivity simulations (Tab. 4). Left: Mace Head station, close to
the Western border of the domain and sensitive to BC (ΨBC ~0.95). Right: Heidenreichstein
station, by the centre of the domain and less sensitive to BC (ΨBC ~0.63).
3.2 Aerosol
3.2.1 Effect of alternative BC on surface PM10
Similarly to ozone, we study the effect of alternative BC on simulated surface PM10 using
the same simulations listed in Tab. 4. For this study, we choose to introduce alternative BC
into CHIMERE only for dust, because the inflow of Saharan dust into the European domain
is expected to contribute much more to the PM10 simulation than the other species (Curci et
al., 2008; Curci & Beekmann, 2007). While transboundary pollution from anthropogenic
sources is expected to impact background levels of PM (Park et al., 2003; 2004), Saharan dust
may episodically yield to the exceedance of the PM10 limit for the protection of human
health of 50 µg/m3 (Gobbi et al., 2007; Koçak et al., 2007; Perrino et al., 2009). It is estimated
that in Italy the subtraction of natural dust to PM10 may yield to a reduction from 5% to
50% of the number of threshold exceedances depending on the meteorology and the station
type (Pederzoli et al., 2010).
In Fig. 10 we compare the boundary conditions to CHIMERE from the Southern border in
the four simulations. GEOS-Chem monthly mean dust values are higher than LMDz-INCA,
and similarly to ozone the time-resolved BC have a much higher variability, with differences
of ±50% and one episode with hourly values three times higher than monthly values.
Fig. 10. Timeseries of the dust boundary condition summed over all CHIMERE size-bins and
averaged over the south side of the European domain (bottom side of the box in Fig. 2). For
explanation of the simulation labels please refer to Tab. 4.
In Tab. 6 we report the average statistical indices over all available EMEP stations of the four
simulations. The higher dust values in GEOS-Chem BC drastically reduce the model bias
from -40% to -7%, but the “noise” introduced by the large dust variability gradually
degrades the correlation and the gross error as we increase the BC time resolution. This fact
points out how tricky is the simulation of the Saharan dust contribution on European PM10
levels.
Simulation Observed mean Modelled mean MB MNBE MNGE r

CTRL 17.5 9.0 -8.5 -41.9 47.4 0.63
BCGM 17.5 15.1 -2.4 -8.6 42.8 0.53
BCGD 17.5 16.0 -1.5 -6.9 50.2 0.50
BCGH 17.5 16.0 -1.5 -7.0 50.3 0.50
Table 6. Statistical indices of sensitivity simulations against EMEP daily PM10
measurements for June-July 2005. Values are averaged over all times and stations available.
In Fig. 11 we compare the PM10 timeseries at two EMEP stations, one near the South-
Western border of the domain and more affected by Saharan dust (Barcarrota, Spain), and
another to the North (Schauinsland, Germany). At the Spanish site, higher dust values in
GEOS-Chem BC reduces the mean bias from -14 µg/m3 to less than 1 µg/m3, but the
correlation decreases from 0.77 to 0.56 in CTRL and BCGH runs, respectively. The better
resolved BC allow the model to better capture the observed PM10 variability by the end of
the simulated period, but they also induce episodic overshoots during the first period of
simulation that are completely unrealistic. Very similar features may be also noted at the
German site, indicating that the importance of dust BC are not limited to the Southern part
of the European domain.
Fig. 11. PM10 timeseries in June-July 2005 as observed at two EMEP stations and simulated
with CHIMERE with four sensitivity simulations (Tab. 4). Left: Barcarrota station, close to
the South-Western border of the domain and strongly impacted by Saharan dust. Right:
Schauinsland station, by the centre of the domain.
We now focus on the dust episode of 27-29 July 2005. In Fig. 12, the daily AOD observed by
MODIS/Aqua between 24-29 July clearly tracks a dust cloud swapping Southern Europe
from West to East. In Fig. 13 we show the same episode as recorded at ground level by the
EMEP network and simulated by CHIMERE. The introduction of time-resolved BC helps the
model in better reproducing both timing and magnitude of the event. Unfortunately, as we
have seen in previous timeseries, this is not a general conclusions and further work is
certainly warranted on the dust BC issue.
Fig. 12. The Saharan dust episode of July 2005 as seen from space through daily Aerosol
Optical Depth (AOD) observations by MODIS/Terra.
Fig. 13. The dust episode observed at EMEP stations and simulated with CHIMERE using
different time-resolutions for the boundary conditions.
3.2.2 Eye-witness of a Saharan dust event over Central Italy

In a sort of “divine intervention”, Sahara desert decided to produce one of its episodes
while writing this chapter, during the first days of September 2011. The event was eye-
witnessed by the author, and by its fellow citizens of L’Aquila in Central Italy, during the
days 2-4. A large “bubble” of dust travelled over the South-Western Mediterranean and it
was captured by the MODIS/Terra satellite instrument, as depicted in Fig. 14, which
estimated a maximum optical thickness of more than 1.5. In Fig. 15 we show the striking
effect on atmospheric visibility as observed from the ground: the mountain peak by the
centre of the pictures, having a distance of about 25 km from the shot location, was almost
obscured by the dust layer. The latter did actually hit the ground, as witnessed by the
PM10 monitoring station in L’Aquila valley, which exceeded 50 µg/m3 on September 3rd
(Fig. 16), and also by the dust deposited over surfaces at the ground (e.g. the author’s car
depicted in Fig. 15).
Sep 1st Sep 2nd Sep 3rd Sep 4th

Fig. 14. The Saharan dust event over Italy in September 2011 as seen from MODIS/Terra
AOD observations.
Fig. 15. Left: view of L’Aquila valley in a clean summer day (10/09/2011); the mountain
peak in the centre is at a distance of about 25 km. Middle: same view during a Saharan dust
event (03/09/2011). Right: dust deposited over ground surfaces during the night.
Fig. 16. PM10 concentration measured in L’Aquila at the ground monitoring station across
the September 2011 Saharan dust event.
Interestingly, Fig. 17 shows that the arrival of the dust layer was qualitatively predicted by
the ForeChem experimental chemical weather forecast system operating at University of
L’Aquila (Curci, 2010), consisting of MM5/CHIMERE models automatically running, which
is fed with the default monthly boundary conditions from LMDz-INCA global model (see
Sec. 2.1).
L’Aquila
Fig. 17. Saharan dust event over Italy in September 2011 as forecasted with MM5/CHIMERE
(ForeChem experimental chemical weather forecast operational at University of L’Aquila,
http://pumpkin.aquila.infn.it/forechem/). Images show the fraction of PM10 at the ground
due to dust from outside the domain, which is a nest within a European scale domain.
Boundary conditions to the latter are provided with monthly mean fields from the LMDz-
INCA global model.
4. Conclusion
The effect of initial (IC) and boundary conditions (BC) on the simulation of surface ozone
and PM10 over the continental scale European domain is evaluated with several sensitivity
tests of the CHIMERE chemistry-transport model.
Zeroing alternatively IC and BC in the model, and comparing the results with a reference
run, we estimate an optimal model spin-up time of 9 days for the domain used in this study
(35°-58°N; 15°W-25°E; 79 x 47 cells at 0.5° horizontal resolution). The BC have a significant
impact on simulated ozone, especially in a belt of about 1000-2000 km around the domain
borders. There, BC dominates ozone variability, while in the interior of the domain they
have a weight similar to the local photochemical production. Through the BC test, the
surface ozone lifetime is estimated to be 1-3 days over the continent and longer than 5 days
over the oceans.
The impact of different time-resolution of BC is studied feeding the CHIMERE model with
GEOS-Chem global model simulations. With respect to the reference BC, provided by five
years monthly mean LMDz-INCA model simulations, the GEOS-Chem model has generally
lower ozone and enhanced dust values during the period of simulation (June-July 2005). The
positive ozone bias with respect to EMEP measurements is alleviated by GEOS-Chem BC,
and also the introduction of BC better resoled in time benefit model skills. The average
correlation increases from 0.55 to 0.59 and the normalized bias decreases from 28% to 17%.
The large improvement is noticed when passing from monthly to daily BC, while hourly BC
do not produce further improvements. We noticed, however, that time-resolved BC may
episodically worsen model skills.
The introduction of different aerosol BC is tested focusing on dust, because of the prominent
role that Saharan dust events play on the PM10 levels especially in Southern Europe. GEOS-
Chem predicts higher dust concentrations with respect to LMDz-INCA, and its use as BC
alleviates the CHIMERE low bias with respect to EMEP measurements. However, the
agreement with observations get better during the events by the end of the simulated period
(July 2005), but worsen at the beginning (June 2005). In particular, GEOS-Chem has a tendency
to episodically overshooting dust at unrealistic levels. The introduction of time-resolved dust
BC may allow the model to better reproducing both time and magnitude of Saharan events,
but this is not a general conclusion with models’ set-up used in this study. Further work on
dust BC for European scale models is certainly needed in the future, possibly combining
satellite observations with ground measurements of the aerosol composition and size-
distribution that may better constrain the dust contribution to particulate matter.
5. Acknowledgment
The author was supported by the Italian Space Agency (ASI) in the frame of QUITSAT and
PRIMES projects.
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8
Recovery and Reuse of SO2 from

Thermal Power Plant Emission
Arun Kumar Sharma, Shveta Acharya,
Rashmi Sharma and Meenakshi Saxena
Department of Chemistry,
S.D. Govt. College, Beawar, Rajasthan
India
1. Introduction
Thermal power plants are major sources of air pollutants. Three major air pollutants emitted
from thermal power plant are Suspended Particulate Matter (SPM), Sulphur di oxide – (SO2),
Sulphur tri oxide (SO3), and (NO2, NO3). The amount of pollutants emitted from any power
plant depends upon the type of the fuel used, burning method and type of control equipment.
These pollutants finally found in ambient air. Coal is re-emerging as a the dominant fuel for
power generation in various power plants. 1 Various coal such as petcock, lignite, bituminous
etc. used in power plants in which % S have 6.0 %,4.0 % and 3.8 % respectively. The common
elements in fuel are Carbon, which is principle combustible constitute of all fossils. Oxygen,
nitrogen, hydrogen, and Sulphur (S) are not combustible elements. Sulphur in coal cannot be
destroyed it can only be converted to one form to another During the combustion process ,
Sulphur react with oxygen and formed SO2 and SO3.
SO2 is a major constituent in air pollution.2 and affects the environment by no. of ways like
acid rain, corrosions and severe damage to the health. SO2 causes a wide variety of health
and environmental impacts because of the way it reacts with other substances in the air.
Particularly sensitive groups include people with asthma who are active outdoors and
children, the elderly, and people with heart or lung disease. Intensity of SO2 emission can be
observed by following example. “ A typical 6 MW power generation unit using furnace oil
containing 2 % Sulphur will emit 388 tons of SO2 per year, based upon 320 working days or
A 22.5 MW power generation unit will emit 1690 tons of SO2 per year by using Pet Coke.”3-4
2. Review of literature
The acid rain problem is mainly attributed to anthropogenic sulphur dioxide and, to a lesser
extent, nitrogen oxide emissions. Sulphur dioxide can be directly removed from the
atmosphere through dry or wet deposition. The main sink of atmospheric SO2, however, is
the oxidation to SO42− in the gas phase and in the liquid phase of clouds, fog and rain. These
processes are, besides the oxidation of nitrogen compounds, the major source of acidity in
acid rain or acid fog. The relative importance of different pathways for atmospheric
oxidation of sulphur dioxide can vary under different conditions such as relative humidity,
intensity of solar radiations, temperature and degree of air pollution. Under favourable
conditions the oxidation of sulphur dioxide can occur in the atmospheric aqueous phase at
significantly faster rates than in the gas phase. It is believed that, on a global scale, more
than 70% of the global oxidation of SO2 to SO42− occurs within cloud droplets (Langner and
Rodhe 1991).The oxidation of sulphur dioxide has been one of the most frequently studied
reactions in aqueous atmospheric droplets. Three reaction pathways are considered to be
dominantly responsible for oxidation of SO2 in atmospheric water droplets. These are the
oxidation of dissolved SO2 by H2O2, O3 and O2 in the presence of transition metal ions as
catalysts (Seinfeld and Pandis 1998; Warneck et al. 1996). In acid solutions the major oxidant
is H2O2, whereas the role of O3 becomes more important above pH 6 (Calvert et al. 1985;
Ibusuki et al. 1990; Seinfeld and Pandis 1998). Oxidation by molecular oxygen may also be
important if cloud water contains sufficient amount of transition metal ions (e.g., Fe, Mn) for
autocatalytic reactions to occur. This process may play an important role in highly
industrialized areas where various transition metals are present in atmospheric water in
relatively high concentrations (Seigneur and Saxena 1984). Catalytic autoxidation of S(IV) is
the subject of a number of studies (e.g. Penkett et al.1979; Pasiuk-Bronikowska and
Bronikowski 1981; Martin 1984; Martin and Hill 1987; Ibusuki and Takeuchi 1987; Kraft and
van Eldik 1989; Grgić et al. 1991, 1992; Berglund and Elding 1995; Novič et al. 1996; Turšič et
al. 2003). It is claimed that at pH 4, transition metal catalysed pathways could account for up
to half of the oxidation of S(IV) to S(VI) (Graedel et al. 1985). According to present
knowledge, iron(II/III) and manganese (II/III) are the most important catalysts in
atmospheric droplets (Coichev and van Eldik 1994;Brandt and van Eldik 1995; Seinfeld and
Pandis 1998). These metals are the only efficient catalysts at low pH. In addition, both iron
and manganese are common constituents of tropospheric aerosols and water droplets even
in remote areas due to their generation from erosion of the earth’s crust. Other transition
metals such as Cu(II), Co(III), Sc(III), Ti(III), V(III) and Cr(III), are also catalysts, but with a
substantially lower effect on the reaction rate (Ibusuki et al. 1990; Grgić et al. 1991; Sedlak
and Hoigné 1993). The catalytic oxidation of S(IV) is a free radical chain reaction. Its
mechanism and kinetics are so complex and sensitive to the conditions under which the
process occurs that even a minor change in experimental conditions can cause a change of
the dominant path of the reaction course, and thus lead to diverse results. Despite numerous
studies of the metal catalysed S(IV) oxidation there still exist serious discrepancies in rate
expressions, rate constants, pH dependencies, activation energies, reaction mechanisms etc.
Recent studies show that the sulphur(IV) oxidation in atmospheric water droplets can be
affected by other reactions. In particular, organic chemistry may be especially important.
Organic compounds may dissolve into water droplets and react with sulphoxy radicals and
transition metal ions, and thus alter the rate of catalytic S(IV) oxidation (Martin et al. 1991;
Pasiuk-Bronikowska et al. 1997; Grgić et al. 1998; Pasiuk-Bronikowska et al. 2003a,b; Ziajka
and Pasiuk-Bronikowska 2003, 2005).Recently, the inhibiting effect of such organic ligands
as oxalate, acetate and formate in the iron-catalyzed autoxidation of sulphur(IV) oxides in
atmospheric water droplets has been suggested. Grgić et al. (1998, 1999) and Wolf et al.
(2000) reported the strong inhibiting effect of oxalate on the Fe-catalysed S(IV) oxidation in
aqueous acidic solution. Acetate and formate also inhibit the reaction, but to a much lesser
extent than oxalate (Grgićet al. 1998). Very recently, the influence of some low weight mono-
(formic, acetic, glycolic,lactic) and di-carboxylic acids (oxalic, malic, malonic) on the Mn(II)-
Recovery and Reuse of SO2 from Thermal Power Plant Emission 171
catalysed S(IV) oxidation has also been investigated (Grgić et al. 2002; Podkrajšek et al. 2006).
It has been established that mono-carboxylic acids inhibit the oxidation, with the strongest
influence 2 J Atmos Chem (2008) 60:1–17 found for formic acid. The lowest inhibition was
caused by acetic acid. From among dicarboxylic acids, oxalic acid slows down the S(IV)
oxidation, although to a lesser extent than mono-carboxylic acids, while malic and
malonic acids have practically no influence. The effect of organic compounds in
atmospheric water on the transition metal-catalysed oxidation of sulphur(IV) is not fully
known yet and more work in this area is needed to understand these processes better. The
purpose of the present study was to study the kinetics of the Mn(II)-catalysed S(IV)
oxidation and to determine the inhibiting effect of acetic acid on this process under
different experimental conditions representative for heavily polluted areas. The
experiments were carried out at Mn(II) and CH3COOH concentrations in the range 10−6–
10−5 and 10−6–10−4 mol/dm3, respectively, and at initial pH of the solution in the range
3.5–5.0; initial concentrations of S(IV) were around 10−3 mol/dm3. S(IV) liquid-phase
concentration of 1×10−3 mol/dm3 corresponds to 0.6 ppm SO2 in the gas phase over a
solution of pH=5, or 7 ppm over a solution of pH=4, or 20 ppm over a solution of pH=3.5.
Such high SO2 gas-phase concentrations are found in heavily polluted areas as well as in
power plant and volcanic plumes. In highly polluted locations, for example in large urban
areas where coal is used for domestic heating purposes, or for poorly controlled
combustion in industrial installations, SO 2 concentrations are rather high and vary
between 0.1 and 0.5 ppm, and sometimes they are even higher (Ferrari and Salisbury
1999). High sulphur dioxide concentrations are being recorded in some of the megacities
in developing countries where burning of coal is the main source of energy. The greatest
problems related to sulfur dioxide occur in Asia (mainly in Chinese cities and some
Middle-East cities such as Teheran, Tbilisi and Istanbul)(Baldasano et al. 2003). In Asia
there are cities [e.g. Guiyang (424 μg/m3), Chongquing (340 μg/m3)] with average annual
values of more than six times the WHO guideline value (Baldasano et al. 2003). Also in
Africa some of the urban areas, and especially industrial areas, experience high
concentrations of sulphur dioxide (WHO 2006). Weekly average concentrations in
Zambia’s copper belt (Nkana, Mufulira and Luanshya) were found to range from 167 to
672 μg/m3, the highest weekly average being 1,400 μg/m3. Studies undertaken on the
impact of the Selebi Phikwe copper smelter in Botswana show that there are large areas
experiencing concentrations above 100 μg/m3. Short term measurement indicated 1-h
average concentrations of more than 1,000 μg/m3 (WHO 2006). Also some of the heavily
industrialized areas in Europe may still be experiencing high levels of sulphur dioxide. In
some cities in the north western corner of the Russian Federation, close to large primary
smelters, daily concentrations of sulphur dioxide exceed 1,000 μg/m3 (WHO 2006). From
the point of view of atmospheric chemistry, especially fast chemical reactions,
concentrations averaged for shorter periods e.g., for 1 h or even for several minutes, are
more relevant. These concentrations are closer to actual concentrations at which fast
reactions proceed in the atmosphere. Concentrations averaged for shorter periods are
considerably higher than those averaged for longer periods. Peak concentrations over
shorter averaging periods may still be very high, both in cities with a high use of coal for
domestic heating and when plumes of effluent from power station chimneys fall to the
ground (fumigation episodes). Transient peak concentrations of several thousand
Snap. 1. Photographs showing air pollution by industries along with molecular structure
of SO2.
Snap. 2. Photographs showing Acid rain effect of SO2.
Snap. 3. Photographs showing Acid rain effect of SO2 on monuments of India.

microgram per cubic meter are not uncommon (WHO 2000). Concentrations of SO2 can
reach tens of parts per million in power plant (Jaakkola et al.1998) and volcanic plumes
(Gauthier and Le Cloarec 1998; Shinohara 2005). Under stable atmospheric conditions, SO2
may be transported relatively great distances at appreciable concentrations. In very stable
power station plumes SO2 concentrations may be greater than 1.0 ppm over 70 km from
their source (Stephens and McCaldin 1971). J Atmos Chem (2008) 60:1–17 3
Concentrations of Mn(II) and acetic acid in solutions used in our experiments correspond
to those found in rain-, cloud- and fogwater in heavily polluted urban and industrialized
areas. Manganese is one of the most abundant transition metals in atmospheric liquid
phases (wet aerosol, cloud, fog, rain). The only source of these metals in the atmospheric
aqueous phase is the dissolution of aerosol particles incorporated in water droplets. The
common particles containing trace metals are emitted from both anthropogenic (fossil fuel
combustion, industrial processes) and natural (windblown dust, weathering, volcanoes)
sources. Particles from anthropogenic sources contribute significantly to metal
distribution in atmospheric droplets due to their high metal content and solubility. In
consequence, trace metal concentrations in atmospheric waters are higher in urban and
industrial areas (Colin et al. 1990). In atmospheric waters, manganese is mainly found as
Mn(II), which is more soluble than manganese(III) (Deutsch et al. 1997). Mn(II) exhibit a
large variation in solubility dependent on the nature of the particles, but this solubility is
pH-independent (Millet et al.1995). Concentrations of Mn in rainwater are typically lower
than those observed in fog and cloud water samples. In urban and industrial areas
manganese concentrations range from 10−7 to 10−6 mol/dm3 in rain (Deutsch et al. 1997;
Patel et al. 2001), and from 10−6 to 10−5 mol/dm3 in fog- and cloudwater (Millet et al.
1995; Brandt and van Eldik 1995) Acetic acid is one of the most abundant carboxylic acids
in the troposphere and it is found in rain, clouds, fogs, and aerosol particles from remote
to highly polluted urban areas. The atmospheric sources of carboxylic acids are numerous
and they comprise: primary biogenic emissions, primary anthropogenic emissions and
photochemical transformations of precursors in aqueous, gaseous, and particulate phases
(Chebbi and Carlier 1996). Direct anthropogenic emissions of carboxylic acids (e.g. from
incomplete combustion of fossil fuels, wood and other biomass material) and/or photo-
oxidation of anthropogenic organic compounds are the main sources of these compounds
in urban and industrial environments (Chebbi and Carlier 1996; Kawamura et al. 1996).
Concentrations of organic acids are generally elevated in the urban as compared with the
nonurban atmosphere (Meng and Seinfeld 1995). In urban sites concentrations of acetic
acid range from 10−7 to 10−5 mol/dm3 in rain (Chebbi and Carlier 1996; Kawamura et al.
1996), and from 10−6 to 10−4 mol/dm3 in cloud and fogwater (Meng and Seinfeld 1995;
Brandt and van Eldik 1995; Millet et al. 1996; Raja et al.
3. Basics and scopes of the work – Flue Gas Desulphurization (FGD)

Flue gas desulphurization (FGD) is the current state-of-the art technology used for removing
sulphur dioxide from the exhaust flue gases in power plants. SO2 is an acid gas and thus the
typical sorbent slurries or other materials used to remove the SO2 from the flue gases are
alkaline. The reaction taking place in wet scrubbing using Ca (OH) 2 and NaOH slurry
produces CaSO3 and Na2SO3 and can be expressed as:
Ca(OH)2 (solid) + SO2 (gas) CaSO3 (solid) + H2O (liquid)
2NaOH (solid) + SO2 (gas) Na2SO3 (solid) + H2O (Liquid)
Some FGD systems go a step further and oxidize the CaSO3 and Na2SO3 to produce
marketable CaSO4 · 2H2O (gypsum) and Na2SO4 (Sodium Sulphate): 5-6
CaSO3 (solid) + ½O2 (gas) + 2H2O (liquid) CaSO4 · 2H2O (solid)
Na2SO3 (solid) + ½ O2 (gas) Na2SO4 (solid)
3.1 Mechanism
When sulfur dioxide (SO2) in the flue gas contacts scrubber slurries, the pollutant transfers
from the gas to the liquid phase, where the following equilibrium reactions are
fundamentally representative of the transfer process.
SO2 +H2O H2SO3 H+ + HSO3- H+ + SO3-2 (1)

when lime hydrated powder or caustic flakes introduced to water will raise the pH
according to the following mechanism.
Ca(OH)2 Ca +2 + 2 OH -1 (2)
NaOH Na+1 + OH -1.. (2.1)

However, Ca(OH)2 is only slightly soluble in water, so this reaction is minor in and of
itself. In the presence of acid, calcium hydroxide reacts much more vigorously and it is the
acid generated by absorption of SO2 into the liquid that drives the lime dissolution
process.
Ca(OH)2 + 2H+ Ca+2 + 2 H2O (3)
NaOH + H+ Na+ + H2O (3.1)

Equations 1, 2 and 3 when combined illustrate the primary scrubbing mechanism.
Ca(OH)2 + 2 H+ + SO3 -2 Ca+2 + SO3 -2 + 2H2O (4)
2NaOH + H+ + SO3 -2 Na 2SO3 + H2O + OH- (4.1)

In the absence of any other factors, (for example, oxygen in flue gas) calcium and sulfite ions
will precipitate as a hemihydrate, where water is actually included in the crystal lattice of
the scrubber byproduct.
Ca+2 + SO3 -2+ ½ H2O CaSO3.1/2 H2O.. (5)

However, oxygen in the flue gas has a major effect on chemistry, and in particular on
byproduct formation. Aqueous bisulfite and sulfite ions react with oxygen to produce
sulfate ions (SO4-2).
2 SO3 -2 + O2 2 SO42−... (6)

Approximately the first 15 mole percent of the sulfate ions co-precipitate with sulfite to form
calcium sulfite-sulfate hemihydrate [(CaSO3·CaSO4)·½H2O]. Any sulfate above the 15
percent mole ratio precipitates with calcium as gypsum.
Ca+2 + SO42− + 2H2O CaSO4.2H2O (7)
2Na+ + SO42− Na2SO4... (8)

Calcium sulfite-sulfate hemihydrate is a soft, difficult-to-dewater material that previously
has had little practical value as a chemical commodity. Gypsum, on the other hand, is much
easier to handle and has practical value. These factors are driving utilities to install forced
oxidation systems for gypsum production.
There are three control technologies which have major application in the field of Sulphur di
Oxide control.7-8
 Adsorption.
 Catalytic Oxidation / reduction.
 Absorption.
Adsorption is a control technology for control of SO2 from stack gases but suffers from
several following drawbacks viz:
1. Higher energy requirements.
2. Penetration of SO2 in the granule is difficult.
3. Highly active absorbent surfaces cause oxidation of SO2 to SO3 which react with
moisture in flue gases to form acid.
4. Regeneration techniques are costlier.
Catalytically oxidation / reduction is a control technology for control of from stack gases
but suffers from several following drawbacks viz:
1. Higher energy requirements
2. Large equipment size.
3. Costly Catalysts.
4. Regeneration and disposal of catalysts is also a problem
5. Contractor design is complex.
Absorption is a control technology for control of SO2 from stack gases is most widely
practiced.
However this technology also suffers from following drawbacks:
1. Stack gas cooling and reheating is required.
2. Mist elimination is required.
However these problems can be easily encountered with proper engineering design used.
Besides this less operator’s intensiveness, less cost and ease of handling of liquid sorbent
makes it an attractive option. It is one of the most widely used control technology employed
for removal of SO2 9-10
4. Material and methods

All experiments were conducted on Stack monitoring Kit (Model No. and Make -VSS1, 141
DTH -2005,Vayubodhan). First of all Stack monitoring kit of SO2 monitoring were set up for
experiment at chimney inlet of Boiler of thermal power plant. Flue gas containing SO2 were
supplied from chimney via probe connected with flexible pipe of stack monitoring kit. The
flow of flue gas were controlled using an inlet line Rota meter and was maintained at a
value of 3 liter per minute and other end of flexible pipe carrying air and SO2 respectively
were connected to a impinger of 10 cm diameter and 100 cm length. The impinger were
filled with 100 ml of scrubbing media in this experiment i.e. Sludge solution, Calcium
hydroxide solution, Sodium hydroxide solution.
The concentration of SO2 in flue gases was first measured by Stack monitoring Kit.
K2 (Vt - Vtb) N (Vsoln)

CSO2 = --------------------------------------------------
Vm(std) * Va
CSO2 = Concentration of sulphur dioxide, dry basis converted to standard conditions,

mg/NM3.
N = Normality of barium per chlorate titrant mili equivalent/ml.
K2 = 32.03 mg/meq.
Vt = Volume of barium per chlorate titrant used for the sample, ml.
Vtb = Volume of barium per chlorate titrant used for the blank, ml
Vm(std) = Dry gas volume measured by the dry gas meter, corrected to standard conditions,
NM3.
Va = Volume of sample aliquot-titrated, ml.
Five sets of reading were taken by varying concentration of every solution. 100 ml of
solution were taken in first two different impinges for better absorption of SO2 and 30 ml
of H2O2 was taken in the third for determination of remaining SO2. Respective sulphate
were formed in solution. Dissolved sulphate were extracted from solution by heating till
dryness. Three parameters regards to % SO3 (gravimetric), % SO2 (Volumetric) and %
alkalinity were analyzed in precipitate. The methods used as Indian standard method
from bureau of Indian standard.11-16 During the experiments pipette out 10 ml of NaOH
solution in every 15 minutes and pH were analyzed, titrate with 1M oxalic acid
determination for fall in conc. of NaOH. Similarly Experiments were conducted on
Indirect Flow ( By taking water in first impinger) and Direct Flow ( Without Water in First
impinger). Similarly all experiments were conducted at different temperatures and at
different times of interval for reaction. Operating condition of SO2 absorption is given in
table – 1. Experimental set up shown in figure – 12 and schematic diagram of
experimental protocol shows in figure – 11
S. No. Operating Condition Value
1 Initial Concentration of Scrubbing media Varying
2 pH of solution Varying
3 Total liquid hold up 100 ml
4 Temperature of solution Varying
5 Time period for reaction Varying
6 Flow of flue gas in impinger 3 LPM
7 SO2 load in flue gas 3000 – 3200 ppm
8 Flue gas Temperature 135 oC
9 Flue gas flow in duct of ESP O/L 150522 M3/hr
10 Pet Coke Feeding Rate 13 Ton/ hr
11 Lime Stone Feeding Rate 1.0 Ton/hr
Table 1. Operating condition of SO2 absorption in Scrubbing media.

Initial Concentration of Concentration of

Concentration of
SO2 at I/L of SO2 at O/L of Recovery of SO2
S. No Sludge Sample
absorbing media absorbing media (%)
(%)
(ppm) (ppm)
1 5.00% 2950 1134 62.56
2 10.00% 2950 1205 60.18
3 15.00% 2950 1444 52.08
4 20.00% 2950 1734 42.25
5 25.00% 2950 1795 40.16
Table 2. Effect of Conc. of sludge solution and recovery of SO2.
Concentration Yield of Percent

Percent Percent L/G
S. No of Sludge precipitate Mg+2 SO2 (By
CaSO4 Alkalinity ratio
Sample (%) (g) Volumetric)
1 5.00% 5.25 7.72 5.54 2.6 0.0014 33.89
2 10.00% 10.56 5.91 5.20 2.44 0.0028 50.84
3 15.00% 15.56 4.34 3.65 1.72 0.0144 67.79
4 20.00% 20.56 2.55 3.09 1.45 0.0158 84.74
5 25.00% 25.89 1.95 1.73 0.81 0.0201 101.69
Table 3. Analysis results of precipitate which was prepared by sludge solution and SO2.
Initial Concentration Concentration of

Concentration of of SO2 at I/L of SO2 at O/L of Recovery of SO2
S. No
Ca(OH)2 (%) absorbing media absorbing media (%)
(ppm) (ppm)
1 5.00% 2980 621 80.15

2 10.00% 2980 739 76.2
3 15.00% 2980 898 70.85
4 20.00% 2980 1097 64.18
5 25 .00% 2980 1279 58.06
Table 4. Effect of Conc. of Ca(OH)2 solution and recovery of SO2.
Concentration Yield of Percent

Percent Alkalinity
S. No. of Ca(OH)2 precipitat Mg+2 SO2 (By L/G ratio
CaSO4 Percent
Sample e (g) Volumetric)
1 5.00% 5.55 3.61 8.75 4.12 0.02 33.55
2 10.00% 10.89 2.41 7.51 3.53 .0216 50.33
3 15.00% 15.06 1.96 7.34 3.45 .0252 67.11
4 20.00% 20.42 1.29 5.03 2.36 .0324 83.89
5 25.00 % 25.18 1.24 4.18 1.96 .0540 100.67
Table 5. Analysis results of precipitate which was prepared by Ca(OH)2 solution and SO2.
Initial Concentration Concentration of SO2

Concentration of of SO2 at I/L of at O/L of absorbing Recovery of
S.No.
NaOH (%) absorbing media media SO2 (%)
(ppm) (ppm)
1 5% 3067 75 97.96
2 10 % 3067 158 95.08
3 15 % 3067 306 90.18
4 20 % 3067 324 88.02
5 25 % 3067 455 85.19
Table 6. Effect of Conc. of NaOH solution and recovery of SO2.

Percent
Concentration Yield of SO3 Percent SO2
S. Percent Percent L/G
of NaOH precipitate (By (By
No. Na2SO4 Alkalinity ratio
Sample (g) gravimetric volumetric)
method)
1 5% 4.88 20.76 35.49 39.21 0.62 16.30
2 10 % 9.76 5.67 17.00 25.61 1.17 32.60
3 15 % 14.15 1.49 9.81 20.54 1.64 48.90
4 20 % 18.62 0.52 5.77 19.47 1.68 65.21
5 25 % 23.28 0.24 3.99 17.62 1.75 81.51
Table 7. Analysis results of precipitate which was prepared by NaOH Solution and SO2.
Volume of 1 M
Oxalic acid
Time consumed in Conc. of NaOH
S. No. pH of solution
(Min.) titration using (%)
phenolphthalein
indicator (ml)
1 0 12.57 20.05 80.06
2 15 10.62 15.56 62.2
3 30 8.82 3.5 14.2
4 45 7.95 1.23 4.8
5 60 5.62 0.56 2.2
6 75 4.75 0.32 1.2
Table 8. Effect of pH of NaOH solution for absorption of SO2.
Concentration of
Initial Concentration SO2 after formation Recovery
S. No. Flow of SO2 gas
of SO2 (ppm) of Sodium sulphate (%)
(ppm)
1 Direct 3050 145 95.25
2 Indirect 3050 1818 59.62
Table 9. Effect of direct and indirect flow of flue gases in NaOH solution and removal
efficiency of SO2.
Yield of
S. Flow of % SO3 % % SO2 Alkalinity
precipitate
No. SO2 gas (Gravimetric) Na2SO4 (Volumetric) (%)
(in gm)
1 Direct 9.55 1.79 3.17 39.21 1.12
2 Indirect 9.02 .233 .413 20.01 1.72
Table 10. Analysis results of precipitate which was prepared by varying the flow of flue
gases in NaOH solution.
Conc. of SO2 after

Temperature of Initial Conc. of
S. No. formation of Recovery (%)
NaOH solution SO2(ppm)
Sulphate(ppm)
1 20-25 oC 3080 302 90.18
2 25-30 oC 3080 566 81.62
3 30-35 oC 3080 675 78.08
Table 11. Effect of temperature of NaOH solution and recovery of SO2.
Temperature of Yield % % % %
S.No
NaOH Solution (g) SO3 SO2 Na2SO4 Alkalinity
1 20-25oC 9.77 0.62 38.72 1.100 1.68
2 25-30oC 9.25 0.42 31.92 0.745 1.80
3 30-35oC 9.06 0.22 17.87 0.390 1.95
Table 12. Analysis results of precipitate which was prepared by different temperature of
NaOH solution and SO2.
Initial conc. of Conc. of SO2

Time for
S.No SO2 after formation Recovery (%)
reaction(Min)
(ppm) of SO4(ppm)
1 20 3075 761 75.25
2 40 3075 609 80.18
3 60 3075 360 88.27
Table 13. Effect of time intervals of reaction and recovery of SO2.

Time of
Yield % % % %
S.No Reaction
(g.) SO3 SO2 Na2SO4 Alkalinity
(Min)
1 20 8.62 1.63 26.68 2.89 1.16
2 40 8.95 2.35 29.34 4.17 0.96
3 60 9.02 3.06 36.51 5.03 0.75
Table 14. Analysis results of precipitate which was prepared by different times of intervals
of reaction between NaOH solution and SO2.
Fig. 1. Comparative Study of recovery of SO2 with three different reagents.

Fig. 2. Comparative Study of Conc. of three different reagents with % SO3 (Gravimetric) of
precipitate.
Fig. 3.Comparative Study of Conc. of three different reagents with % SO2 (Volumetric) of
precipitate.
Fig. 4.Comparative Study of Conc. of three different reagents with % sulphate of precipitate.
Fig. 5. Comparative Study of Conc. of three different reagents with % alkalinity.

Fig. 6. Comparative Study of recovery of SO2 with different parameters.
Fig. 7. Comparative Study of % SO3 of precipitate with different parameters.

Fig. 8. Comparative Study of % Sulphate of precipitate with different parameter.
Fig. 9. Figure depicting relation between pH of NaOH solution and absorption of SO2.
Fig. 10. Figure depicting relation between time period and falls in conc. of NaOH.
Fig. 11. Schematic diagram of experimental protocol.

Fig. 12. Experimental Set Up by using SO2 monitoring kit for absorption of SO2.
Fig. 13. Experimental Set Up by research scholar using SO2 monitoring kit.
Fig. 14. Comparative Study of % SO2 (Volumetric) with different parameters.
Fig. 15. Comparative Study of % Alkalinity with different parameters.
5. Result and discussion

Table -2 to 7 reports that relation between recovery of absorption of SO2 using varying
concentration of Sodium hydroxide, Calcium hydroxide, and Sludge with analysis results of
precipitate. As can be seen from figure – 1 that recovery of SO2 using, Calcium hydroxide,
and Sludge is far below that using Sodium hydroxide. Figure -2 shows the results of % SO3
(Gravimetric) of precipitate which was prepared by three different reagents and SO2
contained in flue gases. It is reported that % SO3 is higher in case of NaOH as to others.
Figure -3 shows the results of % SO2 (Volumetric) of precipitate which was prepared by
three different reagents and SO2 contained in flue gases. It is reported that % SO2 is higher
in case of NaOH as to others. Figure -4 shows the results of % respective Sulphate of

precipitate which was prepared by three different reagents and % SO2 in flue gases. Figure -
5 shows the results of % alkalinity of precipitate which was prepared by three different
reagents. We know that alkalinity is the reverse of % SO2 and it is confirmed by figure – 5.
Figure -9 and table – 8 reports that effect of pH of NaOH solution and absorption of SO2 and
it is confirmed that when increase in the time period for absorption of SO2 in NaOH
solution, then there is a significant decrease in pH. Figure -10 reports that with the increase
of time period for absorption of SO2 in NaOH solution there is a significant decrease in conc.
of NaOH Solution. Table -9 shows recovery of SO2 using different parameters like time
period for reaction , temperature of Solution and flow of flue gases in impingers with
analysis results of precipitate. Figure – 6 reports that recovery of SO2 with different
parameters. Figure – 7 reports that % SO3 in precipitate which was prepared by exhaust SO2
using different parameters. Figure – 8 reports that amount of % Sulphate which was
prepared by SO2 using different parameters. Figure – 14 reports that amount of % SO2
(Volumetric) which were prepared by exhaust SO2 using different parameters. Figure – 8
reports that amount of % Alkalinity which were prepared by SO2 using different parameters.
6. Conclusion
From the comparative study of three different reagent regarding to removal of SO2 , it is
observed that Sodium hydroxide is superior as compare to calcium hydroxide and sludge.
The initial rate of absorption is higher for Sodium hydroxide as compared to calcium
hydroxide and Sludge. All the absorption methods coupled with a chemical reaction. It may
be suggested that Sulphur dioxide is a weak acid and it is a well known fact that reaction of
a weak acid with a strong base is fast, meaning stronger the base faster would be the
reaction Therefore Sodium hydroxide is a strong base compared to calcium hydroxide and
sludge so this evident that Sodium hydroxide is a better solvent for removal of SO2.
The lower Conc. of the reagent is found to be optimum. Increasing conc. of solution is not
very fruitful for maximum absorption of SO2 in exhaust flue gases. This is because of load of
SO2 in flue gases is very low (at ppm level), so the reagent remains as it is in solution after
completely absorption of SO2.
The pH of the solution should be alkaline. Because of nature of SO2 is acidic and reaction is
restricted in acidic solutions
The temperature of solution should be lower i.e. 20- 25 oC. Because of at higher temperature
reversible reaction may be take place and partially formed product may be change in to
initial reactants.
The time period of the absorption of SO2 should be maximum for completely absorption
of SO2.
The direct flow of flue gases in to impingers containing solution will results maximum
absorption of SO2 instead of indirect flow of flue gases because of in indirect SO2 react with
water form sulfurous acid.
On the basis of our study we can recommended that if flue gas desulphurization system
(FGD System) is set up before Chimney then maximum SO2 is trapped, resulting lowers the
SO2 conc. in environment and lowers the air pollution.
7. FGD design and equipment

7.1 Purpose
Air pollution is one of the very important issues world-wide. The wet limestone-gypsum
process has been the most popular method adopted to eliminate SO2 emitted from thermal
Power Stations. However, due to the relatively high construction cost, its further
implementation has inevitably limited and the development of more economical FGD
technology has been sought.
Hence, Hitachi Compact FGD System was developed, for the purposes of simplification
and cost reduction utilizing features of the latest FGD technology fully. The first System
was delivered to Peoples Republic of China under the”Green Aid Plan”, which has been
organized and managed by the Ministry of International Trade and Industry (MITI),
Japan, in order to implement their policy to transfer environmental preservation
technology to neighbouring countries and it contributes to global environmental
preservation and the technologies, such as, higher gas velocity in the absorber and
adoption of horizontal flow spray absorber instead of conventional vertical flow spray
absorber shortened duct length. Eventually it helps to accomplish a lower construction
cost.
7.2 Performance
The absorption and forced oxidation mechanisms are the same as the conventional wet
limestone gypsum FGD technology, so it is possible to achieve more than 80% of SO2
removal efficiency. Also, because of higher gas velocity under the same conditions of gas
versus liquid ratio, it is possible to maintain the same SO2 removal efficiency.
In the method of horizontal spray tower, it is possible to achieve high dust removal
efficiency as in the vertical spray tower.
7.3 Special features

1. Absorber, having functions of dust removing, SO2 absorbing, SO2 oxidization
simultaneously
2. Adoption of horizontal flow spray absorber and simplified flue duct make a compact
arrangement.
3. Use of limestone of easy handling and low cost
4. High Ca utilization factor
5. Complete oxidation in the absorber
6. High dust removal efficiency at spray part
7. Re-use of by-product gypsum as salable gypsum
8. Easy to retrofit to existing plant
7.4 Process description

The SO2 contained flue gas flow into FGD system through duct. The SO2 is absorbed and
removed by the chemical reaction of limestone slurry sprayed through horizontal flow
spray as an absorbent. By injecting air in the absorber tank, the absorbed and removed SO2
forms gypsum, then, the gypsum slurry is delivered outside system, as in the method of
latest wet limestone gypsum FGD system.
In the absorber :
SO2 + H2O H2SO3
CaCO3+ 2H2SO3 Ca(HSO3)2 + CO2 + H2O

In the tank :
Ca(HSO3)2 + O2 + 2H2O CaSO4.2H2O + H2SO4
CaCO3 + H2SO4 + H2O CaSO4.2H2O + CO2

It shows the same reaction characteristics as in conventional one. From the absorbing
tower’s structural view point, adoption of higher gas velocity and horizontal spray tower
eliminate certain portion of duct for up and down and both of Duct’s capacity and system’s
cost can be reduced tremendously.
Also, it is possible to reduce both auxiliaries and installation space by making the system
compact.
7.5 Process flow sheet

7.6 Outline of absorber
8. References
[1] Sheth K.N. Patel and Patel Neha J, effect of concentration in absorption of Sulphur
dioxide with sodium hydroxide, Env. Poll. Cont. J., 9, 14-18. (2006)
[2] B. Buecker, Wet lime stone Scrubbing fundamentals, power engineering, 110, 32-37, (2006)
[3] Ram S. Gosavi, Flue gas desulphurization – An Overview of system and technologies,
Env. Poll. Cont. J., 8 , 5-8. (2005)
[4] Maohong fan, C brown, a process for synthesizing polymeric ferric sulfate using sulphur
di oxide from coal combustion , Int. J. Env. Poll., 17 ,102-109. (2002)
[5] Shih-Wu Sung, Robert C. brown, synthesis, characterization and coagulation
performance of polymeric ferric sulphate, Int. J. Env. Poll., 128, 483-490. (2002)
[6] Aron D. Butler, Maohong Fan , Robert C. brown, Comparison of polymeric and
conventional coagulants in arsenic removal, J. Env. Engg., 74, 308-313, (2002)
[7] C. Dene, FGD chemistry and analytical methods handbook , power engineering, 2, 48-55,
(2002)
[8] B. Buecker, gypsum seed recycle in lime stone scrubber, power engineering, 110, 10-12,
(1986)
[9] Arthur kohl , Richard B. Nielsen, gas purification , fifth edition gulf publishing company, 10,
42-49, (1975)
[10] Slack A. V, Hollindon G.A, Sulphur di oxide removal from stake gases, Second edition
Noyes Data Corporation, 11, 45-55 (1971)
[11] Indian standard method for Measurement of emission from stationary sources. IS 11255
(Part 2) 1985 IS 5182 (Part 2) 2001
[12] Indian standard methods of sampling and test for quicklime and hydrated lime (1 st revision)
IS No. 1514.
[13] Indian standard methods of chemical analysis of limestone , dolomite and allied materials
,determination of iron oxide , calcium oxide and magnesia (1 st revision) IS No 1760 Part 3
1992.
[14] Indian standard methods of Sodium bi Sulphite technical (fourth revision). IS 248: 1987
[15] Indian standard methods of Caustic soda, pure and technical (third revision). IS 252 :1991
[16] Indian standard methods of sampling and test (physical and chemical) for water used in
industries: IS 3025-1964.
9
Design Efficiency of ESP

Maria Jędrusik and Arkadiusz Świerczok
Wroclaw University of Technology
Poland
1. Introduction
Electrostatic precipitator (ESP) is a highly efficient device for cleaning exhaust gases from
industrial processes. Fig. 1 shows a photograph of electrostatic precipitator (ESP) for
cleaning flue gases from a power boiler, and Fig. 2 shows the inner part of the ESP.
The basic components of ESP are: a chamber comprising discharge and collection electrodes,
and high voltage (HV) supply unit - shown in Fig. 3. The ESP operation is based on the
utilization of the influence of electric field on charged dust particles flowing between the
electrodes. The Discharge electrodes (DE) are connected to a direct current (DC) HV power
supply of negative polarity and the collecting electrodes to the positive pole of the supply,
which is additionally grounded. The raw exhaust gas is subjected to electron and ion
currents which charge the dust particles negatively, and cause their movement towards the
collecting electrode. The precipitation of dust particles from a gas stream as well as its
collection occurs mainly because of the electrophoresis forces.
Fig. 1. Electrostatic precipitator in Thermal-Power Station.

Fig. 2. Inner part of the ESP.
Dust particles collected on the CE surfaces partly give up their charge and the dust layer is
kept on the CE electrodes by means of mechanical and electrical forces. Afterwards the
collected dust layer is knocked down mostly by mechanical rapping systems.
HV supply discharge gas outlet

electrode
collecting
electrode
gas inlet chamber
hoppers
Fig. 3. Typical arrangement of wire-and-plate precipitator with horizontal gas flow.

Design Efficiency of ESP 199
2. Kinetics of dust particle charging

The dust particles in ESP are charged as a result of taking over the electric charge from gaseous
ions. The source of gas ionization is a negative corona discharge originating at the DEs.
The discharge takes place due to strongly inhomogeneous electric field in the vicinity of
appropriately formed DE surface, for example, in the form of thin round wire or a similar
element with mounted spikes. The empirical equation of the corona-onset electric field
strength on DE spikes has been given by Peek (Peek, 1929).

Eo  A  B (1)
ro
where:
- Eo – initial electric field strength, V/m
- A, B – experimental coefficients characterizing gas type and discharge polarity. For an
ESP with negative discharge polarity Robinson (Parker, 1997) advices to use empirical
values: A=3.2106 V/m, B=9104 V/m½,
- ro – DE curvature radius, m
-  – relative density of gas, -
The magnitude of supply voltage at which the corona discharge begins on the DE surface is
called the corona onset voltage. Above this level, develop the electron avalanches from the
discharge electrode towards the plate. The electrons emitted from the spikes are accelerated
in the strong electric field and gain energy necessary for avalanche ionization of atoms and
gaseous molecules. Additional source of electrons in the discharge is also the so called
secondary emission due to positive ions impacting the DE. The avalanches originating from
DE develop in the direction of CE. Electrons from the avalanche head are quickly attach to
neutral gas molecules , which-become negative gas ions. Dust particles get electric charge
due to non-elastic collisions with negative as well as positive gas ions. In the charging
process of dust particles, two distinguish basic mechanisms are considered (White, 1990):
- field charging,
- diffusion charging.
An equation describing the charge on a dielectric spherical particle for the field charging
mechanism has been given by Pauthenier and Moreau-Hanot (Pauthenier & Moreau-Hanot,
1932) in the following form:
t
q f  qs  (2)
t 
where: qf – particle charge obtained from field charging,
3 w
qs   o Ed 2 – particle saturation charge,
w  2
4 oE
f  – field charging constant,
j
- εw – dielectric constant of particle material ,

 C2 
- εo – dielectric constant of free space  8.85  10 12 
 Nm2 
- E – electric field strength,
- t – charging time,
- d – particle diameter.
White in 1963 (White, 1990) has given the equation of particle charging for diffusion
mechanism in the form of:
2  o kTd  t 
qd  ln  1   (3)
e   d 
where:
- qd – particle charge obtained from diffusion charging
- k –Boltzmann constant (1.38·10-23 J/K)
- T – temperature
- e – electron charge, (e = 1.6710-19 C)
- d – diffusion charging constant
 o 8m j k T
d  (4)
e 2 Nd
- N – number of unipolar ions in the unit volume (ion density)
- m –mass of an ion
It was experimentally demonstrated that a total charge of dust particle can calculated with
practically sufficient accuracy as a sum of field charge (2) and diffusion charge (3).
q p  t   q f  t   qd  t  (5)
It should be noted that all of the above mentioned charging theories apply only to spherical
particles. When taking into account industrial dust particles it is necessary to use their
equivalent dimensions (diameter).
In typical industrial ESP, the dust size distribution at the precipitator inlet does not comprise
fine particles –below 4 µm, and the electric field is usually over 1 kV/m. Therefore, based on
the research results presented in the literature, it is generally accepted that the mechanism of
diffusion charging may be ignored. This also proves that the Pauthenier’s & Moreau-Hanot
equation describes the kinetics of dust particle charging with sufficient accuracy.
3. Dust particle motion in ESP

In order to characterize the movement of charged particle in an ESP it is necessary to assume
the equilibrium of forces acting on the particle. After some simplifications it can be said that
the following forces are acting on a dust particle in an ESP: the inertia force, electric force
and drag force of the medium, where:
 
du
Fi  m  (6)
dt
 
Fe  qs  E (7)
 d    
Fd  c d (Re)   g   v  u v  u (8)
8
The motion of any dust particle may be described as by the Newton second law:
  
Fi  Fe  Fd  0 (9)
The scheme of particle motion in electric field illustrates Fig. 4.
L corona wire
dust particle
gas flow
v
h
w
u
plate
Fig. 4. Schematic diagram of particle motion in electric field (plate to plate configuration).
In the vector form, the equation of motion becomes:

 
du d    
m  c d  Re   g  v  u  v  u  qs E (10)
dt 8
where:

- v - vector of gas velocity

- u - vector of particle velocity
- g - gas density
 
- v  u - particle velocity in relation to gas velocity
- cd(Re) – dynamic drag coefficient
- m – particle mass
It should be emphasized that the dominant role in this equation play the electric force and
drag force of the gas medium. In the steady state motion the inertia force can be omitted
because of its low value comparing to the electric force (Parker, 1997).
The equation (10) finally gets the form:
d     
c d  Re    g  v  u  v  u  qs E  0 (11)
8
3.1 Theoretical migration velocity

Accepting for further consideration the simplest case of spherical particle steady motion in
electric field –in the range of Stoke’s law (Re ≤ 0.1), equation (11) can be transformed to the
form:
qsE  3 µd· w  0 (12)
where: w – particle relative velocity normal to CE surface; so called migration velocity

 
w   v  u
Theoretical value of the migration velocity, calculated from equation (12) equals to:
qs  E
w (13)
3 d
The minimum range of the size of particles to which the Stoke’s equation can be applied is
the case when the particle diameter is of the order of magnitude of mean free path of gas
molecules  . For particles smaller than 1 μm it is necessary to take into account the
Cunningham slip correction factor:
qsEC u
w (14)
3 d
where:
2
Cu - Cunningham slip correction factor (White, 1990); C u  1  0.86
d
The formulas used for the calculation of theoretical migration velocity do not take into
account many factors affecting the movement of dust particle in electric field such as:
inertia, inhomogeneity of electric field strength distribution, gas velocity, and electric
wind velocity.
In the electrostatic precipitation process with a spike and plate electrodes arrangement there
exists an electro-hydro-dynamic (EHD) flow, which is an effect of mutual interaction of
electrically neutral main gas stream and gas ions movement under the influence of electric
field. To describe such flow field it is necessary to use dimensionless parameters determined
by IEEE-DEIS-EHD Technical Commitee (IEEE-DEIS-EHD TC, 2003).
Lv
Re  (15)

L3  j0
Ehd  (16)
  g b  A
 0  E 0 2 L2
Md  (17)
 g 
where:
- L – characteristic length, i.e. distance between the electrodes, m
- j0 –total discharge current, A
- v - average gas velocity, m/s
- ν – kinematic viscosity coefficient, m2/s
- Md – the Masuda number,
- Re – the Reynolds number,
- b – ions mobility: 1.8·10-4, m2/Vs
- Ehd – electro-hydro-dynamic (EHD) number,
- E0 – field strength at corona onset, V/m
- ρg – gas viscosity, kg/m3
- A – CE surface for discharge current calculations, m2
For specified ESP arrangement, the Reynolds number depends on gas flow velocity, and the
EHD and Masuda numbers are the functions of discharge voltage, field geometry, and
ionization parameters of the gas.
3.2 ESP precipitation efficiency

The basic equation describing precipitation efficiency from the probability theory has been
given in 50-ties by White (White, 1990) and latter modified by Matts & Oehnfeld to the
following form:
 L 
 ( d )  1  exp  wt ( d )   (18)
 h v
where:
- (d) – precipitation efficiency for a particle with diameter d,
- wt(d) –theoretical migration velocity, m/s

- L - length of electric field, m
- h – wire-plate distance, m
The total precipitation efficiency C(d) can be calculated from the formula:
dmax
C ( d )   q3 ( d ) (d ) (19)
dmin
Often an alternative way to determine the total efficiency of precipitation is calculate it by

measuring the dust concentration before and after ESP.
4. The influence of combustion process and fired coal parameters on

physical & chemical properties of generated fly ash
4.1 Chemical composition of fly ash
The fly ash collected in an ESP is a mixture of different compounds, mainly of silicon and
aluminum oxides with average substitute diameter of about 15 μm and submicron particles
with diameter below 1 μm (ca. 2wt.%). Characteristic properties of fly ash having the
greatest influence on ESP operation are (Parker, 1997): diameter, form and structure of
particles, their propensity for agglomeration and cohesion, electrical resistivity, chemical
composition and reactivity. The chemical composition of fly ash allows to estimate its
predictable electrical resistivity value and, by this way, the required size of the ESP
(Chambers et al., 2001). Actually, it often becomes necessary to adapt an existing ESP to new
(changed) operational conditions, for example, after installing flue gas desulfurization
equipment (Parker, 1997). Also the installation of low-emission burners in boiler results in
increasing amount of combustible elements in fly ash (LOI). In that case takes place, changes
of the gas-dust medium parameters as well as its electric resistivity can be expected. Former
experiences with the electrostatic gas cleaning process led to the conclusion that the dust
electrical resistivity is an important parameter influencing the operational efficiency of ESPs.
If the dust electric resistivity exceeds 1011–1013 Ω·cm it is the so called high resistivity dust,
which is difficult to collect. If the resistivity lies between 1010–1011 Ω·cm, it is in the optimal
range for the collection. The chemical composition of fly ash is closely related to the coal
quality. An increase of silicon and alumina compounds in the fly ash (SiO2, Al2O3) may lead
to the increase of fly ash electric resistivity and by that to decrease of the ESP collection
efficiency. It has been observed that for brown coal fly ash, the electric resistivity increases as
the percentage of alkali compounds (CaO + MgO) exceeds 3-6 times that of iron trioxide
(Fe2O3). However, significant amount of sodium and potassium compounds in fly ash cause a
decrease in its resistivity that is particularly noticeable by high content of (SiO2 + Al2O3)
(Bibbo, 1994; Bickelhaupt, 1985; Parker, 1997).
A substantial influence on the fly ash electric resistivity has the content of sulphur trioxide
in the flue gas entering into ESP, as shown on Fig 5. When firing coal in a combustion
chamber, the sulphur contained in the coal is oxidized to SO2. Depending on the combustion
conditions, 0.5-3% of that sulphur dioxide is further oxidized to SO3. At the temperature of
sulphur acid dew point, the condensation of SO3 on particle surfaces takes place – or more
precisely- H2SO4 is formed on it in the form of very thin film.
1E+013
without SO3
Electrical resistivity, ohmcm
1E+012
1E+011
3,8 ppm SO3
1E+010
6,8 ppm SO3
1E+009
50 100 150 200 250 300
Temperature, oC
Fig. 5. Electric resistivity of fly ash as a function of SO3 injection (Parker, 1997).
In Table 1 are presented selected characteristic parameters of fly ash resulting from
combustion of hard coal and brown coal in different power boilers.
Chemical
composition, Fly ash type
%
E D B C W A JG G
SiO2 54.0 41.00 41.60 37.60 45.67 54.20 47.44 28.99
Fe2O3 4.21 10.30 6.50 7.01 8.94 5.30 6.91 3.67
Al2O3 4.42 30.60 21.90 21.60 21.65 32.10 19.65 17.14
TiO2 1.03 2.08 0.85 0.81 1.09 1.40 0.99 0.86
CaO 25.90 3.03 11.90 14.30 8.23 0.81 3.98 2.82
MgO 4.43 1.97 2.29 2.47 2.60 1.09 1.41 1.01
SO3 4.72 2.80 6.27 6.58 1.57 0.27 0.73 2.26
K2O 0.24 1.28 2.24 1.87 4.83 2.65 3.03 2.68
P2O5 0.26 0.22 0.15 0.16 - 0.55 0.01 0.01
Na2O 0.09 3.61 1.22 1.48 1.32 0.48 1.33 1.14
Un-burned coal 0.63 0.14 2.38 2.68 3.50 0.61 13.77 28.60
Density, kg/m3 2500 1954 2580 2690 2210 2031 1550 1580
Resistivity, cm 4.4 x 10 3.2 x 10 2.0 x 10 1.8 x 10 3.2 x 10 1.8 x 10 5.110 5.0107
8 7 8 8 7 8 7
Table 1. Properties of fly ashes.

The influence on chemical composition of fly ash have the quality of fired coal and the
combustion parameters. Because both of the mentioned parameters vary with time, the
chemical composition of fly ash is also changed with time.
4.2 Dust particle size distribution

Knowledge of the particle size (granulation) distribution is essential to estimate an ESP
collection efficiency. The fly ashes coming after combustion of solid fuels are polydisperse
and diameter of the particles ranges from fractions of micrometer up to several millimeters.
Determination of particles size is a difficult task because of various shapes of the particles,
from spherical forms -created as an effect of sublimation and condensation, spatially
expanded, inside-empty structures of un-burned coal, snow-flake like flat particles, to
fibrous particles. In order to compare the dust size distributions, a equivalent particle
diameter has been introduced. It depends on the method of size analysis: the projected
diameter (determined by the analysis under projecting microscope or by sieve analysis) or
dynamic diameter (obtained using the blow away method in counter-flow, or
sedimentation).
The fly ash size distribution is most often presented as fraction of particles qr(di) in a range
from di to di + dd, or the total number of particles Qr(di) smaller than di (cumulative size
distribution). The particle distribution in a certain size range may be represented by its mass,
volume or number ratios. These ratios are called the mass, volumetric and number fractions
with the index r equal to 3 (mass and vol.) or 0 (number), respectively (Masuda et al., 2006).
Examples of fly ash size distribution coming from different boilers fired with hard or brown
coal are presented in Figs. no 6, 7 & 8. The analysis has been done with an automatic particle
size analyzer Mastersizer S made by Malvern Instruments Ltd. Results of the presented
analyses show that the combustor type (boiler type) is a crucial element in forming the fly
ash size distribution character.
100
ash W
Cumulative percent, vol%
ash E
80
60
40
20
0.1 1 10 100 1000

Particle diameter di, µm
Fig. 6. Particle size distribution Q3(di) of fly ashes from PC boilers fired with hard coal (fly
ash W) and brown coal (fly ash E).
100
ash C

ash D
80
60
40
20
0.01 0.1 1 10 100 1000

Particle diameter di, µm
Fig. 7. Particle size distribution Q3(di) of fly ashes from PFB boilers fired with hard coal (fly
ash C) and brown coal (fly ash D).
100
ash G
ash JG
80
60
40
20
0.01 0.1 1 10 100 1000

Particle diameter di , µm
Fig. 8. Particle size distribution Q3(di) of fly ashes from grate stoker boilers fired with hard
coal.
The influence of ESP device on fly ash size distribution is presented in Fig. 9. At the outlet of
a high efficiency ESP (C>99.9 %), the fly ash comprises mainly of fine particles having
diameter below 20 µm.
10
inlet
outlet
8
Size distribution, vol%

6
0.01 0.1 1 10 100 1000

Particle diameter d i , µm
(a)
100
Cumulative size distribution, vol%
inlet
outlet
80
60
40
20
0.01 0.1 1 10 100 1000

Particle diameter d i , µm
(b)
Fig. 9. Particle size distribution at an ESP inlet and outlet: (a) particles fraction qr(di), (b)
cumulative size distribution Q3(di), fly ash from grate stoker boiler fired with hard coal.
4.3 Particle forms of a fly ash

Different methods of measuring fly ash size distribution utilize the same geometric
parameter i.e. particle substitute diameter. But as it was mentioned before, the actual shape
(form) of particles are rare spherical that also influences their separation process in an ESP.
In Fig. 10 are shown different particle-shape patterns, which can be found in various fly
ashes: spherical forms (spherules) and sharp-edged (Fig. 10a), particles in the form of fibers
and particles with a very irregular shapes (Fig. 10b). Moreover there is also visible a
significant particle size diversification. Scanning Electron Microscope (SEM) micrographs
taken at high magnification show the complexity of the forms of particles, which are often
agglomerates of many smaller particles having different diameters.
(a) (b)
Fig. 10. SEM pictures of fly ash particles from hard coal fired boilers: (a) in a grate stoker
boiler (fly ash G), and in a PC boiler (fly ash C) (magnification 700x).
On the photo (Fig. 11) are shown characteristic shapes (forms) of fly ash particles coming
from brown coal fired boilers with different combustor systems.
(a) (b)
Fig. 11. SEM pictures of fly ash particles coming from coal fired boilers: (a) brown coal fired
in fluidal bed boiler (fly ash D), (b) brown coal fired in PC boiler (fly ash E) (magn. 230x).
The elemental analysis carried out by Energy Dispersive X-Ray spectroscopy (EDX) method
demonstrates that most of the particles are alumina-silica (Al2O3-SiO2) aggregates (Fig. 12)
as well as spherical granules of two kinds: built of alumina-silica and spherical forms of iron
oxides (Fig 13). In addition to that in the fly ash were found particles with compounds
characteristic of carbonates, sulfates and oxides (quartz, feldspar, calcite and gypsum), with
considerable addition of titanium, iron, potassium, calcium, plus small content of sulfur and
potassium (Grafender, 2010).
(a) (b)
Fig. 12. Fly ash particles composed of alumina-silicates (magn. 700x) - (a) and their
elemental analysis - (b), fly ash from CFB boiler fired with brown coal (fly ash D).
(a) (b)
Fig. 13. Fly ash particles of spherical form composed of iron-oxides (magn. 100x) - (a) and
their elemental analysis - (b), fly ash from grate stoker boiler fired with hard coal
(fly ash JG).
5. Discharge Electrode (DE) model investigation

5.1 Testing bench
The model investigations of discharge electrodes (DE) have been carried out in a laboratory
arrangement comprised of pilot ESP with horizontal air flow, as shown on Fig. 14. The
chamber is made of organic glass (2000 mm long, 400 mm wide and 450 mm high) that
enables visual observations as well as photography of the phenomenon occurring in the
inter electrode region.. Tests were carried out with air flow at a temperature of 20C ,
pressure 1000 hPa and at humidity of 60% (Jędrusik & Świerczok, 2009).
1 2 3 4 5
9 8 7
Fig. 14. Laboratory arrangement for DE testing in a pilot ESP : 1 – fly ash feeder, 2 – pilot
ESP chamber, 3 – CE (collecting electrodes), 4 – DE (discharge electrodes), 5 – dust meter,
6 - thermo anemometer , 7 – exhaust fan with rotational speed control, 8 – final filter,
9 – HV (high voltage) supply unit.
5.2 V-I (voltage-current) characteristics

In Fig. 15 are shown various constructions of tested rigid discharge electrodes (RDE). In
electrodes of this type, both functions of the construction: mechanical supporting and
electric-discharge generation have been separated via mounting the active spikes as
replaceable elements that allows replacement of the emission points without changing the
supporting part. The V-I characteristics shown in Fig. 16 allows to divide the considered
RDE constructions into two groups:
1. ‘aggressive’ (with steep V-I curve) – the so called ‘RDE-3’, having discharge onset at a
level of U0=10 kV and the ‘barbed type’ with higher onset voltage of about U0=22 kV;
and
2. ‘smooth’: RDE-1 with discharge onset level of U0=16 kV and RDE-2 with U0=14 kV
(Jędrusik & Świerczok, 2011).
The tests have shown that modification of spikes orientation and spacing influences the V-I
curvature, what can be seen in Fig. 17. That gives the possibility to select and optimize DE
electrodes according to required precipitation efficiency and the expected shape of its V-I
characteristic. This becomes important when fly ash parameters are changed (mainly its
resistivity), for example, as a result of changing the kind fired fuel. Hitherto existing
experience shows that for efficient precipitation of high-resistivity fly ash the DE
construction should allow a high discharge voltage and uniform discharge current
distribution. Such electrode is called " high voltage & moderate discharge current electrode".
13 10 10 12
10
42
60
100
180
42 60
6.5
2.4 60
42
(a) (b) (c) (d)

Fig. 15. Forms of discharge electrodes (DE): (a) ‘barbed tape’, (b) RDE–1, (c) RDE–2,
(d) RDE–3.
1200
Discharge current density, A/m2
barbed tape
RDE-3
RDE-1
800 RDE-2
400
10 20 30 40 50 60
Supply voltage, kV
Fig. 16. V-I characteristics of DE electrodes shown on Fig. 15.

1200 1200
n=9 perpendicular
parallel
n=5
Discharge current, µA
Discharge current, µA
n=4
800 800
n=3
400 400
0 0
0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70
Supply voltage, kV Supply voltage, kV

(a) (b)
Fig. 17. V-I characteristics of RDE-2 electrode: (a) effect of discharge spikes number,
(b) normal and parallel orientation of the spikes to the collection electrode CE.
At the end of 90s (of the 20th century) there were carried out many laboratory tests with
various constructions of DE as well as with numerical modeling of phenomenon occurring
in an electric discharge field regions for different ‘spikes’ of the electrodes (Brocilo et al.,
2001; Caron & Dascalescu, 2004; Chung-Liang & Hsunling, 1999; Hsunling et al., 1994;
McCain, 2001).
Regardless of those investigations, there still lack unambiguous criteria for the selection
from various available constructions of DE. Very often ESPs are equipped with similar type
of DEs irrespective on the gas-dust characteristic parameters or inter electrode spacing.
5.3 The influence of selected fly ash parameters on precipitation efficiency

In order to show the influence of fly ash chemical composition on precipitation efficiency a
several measurements were done on a pilot ESP with selected fly ashes (parameters
presented in Table 1) and selected DE constructions.
To illustrate the results, in Fig. 18 are shown characteristics of precipitation efficiency for
three different fly ashes. The curves demonstrate that high content of compounds like Al2O3
(32.1%), SiO2 (54.2%) with traces of SO3 Na2O in the fly ash decreases the ESP precipitation
and efficiency -at the specific experiment conditions. For example, a 10% decrease of Al2O3
in the fly ash and increase of SO3 up to 6% and Na2O up to 1% cause an increase in the
precipitation efficiency of fly ash that may indicate a favorable influence of sodium content
in the fly ash (Jędrusik & Świerczok, 2006; Jędrusik, 2008 ).
0.95
Precipitation efficiency
0.9
0.85
ash A
0.8 ash B
ash C
0.75
20 30 40 50 60
Supply voltage, kV
Fig. 18. Precipitation efficiency vs. supply voltage for RDE-2 electrode.
There was also tested the influence of unburned coal (LOI) content in fly ash on the
precipitation efficiency, and an example of experimental results are presented in Fig. 19.
1
0.96
0.92
0.88 ash G
ash JG
0.84
20 30 40 50 60
Supply voltage, kV
Fig. 19. Precipitation efficiency as a function of supply voltage for RDE-3 electrode and fly
ash from hard coal fired grate stoker boiler.
The characteristics shown in Fig. 19 present the influence of unburned coal content in fly ash
on the precipitation efficiency that was already observed in research works in 70’th of the
20th century. An increase of unburned coal percentage by over 15% decreased the
precipitation efficiency (Hagemman & Ahland, 1973).
There was also tested the influence of biomass (of plant origin) co-firing in power boilers on
precipitation process in the ESP, what is shown in Fig. 20.
0.95
0.9
0.85
0.8 ash C
ash W
0.75
ash B
0.7
20 30 40 50 60
Supply voltage, kV
Fig. 20. The relationship between precipitation efficiency and a biomass percentage in the
co-firing process (hard coal), RDE-2 electrode.
It is shown that the collection efficiency depends on electrical parameters of the supply
voltage and the biomass percentage. The collection efficiency increases with an increase of
the supply voltage of the discharge electrode, but it is saturated for a certain voltage
magnitude, of about 50 kV, for that specific case. Further increase of the voltage can even
cause a slight decrease of collection efficiency. It was also determined, that small addition of
biomass (10%) to bituminous coal (ash B) causes an increase of the collection efficiency,
whereas for higher content of biomass, 50% (ash W) or larger, the collection efficiency
decreases. These preliminary results indicate that further research on the effect of co-fired
biomass content on the collection efficiency is required in order to optimize the operational
parameters of electrostatic precipitator (Jaworek et al, 2011).
The optimization of DE (corona electrode) design should include not only the parameters of
the electric field, but also the physical and chemical properties of the fly ash. In summary,
the choice of an appropriate design of the discharge electrode should be based on a
thorough examination of the dust particles and flue gas properties.
5.4 Current density distribution and patterns of precipitated dust on (CE) electrodes
The measurements of current density enables better estimation of selected DE constructions
especially in connection with local accumulation of fly ash on CE surfaces. The deposition of
dust in an ESP creates collection patterns, which shape depends on the electric field forces
in the inter-electrode space (Miller et al. 1996a, 1996b).
A measuring arrangement diagram is shown on Fig. 21.
1 2
1000 170
3
170 4
400
5
y=300 pA
450
x=200 6
Fig. 21. Measuring arrangement of discharge current distribution on the CE surface:

1 – collecting electrodes, 2 – discharge electrodes, 3 – HV supply unit, 4 –measuring panel,
5 – pico-ammeter, 6 – measuring zone.
In Fig. 22 is presented discharge current distribution for RDE-3 electrode (Fig. 15d) with
‘spikes’ pointed perpendicularly at the surface of CE. In Fig. 23 is shown pattern of collected
fly ash on CE electrodes for this DE construction.
Discharge
electrode
Fig. 22. Discharge current distribution for RDE-3 electrode - supply voltage 50kV.
Fig. 23. Pattern of collected fly ash on CE electrodes for RDE-3 electrode.
From the results appears that the highest value of discharge current density is opposite the
DE ‘spike’. Hence the uniformity of discharge current distribution, which is important for
high precipitation efficiency, will depend on the DE ‘spikes’ number and their configuration
(Blanchard et al., 2002, McKinney et al., 1992). For this reason it is crucial to use DE
constructions, which limit the number and area of regions with very high or very low
current density. Observation of the collection patterns on CE surfaces enables qualitative
assessment of the discharge current distribution on the electrode. There is visible a
significant correlation between the collected fly ash patterns and the measured distribution
of discharge current. From the studies presented in (Miller et al., 1996a) also results that the
collected fly ash layer density depends on the collection pattern, in which the highest
density of the fly ash layer appears opposite the DE ‘spikes’, that should be related to the
electric field distribution between the electrodes. This phenomenon may also be utilized in
designing and selecting DE for collection of submicron particles.
6. Summary
The results presented in this Chapter have shown that different constructions of RDE
electrodes in ESPs, their ‘spike’ number and geometrical configuration have to be used
depending on physical and chemical properties of fly ash. Although the model studies have
been carried out for only a few types of DE constructions and selected kinds of fly ashes, the
experimental results, confirmed by the literature's data, had shown the influence of fly ash
chemical composition as well as DE construction on the total collection efficiency of ESP. It
was confirmed that some components of fly ash (e.g. Na2O or Al2O3) have different effect on
the collection efficiency, depending on DE construction and the type of fired coal (hard or
brown coal). The results of measurements obtained for selected DE constructions in a pilot
ESP have shown that the construction of DE, i.e., shape of their ‘spikes’, number of spikes,
and their orientation relative to the collection electrode, have an influence on voltage-
current characteristics and the corona onset voltage. These results suggest that voltage-
current characteristics can be changed to some extent via changing the discharge electrode
geometry (shape of spikes) or the modification of electrodes configuration. The possibility of
the formation of V-I characteristics adequately to the existing collection conditions, enables
more effective exploitation of H.V. supply units, in order to get higher collection efficiency
of ESP and increasing energy efficiency of the supply unit. The presented results indicate
also on new possibilities of more efficient removal of submicron particles in industrial ESPs.
7. References
Bibbo P.P. (1994). Agential flu gas conditioning for electrostatic precipitator, Proc. of the
American Power Conference, Illinois Institute of Technology, USA, Vol. 56/V1,1994
Bickelhaupt R.E. (1985). A study to improve a technique for predicting fly ash resistivity
with emphasis on the effect of sulfur trioxide, Prepared by U.S. EPA, Washington
DC, 20460 SORI-EAS-85-841, November 1985
Blanchard D., Atten P., Dumitran L.M. (2002). Correlation between current density and layer
structure for fine particle deposition in a laboratory electrostatic precipitator, IEEE
Transaction on Industry Applications, Vol. 38, no. 3 May/June, pp. 832-839.
Brocilo C., Chang J.S., Findlay R.D. (2001). Modeling of electrode geometry effects on dust
collection efficiency of wire-plate electrostatics precipitators, Procee. 8th ICESP, Vol.
1, Southern Comp. Services Inc., Birmingham, Alabama, USA, A4–3 Series, May
14–17, 2001
Caron A. & Dascalescu L. (2004). Numerical modeling of combined corona – electrostatics
fields, J. of Electrostatics, Vol. 61, pp. .43-55
Chambers M., Grieco G.J., Caine I.C. (2001). Customized rigid discharge electrodes show
superior performance in pulp & paper applications, Procee. 8th ICESP, Vol. 1,
Birmingham, Alabama, USA, May 14–17, 2001
Chung-Liang Ch. & Hsunling B. (1999). An experimental study on the performance of single
discharge wire-plate electrostatic precipitator with back corona, J. Aerosol Sci., Vol.
30, No. 3
Grafender A.M. (2010) Pyły atmosferyczne pod mikroskopem, Energetyka Cieplna i
Zawodowa, 2/2010, pp. 22-25
Hagemann H. & Ahland E. (1973). Abgasentstaubug von mit Steinkohlenstaub gefeuerten
Wasserrohr, Staub-Reinhalt. Luft, 33 (1973) Nr. 9, pp. 367-372
Hsunling B., Chungsying L., Chung-Liang Ch. (1994). A model to predict the system
performance of an electrostatic precipitator for collecting polydispersed particles,
J. of Air and Waste Manage, ASSOC, Vol. 45, pp. .908-916
IEEE-DEIS-EHD Technical Committee (2003). Recommended international standard for
dimensionless parameters used in electrohydrodynamics, IEEE Trans. Diel. Electr.
Insul. 10-1, pp. 3-6
Jaworek A., Jędrusik M., Świerczok A., Lackowski M., Czech T., Sobczyk A.T. (2011).
Biomass co-firing. New challenge for electrostatic precipitators, Procce. XII
International Conference of Electrostatic Precipitation, ICESP XII, Nuernberg, 10-13 Mai
2011
Jędrusik M. & Świerczok A. (2006). Experimental test of discharge electrode for collecting of
fly ash of different physicochemical properties. Procee. International Conference on
Air Pollution Abatement Technologies – future challenges. ICESP X, Cairns,
Queensland, Australia, 25-29 June 2006,
Jędrusik M. (2008). Elektrofiltry. Rozwinięcie wybranych technik podwyższania skuteczności
odpylania, Oficyna Wydawnicza Politechniki Wrocławskiej, ISBN 978-83-7493-387-2,
Wrocław
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on electrostatic precipitation process, Journal of Electrostatics, 67, pp. 105-109
Jędrusik M. & Świerczok A. (2011). The influence of unburned carbon particles on
electrostatic precipitator collection efficiency, Journal of Physics: Conference Series
301 (2011) 012009, doi:10.1088/1742-6596/301/1/012009
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Taylor & Francis Group, ISBN: 1-57444-782-3
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plane coronas, IEEE Transaction on industry Applications, vol. 28, No.6 Nov/Dec,
pp. 1424-1431
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use In ESP modeling, Procee. 8th ICESP, Vol. 1, Birmingham, Alabama, USA, May
14–17, 2001
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laboratory-scale electrostatic precipitator with barbed discharge electrodes, Procee.
6th International Conference on Electrostatic Precipitation, Budapest, Hungary, 18-21
June 1996
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favourable EHD-field with low dust layer erosion in electrostatic precipitators,
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18-21 June 1996
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10
Allergens, Air Pollutants and Immune System

Function in the Era of Global Warming
Barbara Majkowska-Wojciechowska and Marek L. Kowalski
Departament of Immunology, Rheumatology and Allergy, Medical University of Łódź
Poland
1. Introduction
Nowadays, almost half of the world's population lives in or near areas where the quality of
air is poor. Rapid changes in the environment related to the“industrial revolution” have
changed the earth within almost no time. These civilization changes are usually positive, as
they lead to technological advancement, raising living standards, providing better health
care and hygiene. They are however accompanied by unforeseeable climatic changes and
negative health effects, which result from progressive contamination of the biosphere, as
well as excessive exposure to toxins and allergens. They, in turn, lead to a growing number
of immune system dysfunctions or even deaths in animals and humans.
It is estimated that in the 20th century, only around 100,000 chemical substances were
introduced. However, the pace at which new ones are being introduced is still growing. In
2009, 50 million synthesized chemical compounds were entered into the international register,
“The world’s largest substance database” and of that number, 143,000 compounds were used
for industrial purposes. At present, as it has been recently updated (04 November 2011), the
number of the registered compounds is now 63, 839, 600 which means an increase of more
than 20% within less than two years 59. It is a fact that the air in urban city agglomerations is
contaminated with hazardous compounds which appear as a result of the process of
incomplete burning of minerals used in transport, power and other industries. Some of them
exacerbate the greenhouse effect and cause disorders in the immune system. Additionally, we
should not neglect the widespread pollution of rural areas. Pollution also brings about
disorders in the immune system in humans, domestic animals as well as wild animals.
Although the concentration of certain chemical substances is monitored in the air, water and
food, some studies have shown that the influence of the concentration on dysfunctions of
immune system in an individual is very complex and often difficult to explain. When the
homeostasis of the immune system is disturbed it is difficult to treat such cases.
The immune system is a highly complicated, even intelligent, system with a characteristic
hierarchy. Studies show that the system often has difficulty in adapting to environmental
changes. More and more immune pathologies are appearing. They start with
immunosupression, immunomodulation and finish with autoagression and allergy. The
reasons for these phenomena are still being examined. Epidemiological, clinical, as well as
toxicological, examinations conducted on humans and animals are the grounds for
evaluation of health effects resulting from environmental pollution. The analysis of factors
222 Air Pollution – Monitoring, Modelling, Health and Control
related to local and global environmental changes, particularly the toxicology of the urban
environment, which might affect the proper functioning of the immune system is highly
important from the point of view of public health. It is known already that environmental
toxins can lead to reduced resistance of the epithelium and facilitate the contact of
inhalatory allergens with the “network” of dendritic cells. The activation of these cells by
toxic compounds make the allergens more recognizable. The exposure to the factors might
lead to oxidative stress through the production of reactive oxygen (ROS) and nitrogen
species (RNS) at an amount which cell defensive mechanisms cannot manage.
Environmental toxins, depending on the dose, can cause permanent changes, including
epigenetic ones. Recently, the clinical evaluation of immune system dysfunctions has been
thoroughly analysed; the genetic and environmental aspects are taken into consideration, as
well as any climatic changes which might lead to an increase in the allergogenic potential of
natural organic compounds that might directly affect the immune system 98. All these
factors and related compounds are potent. Their health implications might be unforeseeable,
instant, long-term, irreversible or permanent. The aim of the study is a review of modern
environmental toxins, their relationship to the process of global warming, the appearance of
disturbances in the immune system as well as chronic inflammatory diseases of the
respiratory system.
2. Classification of air pollutants

Air pollutants are usually classified as natural and anthropogenic. Another classification
also takes the environment into consideration.
2.1 Natural pollutants

Natural pollutants – geological (e.g. volcanic ash emission, fires, emission of minerals
coming from soil erosion). On the European scale, the pollution is monitored with satellite
data from the UE MACC 2010 international research project. The European database for
biogenic pollution (from 35 countries in Europe): pollen and fungal spores, can be found on
http://www.polleninfo.org/.
2.2 Anthropogenic pollutants

Anthropogenic pollutants – chemical compounds which are produced as a result of human
activity. They appear in industrial and metallurgical technological processes; they are
combustion products of fossil fuels, dust and aerosols. The last category comprises pollutants
which pose a health hazard for a man - NOx O3, SO2, CO, nicotine smoke, hydrocarbons, lead,
chromium, particulate matter (PM), including nanoparticles. There has been a rapid increase in
the number of reports demonstrating a close relationship between the exposure to
anthropogenic substances and disorders of the immune, respiratory and cardiovascular
systems or even a growing number of deaths. Findings show that poor air quality results in
dysfunctions of the immune system. They, in turn, lead to the poverty of people inhabiting the
particular region 105,118. The classification of pollutants is also based on the number of
particles in the air, their origin and state of aggregation, while a further classification concerns
the place where the pollutants are measured e.g. city/rural environment, air inside/outside a
building. This study aims at presenting the influence of particular toxins on human health and
we try to give a detailed description of those toxins one by one.
Allergens, Air Pollutants and Immune System Function in the Era of Global Warming 223
2.3 Dirty dozen: Examples of compounds which heavily pollute the environment and
cause immune pathologies
The Environmental Protection Act and directives issued by the European Parliament and
the European Council as of 21 May 2008 provide the necessity of constant monitoring of air
and 12 of its components which pose a health hazard:
 nitrogen dioxide NO2,
 sulfur dioxide SO 2
 carbon monoxide CO,
 benzene C6H6,
 ozone O3,
 particulate matter PM10,
 lead Pb in PM10
 arsenic As in PM10,
 cadmium Cd in PM10,
 nickel Ni in PM10,
 benzopyrene in PM10,
 particulate matter PM2,5.
According to the provisions of the European Union, this act must enforced in all member
states and its established regulations are required to be respected by cities with populations
above 100,000 37.
2.4 Urban outdoor pollution

Large cities are spread all over the world. In Europe, around 75% of the population live in
cities. Therefore, the majority of scientific research on the topic of air pollution is performed in
cities. The pace of migration from rural areas to cities is still fast. Unfortunately, city dwellers
pay a huge price for living in large agglomerations where even breathing puts their life at risk.
The air in major cities contains over 700 substances, both organic and inorganic compounds, as
well as metals (e.g. lead, cadmium, manganese, mercury) and their compounds with other
stable inorganic and organic substances, including DEP, soot, dust, smoke, dioxins, metals,
polycyclic aromatic hydrocarbons (PAHs) – pyrenes, benzoapyrenes, dibenzofurans,
polychloro aromatic hydrocarbons (VOC), fungal and pollen allergens and many others.
In polluted city environments, there is a deficiency of bacterial flora with probiotic and
saprophytic properties (e.g. bifidobacterium, lactobacillus) and so the inhabitants are
exposed to pathogenic microorganisms (e.g. Staphylococcus ureus, Candida albicans) 86.It
has also been confirmed that dust collected in city areas is characterized by higher oxidative
activity, mainly because of the presence of metal ions Fe3+. In healthy people a typical
concentration of dust (< 0.2 ppm) usually causes reversible effects such as irritation of the
mucous membrane in the conjunctiva and upper respiratory tract.
2.5 Rural outdoor pollution

Air quality in rural areas is much less frequently monitored. Intensive agricultural
developmentand other industries contribute to progressing soil and water pollution with
the remnants of fertilizers and pesticides, which impoverishes soil and causes wood atrophy
(Figure 1). In water reservoirs, algae bloom, block access to oxygen and cause eutrophication
Fot. Agnieszka Wojciechowska

Fig. 1. The effects of plant vegetation in unpolluted (Łódź, Arurówek) and polluted
(Krzewo) areas in central Poland.
of water ecosystems. The agricultural industry also contributes to the excessive emission of
nitrogen compounds; NH3 and NH4+ions have been used on a huge scale in artificial
fertilizers since the 1st half of the 20th century. Nitrogen compounds and other substances
coming from rural areas are bound by PM particles and often transported over longer
distances by acid rain. Many compounds which are found in weed-killing agents may
irritate the respiratory system and even block receptors for hormones or neurotransmitters;
many pesticides are inhibitors of acetylcholinesterase. They negatively influence the
homeostasis of the body and its immune system. Pesticides and toxic herbicides may also
have immunotoxic and immunosuppressive properties. They can act by causing
deactivation of lysozyme, an important protective factor against pathogenic Gram(+)
bacteria present in saliva, tears, secretion of mucosa and body fluids in phagocytes 20.On
the level of adapted immunity, they can act by, among other things, inhibiting lines of T
CD4(+), CD25(+)lymphocytes and T reg lymphocytes 30.
2.6 Indoor pollution

Poor air quality inside a building might constitute a serious environmental threat 41. It has
been confirmed that air pollution inside buildings is usually 2 - 5 or even 100 times higher
than outside 62.Interestingly, not only pollutants coming from outside are responsible;
pollen,house-dust allergens such as mite allergens and cockroach allergens, as well as
fungal spores, animals, household cleaning products, building materials, air fresheners,
naphthaline and even dry-cleaned clothes also exert an allergenic effect 40. House owners
are also threatened with breathing fumes emitted during the process of burning traditional
biofuels, such as gas, coal and wood, as well as highly toxic nicotine smoke, which contains
more than 6000 toxins. One such component of cigarette smoke is nitrogen oxides, whose
level ranges between 200 mg/m3 and 650 mg/m3 147. The WHO defines the 1-h limit value
of 200μg NO2/m3 air. Due to their poor water solubility, the site of immunotoxicity of nitric
oxides is the upper respiratory tract. The unfavorablesituation inside buildings could be
improved quite easily. For example, the use of chemical products could be reduced or the
building occupants could stop smoking nicotine, since the filtration of air polluted with
nicotine smoke is hardly effective 22.
Another world concern is pollution with bisphenol or tributyltin (TBT), compounds which
can be found in house dust, as well as outside, and which can seriously impair the immune
system in humans and animals.
Bisphenols (PBA, PBC) belong to a group of extremely dangerous toxic indoor compounds
which have been in use for more than 50 years. Bisphenols can be found in many everyday
products made of polycarbonate. Exposure to bisphenols is hazardous even in intrauterine
life. Bisphenols have been identified in the blood of infants whose mothers used simple
devices for recycling domestic waste while pregnant; they were exposed to polychlorinated
biphenols (PBC) by breathing them in. The infants’ birth weight was lower and their Apgar
scores were worse 146. The list of sources of biphenols is long. The compounds accumulate
in house dust, which is highly dangerous for children. They can be found in commonly used
plastic objects such as bottles for babies (although the production of bottles containing BPA
in EU countries was banned in March 2011, and the import and sale of such bottles was
banned in June 2011), plastic bottles for milk and drinks, kitchen utensils, wrapping food
foil, dental fillings, dentures, dental bridges, food and medicine packaging, as well as plastic
elements within various medical devices such as inhalers, dialyzers, pacemakers, contact
lenses and protective masks. They are also components of paper and are found in fire
retardant agents in furniture and fabrics as well as in electric cables.
Bisphenol easily penetrates the skin, air passages and the alimentary tract. It can induce
dangerous epigenetic changes in reproductive cells, disturbing chromosome division
(aneuloplodia) thus potentially leading to Down syndrome. After heating or sterilizing these
articles (e.g. bottles for babies) polycarbonates are slowly degraded and, as a consequence,
bisphenol molecues are released dozens of times faster. Due to the similarity of PBA
molecues to estrogens, these compounds induce many hormonal disturbances, mainly in the
thyroid and pituitary gland; they alsoinfertility, neoplastic diseases , diabetes, obesity as
well as have neurotoxic properties 125.
Due to their high toxicity, tributyltins (TBT) are also regarded as some of the most
dangerous substances polluting the indoor environment. TBT have been found in the air
inside many public buildings and private houses 97. Many analyses have confirmed their
immunosuppressive character, which might lead to impairment of anti-infectious immunity
and development of neoplasms. Despite this, TBT have been widely used in agriculture and
industry since the 1960s. Nowadays they can be found in plastics, herbicides, household
cleaning agents and building materialsdespite a considerable body of alarming information
concerning their negative effects. They are in recycled products and their production has not
been banned, yet. They are used for conserving wooden objects, hulls in ships, in textiles,
plastic products, fungicidal, insecticidal and bactericidal agents, commercial catalysts and
even toiletries,especially in antibacterial additives for washing liquids and soaps, pampers
diapers and toys for children 74. These toxins have also been traced in many alimentary
products, even in the milk of breastfeeding mothers. Toxicologists warn against using
plastic boxes, toys and other products, even those which were permitted to be sold by the
FDA, because of their potential effect on cell metabolism. By disturbing endogenic steroid
hormones and modifying the activity of many drugs, they induce irritation of respiratory
passages, skin and eyes, and have neurotoxic properties 133. It has been confirmed that
TBTs activate peroxisome proliferator-activated receptors (PPARs), present on cells, which
might lead to metabolic disorders, upset the lipid balance and as a consequence, lead to
diabetes and obesity 29. Nevertheless, there are hopes that recently isolated bacterial
strains (class Bacilli and c-Proteobacteria) might play a role in the biodegradation of TBT 4.
2.7 Air Quality Index (AQI)

In most countries all over the world, the level of air pollution is constantly monitored.
However, for many people, the data is inaccessible or cannot be understood. In American
countries there is one general air pollution indicator called the Air Quality Index (AQI) 60,
thanks to which, it is possible to provide a daily practical and yet complex evaluation of
many pollutants on the American continent and show to what extent air quality might have
a negative influence on health. The AQI values are presented on a six-grade scale. In
European countries there are initiatives to introduce a uniform index evaluating air quality
which might improve the system of sending information and warnings. The levels of EPA
Air Quality Index and their relationship with oxidative stress biomarkers in epithelial cells
are shown in figure 2.
Fig. 2. Levels of oxidative stress biomarkers in epithelial cells and their relationship with the
EPA Air Quality Index. It has been developed on the basis of the “Air Quality Index (AQI) -
A Guide to Air Quality and Your Health”
http://www.airnow.gov/index.cfm?action=aqibasics.aqi, and Xiao GG, Wang M, Li N, Loo
JA, Nel AE. Use of proteomics to demonstrate a hierarchical oxidative stress response to diesel
exhaust particle chemicals in a macrophage cell line. J Biol Chem. 2003;12;278:50781-90.
2.8 Allergens and environmental toxins

A great number of atmospheric aerosols are of biological character. It has been estimated
that bioaerosol constitutes 5 – 10% of the total volume of PM 100. Plant pollen and fungal
spores are dominant in rural areas rather than in cities. However, city inhabitants more
frequently suffer from pollen allergy 95. According to scientific findings, the main factor
favouring pollen allergy might be oxidative stress connected with the synthesis of NADPH
endogenous oxidase in pollen grains such as those of birch or ambrosia, and air pollution of
oxidative character. They can have a negative, pro-oxidative influence on cells of the
epithelium of the respiratory tract, activation of dendritic cells and stimulation of pro-
inflammatory processes which might contribute to the development of the allergy
113,5.The evaluation of the dose-response relationship between the exposure to pollen and
allergy symptoms is unclear. An interesting study was performed by scientists in Basel,
Switzerland in which they gathered a database on the levels of birch and grass as well as the
incidence of allergy over a period of 39 years. It concluded that within 20 years (from 1969 to
1990) with the increase in the level of pollen, there was an increase in the incidence of hay
fever and allergy to birch and grass pollens. In the two subsequent decades (from 1991 to 2007)
scientists observed the decrease in pollen of these taxons, which was accompanied by a
decrease in the incidence of allergy 45. Other experiments have not shown a dose-response
relationship between the sIgE level in serum and exacerbation of clinical symptoms induced
by Timothy pollen 65. It should be remembered that environmental allergens are most often
the proteins of living organisms sensitive to changes in the natural environment, such as
temperature, osmolarity, humidity, pH and exposure to toxins. Modern methods of molecular
research facilitate introducing detailed patterns ofenvironmental stress response (ESR) caused
by environmental pollution; not only in terms of genetics, proteomics and kinetics of their
synthesis but also in terms of the virulence/allergenicity of proteins, as well as the response of
the immune system to synthesized compounds. The synthesis of co called pathogenesis-
related proteins (PRS), which might be both allergens and toxins, is one of the forms of plant
and fungal spore response to air pollution.
2.9 Pollen allergens and environmental pollutants

Plants are considered to be highly efficient, ecological air filters whose filtering capacity grows
with the growing level of pollutants.They are able to absorb and accumulate magnetic
nanomolecules (Fe3O4) 151 and even 97% of toxic VOCs (volatile organic compounds) from
the atmosphere 72. Rarely are the potential consequences for flora, fauna and a human
considered. We already know that air pollution absorbed from the atmosphere contributes to
the growth, development and yielding of plants. They have a toxic influence on generative
tissues and decrease the production of plant pollens; for example, herbicides commonly used
for killing weeds inhibit the production of pollens in arable crop 36.
Pollen grains are too large to get to the lower airways and the symptoms of allergic reaction
depend on allergens emitted after the destruction of the pollen exine. It has been concluded
that gas pollutants, found in PM, react with the hydrocarbons of the cell wall leading to the
modification of its structure and changes in the shape of the pollen grain, which facilitates
the release of allergenic proteins. Sometimes, under the influence of these changes, plants
produce a greater number of grains but of smaller size. They can also penetrate the plant
tissues and interfere with their physiological processes, the course of photosynthesis and the
cell metabolic pathway. They induce some damage to cells and mutations. For example,
upon penetrating the cell, SO2 can react with water and become sulfuric acid, which inhibits
the process of photosynthesis and damages cells 115.
Pollen allergens can remain in the air for as long as for a few weeks and join many
pollutants. The presence of aeroallergens/air pollutants interactions appears to increase the
morbidity from aeroallergens, but immunomodulation mechanisms are not clear. It is
possible that allergens interact with environmental pollutants to increase their interactive
effects(figure 3).Microscopic analysis showed that in a polluted environment, the exine
(outer layer of the pollen) thinner, distorted and more susceptible to breaks, which favours
the emission of allergens 26. Also allergens emitted from pollen grains can change their
properties under the influence of chemical substances 115. It was confirmed that O3
induces changes in intracellular signal transduction, which leads to changes in gene
expression and changes in the structure of allergen proteins. Air pollution might also induce
post-translational modifications of allergenic proteins. Chehregani et al. 25 confrimed that
after 5 to 10 days' exposure to Diesel’s particles (DEP) there was an increase in allergenic
potential of Lilium martagon pollen grains; immunoblotting subsequently confirmed the

existence of modified or new protein (35 kD), which reacted with IgE antibodies of
sensitized animals.Bommel at al. 18stated that pyrene – an important component of DEP
can aggravate an allergy by the induction of IL4 production. Exposure of human nasal
epithelium to DEP and allergens (in vivo) contributed to a decrease in the IFNand an
increase in Th2 cytokines 135. DEP particles can also act as allergic carriers, which intensify
the presentation process by antigen presenting cells (APC) 66. DEP particles can also
induce epigenetic changes and in that way stimulate Th2 response, as confirmed by in vivo
research 93. The destruction of the exine by environmental toxins favours the release of
Fig. 3. Greater allergenicity of pollen allergens, collected from polluted areas, would be
determined by chemical reactions between pollutants and pollen extracts and nonspecific
modulation of synthesis machinery for many proteins, lipids and enzymes in response to
environmental stress. Adopted from: Risse U, Tomczok J, Huss-Marp J, Darsow U, at al.
Health- related interaction between airborne particulate matter and aeroallergens (pollen).
Journal of Aerosol Sci. 2000;31, Suppl.:27-28.
phytoprostanes (lipophylic counterparts of prostaglandins) from pollen grains. The

phytoprostanes are highly water soluble; they can get to the lower airways and inhibit the
production of IL12 by dendritic cells, thus favouring Th2 response 31.
Many scientists point out the effect of pollution on climate warming, intense expansion of
thermophilic plant species and readier exposure to their allergens, e.g. ambrosia allergens
152. It is true that in some countries climatic warming lengthens the flowering season,
contributes to the increase in the number of pollen grains, synthesis of modified proteins
and allergenicity of some of the proteins. Strong winds resulting from weather anomalies
transport pollens and their allergens. Together with toxins, which react with pollens and
allergens, they cover long distances.
In their studies, Eckl-Dorna et al 38 showed that increased concentration of ozone

contributes to the increase in the number of allergens of rye pollen from groups 1, 5, 6 as
well as panallergens such as profilins. However, according to other studies, some air toxins
can reduce the level of allergens. The exposure of grass pollen to an increased level of many
toxins simultaneously, e.g. NO2+O3 or NO2+SO2 induced the decrease in levels of typical
allergens; Phl p1b, Phl p4, Phl p5, Phl p6 and Phl p13, detected with an immunoblotting
method and specific IgE antibodies of sensitized rats. The decrease in the levels of these
allergens, according to the authors, might have resulted from mechanical or post-
translational modifications of these proteins, under the influence of pollutants. It was
difficult to detect them since the test highly sensitive and specific. There are plans to carry
out further studies with the use of spectrometric methods which should make it easy to
describe possible molecular changes in the epitopes of pollen allergens.
The existence of pollen grains in the atmosphere is based on the regular cycle of
vegetation and flowering. The exposure to plant pollen fungal spores depends on many
factors, among others, geographical latitude, global and local air circulation, weather
factors, the level of urbanization of the environment and air pollutants. Numerous
parameters characterizing climate warming, perceivable in many regions all over the
world, influence the course of phenology and pollen distribution. Direct factors, such as
temperature and precipitationas, well as more extreme weather phenomena, either induce
the production of pollen or reduce it.
The indirect effects of higher temperature include the early blooming of trees, transport of
pollen over a long distance and modification of flora (including the expansion of
thermophilic taxons ofplants such as ambrosia). In many centres which carry out long-term
agrobiological and phenological studies, earlier and longer flowering seasons of allergenic
plants have been observed. Biological observations performed by Ariano et al. 9 in Italy for
27 years showed a 25% increase in the level of pollen as well as an increase in the length of
pollen seasonsParietaria (=85 days), olive (=18 days) and cypress (=18 days). It was
shownthat intensive exposure to pollen allergens contributed to the increase in the
incidence of allergic episodes in people sensitized to pollen allergy in comparison to mite
allergens. Kosisky et al 81 published the results of their twelve-year observations from
Washington. They stated that although the level of pollens measured globally did not
increase, the number of days with higher pollen counts did: by about 258% for grasses and
by almost 12% for trees. Studies conducted in Switzerland over 21 years, gathered by Clot
28 showed no particular changes in the pollen level. It should be pointed out that intensive
production of pollen by plants can depend on many other factors, such as artificial fertilizers
in the environment, an increase in the size of rural areas because of not cultivating arable
land, development of soil erosion and desertification 112.
Apart from plant pollen levels, aeroallergens are also the subject of studies. Singer et al 123
showed a dangerous increase in allergen content in ambrosia pollen grains under the
influence of increased concentrations of greenhouse gases. The response to the raised
amount of CO2 was a raised level of the most important allergen of that taxon, Amb a1,
despite the fact the number ofambrosia pollen grains produced did not increase 21. The
results of a study performed in London showed the effect of allergen activity and air
pollution (<PM 10) synergy can be spectacular; asthma was aggravated as a result of a 25%
increase in IgE levels in the serum of patients sensitized to grass or tree pollen 50. Air
pollutants induce adjuvant effects which favour inflammatory processes, immunization and
aggravation of asthma and allergy. Many studies highlight a positive relationship between
the number of hospitalizations, high level of plant pollen and exceeding the maximum
concentration of air chemical pollutants, especially SO2and PM particles.
2.10 Environmental pollution and pathogenesis-related proteins (PR)

It was confirmed that in unfavourable environmental conditions such as a pest invasion, the
presence of microorganisms and fungal spores, exposure to fertilizers, air pollution caused
by ozone, ultraviolet rays, phytohormones, pesticides, artificial fertilizers, the growth of
temperature, plant cells synthesize pathogenesis-related proteins (PR), which are very often
allergenic for humans. Interestingly, about 25% of the described plant allergens gathered in
the database of International Union of Immunological Societies (IUIS), are (pathogenesis-
related (PR) proteins. The mechanisms of their synthesis are still unknown. PR proteins,
including, among others, isoflavone reductases and plant antibiotics, are numerous and
usually belong to various families. The most common PR proteins have been classified into
17 families, marked PR1 – PR 17 according to taxonomic classification, molecular sequence,
biochemical and functional characteristic as well as the response generated by the human
immune system 137,138.
Many PR proteins have a high allergenic potential and great cross-reactivity. For example,
PR-3 is a chitinase, the synthesis of which is an common reaction of plants to heavy metals,
and the expression of Cup a 3, a PR-5 cypress allergen, is significantly higher in the pollen of
plants grown in polluted areas 127. PR proteins from group10 include ribonucleases and
proteins similar to the main allergen of birch pollen: Bet v 1 and e.g. hazelnuts: Cor a 1 124.
The enhanced synthesis of PR in plant cells and pollen contributes to a growing number of
allergic reactions, including dangerous oral allergy syndrome (OAS) and even
analyphylactic reactions. In sensitized patients suffering from pollen-food allergy syndrome,
the first syndrome is allergy to inhalant allergens 19, especially in the city environment.
Interestingly, until recently, pollen grains have been considered simple, even primitive
structures, dependent on vegetative organs of plants and inactive in a metabolic sense.
However, thanks to the analysis of the pollen genome and the profile expression of
particular genes, it has been possible to have a greater insight into the unusual
transcriptional dynamics of pollen. It was concluded that while ripe pollen is relatively
resistant to air pollution in dry air, an increase in humidity triggers a cascade of reactions
resulting in activation of highly dynamic metabolic processes, as well as a rapid increase in
the process of gene transcription, synthesis of new compounds and conformational
modifications of the existing proteins. A classification of transcripts carried out with
bioinformatical analysis (DNA-ChipAnalyzer, GeneChip ® Array Genome) has made it
possible to identify more than 51,000 compounds, many of which have been classified as PR
proteins. In various stages of pollen life, i.e. starting with its creation, then development and
germination of pollen tube, there are many changes in gene profiles and expression which
take place and which depend on external factors and the toxins present 91. It can be
concluded that plant pollen should be treated as an aerobiological index for atmospheric
pollution.
3. Allergens of fungal spores and pollution

Fungal spores are important elements of bioaerosols. Continual climate warming,
demonstrated by an increase in temperature, precipitation and floods, causes increased
exposure to fungal spores, both in the internal and external environment. Fungal spores
have a many-faceted influence; they can induce mycosis, and the proteolytic enzymes and
toxic products of metabolism known as called mycotoxins can damage epithelial protective
barriers and have pro-inflammatory cancerogenous properties. β-glucans of fungal spores
have adjuvant effects which indirectly favour the development of allergies by activating Th2
lymphocytes 67.
Exposure to fungal spores and plant pollen is measured by the volumetric method:
measuring the number of spores per 1m3. Another method involves measuring the level of
fungal products e.g. 1 – 3 β-glucans, which can demonstrate pro-inflammatory properties,
both in atopic and non-atopic patients. According to Becker et al 12 the incidence of
allergies to fungal spores (unlike to pollen allergens) can be underestimated due to lack of
proper standardization of commercial extracts of some fungi such as Aspergillus or
Penicillium. The spores of widely known fungi such as Cladosporium, Penicillium,
Aspergillus, Helminthosporium and many other species are considered pollutants and
infectious factors, as well as important risk factors for the development and aggravation of
allergies and asthma. Studies carried out in the north of Poland indicated a minor influence
of air pollution on the number of Alternaria and Cladosporium spores in 1m3 51. Some
other studies have shown that pollutants can cause an increase in virulence of fungal spores.
It has been confirmed that pollution induces the increase in the synthesis of melatonin in the
conidia of Aspergillus fumigatus fungi, which leads to aggregation and makes them more
resistant to lysis after being phagocitized by macrophages. The melatonin of mould spores
can also contribute to the increase in virulence by not inhibiting apoptosis in macrophages
which phagocitosethe conidia of fungal spores. It also increases their resistance to
ultraviolet rays 139.
Research on Aspergillus fumigatus showed demonstrated the possibility of activating a
dozen or so mechanisms of cell signalling, mainly mitogen-activated protein kinase
(MAPK). It was concluded that, like in plants, environmental factors activated the genes
responsible for the synthesis of PR proteins, enzyme modification and synthesis of pigment
which intensified the virulence of fungal spores, induced inflammatory processes and killed
experimental animals 1. Studies carried out inpolluted areas in Asia indicated that
increases in air temperature, wind speed, rainfall and pollutants (e.g. solid particles –
aerodynamic diameter ≤10 μm (PM10) and carbohydrates) increased the number of fungal
spores in the atmosphere 24.People who suffer from low resistance to fungal spores can
develop serious infections such as Aspergillosis. It was stated that the exposure of the
respiratory system to Aspergillus fumigatus spores can stimulate the production of IFN-γ
by specific Th1 (CD4+) lymphocytesor Th2 (CD4+) cytokines, thus favouring allergies,
depending on the phenotype of experimental animals 117,84.
The studies showed that the conidia of Cladosporium spp., Stachybotrys spp. and
Aspergillus niger are considerably resistant to the activity of pollution, also with ozone
80.Only high levels of ozone (which increase in cities when the temperature is >30 °C
and humidity is low 40%) can inhibit the development of fungal spores e.g.
Cladosporium spp 39,141.
3.1 Fungal spores can be considered serious air pollutants

It was concluded that the exposure to Aspergillus fumigatus and allergens of house-dust
mites favours the development of asthma and the allergic inflammation of the respiratory
tract. It thus enhances the activation of congenital and acquired immunological response.
Fukahori et al. 47showed that a strong reaction of dendritic cells to a simultaneous
exposure to fungal spores and Der f1 might result from the activation of TLR2 receptors by
the β-D glucan of the fungal spores, which in turn, leads to a synergetic activation of
dendritic cells by mite allergens. Stimulation or blocking of TLR receptors as well as
increases in IL-10 and IL-23 can change the balance of Th1/Th2/Th17/Treg and their
influence on the course of allergic reactions. Recently Liu et al 93 presented the results of
the exposure of Th2 lymphocytes in mice sensitized to Aspergillus fumigatus allergens and
DEP particles. During in vitro studies they noticed epigenetic changes which involved
hypermethylation of IL4 and IFNγ gene promoters, which led to polarization of Th
lymphocytes toward Th2. Methylation of both the gene promoters was correlated with an
increase in IgE level, which might imply that proteins of fungal spores, like air pollutants,
can play a role in the pathogenesis of asthma and allergy through epigenetic mechanisms.
4. The environmental pollution and the oxidative stress

4.1 Pathways of toxin penetration.
Particles of dust and toxins are mostly absorbed by the lungs but also by the skin and
alimentary tract and even by the placenta, which has a negative influence on a foetus.
4.2 Exposure to toxins of respiratory epithelium.

Human lungs constitute an area of 100 -140 m2 , they are strongly vascularized and are
constantly exposed to infectious factors and environmental pollution. Healthy lungs absorb
air at the rate of 14 breaths per minute, which equals about 10 litres per minute and about
10,000 – 15,000 litres per day. Inhaled air, before it gets to the lowest located parts of lungs,
is partly filtered and climatized. The mucous membrane in the nose prevents the largest
polluted particles from getting inside the body. In order to cleanse themselves, lungs use
their cilia, which expel polluted mucosa at 16 beats per second. The respiratory epithelium is
a protective barrier which actively protects the body and, if needed, activates the cells of the
immunological system. Proteins such as filaggrin, loricrin and involucrin play an important
role in reinforcing the epithelium against attack. They make it stronger and more resistant to
invasion of microorganisms, allergens and chemical compounds. It was concluded that both
epigenetic changes in genes caused by environmental pollution and cytokines of Th2
lymphocytes e.g. IL 4, IL13, TNF-α inhibit the production of filaggrin and other proteins,
which might favour immunization, development of atopic dermatitis, allergy and asthma
due to increased epithelial permeability 76,102. In sensitive people, air pollutants,
including allergens, can be bound by proteins and lipids of the epithelial cell membrane and
thanks to them, can penetrate the inside of the cell.
Epithelial cells can initiate various protective initiatives against air pollution. One example
might be the activation of numerous genes (300 – 550). The activation usually leads to the
growth of the synthesis of pro-inflammatory cytokines and activation of cells which
phagocytose many fractions of dust, allergens and bacteria 101,10. Studies show that
exposure to pollution induces cell stress. This, in turn, activates very complicated mechanisms
adjusted to particular situations through increased expression of particular transcriptional
factors, the synthesis of protein (e.g. SKN-1/Nrf) and the activity of proteasome in utilizing
unneeded particles. These processes facilitate the maintenance of homeostasis of cells and
protects them against activation of neoplastic processes and autoaggression 92.
In high levels of pollution and environmental toxins, these natural mechanisms are
insufficient. It has been confirmed that the amount of PM particle fractions which penetrate
the lungs depends not only on the size of the inhaled particles but also on the ability of the
organism to cleanse and detoxify itself, which is genetically determined. However, in people
who are exposed to nicotine smoke for a long time, neither detoxifying enzymes nor
antioxidative protective mechanisms function properly, which favours bronchial
hyperreactivity, asthma and lung-remodelling process.
Figure 4 shows the relative sizes of inhaled particle, patterns of their airway deposition and
main health effects of air pollution.
4.3 The environmental pollution and the oxidative stress.

Each organism is constantly exposed to both endogenic and exogenic oxidizing compounds.
Endogenous free radicals – reactive oxygen species (ROS), such as: O2– , OH*, H2O2 and
nitrogen - reactive nitrogen species (RNS), e.g. NO*, ONOO– are constant products of
chemical reactions associated with respiration and processes within cells such as activated
phagocytes and eosinophils active in allergic processes, and are considered the main source
of ROS. In physiological conditions, free radicals pose no threat because of natural
enzymatic and nonenzymatic protective systems of an anti-oxidative character 99.
Exogenous free radicals are neutralized mainly in the mitochondria of lung epithelial cells.
The key antioxidant is glutathione. The synthesis of protective compounds in relation to
ROS is stimulated among others by the activation of transcription factors, e.g. Nrf2, which
leads to the activation of proteases and antioxidants and modulates inflammation by the
inhibition of the NF-B pathway. The activation of the Nrf2 metabolic pathway is important
in the prevention of many inflammatory diseases, neurodegenerative diseases, diabetes,
pulmonary fibrosis and neoplasms, additionally, Nrf2 overexpression in neoplastic cells

protects the cells against the cytotoxic activity of antineoplastic drugs 126. The activation of
Nrf2 might ameliorate the degree of lung impairment caused by nicotine smoke 130.
Fig. 4. Relative sizes of inhaled particle, patterns of their airway deposition and main health
effects of air pollution. PM - particulate matter, UFP-ultrafine particles (particles <100 nm).
Adopted from: Chang C. The immune effects of naturally occurring and synthetic
nanoparticles. Journal of Autoimmunity. 2010;34:234-246.
4.4 The oxidative stress and the cascade of inflammatory effects induced by
polluted air
The hierarchical model of oxidative stress presented in figure 2 shows the negative effects of
the exposure to environmental pollution.
Level 0: Preventing the production of free radicals.

A lot of enzymes prevent the development of chain reactions leading to appearance of free
radicals, e.g. glutathione peroxidase.
Level 1: Antioxidative cell protection.
The first stage of protection includes binding free radicals and breaking the cascade reaction.
Here antioxidative enzymes and metalloproteins, i.e. proteins which bind ions containing
copper and iron, are active. The second stage of protection includes ROS “scavengers”:
flavonoids, vitamin A, vitamin C, bilirubin, uric acid and glutathione. Relatively mild
oxidative stress stimulates cell structures mainly through Nrf2 nuclear transcription factor
for transmission signals for the expression of proper genes, production and activation of a
numerous group of antioxidants.
Level 2: Inflammation.
If protective mechanisms turn out to be insufficient in neutralizing the excessive number of
free radicals, it is difficult to maintain homeostasis. Moreover, an increase in the cascade
expression of many pro-inflammatory genes for cytokines, chemokines, adhesive molecules
and the heat-shock proteins active in inflammatory processes 71. The activity of NF-B
transcription factor inhibits Nrf2, which decreases the expression and gene transcription of
antioxidants essential in detoxification. The disturbance of the proper function of Nrf2 genes
can also impair antigen presentation in the mechanisms of major histocompability complex
class II, which makes the body more susceptible to both allergic and infectious diseases
144.It has also been confirmed that the exposure of a mouse with Nrf2−/− to DEP particles,
even to small doses , leads to an increase in bronchial hyperreactivity and oesinophilic
inflammation of the respiratory system 87.
Level 3: Damage to mitochondria, cell apoptosis.
The third level of oxidative stress which is impossible to neutralize by protective
mechanisms breaks the protective system. Great stress induces changes to Ca2+ ion
concentrations, permeability of mitochondrial membrane and disturbances of mitochondrial
functions. It contributes to energetic insufficiency of epithelial cells and the release of factors
leading to apoptosis. Such processes are induced especially by PM particles and ultra small
dust particles (UPF<0.1 m) collected in urbanized city areas as they are characterized by a
higher potential for ROS induction in cells than PM10 and PM2,5 particles 88.It is worth
mentioning that apoptosis protects the body against the development of neoplasms,
especially in the polluted environment.
4.5 Reactive oxygen species (ROS) and bronchial asthma

Excessive exposure to environmental pollution leads tothe development of unnecessary
ROS and RNS species. They attack cell membranes, disturb their electric potential and
proper function of ion pumps. Oxidized cholesterol favours the development of
atherosclerotic plaque. Overactive pro-oxidative processes might induce imbalances and
induce the oxidizing process. The synergy of endogenous and exogenousanti-oxidants,
which might neutralize free radicals, plays a key role in the protection against the
development of inflammation of the respiratory passage and aggravation of asthma. The
activation of the Nrf2 pathway is to a great extent, proof of adaptation to the natural
environment and factors. The anti-oxidative activity of Nrf2 is reduced in patients with
severe asthma 104. Children with severe asthma demonstrated posttranslational
modifications of Nrf2 and impaired protection against free radicals. Thus, it was stated that
”redox status” and the activity of Nrf2 can be invaluable in the assessment of asthma
severity 43.
5. The role of aryl hydrocarbon receptor (AHR) in immunotoxicity

AhRs are considered the most important receptors in the detoxification and discharge of
toxinsand are represented by a few proteins, including Hsp90 (heat-shock proteins). They
are present in the cell cytosol and naturally activated by bilirubin, arachidonic acid,
eicosanoids such as prostaglandins, leukotriens, metabolites and some natural compounds
present in food (tryptophan derivatives, diet carotenoids). It was discovered that AhRs are
activated by over 400 exogenous compounds and that in turn, the activation of an AhR
triggers the activation of cell transcription factors.
The TCDD dioxin is one of the strongest AhR ligands as it can securely bind these receptors.
Unfortunately, toxins accumulate in the body and, as the half-life for dioxins is between 7
and 10 years, long-term AhR activation might be favoured with a consequential activation of
genes encoding the enzymes metabolizing xenobiotics, which induces a chronic suppression
of the immune system. Therefore TCDD is regarded as one of the most toxic and
carcinogenic environmental toxins 56. The receptors, having bound to ligands, move to the
nucleus, where they activate gene expression , especially those responsible for the synthesis
of enzymes involved in the metabolism of toxins, such as superoxide dismutase, glutathione
peroxidase and aromatic hydrocarbons hydroxylase (from cytochrome P450 group).
Binding an AhR to a toxin leads first of all, to the development of toxic metabolites.
Secondly, it induces changes to gene transcription. Researchers observed stimulation of the
transcription of cytokine IL-17, which leads to the recruitment and differentiation of
neutrophils, and IL-22, which is essential in the synthesis of defensins necessary in
antibacterial immunity. An excess of IL-17 can disturb the balance of Th1/Th2 as well as the
balance of Th17/Treg and, consequently, contribute to intensive development of
inflammation, autoimmune and neoplastic diseases 150. Exposure to TCDD increases risk
of the development of granulocytic leukemia by up to 400%. The onset of the disease might
happen even 15 years later 14. An excessive amount of toxins might bind to DNA, RNA as
well as cell proteins and induce a number of pathologies 54,68,143.
6. Dysfunctions of immune system in the polluted environment

Environmental pollution might cause immunomodulation and the immunosuppression of
immune response 128, demonstrating insufficient anti-infectious and anticancer immunity
57; they may also concern hypersensitivity, including allergy 15 or autoaggression
42.Research findings indicate that even short-term exposure to toxins in the air can lead to
an increase in the incidence ofdisease and death. It has been estimated that in Canada, air
pollution contributed to about 8% of deaths in 2004 and as many as 10% in 2008 3 The
reaction to chemical agents present in the surroundings varies based on the individual.
Genetic factors, age, sex, physical condition, medicines taken, activity of endogenic
detoxifying enzymes, past diseases and various factors connected with lifestyle, dietary
habits and other risks, such a place of living, exposure to nicotine smoke: they all
determine different reactions to environmental chemical agents. Allergy and atopic
asthma are also effects of interactions between genetic susceptibility and the polluted
environment, which has a great influence on the development of atopic phenotype,
especially during rapid development in the prenatal and postnatal period 58. Intensive
exposure to allergens might have an impact on the development of tolerance. Yet,
coexistence of toxins usually causes adjuvant activity. Early exposure to toxic substances,
e.g. dioxins from nicotine smoke, PM particles, DEP, ozone might stimulate and preserve
the Th2 atopic phenotype dominant in pregnancy. The process can be accompanied by
suppression of Th1 cell proliferation. It might lead to the increased risk of the
development of atopic asthma in children 96.
6.1 The examples of pollutants influence on the immunological response

6.1.1 Coal compounds
Coal destroys ecosystems and pollutes the environment when it is transported, stored and
burnt. Also storing waste has negative implications on the environment. The process of
burning coal is considered the main cause of global warming as it is responsible for the 30
% growth of CO2 and methane (CH4) in the atmosphere compared to the pre-industrial
age 116. Toxic substances in waste and ash (e.g. chromium, cadmium, mercury, arsenic)
can contaminate potable water and food, and volatile fractions of ash can emit radiation
100,000 times stronger which nuclear power stations producing the same amount of
energy.
Health statusis the ability of the body to adapt to changeable surrounding conditions.
However, stress induced by excessive exposure to exhaust fumes and environmental toxins
is directly connected with the development of chronic inflammation of lower air passages
and even leads to the increase in death rate. A memorable smog which happened in
Belgium in 1930 106and in London in 1952, and a high level of SO2, which lasted for 5 days
in the smog, killed thousands of inhabitants of the city. At that time, the energy source was
coal.In Silesia, Poland, where coal was mined on a relatively high scale in Europe,the
mortality rate for young men (until 1989) was about 40% higher than the average national
mortality rate .Also in Germany between 1995 and 1998, researchers observed a higher
mortality rate which was closely connected with air pollution 111. Sang et al. 121
confirmed that an increased risk of hospitalization and death resulting from SO2 exposure
might be connected with its influence on excessive activation of Cyclooxygenase-2 (COX-2)
and prostaglandin PGE2, which leads, among other things, to the development of
inflammatory state and even neurotoxic activity.
Carbon monoxide (CO) appears as the result of exhaust fume emission, fires and volcanic
eruptions. If coal is burned properly, the emitted fumes contain about 1% CO. a safe level
for a human. In the case of insufficient oxygenation, fumes can contain as much as 30% CO.
The compound formed by binding hemoglobin and CO is called carboxyhaemoglobin, and
the process not only occurs 200 times more readily than in the case of oxygen, but the
product is more durable. A thirty-minute exposure to 0.1% – 0.2 % CO leads to death.
6.1.2 Nitrogen compounds

In the 20th century, the amount of nitrogen introduced to the cycle in the biosphere more
than doubled and the process is still continuing. Nowadays, apart from pollutants
characteristic of “the age of coal and steel” (mainly SO2 and PM) many other products of
burning crude oil and its derivatives used in industry, as well as road and air transport
exist. They have been emitted for more than 200 years and their level is constantly
increasing. The transport sector is the second greatest source of CO2 emission in the EU; in
the years 1990 – 2009, its emission increased by 20%. However, these fuels are not burnt
completely and apart from CO2, ever more toxic volatile and reactive nitrogen species (RNS)
known as NOx, O3, SVOC are being released into the atmosphere. It is estimated that transport
is responsible for about 75%of the nitrogen oxide pollution . Apart from emitting pollutants,
vehicles raise dust into the air , which might lead to greater bioavailability of allergens of plant
pollen and fungal spores, as well as particles of latex from car tyres. As a result, there might be
an increase in allergies to plant pollen, fungal spores as well as latex 116.
The natural level of nitrogen oxide ranges from 0.1 to 9.4 g/m3. The WHO defines a 1-h
limit value of 200μg NO2/m3 air, equivalent to 0.1ppm NO2. However, recent studies
showed that thirty-minute exposure of nasal epithelial cellsin tissue culture to 0.1ppm
NO2resulted in cytotoxicity and genotoxicity 78. NO2 levels ranging from 100 ppb to 400
ppb may impair proper functioning of lungs and the level above 5ppm might lead to
damage. 65In many industrial cities, the NO2 level is about 2 ppm 73. It was concluded that
NO2 level in the air outside depends on population density and intensity of transport. 17
Due to their poor water solubility, the site of toxicity of nitric oxides is the upper respiratory
tract. Studies carried out on healthy volunteers demonstrated that a two-hour exposure to
transport pollutants analyzed at an underground station in the centre of Stockholm (in peak
hours) led to the increase in the expression of markers of Treg cells and activation of
fibrinogen in the blood 119Jeng et al 69confirmed that a five-day constant exposure to
PM 10 particles resulted in an increase in fibrinogen level and IL6 level (i.e. cytokines which
stimulate B-lymphocyte differentiation to plasma cells and synthesis of antibodies). But for
people with asthma, even a short exposure to transport pollutants might turn out to be
hazardous. Sixty patients with asthma were naturally exposed to city pollution for two
hours by walking along Oxford Street in London. The studies on short-term exposure to city
exhaust fumes demonstrated that, despite the lack of subjective symptoms, forced vital
capacity (FVC) and one second forced expiratory volume (FEV1) values were considerably
reduced in comparison with the values gathered fromthe control group. Apart from those
different values, an increase in marker level in sputum (such as mycloperoxidase marker -
MPO) and a decrease in pH in respiratory passages were also observed 103.
6.1.3 Particulate matters (PM)

Particulate matters (PM) are emitted directly to the atmosphere (primary PM) or produced
from gas precursors, e.g. SO2, NOx, NH3, VOCs (secondary PM). PM is represented by solid
and liquid particles which can be of organic or inorganic character. It can be inhaled and
accumulated in the lungs. Exhaust fume emission, burning fuels, refining processes and
other kinds of environmental contamination contribute to the production of PM, which is
usually classified on the basis of particle size. The following fractions are monitored most
frequently: PM10 (< 10m), PM2.5 (<2.5 m), PM0.5 (<500nm), PM0.1 (<100nm). PM10 are
usually spherical, aerodynamic particles whose diameter is about 10m. The toxicity of PM
depends mostly on the chemical composition of the particles. Exceeded level of PM is
considered an air quality index in EU countries. In cities, fractions of particles are mostly
<2.5 m, and over 80% of fractions have a diameter of <0.1 m. The new trend, however,
sounds optimistic; between 1990 and 2008 emission of PM particles decreased in European
countries on average by 21%, but slight increase in the fractions of PM 2.5 – 10 m was also
observed 61. Study findings carried out in Łódź in the centre of Poland in 2009 showed the
maximum daily amount of PM10 being exceeded 35 times 64.Research conducted in China
and India indicates that the increase in PM10 level in city air by 10 g/m3contributed to an
increase in mortality rate by 0.6% 27.
PM2.5 might induce some extra disorders in the cardiovascular system. Very small particles
coming from exhaust fumes can enter the bloodstream and reach distant organs such as the
heart and kidneys. There is also the possibility of micro-injuries of endothelial cells
appearing in blood vessels which might affect the activation of coagulation factors and
impair autonomic regulation of heart rate, which in turn, may cause sudden death because
of arrhythmia 44.
The main cell lines involved in immunological response are epithelial cells, dendritic cells,
Th lymphocytes, macrophages, neutrophils, mast cells, basophils and eosinophils. They
protect the body's well-being but in a polluted environment, these cells can also get
involved in the cascade of events leading to inflammation and various pathological forms.
Many studies indicated that exposure to PM10 particles exacerbates symptoms in patients
with asthma, contributes to increasedadministration of anti-asthmatic medications and
frequent visits to emergency medical services 7. Particles appearing in city and industrial
areas are especially dangerous. Studies on air aerosol gathered in Bejing, with a population
of twelve million , indicated that over 99% of PM particles had a diameter smaller than 1m
and the endotoxin level can reach a value of about 1250 pg/mg of aerosol. High
immunomodulating, toxic and even mutagenic potential might be caused by the presence of
many toxins and their easy deposition in lungs owing to very low weight 142. It was
concluded that they can inhibit the synthesis of IFNγ in human leukocytes of peripheral
blood. As a result, the balance of the Th1/Th2 leukocyte population is disturbed. The
dominant leukocytes are Th2 leukocytes which are responsible for the development of
allergy. Simultaneously, anti-infectious and anti-neoplastic immunity gets reduced.
Dockery et al 35 confirmed the relationship between PM2.5 in the air and death rate.
Cohort studies conducted in 6 cities in the US showed that PM2.5 increase by about
10g/m3 in a year entailed an increase in death rateranging from 10.9% to 20.8% 120.
Rezentiti et al 114 concluded that transferring children living in cities to unpolluted
rural areas contributes to quick and considerable improvement of aspects of their health
state such as well-being, peak expiratory flow (PEF) and monitored inflammation
indicators (the decrease in the number of oesinophils in nasal lavage and the level of
nitrogen oxide in exhaled air). Studies performed in Bejing indicate that extremely small
particles stimulate pulmonary oesinophilia and the activation of Th2 response, which
might be connected with the presence of β-glucan of fungal spores in inhaled urban
particulate matter (UPM) 53.
6.1.4 Nanoparticles (ultrafine particles UFP)

Nanoparticles (ultrafine particles UFP). They belong to a class of the smallest PM particles:
<100 nm. Two types of nanoparticles are recognised: natural nanoparticles emitted in the
process of incomplete burning by dieselengines, and synthetic ones (produced deliberately)
which have medical applications (e.g. in antibacterial nanocoating), electronic engineering
and other industries. Many scientists stress their exceptional ability to penetrate the deepest
parts of lungs and the inside of the cell. Research performed with the use of an electron
microscope confirms that nanoparticles can damage even the internal structures of
mitochondria 89. They can easily get to the cardiovascular system and cause arrhythmia by
changing cardiomyocyte contractility 145. It was concluded that they can have some pro-
inflammatory properties, raise blood pressure and favour atherosclerosis 8. During
exposure to UFP, mononuclear cells are chemotactically activated. The exposure also
induces the expression of pro-inflammatory genes in macrophages and endothelial cells and
stimulates the synthesis of pro-inflammatory cytokines, e.g. IL1B, TNF, IL4 48. The
particles act through congenital and acquired immunity mechanisms and influence the
development of Th2-type allergic inflammation of the upper respiratory tract 75. As they
are relatively large and light,they absorb many organic compounds, making them even
more toxic. Li et al 90 statedthat chemical composition of UFP, emitted by high-pressure
diesel engines in trucks, was different for different working cycles of the engines. UFP
particles emitted by stationary trucks directly induced oxidative stress in human aorta
endothelial cells, and UFP particles emitted while the truck was moving contained four
times more metal ions (iron, chromium and nickel) and more intensively activated
inflammatory processes such as the increase in the gene expression for IL-8 chemokines and
monocyte chemoattractant protein -1 (MCP-1) as well as adhesive molecules.
6.1.5 Diesel Exhaust Particles (DEP) – Toxin transporters

Diesel Exhaust Particles (DEP) – toxin transporters. Exhaust fumes which appear in the
process of combustion of fuel oil tend to aggregate into separate, spherical particles which
have a diameter of 0.1-0.5m. The core of the DEPs are tiny specks of soot which are mixed
in with hundreds of organic and inorganic substances. The influence of DEP particleson the
immune system depends on the level of exposure, the particle diameter, their chemical
composition, and their reactions with other chemical compounds, both organic and
inorganic, including allergens and bacterial endotoxins. Experimental and epidemiological
research shows that DEPsin city air have a more toxic action than those in a rural area.
What's more, their effects can be reversible or irreversible, as manifested by various
pathologies such as damage to epithelial cells, pulmonary emphysema, allergic asthma,
cardiological disorders and even acute renal failure 107. Studies have addressed the many
mechanisms responsible for adverse immunological DEP-induced response and have
demonstrated that that epithelial cells in the respiratory system are the first to detect
pollutants and react to them, as DEPs can diffuse through the cell membrane and bind to
receptors in the cytoplasm. One of such receptors is the aryl hydrocarbon receptor (AhR).
Internalization of DEPs to the inside of the cells activates numerous signalling pathways
which induce, inter alia, the synthesis of granulocyte-macrophage colony stimulating factor
(GM-CSF) in the respiratory tract. This is essential in asthma pathogenesis as inducing the
differentiation process of hematopoietic cells into precursors of granulocyte, macrophage
and eosinophil lines favours proinflammatory changes in lungs. Having been exposed to
DEPs , the epithelium releases a number of mediators which have chemotactic properties
and influence dendritic cells. These, in turn, activate naive T lymphocytes, which causes a
proliferation of their clones in various effector lines. Of the examined air pollutants, DEPs from
city areas are considered most allergenic 148.A body of research shows that exposure of
dendritic cells to PM particles stimulates Th to produce IL13 and IL1 and inhibits IFNγ. DEP
extracts induce oxidative stress in bone marrow dendritic cells, which causes disturbances in
the production of IL-12 cytokine, which plays a key role in the process of Th1 lymphocyte
proliferation. Exposure in the early stage of life may be critical for the stability of the Th2
phenotype. As research demonstrates, DEP-induced oxidative stress contributes to the
activation of Th lymphocytes, induction of Th2 cytokine and sIgE synthesis as well as the
proliferation of eosinophils, release of inflammatory mediators, and goblet cell hyperplasia.
Nasal administration of DEP solution performed in healthy non-smokers at a dose of 0.3 mg
(daily corresponding dose in Los Angeles) induced an increase in IgE level in nasal lavage 34.
Many experiments have confirmed that DEPs modify the immunological response in
relation to allergens and induce immunological reactions in the respiratory tract, even in
response to low levels and short exposures 94. They also stimulate increased expression of
cell adhesion (ICAM1 and VICAM1), which might lead to thrombosis, acute ischemic stroke
and an increase in cytokine levels, i.e. IL6 and IL10 as well as histamine and also the increase
in the number of neutrophils and platelets 129. In patients with asthma, DEP exposure
leads to the development of metacholine-induced bronchial hyperreactivity. It was
confirmed that DEPs can weaken antibacterial immune functions. In animal experiments
DEPsproved to inhibit the expression of major histocompability complex class II molecules
which are on antigen presenting cells and inhibit the ability of bacterial antigen presentation
32. They also inhibit the activation of T lymphocytes and the T-dependent immune
response to the dangerous zoogenous bacteria Listeria monocytogenes. They also modulate
IL10 synthesis, which acts as an inhibitory factor for immune response. In such conditions,
bacteria living in phagocytes can easily proliferate 149.
6.1.6 Policyclic aromatic hydrocarbons (PAHs)

Policyclic aromatic hydrocarbons (PAHs) are benzene derivatives such as xylene, toluene,
pyrene and benzpyrene. They penetrate cell membranes, accumulate in the lipids of various
tissues, mainly in the liver and bone marrow. According to research , cigarette smoke is an
important source of PAHs. PAH metabolites were traced in pregnant women living in city
areas in Canada 108. They had strong immunosuppressive properties which, in
experimental animals, were represented by pancytopaenia, inhibition of cell immunity and
also humoral, i.e. IgA, IgE deficiency, in response to thymus-dependent and thymus-
independent antigens, deficiency of proteins of the complement system as well as the
impairment of phagocytosis connected with blocking Fc receptors. Moreover, it was
confirmed that PAHs influence human B lymphocytes and stimulate the effects of class
switching of antibodies, which enhances IgE synthesis 132. Metabolites of these
compounds are also hazardous as they are characterized by genotoxic properties 1,49.
6.1.7 Dioxins
Dioxins – a general name of more than 200 chemical compounds from the group of
chlorinated hydrocarbons. They are built of two benzene rings connected with two oxygen
bridges. They are produced in the burning process of plastic products, the production of
herbicides and disinfectants and while smoking cigarettes. In the air and soil they are not
diluted with rainwater but they accumulate in the body in lipids. They are known as “the
most toxic chemical compounds ever produced by man”. For example, dioxin TCDD –
tetrachlorodibenzodioxin is known for its strong carcinogenic properties. Experiments on
animals showed that dioxins demonstrate immunotoxic properties. The effects of TCDD
exposure merit research as these compounds, even in low concentrations, demonstrate a
wide spectrum of activities and are hence known as “environmental hormones”. Dioxins have
been proven to decrease the expression of major histocompability complex class II and
exposure to larger doses causes atrophy and suppression of the thymus – a place where T
lymphocytes mature 134. When adsorbed,dioxins on PM particles reach the lungs they are
phagocytized by pneumocytes – epithelial cells of the respiratory system. From there they
are transported by blood to the liver where they bind to an AhR receptor. The exposure of
animals even to minimal doses of TCDD (0.01lg/kg of body weight) caused a stable binding
of the compound to the AhR receptor, which inhibited the proliferation of bone marrow
stem cells and activated the immunosuppression 13. They can also bind to estrogen
receptor (ER), which might disturb the activity of estrogens and other hormones, and also
induces degradation of ER receptors 52. These toxins, depending on the size of the
dose,have an impact on CD4+lymphocytes and stimulate their differentiation to T-helper as
well as Th1, Th2 and Th17 effector lymphocytes. They also promote the development of
suppressive Treg lymphocytes.
Although cell proliferation is considered an irreversible process, it has recently been
discovered that dioxins such as TCDD can inhibit the differentiation of B cells into plasmatic
cells by changing the expression of transcription factors. Large doses of these dioxins can
contribute to the change in programming completely differentiated plasmatic cells back to B
lymphocytes. The effects of the change in programming mature B lymphocytes to the cells
which have progenitor phenotype 16. It was stated that they might disturb proper
functioning of steroids. They also play a role in the modulation and synthesis of many
important cytokines, e. g. TNF, IL1, IL6, TGF, TGF and IL4 and the exposure to dioxins
in a pre-natal period induces hazardous immunosuppression 85,131,23. Dioxins were
proved to disregulate the expression of many genes, among others, in epithelial cells of the
respiratory passage, which contributes to the occurrence of many genotoxic symptoms, such
as production of unusual proteins, including ubiquitins, and these in turn, disturb
transcription processes, favour autoimmunization and the development of neoplasms in
fetuses of experimental animals 55,70,140.
6.1.8 Ozone (O3)

Ozone (O3) - is a form of oxygen with three atoms in a molecule. The ozone layer which
spreads at the height 10 – 50 km from the ground positively contributes to thermal balance
of the Earth and absorbs 99% of UV radiation, which has fateful implications for all living
organisms, although the same wavelength is responsible for vitamin D production. O3,
unlike other toxins, is a secondary pollutant, since it is produced from the hydrocarbons and
nitrogen oxides of which air is composed with the use of natural sunlight. The half-life for
tropospheric ozone is around 22 days 63. Ozone is a strong oxidizing, irritating and
bactericidal agent. The reaction of ozone with water molecules leads to its hydrolysis and
the production of free radicals. Reactions of O3 with air pollutants change the chemical
composition of smog. They enhance its irritating properties for the eyes, mucous membrane
of the respiratory passage.
Being a strong oxidant, ozone can react with many biomolecules inside and outside a cell. It
disturbs the metabolism and photosynthesis of plants. It has a negative influence on the
respiratory and alimentary systems and also on the skin. It was stated that ozone might
have caused more than 20, 000 premature deathsand about 200 million episodes of
respiratory failure within only one year 136. Many authors also stress that O3 and
symptoms of allergy, asthma and chronic obstructive pulmonary disease (COPD) are closely
related 33,46,77. The early exposure to ozone might favour the Th2 atopic phenotype,
which leads to a more probable risk of the development of allergy and asthma in children.
Kopp et al 79 conducted studies in which they monitored allergy symptoms in 170
children. They concluded that the symptoms were aggravated as the ozone level rose,
however, after some time, the symptoms became more stable despite the ozone level
remaining relatively high. The researchers showed that frequent inhalations with 0.5 ppm of
ozone and house dust mite (HDM) carried out for six months in young atopic monkeys
induced the amplification of immune response , the increase in IgE levels, oesinophilia,
changes in the respiratory tract, an increase in bronchial hyperreactivity and histamine level
in serum. Inhalations performed exclusively with ozone lead to the increase in histamine
level in serum, probably on the IgE-independent way 122. According to Peden et al 109
ozone induces pro-inflammatory effects with accompanying mechanisms not examined well
yet (in comparison to other air pollutants) in which monocytes and macrophages take part.
Ozone was also confirmed to increase P substances in the respiratory tract 82.
7. Epigenetic changes and environmental pollution

Epigenetic modifications are considered a bridge connecting the genotype and phenotype of
living organisms. Air pollutants can contribute to many epigenetic changes, by changes to
gene expression, e.g. by DNA methylation and changes to histone structure. They also
might facilitate the transcription activation of promoters and modification of RNA segments
or make these processes difficult to occur. The dynamics of epigenetic modifications are
varied 6. It is believed that some genes may become activated only if they are affected by
environmental exposure, for example to nicotine smoke, as well as by PAHs which induce
chromosome aberrations and oncogenic mutations. 110. It can be concluded that epigenetic
changes induced by the polluted environment play a key role in the development of asthma
and allergic diseases. They can modify transcription of genes connected with immune
reactions, induce pro-inflammatory response and simultaneously cause remission or
aggravation of the disease and even control the effectiveness of pharmacological treatment
11,83. These changes are usually reversible but they can also be hereditary. Research is
being performed on epigenetic biomarkers essential in the early stage of life and their role in
the development of asthma and allergy in later life, as well as the relationship between the
findings of clinical observations made during exposure to pollutants and gene expression
for many important factors, e.g. Treg cells.
8. Conclusions
A polluted atmosphere is only one of many examples of destruction of the natural
environment. There is sizeable body of evidence confirming the considerable anthropogenic
influence that exists on air composition and even the climate on the Earth. These human
activities influence all forms of life, including the life of man himself. Our immune system
stays alert and strives to minimize the risk of exposure to hazardous level of air pollutants
which might posses synergistic and antagonistic properties. The degree of sensitivity to air
pollutants is different for each individual. It depends on age, health condition and genetic
factors. It is therefore difficult to determine the maximum levels of environmental toxins.
We are ever more aware of the source of the problems of environmental pollution.
Nevertheless, it is difficult to solve them. Reasonable pro-health education seems to
contribute considerably to the improvement of air quality and the condition of the natural
environment. The mentioned problems should be solved on a world scale.
9. Acknowledgments
We thank Dorota Wawrzyniak for translation of manuscript and Agnieszka Wojciechowska
for all pictures. We are also grateful for the time and efforts of Edward Lowczowski in
reviewing this manuscript.
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AIR POLLUTION –

Copyright © 2012 InTech

Publishing Process Manager Maja Bozicevic

First published March, 2012

A free online edition of this book is available at www.intechopen.com

Chapter 1 Pollution and Air Quality in Târgovişte

Chapter 2 Comprehensive Comparison of Trace Metal

Chapter 3 Effect of Air Pollutants on Vegetation

Chapter 4 Physico-Chemical Characterisation of Aerosol

Chapter 5 Biomonitoring of Airborne Heavy Metal Contamination 97

Chapter 6 Air Quality Study, Comparison Between

Chapter 7 On the Impact of Time-Resolved Boundary Conditions

Chapter 8 Recovery and Reuse of SO2

Chapter 9 Design Efficiency of ESP 197

Chapter 10 Allergens, Air Pollutants and Immune System

This book provides a comprehensive compilation of chapters in air quality modelling,

Pollution and Air Quality in Târgovişte

3.1 Atmospheric pollutants

- - Very light aromatic compound, volatile and water-soluble;

Natural sources: volcanic eruptions, marine phytoplankton, bacterial fermentation in the

Fig. 3. Average annual concentrations: lead in the year 2009 (g/m3).

Total emissions in Dâmboviţa County (t/year)

3.2 Stationary air quality monitoring points

Maximum value 0.058

Minimum value 0.026

Average value 0.049

TSP NO2 SO2 NH3 CH2O

- sampling point: Micro VI (Unirii Blvd., no. 6)

NO2 SO2 NH3

TSP NO2 SO2 H2S CrO3

Measurement units mg/m3 mg/m3 mg/m3 mg/m3 mg/m3

Maximum value 0.057 0.0204 0.0033 0.0045 0.0001000

Minimum value 0.029 0.0087 0.0013 0.0017 0.0000840

Average value 0.037 0.0132 0.0020 0.0028 0.0000893

MAC 0.15 0.1 0.25 0.008 0.0015

AT 0.105 0.07 0.175 0.0056 0.0010

Târgovişte Doiceşti MAC/year

Târgovişte Doiceşti Fieni

Fig. 9. Maximums/24h of the PM10 indicator, measured gravimetrically (months) - year

Average of the Frequency of the

92.2 34.5 68.7 86.7%

4. Air quality status

environmental protection system is the implementation of preventive measures or the

6. The air quality in relation to the population’s health condition

In the prevention of diseases caused by the exposure of the population to different

The gaseous pollutants (nitrogen dioxide, sulphur dioxide, ammonia, sulphuretted

Pehoiu G. (2008). The impact of human activities on environmental quality in Dâmboviţa

Comprehensive Comparison of Trace Metal

3. Speciation and toxicity

3.1 Trace metal uses and their health effects

an olive-green liquid with a germanium-like odour. It was developed as a potential warfare

Occupational exposure to inorganic arsenic compounds through inhalation, ingestion or

persons exposed to inorganic arsenic compounds suffer a higher incidence of angiosarcoma

and other manifestations (e.g., tremor, sweating, dermatography) become more

3.1.8 Metal carbonyls

Ni(CO)4 170.75 1.31 –19 43 390

*Decomposition starts at temperature shown.

4. Comparison of metal concentrations in air samples

Location Character Size Cd Pb Ni Cu As Fe Cr Ref.

Location Character Size Cd Pb Ni Cu As Fe Cr Ref.

Location Character Size Cd Pb Ni Cu As Fe Cr Ref.

Location Character Size Cd Pb Ni Cu As Fe Cr Ref.

[33] Pekney N. J. and Davidson C. I. 2005, Determination of trace elements in ambient