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Self-Study: Submitted in Partial Fulfilment of The Requirements For The Award of
Self-Study: Submitted in Partial Fulfilment of The Requirements For The Award of
Self-Study: Submitted in Partial Fulfilment of The Requirements For The Award of
(Batch: 2016-17)
By:
Ashwini Kumar (DTU/2K14/EN/011)
I hereby certify that the work which is presented in the Self Study entitled “Need of speciation
of particulate matter in ambient air” in fulfillment of the requirements for the award of
Degree of Bachelor of Technology and submitted to the Department of Environmental
Engineering, Delhi Technological University (Formerly Delhi College Of Engineering), New
Delhi is an authentic record of my own work , carried out during a period from January 2017 to
May 2017, under the supervision of Mr. Anunay Gour , Assistant Professor, Department of
Environmental Engineering, Delhi Technological University.
The matter presented in this report has not been submitted by me for the award of any other
degree of this or any other Institute/University.
Signature
Date:
“The successful completion of any task would be incomplete without accomplishing the people
who made it all possible and whose constant guidance and encouragement secured us the
success.”
First of all, we are grateful to the Almighty for establishing us to complete this minor project.
We are grateful to Prof. A.K. Gupta, HoD (Department of Environmental Engineering), Delhi
Technological University (Formerly Delhi College of Engineering), New Delhi and all other
faculty members of our department, for their astute guidance, constant encouragement and
sincere support for this project work.
We owe a debt of gratitude to our guide, Mr. Anunay Gour , Assistant Professor, Department
of Environmental Engineering for incorporating in me the idea of a creative self-study project ,
helping us in undertaking this project and also for being there whenever we needed her
assistance.
I also place on record, my sense of gratitude to one and all, who directly or indirectly have lent
their helping hand in this venture. We feel proud and privileged in expressing my deep sense of
gratitude to all those who have helped me in presenting this project.
Last but never the least, we thank our parents for always being with us, in every sense.
Abstract
India. . The speciation of an element is the distribution of an element amongst defined chemical
species in a system. The determination of chemical species represents the key to the
effects towards ecology. There are four routes by which a substance can enter the body:
inhalation, skin (or eye) absorption, ingestion, and injection. All of them are triggered by the
speciation profile can be done and the harmful health effects of a particular element of the PM
matrix could be studied efficiently using speciation .The bioavailability can also be determined
using the speciation which would trigger as to how the interaction of PM occurs. The specific
source profile of PM can also be developed by speciation studies. All in all the speciation of
particulate matter in ambient air is a big requirement against the challenging air pollution of
today
Table of Contents
Chapter Topic
1.0 Introduction
1.1 Need of speciation
1.2 Nature & Sources of Particulate
Matter Pollutant
1.3 Health & Environmental Impacts
2.0 Chemical Speciation of particulate
matter
2.1 Primary Aerosols
2.2 Secondary Aerosols
2.3 Geological Material
2.4 Sulphate
2.5 Liquid water
2.6 Sodium Chloride
2.7 Elemental Carbon
2.8 Organic Carbon
2.9 Ammonium
2.10 Nitrates
3.0 Need of speciation of Particulate
Matter
3.1 Inefficiency of total element
concentration analysis
3.2 Interaction of particulate matter with
human body; (respiratory system)
depends on speciation profile
3.3 Creation of a nation- wide air
pollution control policy focusing on
selective chemical species
3.4 Health effects linked to PM
components
3.5 Bioavailability
3.6 PM source speciation profiles
4.0 Conclusion
5.0 References
1.0 Introduction
Speciation analysis is the analytical activity of identifying and/or measuring the quantities of one
or more individual chemical species in a sample. The chemical species are specific forms of an
a sample, the data are meant to answer one of the following questions depending on the nature of
the sample:
Are there any risks or benefits related to the probed entity? [1]
Depending on the origin of the sample (environmental compartment, human body, food, and
industrial product) such questions are related to the specific activity of the chemical species, such
as:
biological activity
toxicity
mobility
bioavailability
Since these characteristics are species related, data on the presence of elements and their total
EXAMPLE 1:
The chemical species of a metal can affect its toxicity by influencing its
absorption (or the physical availability for exposure - if the metal is tightly bound to in-
absorbable material, it cannot be readily taken up, e.g. into the blood stream of the
organism)
distribution (the internal transport inside the organism to the tissue on which it has toxic
effects - for example the crossing of the intestinal membrane or the blood-brain barrier)
It is therefore essential that toxicological studies should always consider the species present
EXAMPLE 2:
While arsenic is synonymous to poison for most people, it has become evident that even high
concentrations of arsenic in marine foodstuffs are harmless, since the main species present are
EXAMPLE 3:
Cr (III) compounds do have some positive biological activity and are therefore considered to be
Chemical speciation analysis for the environment is needed to provide information about the
status as well as the processes involved for the emission, cycling, degradation and fate of matter
in the environment.
Chemical analysis is acting as an information science, providing the data necessary to answer
Data on the emission, transport and exchange of matter between different compartments
of the environment.
Data on the chemical and physical effects of pollutants with respect to the energy
Particulate matter (PM) is the general term used for a mixture of solid particles and liquid
droplets found in the ambient air. Some particles are large or dark enough to be seen as soot or
smoke. Others are so small that they can be detected only with an electron microscope. These
particles, which come in a wide range of sizes (“fine” particles are less than 2.5 micrometers in
diameter and coarser size particles are larger than 2.5 micrometers), originate from many
different stationary and mobile sources as well as from natural sources. Fine particles (PM2.5)
result from fuel combustion from motor vehicles, power generation, and industrial facilities, as
well as from residential fire-places and wood stoves.[2] Coarse particles (PM10) are generally
emitted from sources, such as, vehicles travelling on unpaved roads, materials handling, and
crushing and grinding operations, as well as windblown dust. Some particles are emitted directly
from their sources, such as smokestacks and cars. In other cases, gases such as sulfur oxides,
SO2, NOx, and VOC interact with other compounds in the air to form fine particles, which are
called secondary particulate matters. Their chemical and physical compositions vary depending
Inhalable PM includes both fine and coarse particles. These particles can accumulate in the
respiratory system and are associated with numerous health effects. Exposure to coarse particles
is primarily associated with the aggravation of respiratory conditions, such as asthma.[4] Fine
particles are most closely associated with such health impacts as increased hospital admissions
and emergency room visits for heart and lung disease, increased respiratory symptoms and
disease, decreased lung function, and even premature death. Sensitive groups that appear to be at
great risks to such effects include the elderly, individuals with cardiopulmonary disease, such as
asthma in children. In addition to health problems, PM is major cause of reduced visibility and
increased haze in many parts of the world. Airborne particles also can cause damage to paints
PM 2.5 is composed of a mixture of particles emitted directly into the air (primary aerosols) and
The primary types of particles emitted directly include soil-related and organic carbon particles
The main sources of soil-related particles are road dusts, construction, and agriculture.
The main sources of combustion-related particles are diesel and gasoline motor vehicles,
managed and open burning, residential wood combustion, and utility and commercial boilers.
Combustion processes also emit primary fine particles consisting of mixtures of many trace
The principal types of secondary aerosols are organics and ammonium sulfate and nitrate formed
from gaseous emissions of sulfur dioxide (SO2 ) and nitrogen oxides (NOx) which react with
ammonia. Gaseous organics from internal combustion engines as well as other combustion
The main sources of SO2 combustion of fossil fuels in boilers and the main sources of NOx are
mobile sources and combustion of fossil fuels in boilers. Sulfur dioxide, nitrogen oxides, and
ammonia (NH3 ) are important precursors to secondary aerosols (ammonium sulfate, ammonium
bisulfate, ammonium nitrate) and their chemical abundances are useful at source and receptor
Sulfate, nitrate, particulate organic carbon, and ammonium are quite often the major constituents
of PM 2.5. Most of the PM 2.5 and PM10 mass in urban and non-urban areas can be defined by a
combination of the following components that are both primary and secondary aerosols:
Suspended dusts consisting mainly of oxides of aluminum, silicon, calcium, titanium, iron, and
other metal oxides. The precise combination of these components depends on the geology and
2.4 Sulfate:
Ammonium sulfate, ammonium bisulfate, and sulfuric acid are the most common forms of
sulfate in atmospheric particles. These compounds are water soluble and reside almost
exclusively in the PM 2.5 fraction. Most fine sulfates are produced by oxidation of SO 2 gas to
sulfate particles. Sources of SO 2 emissions include coal-burning power plants and copper
smelters.
Soluble nitrates, sulfates, ammonium, sodium, other inorganic ions, and some organic material
absorb water vapor from the atmosphere, especially when the humidity exceeds 70 percent.
Sulfuric acid absorbs some water at all humidity levels. Particles containing these compounds
Salt is found in suspended particles near sea coasts, open playas, and after de-icing materials are
applied. In its raw form, salt is usually in the coarse particle fraction and is classified as a
geological material. When sodium chloride-containing water of fog droplets evaporate, many of
the “dry” core particles are below 2.5 Fm in diameter. Particles that originally contain sodium
chloride may be neutralized by nitric or sulfuric acid; the chloride is driven off and replaced by
equivalent amounts of nitrate or sulfate. Such particles will be classified as nitrate or sulfate and
Particles emitted from combustion sources contain light absorbing elemental carbon, often called
particles, whereas soil- and marine-derived aerosols contain negligible amounts of elemental
compounds that usually contain more than 20 carbon atoms. No single analytical technique can
characterize the organic compounds present. Particulate organic carbon originates from
Ammonium sulfate, ammonium bisulfate, and ammonium nitrate are the most common
compounds containing ammonium. Ammonium sulfate and ammonium bisulfate result from the
Atmospheric ammonia (NH3 ) results from biological decay at the earth’s surface and can absorb
2.10 Nitrate:
Ammonium nitrate is the most abundant nitrate compound resulting from a reversible gas-to-
particle equilibrium between ammonia gas and nitric acid gas, and particulate ammonium nitrate.
The main source of NOx emissions are from the combustion of various fuels. About one-half of
the NOx is from stationary sources, while the remainder is from mobile sources such as spark-
Speciation analysis is the analytical activity of identifying and quantifying one or more chemical
The determination of chemical species represents the key to the understanding of biogeochemical
cycles of contaminants (inorganic and organometallic) in environment, and their harmful effects
to biota and humans.[7] The toxicity of metals, their environmental mobility, their interaction
with solid and liquid phases, tendency to be accumulated in living systems and their resultant
toxicity are strictly correlated with the chemical speciation analysis. That is why; knowledge of
total concentration does not give sufficient information about the potential risks. The failure of
total elemental concentration analysis paves the way ahead for speciation of particulates which
3.2 Interaction of particulate matter with human body; (respiratory system) depends on
speciation profile:
There are four routes by which a substance can enter the body: inhalation, skin (or eye)
absorption, ingestion, and injection.[8] These four routes depict how speciation profile is linked
to particulate matter interaction with the human body thereby necessitating the requirement of
speciation profile for the study of interactions with body especially the respiratory system of the
humans:-
• Inhalation:
For most chemicals in the form of vapours, gases, mists, or particulates, inhalation is the major
route of entry. Once inhaled, chemicals are either exhaled or deposited in the respiratory tract. If
deposited, damage can occur through direct contact with tissue or the chemical may diffuse into
the blood through the lung-blood interface. Upon contact with tissue in the upper respiratory
tract or lungs, chemicals may cause health effects ranging from simple irritation to severe tissue
destruction. Substances absorbed into the blood are circulated and distributed to organs that have
an affinity for that particular chemical. Health effects can then occur in the organs, which are
Skin (dermal) contact can cause effects that are relatively innocuous such as redness or mild
dermatitis; more severe effects include destruction of skin tissue or other debilitating conditions.
Many chemicals can also cross the skin barrier and be absorbed into the blood system. Once
absorbed, they may produce systemic damage to internal organs. The eyes are particularly
sensitive to chemicals. Even a short exposure can cause severe effects to the eyes or the
substance can be absorbed through the eyes and be transported to other parts of the body causing
harmful effects.
• Ingestion:
Chemicals that inadvertently get into the mouth and are swallowed do not generally harm the
gastrointestinal tract itself unless they are irritating or corrosive. Chemicals that are insoluble in
the fluids of the gastrointestinal tract (stomach, small, and large intestines) are generally
excreted. Others that are soluble are absorbed through the lining of the gastrointestinal tract.
They are then transported by the blood to internal organs where they can cause damage.
• Injection:
Substances may enter the body if the skin is penetrated or punctured by contaminated objects.
Effects can then occur as the substance is circulated in the blood and deposited in the target
organs.
3.3 Creation of a nation- wide air pollution control policy focusing on selective chemical
species
With the promulgation of the new Particulate Matter National Ambient Air Quality Standards
(NAAQS), all future designated nonattainment areas and surrounding regions may need to
reduce emission of fine particles and their precursors to permit those areas to attain the NAAQS.
Efficient air quality management requires knowing which sources contribute to the problem and
how much. Determining PM source contributions is complicated due to the fact that often half or
more of the PM mass is composed of secondarily formed species, hiding their point of origin. In
addition, PM has a lifetime on the order of several days, enabling sources up to 1,500 miles away
calculative manner it would enable the authorities to create a nationwide air pollution control
policy focussing on selective chemical species. Focus on selective chemical species could very
well accelerate the fight against air pollution particularly the dangerous particulate pollution.
3.4 Health effects linked to PM components
disorders, severe sickness and premature deaths. Investigating this link, most previous studies
have focused on the effects of different sizes of PM, while very few have investigated the role of
its different chemical components. PM is made up of many different elements, originating from
numerous sources including fossil fuel combustion, transport and industry. Transition metal
components such as copper and iron are thought to be particularly harmful as they have the
potential to produce reactive oxygen species, causing inflammation throughout the body. Over
time, this may cause disease. Findings suggest that not all components of PM are equally
harmful. Long-term exposure to transition metals in particular, commonly emitted by traffic and
industry, may be associated with the inflammation that precedes respiratory and cardiovascular
disease. A time series study , which used principal components of chemical characterised PM2.5
particulate matter reflecting different source categories as its exposure metric, revealed a ranking
of sources in exerting a toxic effect in the order: road traffic > coal combustion, > crustally-
derived particles.[10]
3.5 Bioavailability
PM is deposited in the alveolar regions of the lungs. The efficiency of their adsorption is 60%–
80% [11]. Many epidemiological and toxicological studies have reported a link between PM
exposure and decreased lung function, aggravation of respiratory diseases and increased
pollution sources may provide new insights into the underlying relationship between PM air
pollution and health. Toxicological studies have suggested that the determination of the total
trace element content of airborne particulate matter is a poor indicator of their bioavailability,
mobility and toxicity [12]. Bioavailability is the prime consideration in environmental risk
assessment of toxicity. An evaluation of the potential toxicities of trace elements is based on the
characteristics of their surfaces, strength of their bonds and properties of solutions in contact
with particulate matter. The amount of potentially bio available trace elements in PM can be
estimated from the water-soluble fraction and the fraction extracted by a dilute salt by extracting.
Thus, investigations of the soluble or extractable elements in PM have attracted much more
attention in this field of study. The chemical mobility of elements determined by Int. J. Environ.
Res. Public Health 2015, 12 13087 leaching procedures is a good indicator for their
bioavailability, namely the degree and rate that a substance is absorbed into a living system or is
PM speciation source profiles indicate the chemical species that comprise the PM emissions released
from a specific source. These speciation profiles, commonly expressed as the mass ratio of each
species to the total PM, are used to characterize the different components that are associated with
individual pollutant sources. Currently there are different repositories of PM speciation source profiles
freely accessible, with the objective of being used for different purposes, such as creating speciated
PM emission inventories for photochemical air quality modeling [13] or providing input to the
Chemical Mass Balance (CMB) receptor models (RM). One of the best-known repositories is the
United States EPA SPECIATE database, which has been publicly available since 1988, and it
currently contains around 3000 entries. Source profiles from this American repository are usually used
in European emission and air quality modeling exercises owing to the scarcity of official and well-
established European databases. With the objective of filling this gap, a new database of PM
The SPECIEUROPE is a repository developed in the framework of the Forum for Air quality
Modeling in Europe (FAIRMODE) that contains the chemical composition of PM emission sources
reported in European scientific papers and official reports. Currently, SPECIEUROPE consists of 209
composition) and derived (results of source apportionment studies) profiles.[14] Emission inventories
are datasets used to estimate the amount of air pollutants being emitted to the atmosphere, caused by
an anthropogenic or natural activity, at a certain geographical location for a given period of time.
Emission inventories are generally recognized as key inputs to atmospheric modelling, especially
when they are used to design effective control measures to mitigate the adverse impact of air pollution
4.0 Conclusion
The need for speciation of particulate matter is evident. The total elemental composition studies
are insufficient so as to give the accurate detailing information about the effects of the
particulates. Individual sources profiles can be determined using speciation. Bioavailability can
be justified on its basis and the health effects linked can be concentrated upon. There is a lack of
conclusive literature on the speciation studies which makes it a need of the hour to study the
speciation of particulate matter especially in a country like India which lags behind the world in
control of air pollution measures. A nationwide policy and a comprehensive program can be
developed using the speciation data and records. This could prove instrumental in the go ahead
for the fight against air pollution specially pertaining to the particulate matter. Efficient and
justifiable measures can be taken up for the control focussing on the speciation of particulates in
ambient air. Hence, it is conclusive that speciation of particulate matter is the ultimate need of
the hour and we need to investigate it via practical studies and experiments.
5.0 References
[1] Allen R.W., Mar T., Koenig J., Liu S.L.J., Gould T., Simpson C., and Larson T. Changes in lung
[2] Andersen Z.J., Wahlin P., Raaschou-Nielsen O., Scheike T., and Loft S. Ambient particle source
apportionment and daily hospital admissions among children and elderly in Copenhagen.
[3] J Expo Sci Environ Epidemiol 2007: 17: 625–636. Bell M.L., Dominici F., Ebisu K., Zeger S.L., and
Samet J.M. Spatial and temporal variation in PM2.5 chemical composition in the United States
for health effect studies. Environ Health Perspect 2007: 115: 989–995
[4] US EPA. Environmental Protection Agency. Air Quality Criteria for Particulate Matter.National
Center for Environmental Assessment-RTP Office, Research Triangle Park, NC, report
no.EPA/600/P-99/002aF 2004.
[5] Yue W., et al. Ambient source-specific particles are associated with prolonged repolarization and
increased levels of inflammation in male coronary artery disease patients. Mutat Res 2007: 621:
50–60.
[6] Smichowski, P.; Polla, G.; Gómez, D. Metal fractionation of atmospheric aerosols via sequential
[7] Di Ciaula, A. Emergency visits and hospital admissions in aged people living close to a gas-fired
[8] Richter, P.; Griño, P.; Ahumada, I.; Giordano, A. Total element concentration and chemical
fractionation in airborne particulate matter from Santiago, Chile. Atmos. Environ. 2007, 41,
6729–6738.
[9] M. Guevara, F. Martínez, G. Arévalo, S. Gassó and J. M. Baldasano, Atmos. Environ., 2013, 81, 209
[10] H. Simon, L. Beck, P. V. Bhave, F. Divita, Y. Hsu, D. Luecken, J. D. Mobley, G. A. Pouliot, A. Reff,
[11]Schichtel, B.A.; Husar, R.B. Aerosol types over the continental U.S.: spatial and seasonal
patterns. Presented at the A&WMA Conference, Kansas City, MO, 1992; Paper 92-60.07. 2.
[12]Pope III C.A., Burnett R.T., Thurston G.D., Thun M.J., Calle E.E., Krewski D., et al. Cardiovascular
[13]Sarnat J.A., Marmur A., Klein E., Kim E., Russel A.G., Sarnat S.E., Mulholland J.A., Hopke P.K., and
Tolbert P.E. Fine particle sources and cardiorespiratory morbidity: an application of chemical
mass balance and factor analytical source-apportionment methods. Environ Health Perspect
[14]Thurston G.D., Ito k., Mar T., Christensen W.F., Eatough D.J., Henry R.C., Kim E., Laden F., Lall R.,
Larson T.V., Liu H., Neas L., Pinto J., Stolzel M., Suh H., and Hopke P.K. Workgroup Report: