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ABSTRACT

Atmospheric particulate matter (PM) is the subject of extensive research from the beginning of
90`s, by atmospheric scientist worldwide because of its impact on global as well as regional
climatic dynamics, chemistry of atmosphere, biogeochemical cycle and activation of cloud
condensation nuclei (CCN) and create negative impact on human and ecosystem wellbeing by
spreading allergies and contagious ailments of respiration, cardiovascular system and
reproductive system. In India, PM10 reflects their origin from anthropogenic sources such as
vehicular emissions, coal combustion, industrial setups, biomass/waste burning, fossil fuel
combustion, construction activities and sea salt etc. Organic constituents of PM10 is a mixture of
numerous organic compounds, including alkanes, alkanols, alkanoic acids, carbonyl compounds,
anhydrosugars and aromatic compounds that serve as specific signatory molecules or receptor
tracers to their sources in conjunction with Volatile Organic Compounds (VOCs) and inorganic
species. Organic compounds are characterized by their limited existence, specificity of the source
and molecular stability. Major factors affecting the characteristics of organic constituents of
atmospheric particulates are: source strength, geology and morphology of the area, diversity in
flora and fauna, incident solar fluctuation and meteorological parameters. In spite of progress
and techniques developed in the last decades, understanding the composition, sources, formation
pathways and fate of organic compounds in nature still remains an interesting and challenging
task because airborne particulates exhibit seasonal fluctuations and deviations from pre-
identified characteristics.
Many source apportionment studies have been done for PM10 in Delhi but there is no systematic
study reported over the NCR (India) on the implications of outflow and inflow of organic
pollutants from and towards Delhi, India. The transport of pollutants emitted from various
sources over the region may have climatic as well as health effects. Identification of organic
compounds that could act as tracers would help in assessment of the diffusion of aerosols and the
movement of pollutants over the NCR with their possible impact. Moreover, by using the
concentration data of organic markers present in atmosphere of Delhi-NCR, the receptor models
[Positive Matrix Factorization (PMF), Unmix and Principal Component Analysis (PCA)] could
provide more extensive details on the source apportionment of organic constituents of PM and
their relative contribution so that more effective strategies to mitigate air pollution could be
developed.
The aim and objectives of the present study is to evaluate the composition, spatio-temporal
variations and source profiles of organic molecular markers of PM10 in NCR, India.
 The continuous 24 h ambient monitoring (from January 2015-December 2015) was
performed at (I) a traffic hotspot i.e. IGDTUW, Delhi (II) a semi-urban site surrounded
with agricultural fields i.e. CSIR-NPL, New Delhi (III) an industrial hub of Haryana i.e.
NIT, Faridabad. All the sampling sites represent different ambience and environmental
zones (heavy traffic, semi-urban and Industrial zones), which could lead to a better
prospective towards study of spatial variations of organic markers and their atmospheric
dynamics. The mass concentration of PM10, total Carbon (OC and EC), non-polar and
polar organic molecular markers associated with PM10 were assessed to study their
spatio-temporal trends at all three locations of NCR, India.
 The major sources of high levels of PM10 at NCR, India were found to be HDVs exhaust,
construction dust, Municipal Solid Waste (MSW) burning, brick kilns, Steel and
aluminium smelting industries, electroplating units pharmaceutical, textiles and smoke-
emitting industries.
 The aerosols, at the semi-urban site of CSIR-NPL, were influenced by agricultural
activities at the University campus of Indian Agricultural Research Institute (IARI,
PUSA) at near vicinity.
 At IGDTUW, Delhi PM10 concentrations were considerably higher as compared to other
sampling location of the study. PM10 levels in NCR, India has sharply increased after
2003-04 and exceeded NAAQS (100 µg m-3) levels. The episodic dust storms, Western
disturbance and other climatic episodes have affected the dynamics of climatic
circulations and particle deposition in ambient atmosphere. The wind direction has been
reported to be West and South-West: originated in extremely dry weather of Rajasthan
and therefore dusty conditions prevailing in Delhi leads to elevations in coarse fraction of
PM (Press release, IMD, 2015).
 Annual average concentrations of OC and EC were recorded with seasonal variations
followed a regular trend (winter months > summer months > post-monsoon months >
monsoon months throughout the year at semi-urban site of Delhi. Comparatively, the
seasonal variations of OC and EC at traffic hotspot were (winter months > post-monsoon
months > summer months > monsoon months). On the contrary, annual average
concentrations of OC and EC reported to be followed an irregular trend throughout the
year at Faridabad.
 The annual average level of n-alkanes (C8-C40) associated to PM10 was 106.74±78.2 ng
m-3 at Faridabad; 243.7±5.5 ng m-3 at IGDTUW and 182.71±6.4 ng m-3 at CSIR-NPL.
 At IGDTUW, Delhi, the annual average concentration of PAHs in PM10 was 288.0±19.4
ng m-3 with higher values in winter than summer. Being a traffic hotspot, aerosols were
loaded by low molecular weight (LMW) PAHs at IGDTUW, Delhi. The dominance by
most of the 4 ring PAHs is typical of freshly emitted smoke from vehicular exhaust. The
higher concentration of BghiP (74.94±19.6 ng m-3) indicates very high emissions from
automobile exhausts (gasoline traffic emission). Similar seasonal trends were also
reported at CSIR-NPL, New Delhi with higher values in winter (27.77±8.0 ng m-3) than
summer (17.92±5.4 ng m-3), monsoon (25.30±9.8 ng m-3) and post-monsoon (24.08±4.1
ng m-3).
 The PAEs showed significant seasonal and temporal variations with higher
concentrations in winter months than in summer months at the traffic hotspot- IGDTUW,
Delhi and at CSIR-NPL but at industrial site with no seasonal predominance suggesting
that sources are relatively stable over the whole year. DBP, DOP and DEHP were the
dominant species among all the PAEs.
 Organic acids were detected at all the three sites of NCR, India; includes Fatty acids
(FAs), dicarboxylic acids (DAs), resinic acids (RAs) and aromatic acids (AAs). The
LMW-FAs < C20:0 were dominant at IGDTUW, which is a University campus with
residential hostel facilities and heavy traffic junction nearby. Thus the emissions of n-
alkanoic acids were majorly from cooking activities and vehicular traffic, which have
better deposition rate in winter months than summer months. On the other hand, the
annual averaged levels for mid-range FAs (C12- C20) at this industrial site and semi-urban
site were found to be very less than IGDTUW. Moreover, there were no prominent
seasonal variations.
 The average concentrations of LG were reported to be 347.3±24.4 ng m-3 at IGDTUW,
representing considerable amount of uncontrolled burning of biomass or refuse near the
site. Average concentrations were very lower at Faridabad as compared to IGDTUW,
Delhi. The annual average concentrations at CSIR-NPL, New Delhi were lower as
compared to IGDTUW, Delhi but higher than NIT, Faridabad.
 Source apportionment study was done on the basis of diagnostic ratios (DRs) and
receptor models (RMs). Diagnostic tools like CPI, Cmax, WNA%, OEP curves and
distribution curves were used for homologues series of hydrocarbons and FAs.Diagnostic
and isomer-pair ratios were used to assess the source of origin of PAHs. For source
profiling of diacids, diagnostic ratios of various diacids pairs have also been estimated.
Further, to confirm all the outcomes RMs such as PCA, PMF and UNMIX were used for
source apportionment at all three sites of NCR, India. UNMIX extracted least number of
sources for all the sites whereas PMF ascertained to be best fit by extracting maximum
number of sources at different regions of NCR, India.
 This is a pioneer study as no such study at Faridabad or any other region of NCR has
been reported till the date. Even at IGDTUW, Delhi and CSIR-NPL, New Delhi, no such
source apportionment studies of organic compounds has been reported. This study would
serve as basis for future assessment of strategies and priortization of control measures to
combat the atmospheric pollution and developing a better air quality to lower the health
risk to the regional population.