ASSESSMENT OF HEALTH RISK DUE

TO PRESENCE OF HAZARDOUS AIR

POLLUTANTS IN DIVERSE URBAN
BUILT-UP AREA

Supervisor: Candidate:
Dr. Chirashree Ghosh Ankita Banerjee
17225
Associate Professor
Department of Environmental Studies
Department of Environmental
Studies
Increased urbanization
in Delhi and adjoining
areas increases Urban
Heat Island effect.

Increasing traffic and

other sources of air
pollution.

Image of June 5, 2018

by Landsat 8.

2
 OBJECTIVES OF STUDY

• To monitor VOCs and in particular, hazardous group of VOCs like

Benzene, Toluene, Ethylbenzene and Xylene (BTEX) and tropospheric
ozone in different indoor and outdoor sources of residential built up and
1 mixed land use area for the duration of three months.

• To analyze secondary data of VOCs and ozone for understanding the

association of VOCs and ozone at one representative site of Delhi during
2 different seasons.

• To estimate ozone forming potential (OFP) using Maximum Incremental

Reactivity (MIR) scale.
3
3
 INTRODUCTION

• An air pollutant is any gas or particle that is present over and

above the ambient levels.

Major classes of outdoor air pollutants: Common pollutants in indoor air:

Particulate pollutants Asbestos
Ozone (O3) Biological pollutants
Carbon monoxide (CO) Carbon monoxide (CO)
Sulphur oxides (SO2, SO3) and hydrogen Formaldehyde/pressed wood products
sulphide (H2S) Lead
Oxides of Nitrogen (NO2) Nitrogen dioxide (NO2)
Lead (Pb) and other metals Pesticides
VOCs, solvents, pesticides and methane Indoor Particulate Matter (PM)
(CH4) Environmental tobacco smoke or second hand
Bio aerosols (molds, bacteria, pollen and smoke
others) Volatile Organic Compounds (VOCs)
4
5
 VOLATILE ORGANIC COMPOUNDS

Group of organic compounds with vapour pressure of 0.01 kPa or

higher at 20° C (Wang et al, 2002).

Anthropogenic emission
sources are leakages from
petrol and CNG filling stations,
tankers and pipelines, vehicular
exhausts, tobacco smoke,
industrial agents, gasoline
evaporation, spray cans of
various types used in
households, waste
decomposition, municipal solid
wastes (MSW) etc.
Biogenic sources consist
Discharge into the atmosphere
decomposing vegetation and
causes photochemical ozone,
leaf litter, plant secondary
Peroxy acetyl Nitrate (PAN)
metabolites, wetlands etc, and
and Secondary organic aerosols
have minimal contribution to
(SOAs) formation (Hajizadeh
the ambient air VOCs load
et al; 2017).
(Hajizadeh et al; 2017).

6
TROPOSPHERIC OZONE

Ground level ozone, a

secondary pollutant produced
on reaction of primary air
pollutants nitrogen oxides
(NOx) and volatile organic
compounds (VOCs) in the
presence of sunlight.

The ozone forming potential

(OFP) for each VOC species
determines their chemical
reactivity, determined using the
Maximum Incremental
Reactivity (MIR) Scale,
developed by Carter in 1994.
7
Document
searches on health
effects caused by
ozone and Volatile
Organic
Compounds
(VOCs).

Source: Scopus

8
List of Indoor Air Quality Guidelines:
PARAMETER WHO* OSHA** NAAQS (2004)***

OZONE 0.064 ppm (8 hr) 0.1 ppm 0.12 ppm (1 hr)

TVOCs NA 0.75 ppm 1 ppm

• * World Health Organization

• ** Occupational Safety and Health Administration (OSHA) Permissible Exposure Limit
• *** The National Ambient Air Quality Standards by U.S. Environmental Protection Agency

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 REVIEW OF LITERATURE
International Status of BTEX
Photochemical reactions of BTEX pollutants give rise to other secondary
pollutants like ozone and Secondary Organic Aerosols (SOAs) (Deghani et al;
2018).

BTEX are most ubiquitous species of NMHCs (69% of total NMHCs), thus
can be used for principal component analysis as tracers for identification and
evaluating possible emission sources and contribution in ozone formation
episodes (Duan et al, 2008).

The Ozone Forming Potential (OFP) and SOA formation potential can be
used to analyze chemical reactivity for each VOC species (Feng et al; 2018).

10
 NATIONAL STATUS OF BTEX

• Studies in Delhi found toluene to be the most ubiquitous species,

varying from 42% to 50% of the total BTEX in different sites, closely
followed by benzene (26% to 30%) of total BTEX. Concentrations
were highest in winter followed by monsoon and least in summer.
Main sources were gasoline emanating from vehicular exhaust in
dense traffic conditions (Saxena and Ghosh, 2012).

• Benzene in nearly all sampled sites in Dehradun exceeded Central

Pollution Control Board (CPCB) limits of 5 µg/m3 of the National
Ambient Air Quality Standards (NAAQS), 2009 for industrial,
residential as well as ecologically sensitive areas (Bauri et al, 2015).

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 HEALTH IMPACTS OF BTEX

• BTEX are respiratory irritants, cause central nervous system damage

(Zhang et al; 2012), premature mortality (Borhani and Noorpoor;
2017), considered as air toxicant or hazardous organic pollutants
(HAPs) causing cancer or having other health effects by USEPA
(Hajizadeh; 2017).
• Benzene is classified as a carcinogen (Group 1) by the International
Agency for Research on Cancer (IARC). Lifetime exposure of 1
µg/m3 or more leads to about 6 cases of leukemia per 1,000,000
inhabitants (WHO, 2000), may also result in arrhythmias, respiratory
irritation and aplastic anemia (Baghani; 2018), hematological
disorders, damage to immune system, menstrual disturbances and
change in size of ovaries (Ebrahemzadih, 2015).
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• Exposure to toluene lead to changes in the central nervous system
causing exhaustion, dizziness, reaction-time latency, lack of
coordination and affects reproductive system (Deghani et al, 2018).
• Ethylbenzene is known to induce eye irritation and an irritant to the
digestive tract (Ebrahemzadih, 2015).
• (m,p and o)-xylenes are the most common contributors to ozone
formation among the BTEX (Na, Hoon and Kim, 2005).

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 INTERNATIONAL STATUS OF OZONE

• NMHCs emitted by natural and industrial activities are sources of

free radicals and precursors of ozone (Duan et al; 2008).
• Ozone formed is directly proportional to levels of radicals formed
from reactions involving VOCs under high NOx conditions, in low
NOx conditions it is the determining factor for ozone formation
(Carter, 1994).
• VOCs/NOx ratio can be used in determine whether the production of
ozone is VOC-sensitive or NOx-sensitive.
• Ozone formation potential can be calculated as product of
concentration of VOCs, based on their MIR coefficient (grams of
ozone produced per gram of hydrocarbon) (Duan et al; 2008).
14
 NATIONAL STATUS OF OZONE

• Based on the MIR scale developed by Carter (1994), m, p-xylenes

were the biggest contributors to formation of ozone in Delhi as
found in a study by Saxena and Ghosh (2017), where toluene and
benzene were contributing the least in ozone formation, in accordance
with studies of Na et al (2005) in Seoul and Grosjean et al (1998) in
Porto Alegre respectively.

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 HEALTH IMPACTS OF OZONE

• High OFP could induce respiratory symptoms like coughing,

wheezing, throat irritation, shortness of breath, chest discomfort, lung
dysfunction and airway inflammation (Hajizadeh et al; 2017).

• High ozone concentrations relates to asthma attacks, hospital

admissions, mortality and morbidity (Hajizadeh et al; 2017), dyspnea,
upper airway irritation, coughing, tightness of chest (Carlisle and
Sharp, 2001), inflammation and irritation of respiratory pathway
(Weshler, 2006).
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 METHODOLOGY

Experimental
Layout

Interpreting results of
Calculating BTEX ratios
TVOCs and ozone
Monitoring of TVOCs and using MIR scale to interpret
concentration on the basis of
ozone at different residential Ozone forming potential
temperature and humidity
sites. using secondary data for
and their possible health
2015 and 2016.
effects.

17
 DESCRIPTION OF SAMPLING SITES

Type of Area(in Roof Height Number of No. of No. of No. of

House Square (in meter) Windows Rooms gallery/ies Balcony/ies
meter)
R1 40-46 2.73 2 1 1 1
R2 77-80 2.91 2-3 2 1 1
R3 110-142 2.91 5 3-4 2 2
MC 55-75 2.80 1 2 1 1

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Sampling sites: R1, R2, R3 and MC.
19
Sampling sites: R3 (red), R2 (yellow) and R1 (blue).
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 EXPERIMENTAL DESIGN

Monitoring of TVOCs and ozone

in the indoor and outdoor air was
conducted using a gas sampler,
Scentroid TR8+ Pollutracker for 8
hours, 10:00 am to 5:00 pm every
week for each type of house selected
in the months of January, February
and March.
Organic Vapour Sampler (Envirotech)
was used for VOCs sampling present in
the indoor environments.
Kestrel, hand-held weather
meter was used for temperature
and humidity data at the time of
sampling.
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 RESULT AND DISCUSSION

Secondary data

BTEX monthly concentration (2015) BTEX monthly concentration (2016)

Concentration (μg/m3)

Concentration (μg/m3)
8 8.00
6 7.00
6.00
4
5.00
2 March 4.00
0 February 3.00
2.00
January March
1.00
0.00 February

Benzene
Toluene January
Ethylbenzene
Xylene

January February March January February March

Source: IMD (Indian Meteorological Department

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• January 2015 has least values of BTEX compounds with significant increase in
February and highest increment in March.
• In 2016, BTEX compounds shows growth from January through March except for
Toluene, which has lower concentration than 2015.
• Toluene was most dominant of BTEX in 2015 with 45% - 48% of total BTEX.
In 2016, amount of toluene ranged 36% - 50%, with highest concentration in
January, in accordance with studies performed in Delhi by Saxena and Ghosh in
2012.
• Benzene was the second most dominant of BTEX, ranging between 22% - 24%
in 2015 and 18% - 22 % in 2016 in accordance with studies carried out by Saxena
and Ghosh in Delhi (2012). The concentrations of benzene was found to be below
standard limits set by CPCB, i.e. 5µg/m3.
• The levels of ethylbenzene and xylenes are among the lowest of all BTEX,
could be because they are less stable than benzene and toluene (Marc et al, 2015).

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Month T/B X/B X/E

January 3.13 0.83 1.17

February 2.23 0.59 0.93

March 2.04 0.81 1.99

VOCs ratios in 2015

Month T/B X/B X/E

January 2.69 0.97 1.60
February 1.65 1.05 1.48
March 1.65 1.05 1.48
VOCs ratios in 2016
T= Toluene, B=Benzene, X= Xylene and E= Ethylbenzene
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Toluene/Benzene (T/B) ratio:
Toluene and benzene are more
stable than xylenes and
ethylbenzene. January,
February and March have
values higher than 1
indicating toluene sources
nearby (Gaur et al; 2016).
Xylene /Benzene (X/B) ratio:
Xylenes have higher reactivity
with radicals than benzene.
Observed X/B ratios in 2015
are lower than 1 indicating
occurrence of photochemical
reactions during daytime. In
2016 higher than 1 ratio in
February and March indicates
lower emission of xylenes
(Gaur et al; 2016).
Xylene/Ethylbenzene (X/E)
ratio: Used to identify
photochemical age of air
mass. In 2015 January and
March show X/E ratios as
1.17 and 1.99, indicative of
Atmospheric lifetimes:
low photo chemical reactions.
Benzene- 1.9 days
February has a X/E ratio of
Toluene- 9.4 days
0.93 indicative of an aged air
Ethylbenzene- 1.7 days
mass. In 2016 February and
Xylene- 14-31 hours
March have similar BTEX
concentrations thus similar
X/B. January with low
temperature shows high X/E
ratio of 1.60 (Gaur et al;
2016).
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 OZONE FORMATION POTENTIAL
2015
VOCs MIR Concentration (µg/m3) Ozone formation potential (µg/m3)
Coefficient
January February March January February March
Benzene 0.72 0.35 2.63 3.47 0.25 1.89 2.50
Toluene 4.80 1.10 5.87 7.10 5.28 28.20 34.11
Ethylbenzene 3.04 0.25 1.67 1.43 0.76 5.09 4.34
Xylene 7.72 0.29 1.56 2.84 2.27 12.09 21.98

Salient Observations (2015):

 The levels of ozone formation potential are less than the standard of 100 µg/m3, set by NAAQS
(2009) for all months and for all the BTEX species.

 Toluene contributes the maximum to the ozone formation potential (OFP) among all the BTEX
species in accordance with studies of Tunsaringkarn, et al, in Thailand in 2014.

 March is the month with the highest ozone forming potential (OFP) of all BTEX species.
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 2016
VOCs MIR Concentration (µg/m3) Ozone formation potential (µg/m3)
Coefficient
January February March January February March
Benzene 0.72 1.45 1.74 1.73 1.04 1.25 1.25
Toluene 4.80 3.91 2.87 2.86 18.76 13.79 13.73
Ethylbenzene 3.04 0.88 1.24 1.23 2.68 3.76 3.74
Xylene 7.72 1.42 1.83 1.82 10.95 14.13 14.07

Salient Observations (2016):

 February and March show similar trends in ozone forming potential (OFP) among the BTEX
species.

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 GENERATED DATA
Average Temperature (OC)
MONTHS R3 IN R3 OUT R2 IN R2 OUT R1 IN R1 OUT MC IN MC OUT

NOVEMBER 23.6 25 23.2 27 24 26.6 25 29

DECEMBER 19 22 21.3 24.3 19.3 19.6 20.2 28.6

JANUARY 16.8 17.5 22.4 28.7 18.3 24.5 18.2 19.5
FEBRUARY 20.5 24.4 30.1 28.6 19.8 28.2 23.9 30.4
MARCH 29.7 32.1 28.6 33 27.4 32.0 30.3 30.5

Relative Humidity (%)

MONTH R3 IN R3 OUT R2 IN R2 OUT R1 IN R1 OUT MC IN MC OUT
NOVEMBER 55.7 58.8 64.7 52.5 63.8 53.2 63.8 52.5
DECEMBER 59 57.9 58.5 39.8 58.6 41.7 58.6 30.2 IN: Indoor
JANUARY 59.9 53.6 54.4 30.3 56 37.5 61.7 54.6 OUT: Outdoor
FEBRUARY 59.6 47 39.8 37.2 65.8 35.3 53.5 38.9 MC: Mixed Cluster
MARCH 28.2 28 41.9 29.6 42.5 28.7 35.3 34.9
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TVOCS VARIATION IN INDOOR AND OUTDOOR
ENVIRONMENTS AT VARIOUS MONITORED SITES
5

4.5

4
Nov
Concentration (ppm)

3.5
Dec
3
Jan
2.5
Feb
2

Mar
1.5

0.5

0
R1 In R2 In R3 In MC In R1 Od R2 Od R3 Od Mc Od

In: indoor Od: Outdoor NAAQS Indoor Guidelines: 1ppm, No outdoor guidelines

29
• Seasonal TVOCs profile showed dominantly higher value in Mixed Cluster zone (Indoor &
Outdoor) and on R1 (1 BHK houses), in indoor environment.
• The indoor environment of R1 housing, have most humid indoors as it is situated close to the
Najafgarh drain. January the coldest month shows lesser amount of TVOCs concentration due
to lesser volatility, gradually increases through February and March as the temperature increases.
The mixed cluster houses (R4) shows the highest amount of TVOCs in all months exceeding
the NAAQS limit of 1ppm in indoor environments with average of 4 ppm.
• December has highest TVOCs in indoor environments as it is the winter season and people
tend to keep their doors and windows shut all the time thus less ventilation occurs. November
and December show maximum amount of outdoor TVOCs in mixed cluster area (R4), as
approaching winter seasons increases biomass burning and due to the various eateries and
vendors in nearby area adding to TVOCs load.
• High relative humidity allows polar substances to be dissolved from the surface by water
vapor (Wolkoff, 1998), also affects rate of emission of VOCs from various VOCs containing
compounds (Andersen et al, 1975), in accordance with a study wherein most humid months
show maximum TVOCs concentration in indoor environments.

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OZONE VARIATION IN INDOOR AND OUTDOOR
ENVIRONMENTS AT VARIOUS MONITORED SITES
0.3

0.25
Nov
concentration (ppm)

Dec
0.2
Jan
Feb
0.15 Mar

0.1

0.05

0
R1 In R2 In R3 In MC In R1 Od R2 Od R3 Od Mc Od

In: Indoor Od: outdoor NAAQS Indoor Guidelines: 0.1ppm

31
• Mixed Cluster area recorded alarming ozone concentrations in all months,
crossing permissible limit of 0.1 ppm set by NAAQS while for outdoor
environment it is much lower.
• Ozone in indoor environments is always seen to be higher than the NAAQS
guidelines of 0.1 ppm at all sites (R1, R2, R3 & R4) in indoor
environments.
• The outdoor environments have ozone values less than the 0.1 ppm due
to mixing of air masses by circulation as well by photodegradation.
Mixed land use area (R4) shows higher trend in the ozone concentrations in
indoor environments with an average of 0.26 ppm directly following from
the high TVOCs concentrations in the homes, followed by the type R1
homes with less built-up area and nearby a drain.

32
 CONCLUSION

• From the compiled data of TVOCs and ozone for the month of
November, December (procured data), January, February and March
(generated data), we observed a trend of higher TVOCs concentration
in winter months which directly correlates to higher amounts of ozone
owing to lesser volatility of the TVOC in low temperatures. This could
prove to be a major concern in indoor environments as seen in many
sampling sites where the values reached much above the NAAQS
guidelines for indoor environment.

33
 SUGGESTIVE MEASURES

• A good ventilation is paramount to healthy indoor environments along

with regular checks in leakages and faults in fuel sources.
• The ubiquitous nature of VOCs and the health hazards caused by them
is reason enough to conduct further researches to understand
mechanisms of diseases.
• Imposition of ambient level guidelines to maintain safe levels of
toxicants in the atmosphere.

34
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 ACKNOWLEDGEMENTS

I am most thankful to:

my supervisor, Dr. Chirashree Ghosh, for all the support and guidance
throughout carrying out this work.
To the head of the department and all the professors of the Department of
Environmental Studies for their valuable lectures and to all the lab staff for their
support.
Mr. Arun Kumar, research scholar, and all the other researchers, Guncha Sharma,
Priyanka Sharma, Shailender Kumar and Abhinav Garg at EPL lab for their timely
support and helpfulness.
To the residents of Reids Lines and Malka Ganj for their cooperation in
conducting sampling.
Dr Pallavi Saxena for teaching me patiently the basics of research.
37
THANK YOU!

38
 PRIMARY AIR POLLUTANTS

Distribution of primary air pollutants

• The pollutants emitted directly into the
atmosphere from their sources are 5
known as primary air pollutants. 15
They can act as direct-emitting 48
pollutants or as precursors for other
pollutants, i.e. form secondary 16

pollutants on reaction with other

species in the atmosphere.
• They primary pollutants are oxides of
16

Nitrogen (NO and NO2), Sulphur

dioxide (SO2) ,Carbon monoxide
(CO), Volatile Organic Compounds
(VOCs) and particulates. Carbon monoxide Sulphur oxides
Nitrogen oxides Volatile organic compounds
Particulate matter
39
 PRIMARY AIR POLLUTANT SOURCES

Primary air pollutant sources

7% 2%
• Transportation 16%

• Fuel combustion in stationary

46%

sources
• Industrial processes 29%

• Solid waste disposal

Transportation Fuel combustion in stationary sources

Industrial processes Miscellaneous
Solid waste disposal

40
41