1. Delhi Zonal Centre. Delhi
ESTIMATING CONTRIBUTION OF PRECURSORS OF SHORT LIVED CLIMATE FORCER TO CLIMATE CHANGE IN SOME
URBAN AREAS OF INDIA
Dr. Anjali Srivastava
Retd Director Grade Scientist of National Environmental Engineering Research Institute,
Delhi Zonal Centre. Delhi
Sustainable Lifestyle = Positive Climate Action

2.
Objective .
This presentation explores the impact of VOC emissions on climate change.
From a P2 perspective, VOCs are usually of interest due to their
role in ground-level ozone production
its impact on human health.

3. Potential VOC Impacts on Climate
Potential VOC Impacts on Climate .
Direct Radiative Forcing
Indirect Radiative Forcing
Indirect CO2

4. Direct Radiative Forcing
Direct Radiative Forcing .
Depends on IR-absorption “Cross-Section”
Highwood et al., 1999, Estimated Direct Radiative Forcing due to Non-Methane Hydrocarbons and found some VOCs are effective absorbers, but have very short lifetimes, so they are not important for direct forcing
Depends on a molecule’s atmospheric lifetime
Global Warming Potential (GWP) is calculated relative to CO2
Effect calculate for long time periods (typ. 100-yr)
Short-lived compounds are hard to quantify
VOC breakdown products quickly multiply
Both reactants and products do not survive long enough to be “well-mixed” thus more difficult to model their effect

5.
Location of the absorption bands decide The effectiveness of a chemicals IR absorption for warming . Much of the spectrum is now saturated by the existing CO2 and water in the atmosphere; c.f. “atmospheric window” .

6. Atmospheric Lifetimes of VOCs
Atmospheric Lifetimes of VOCs .
Most VOCs have short atmospheric life time due to its photolysis reaction with OH radical, NO3 radical and reaction with ozone.
A “climate forcer” is any gas or particle that alters the Earth’s energy balance by absorbing or reflecting radiation
&
“short-lived climate forcers” are those which stay in the atmosphere for a few days or weeks
Ozone has life time of 4 to 18 days
VOCs have life time in the range of minutes to ten of years

7.
Indirect GWP for VOCs .
Due to impact of VOC chemical reactions on atmospheric ozone & methane concentrations
Calcs. from 3D atmos. transport/reaction models
From IPCC AR4

8. .
NMVOCs have impact through effect on CO2, O3 and CH4 i.e indirect impact

9. Fate of VOC’s Chemical reaction Physical removal Rates dependent on:
Fate of VOC’s .
Chemical reaction
Reaction with OH, NO3 radicals and O3
Physical removal
Aerosol formation (wet and dry deposition)
Rates dependent on:
Temperature and light
Local concentration
e.g., for ozone, VOC-limited vs NOx-limited
Weather

10. Characterization of VOCs
Characterization of VOCs .
Reactivity based on individual compounds
Structure-based (QSAR) models e.g., alkanes more stable than alkenes
MIR (Maximum Incremental Reactivity)
POCP (photochemical ozone creation potential)
Results from global/regional models
POCP response to “pulse” of given compound or source
More realistic/comprehensive view of indirect effect

11. Best estimates of climate forcing
Estimated Radiative Forcing Associated with Short-Lived Climate Forcers as Compared to CO2 .
Best estimates of climate forcing
(Adapted from IPCC Synthesis Report, 2007)

12. PRECURSOR OF OZONE ARE VOCs
PRECURSOR OF OZONE ARE VOCs .
VOCs are organic substances which are volatile and are photochemically reactive. VOCs are part of the large hydrocarbon family
includes a long list of individual substances, many of which are toxic & persistent
Their sources are both natural and anthropogenic

13. VOC concentrations in Urban Kolkata
VOC concentrations in Urban Kolkata
Map of Kolkata locating the sampling sites the .

14. VOC concentrations in Urban Mumbai
Oute r
cord on
VOC concentrations in Urban Mumbai .

15. VOC concentrations in Urban Delhi
VOC concentrations in Urban Delhi .

16. Environments in present Life style
Schools & colleges
Industrial
Corporate offices
Malls
Restaurants
Transport
Discos
Environments in present Life style
WAR

17. VOC Concentrations in Indoors of Urban Areas
VOC Concentrations in Indoors of Urban Areas
Ninety eight VOCs identified in indoors
Aldehydes (22)
Ketones (8)
Alkanes
(10)
Aromatics (27)
Halogenated
Aromatics (14)
Alkanes (8)
Misc Class (7)
Acids (2) . 15 20 25 30 35 40 45 10 50 60 70 80
Hexanal
m.p.-Toluaraldehyde
o-Toluaraldehyde
Valaraldehyde
Iso-valaraldehyde
Benzaldehyde
Crotonaldehyde
Butanal
Propanal
Arolein
Acetone
Acetaldehyde
Formaldehyde
mAu

18. Source Contribution to Total VOC –Kolkata
Source Contribution to Total VOC –Kolkata .
Industrial
Residential cum
Commercial
Petrol Pump
Traffic Crossing

19. Source Contribution to Total VOC – Mumbai
Source Contribution to Total VOC – Mumbai
Residential
Commercial
Industrial
Traffic Intersection
Petrol Pump .

20. Source Contribution to Total VOC –Delhi
Source Contribution to Total VOC –Delhi
Residential
Commercial
Industrial
Traffic Intersection
Petrol Pump .

21. VOCs in Rural Areas of Kolkata (Sunderbans)
VOCs in Rural Areas of Kolkata (Sunderbans)

22. VOCs in Rural Areas of Kolkata (Sunderbans)
VOCs in Rural Areas of Kolkata (Sunderbans)

23. Aldehydes in Rural Areas of Kolkata (Sunderbans)
Aldehydes in Rural Areas of Kolkata (Sunderbans)

24. Environmental Impacts of a few Common HAPs
Environmental Impacts of a few Common HAPs
HAP Species
GWP
ODP
POCP
Acetaldehyde 11
0.641
Benzene
0.218
Carbon Tetrachloride
1400
1.1
Chloroform 4
Ethylene
6.8 1
Formaldehyde
0.519
Methanol
0.14
Methyl Bromide 5
0.6
Methylene Chloride 9
Propylene
4.9
1.123
Trichloroethane
144
0.1
Xylene .
GWP: Global Warming Potential relative to carbondioxide
ODP: Potential to deplete ozone in the upper atmosphere relative to (CFC-11)
POCP: potential to create ozone photochemically, relative to ethylene

26. . INDIA@COP22 Probabilistic Collocation Method for prediction of Ozone
Total Non Carbonyl VOC
Ozone
NOx
Carbonyls
Boundary Values
Ozone [ppb]
Lognormal
(m,σ)
70.11
1.099
NOx [ppt]
19.22
1.595
TVOC [ppt]
472.98
2.534
Carbonyls [ppt]
502.65
3.015
Lognormal Probability Distribution Function

27. Observed & Predicted concentrations of some VOCs and Ozone in Kolkata
Observed & Predicted concentrations of some VOCs and Ozone in Kolkata .
Ozone
Formaldehyde
Acetaldehyde
Toluene
Xylene
X Axis: Observed Concentration, Y Axis: Predicted concentration

28. CO2 equivalent and Ozone produced from VOCs at the dumpsites in Mumbai
CO2 equivalent and Ozone produced from VOCs at the dumpsites in Mumbai
VOCs
Dumpsite-I
Dumpsite-II
CO2-I
(Kg)
CO2-II
CO2 equiv
O3 produced
Per hr (ppb)
Benzene
4.12E+03
1.39E+03
5.51E+03
1.11E-01
3.47E+02
1.17E+02
4.64E+02
9.37E-03
Carbon tetrachloride
7.58E+02
1.99E-01
5.93E+01
1.21E-02
Chloroform
4.46E+00
3.19E-01
4.78E+00
7.81E-05
6.49E-01
5.97E-02
7.08E-01
1.14E-05
Ethylbenzene
7.21E+00
3.73E-01
7.58E+00
3.07E-03
5.18E-01
1.72E-01
6.90E-01
2.21E-04
methylene chloride
1.80E+02
6.71E+01
2.47E+02
6.01E-04
3.70E+00
2.13E-01
3.92E+00
1.23E-05
m-Xylene
3.69E+00
1.23E+00
4.92E+00
2.04E-03
1.17E-01
3.89E-02
1.56E-01
6.46E-05
o- xylene
1.75E+00
5.81E-01
2.33E+00
7.82E-04
1.27E-01
4.23E-02
1.70E-01
5.69E-05
Toluene
1.02E+03
3.37E+02
1.35E+03
4.16E-01
2.09E+02
7.00E+01
2.79E+02
8.57E-02
Total
6.09E+03
1.80E+03
7.89E+03
5.34E-01
6.20E+02
1.88E+02
8.08E+02
9.55E-02 .

29. CO2 equivalent and Ozone formation from VOCs in Mumbai
CO2 equiv (kg)
O3 produced per hr
Monsoon
Winter
Summer
Benzene
3.96E+07
4.46E+07
4.08E+07
797.71
900.09
824.21
Benzene, 1,2,4-trimethyl
3.74E+03
9.29E+03
7.86E+03
0.281
0.70
0.59
Benzene, 1,3,5-trimethyl
6.22E+03
9.01E+03
6.06E+03
0.468
0.68
0.46
Carbon Tetrachloride
3.32E+06
5.17E+06
3.72E+06
2.38
3.69
2.66
Chloroform
2.74E+04
4.14E+04
3.23E+04
0.44
0.66
0.52
Ethane, 1,1,1-trichloro-
1.31E+02
2.22E+02
1.76E+02
0.001
0.002
Ethene, 1,1-dichloro-
2.24E+05
2.74E+05
2.71E+05
20.59
24.99
24.83
Ethylbenzene
1.18E+04
2.07E+04
1.72E+04
3.77
6.62
5.50
isopropylbenzene
3.65E+03
1.07E+04
5.97E+03
1.17
3.44
1.91
methylene chloride
1.43E+05
2.21E+05
1.82E+05
0.45
0.69
0.57
m-Xylene
6.36E+03
7.87E+03
5.55E+03
2.72
3.37
Naphthalene
7.84E+03
1.83E+04
1.30E+04
0.58
1.36
0.96
o-Xylene
3.97E+02
7.62E+02
5.50E+02
0.14
0.26
0.19
Toluene
4.32E+05
5.25E+05
4.65E+05
132.40
161.40
143.06
Total
4.37E+07
5.09E+07
4.55E+07
963.10 .

30. CO2 equivalent and Ozone formation from VOCs in Delhi
CO2 equivalent and Ozone formation from VOCs in Delhi
CO2 equiv (kg)
O3 produced per hr
Monsoon
Winter
Summer
Benzene
7.48E+06
9.23E+06
2.56E+06
150.85
186.17
51.71
Benzene, 1,2,4-trimethyl
4.47E+04
6.52E+04
3.63E+04
3.36
4.90
2.73
Benzene, 1,3,5-trimethyl
5.99E+04
1.16E+05
6.02E+04
4.51
8.70
4.53
Dichlorobenzene
1.47E+03
4.46E+03
3.62E+03
0.12
0.38
0.31
butyl-Benzene
7.58E+03
2.15E+03
5.70E+02
0.57
0.16
0.04
Carbon Tetrachloride
1.97E+06
1.79E+06
1.57E+07
1.41
1.28
11.23
Chloroform
4.11E+04
3.99E+04
6.51E+04
0.66
0.64
1.04
Dichloromethane
4.66E+04
4.93E+04
4.44E+04
4.43
4.69
4.22
Ethane trichloro
5.25E+05
5.93E+05
3.71E+05
3.63
4.10
2.56
Ethene, 1,1-dichloro-
9.56E+03
2.08E+04
1.30E+04
0.88
1.90
1.19
Ethylbenzene
4.69E+05
6.24E+05
3.27E+05
149.96
199.71
104.56
isopropylbenzene
6.65E+04
1.32E+04
1.05E+04
5.00
0.99
0.79
Methane bromochloro
1.43E+05
1.17E+05
1.14E+05
13.79
11.31
11.06
methylene chloride
1.45E+05
1.18E+05
3.76E+05
0.46
0.37
1.18
m-Xylene
3.32E+05
4.62E+05
2.27E+05
142.04
197.68
97.18
Naphthalene
7.70E+03
1.57E+04
1.17
0.96
n-Propylbenzene
3.92E+04
1.15E+05
2.95
8.74
8.65
o-Xylene
5.68E+04
1.72E+05
1.01E+05
19.66
59.55
34.92
p-Isopropyl Toluene
4.42E+03
7.81E+03
4.70E+03
0.33
0.59
0.35
Dichloropropane
1.53E+04
1.50E+04
1.37
10.45
1.34
sec-butylbenzene
5.88E+02
2.78E+03
9.08E+02
0.21
0.07
Toluene
1.08E+06
2.17E+06
7.57E+05
330.96
666.77
232.66
Trichloroethylene
1.24E+06
2.06E+04
115.98
1.93
Total VOCs
1.38E+07
1.58E+07
2.10E+07
953.53
575.23 .

31. Hazard Index and Risk contours due to exposure to air in Kolkata
Hazard Index and Risk contours due to exposure to air in Kolkata .
Hazard Index
Risk

32.
Estimated Value of Cancer Risk in Million Populations from Individual Pollutant in Kolkata .
Compounds
Industrial
Petrol Pump
Residential
Traffic crossing
Overall Average
Benzene
1.4E+02
2.9E+02
4.5E+01
2.0E+02
1.7E+02
Ethylbenzene
5.6E+01
6.6E+01
1.0E+01
4.3E+01
4.4E+01
Chloroform
1.3E+03
6.7E+02
2.1E+03
8.8E+02
1.2E+03
Tetrachloroethylene
1.9E+01
1.4E+01
1.2E+00
1.8E+00
9.9E+00
Methlenechloride
4.9E-01
3.6E-01
6.3E-01
3.3E-01
4.6E-01
Naphthalene
1.1E+02
8.2E+01
5.5E+01
9.8E+01
Carbon Tetrachloride
9.1E+00
6.2E+01
1.1E+01
2.0E+01
Formaldehyde.
9.5E+02
8.2E+02
2.2E+03
Acetaldehyde
3.4E+02
2.8E+02
3.1E+02
4.0E+02
3.3E+02
For 40 Years Residency Period in Kolkata City

33. Inhalation Ambient Air HQ Inhalation Ambient Air Risk
Estimated Risk &Hazard at Traffic Intersections and Petrol Pumps in Mumbai
Monsoon
Summer
Winter
 Traffic intersctions
Inhalation Ambient Air HQ
Inhalation Ambient Air Risk
Total HI of soil
Total risk of soil
Total HI of soil
Total risk of soil
WORLI
3.06
2.62* E-04
8.56* E-04
7.34*E-08
3.5
2.89*E-04
9.63*E-04
8.49*E-08
3.98
3.03*E-04
10*E-04
8.31*E-08 CS
2.31
2.09* E-04
6.77* E-04
6.2* E-08
2.66
2.31*E-04
7.58*E-04
6.7* E-08
2.91
2.59*E-04
8.4*E-04
7.68*E-08
SION
2.06
1.71* E-04
5.93* E-04
4.86*E-08
2.63
2.16*E-04
7.31*E-04
6.06*E-08
3.09
2.56*E-04
9.61*E-04
7.95*E-08
Avg
2.48
2.14* E-04
7.09* E-04
6.13*E-08
2.93
2.45*E-04
8.17* E-04
7.08*E-08
3.33
2.73*E-04
9.34*E-04
7.98*E-08
Petrol Pumps
MAHIM
4.42
3.63* E-04
1.2*E-03
1.07*E-07
4.09
3.31* E-04
1.11*E-03
9.70*E-08
4.77
1.21*E-03
1.17*E-03
10.2*E-08
0.856*E-03
2.89* E-04
9.63*E-03
8.49 E-08
3.03* E-04
0.001
UDYAN
4.2
3.49* E-04
1.08*E-04
3.63
3.01* E-04
1.05*E-03
9.19*E-08
3.81
3.08* E-04
0.9* E-04
9.74*E-08
3.9
3.25* E-04
1.085*E-03
9.61*E-08
3.74
3.07* E-04
1.041*E-03
9.13*E-08
4.19
6.07* E-04
1.087* E-04
9.42*E-08 .

34. Inhalation Ambient Air HQ Inhalation Ambient Air Risk
Estimated Risk &Hazard at Traffic Intersections and Petrol Pumps in Delhi
Monsoon
Summer
Winter
 Traffic intersctions
Inhalation Ambient Air HQ
Inhalation Ambient Air Risk
Total HI of soil
Total risk of soil
Total HI of soil
Total risk of soil
SHAKARPUR
3.17
2.68* E-04
9.26*E-04
7.74*E-08
0.906
9.79* E-05
2.98*E-04
3.11*E-08
3.75
3.22*E-04
1.1*E-03
9.42* E-08
ITO
0.675
8.83* E-05
1.95* E-04
2.38*E-08
1.27
1.15* E-04
3.73*E-04
3.38*E-08
1.76
1.55*E-04
5.09*E-04
4.83* E-08
RAJAGARDEN
1.26
9.58* E-05
3.18* E-04
2.68*E-08
3.04
2.46* E-04
8.05*E-04
6.66*E-08
4.18
3.48*E-04
0.9 * E-07
Avg
1.702
1.51* E-04
4.8* E-04
4.27*E-08
1.74
1.53* E-04
4.92*E-04
4.38*E-08
3.23
2.75*E-04
9.03*E-04
7.75* E-08
Petrol Pumps
IIT
2.22
1.85*E-04
6.35* E-04
5.17*E-08
0.941
1.08*E-04
4.01*E-08
185*E-06
635*E-06 CP
2.95
257* E-04
8.45* E-04
7.48*E-08
2.57* E-04
8.45*E-04
4.13
349*E-06
118*E-05
1 * E-07
RACE COURSE
4.46
3.5 * E-04
14.9*E-04
9.95*E-08
1.63
13.2*E-03
4.54*E-04
3.93*E-08
4.72
377*E-04
13*E-04
7*E-09
3.21
2.64* E-04
9.9* E-04
7.53*E-08
1.8403
16.6*E-05
5.49*E-04
5.14*E-08
3.69
30.37*E-02
1038*E-07
8.62*E-08 .

36. Conclusions Lifestyle emissions contribute to VOCs in Urban Areas
Conclusions .
Lifestyle emissions contribute to VOCs in Urban Areas
Contribution of VOCs in urban air towards ground level ozone is sufficient enough to warrant control of its emissions.
Control strategies can be derived from the isopleths generated under the constraint of constant VOC/NOx ratio, because an upwind location, often do not reflect the conditions in downwind areas, where the VOC/NOx ratio is different.

37.
Conclusions - contd .
VOC/ NO2 ratios observed in Kolkata are primarily high indicating NO2 sensitive conditions. High rate of VOC emissions (due to local activity like biomass burning, roadside cooking etc.) increases the ratio of VOC to NO2 and makes NO2 sensitive conditions more likely.
Health impacts of VOCs cannot be neglected
Regular monitoring of VOCs must be taken up in order to ascertain proper VOC/NOx ratio so that appropriate control measures can be adopted

38.
Sincere thanks to Dr Dipanjali Majumdar, Dr Abba Elizabeth and Dr Mamta Prakash for their contribution towards monitoring and analysis of VOCs at Kolkata, Mumbai and Delhi respectively.

39. THANK YOU Measure to Control HAPS/VOCs
Volatile
Organic
Compounds
Measure to Control
HAPS/VOCs
THANK YOU
Sustainable Lifestyle = Positive Climate Action