Delhi Zonal Centre. Delhi INDIA@COP22 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 www.indiaatcop22.org

INDIA@COP22 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. www.indiaatcop22.org

Potential VOC Impacts on Climate INDIA@COP22 INDIA@COP22 Potential VOC Impacts on Climate . Direct Radiative Forcing Indirect Radiative Forcing Indirect CO2 www.indiaatcop22.org

Direct Radiative Forcing INDIA@COP22 INDIA@COP22 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 www.indiaatcop22.org

INDIA@COP22 INDIA@COP22 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” . www.indiaatcop22.org http://www.globalwarmingart.com/wiki/Image:Atmospheric_Transmission.png

Atmospheric Lifetimes of VOCs INDIA@COP22 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 www.indiaatcop22.org

INDIA@COP22 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 www.indiaatcop22.org

INDIA@COP22 . NMVOCs have impact through effect on CO2, O3 and CH4 i.e indirect impact www.indiaatcop22.org www.catf.us/climate/pollutants/arctic_protection/.../Shindell_Arctic_forcings.pdf

Fate of VOC’s Chemical reaction Physical removal Rates dependent on: INDIA@COP22 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 www.indiaatcop22.org

Characterization of VOCs INDIA@COP22 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 www.indiaatcop22.org

Best estimates of climate forcing INDIA@COP22 Estimated Radiative Forcing Associated with Short-Lived Climate Forcers as Compared to CO2 . Best estimates of climate forcing www.indiaatcop22.org (Adapted from IPCC Synthesis Report, 2007)

PRECURSOR OF OZONE ARE VOCs INDIA@COP22 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 www.indiaatcop22.org

VOC concentrations in Urban Kolkata INDIA@COP22 VOC concentrations in Urban Kolkata Map of Kolkata locating the sampling sites the . www.indiaatcop22.org

VOC concentrations in Urban Mumbai INDIA@COP22 Oute r cord on VOC concentrations in Urban Mumbai . www.indiaatcop22.org

VOC concentrations in Urban Delhi INDIA@COP22 VOC concentrations in Urban Delhi . www.indiaatcop22.org

Environments in present Life style INDIA@COP22 Schools & colleges Industrial Corporate offices Malls Restaurants Transport Discos Environments in present Life style WAR www.indiaatcop22.org

VOC Concentrations in Indoors of Urban Areas INDIA@COP22 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 - 39.720 m.p.-Toluaraldehyde - 37.147 o-Toluaraldehyde - 36.547 Valaraldehyde - 35.760 Iso-valaraldehyde - 34.800 Benzaldehyde - 33.093 Crotonaldehyde - 31.147 Butanal - 29.060 Propanal - 25.320 Arolein - 23.680 Acetone - 23.107 Acetaldehyde - 18.867 Formaldehyde - 14.840 mAu www.indiaatcop22.org

Source Contribution to Total VOC –Kolkata INDIA@COP22 Source Contribution to Total VOC –Kolkata . Industrial Residential cum Commercial Petrol Pump Traffic Crossing www.indiaatcop22.org

Source Contribution to Total VOC – Mumbai INDIA@COP22 Source Contribution to Total VOC – Mumbai Residential Commercial Industrial Traffic Intersection Petrol Pump . www.indiaatcop22.org

Source Contribution to Total VOC –Delhi INDIA@COP22 Source Contribution to Total VOC –Delhi Residential Commercial Industrial Traffic Intersection Petrol Pump . www.indiaatcop22.org

VOCs in Rural Areas of Kolkata (Sunderbans) INDIA@COP22 VOCs in Rural Areas of Kolkata (Sunderbans) www.indiaatcop22.org

VOCs in Rural Areas of Kolkata (Sunderbans) INDIA@COP22 VOCs in Rural Areas of Kolkata (Sunderbans) www.indiaatcop22.org

Aldehydes in Rural Areas of Kolkata (Sunderbans) INDIA@COP22 Aldehydes in Rural Areas of Kolkata (Sunderbans) www.indiaatcop22.org

Environmental Impacts of a few Common HAPs INDIA@COP22 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 www.indiaatcop22.org

INDIA@COP22 www.indiaatcop22.org

. 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 www.indiaatcop22.org

Observed & Predicted concentrations of some VOCs and Ozone in Kolkata INDIA@COP22 Observed & Predicted concentrations of some VOCs and Ozone in Kolkata . Ozone Formaldehyde Acetaldehyde Toluene Xylene X Axis: Observed Concentration, Y Axis: Predicted concentration www.indiaatcop22.org

CO2 equivalent and Ozone produced from VOCs at the dumpsites in Mumbai INDIA@COP22 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 . www.indiaatcop22.org

CO2 equivalent and Ozone formation from VOCs in Mumbai INDIA@COP22   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 1107.97 1007.84 . www.indiaatcop22.org

CO2 equivalent and Ozone formation from VOCs in Delhi INDIA@COP22 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 1 1 1 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 1370.47 575.23 . www.indiaatcop22.org

Hazard Index and Risk contours due to exposure to air in Kolkata INDIA@COP22 Hazard Index and Risk contours due to exposure to air in Kolkata . Hazard Index Risk www.indiaatcop22.org

INDIA@COP22 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 www.indiaatcop22.org

Inhalation Ambient Air HQ Inhalation Ambient Air Risk INDIA@COP22 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 . www.indiaatcop22.org

Inhalation Ambient Air HQ Inhalation Ambient Air Risk INDIA@COP22 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 . www.indiaatcop22.org

Conclusions Lifestyle emissions contribute to VOCs in Urban Areas INDIA@COP22 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. www.indiaatcop22.org

INDIA@COP22 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 www.indiaatcop22.org

INDIA@COP22 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. www.indiaatcop22.org

THANK YOU Measure to Control HAPS/VOCs INDIA@COP22 Volatile Organic Compounds Measure to Control HAPS/VOCs THANK YOU www.indiaatcop22.org Sustainable Lifestyle = Positive Climate Action