Impact of post harvest agricultural

biomass fires on atmospheric composition

of reactive gases and ozone in the N.W.

Indo-Gangetic Plain

Vinayak Sinha and the Atmospheric Chemistry and Emissions Research Group Department of Earth and Environmental Sciences, Indian Institute of Science Education and Research Mohali India International Conference on Atmospheric Chemistry and Agricultural Meteorology Pune ,Co-organized by IMD and WMO , India ; 03rd November, 2015

V. Sinha*,V. Kumar and C.

Sarkar , Atmos Chem Phys ,

14, 5921-5941, 2014

IISER Mohali Atmospheric Chemistry Facility

Chemical Instrumentation: 1. PTR-MS & Gas calibration unit (GCU),

2. CRM-OH Reactivity

3. UV-Photometry [O3] Thermo Fisher Model 49i

4. Chemiluminescense spectrometer[NO&NO2] Thermo

Fisher Model 42i

4. Non-Dispersive Infra Red (NDIR) spectrometer [CO]

Thermo Fisher Model 48i

5. Pulsed UV-Fluorescence [SO2] Thermo Fisher Model 43i

6. Greenhouse gas analyser for CH4, H2O, CO2, N2O and NH3

7. PM2.5 & PM10 analyser, Thermo Fisher Model 5014i Beta

Status of Analyzers and Availability of Data from the IISER

Mohali, Air Quality Station Image from Sinha et al., 2014.

Data is available till date

Surface Site in Mohali: Suburban & Regional

Bay of Bengal

Arabian Sea

Mohali

Delhi

MONSOON

Regional Surface Site : Large Fetch in Summer

OTHER SEASONS

72h back trajectories

Sinha et al., Atmos. Chem.

Phys. Discuss, 2013

IISER Atmospheric Chemistry

(www.iisermohali.ac.in/facilities/AtmosChemfacility/index.html)

First PTR-MS in India at IISER Mohali

Proton Transfer Reaction Mass Spectrometry (PTR-MS)

1) Real time measurements of important VOCs such as

Acetonitrile (biomass burning tracer),

terpenes OVOCs, (Mass range: 512 amu)

2) High sensitivity (10-100 pptV)

3) Rapid response time (0.8-10 seconds)

Flux measurements (e.g. Sinha et al., 2007, ACP)

Validation & Review of Applications :

Blake et al., Chem. Rev., 2009

Emissions Impacts A

I

R

Q

U

A

L

I

T

Y

C

L

O

U

D

S

&

A

E

R

O

S

O

L

Primary Emissions (Gases and Aerosol)

Role of VOC & OH oxidation

OVOC VOC OH

O2

HO,

NOx,

hƲ

O3 SOA

H

E

A

L

T

H

C

L

I

M

A

T

E Approx. 1300 TgC / yr from NMHCs alone

(Goldstein and Galbally, Env. Sci. & Tech,

2007)

CO2

Emissions-Oxidation/Atmospheric Chemistry

-Air Quality-Climate

Isoprene :

Pinene :

O

Methanol :

Dimethyl sulphide :

Marine air tracer

OH

NAcetonitrile :

Acetone :

All at pptV level

sensitivity with PTR-

MS

Acetaldehyde : O

H

Aromatics : Traffic and solvent

Benzene : Toluene :

C-8 and C-9

Aromatics :

OVOCs

Biomass burning tracer

BVOCs

C

arc

ino

ge

ns

&

SO

A p

rec

urs

ors

VOCs: Emission tracers, OH reactants, radical and SOA

precursors

Crop residue burning in the IGP

“Rice-Wheat Cropping System” is prevalent in IGP

In north western IGP, large scale crop residue burning takes place twice

a year => October –November (paddy residue) and April-May (wheat

residue)

12,685 km2 of paddy crop area were burnt in Punjab alone in October

2005 (Badrinath et al., 2006); 261 Gg of CO was released in that season

Very few in-situ gas emission studies (Sahai et al. 2007, Gupta et al.

2004, Venkataraman et al. 2006), only studied GHG and CO emissions

1) What gases are emitted from the fires?

2) How do they influence ambient ozone

formation chemistry in the IGP?

Global Mean

Radiative Forcing

1750 to 2011

AR5,

IPCC [2013]

V. Kumar , C. Sarkar and V. Sinha* ,Submitted, 2015

Daily fire counts observed over the North West Indo-

Gangetic Plain (Dec 2011 to Dec 2012)

Massive Emissions of Carcinogenic Benzenoids from

Paddy Residue Burning

N

Ben

zen

e

To

luen

e

Aceto

nit

rile

pp

bV

Local Time (IST)

C. Sarkar *, V. Kumar and V. Sinha, Current Science , 104 (12), 1703-706, 2013

Day one: Similar back

trajectory, crop residue

burning absent

72 hour back trajectories

for both Mohali and Delhi

and 96 hour fire counts data

were considered

Air masses had

experienced considerable

contact time over regions

where crop residue

burning was active

Day two: Similar back trajectory

as day one, crop residue burning

is active

Air Mass Back Trajectories on Two Days

C. Sarkar *, V. Kumar and V. Sinha , Current Science , 104 ( 12), 1703-1706, 2013

Paddy residue in the field Flask sampling during flaming

Ignition

Flask sampling during smouldering

After 20 min

After 3hours

Analysed in the IISER Lab

Sampling and Analysis of Samples

Benzenoid concentrations at the point source

flaming

Health impacts of Benzenoids

Benzene Muconalde

hyde

1,4 & 1,2

Benzoquinone Benzene

oxide

Key toxic metabolites for cytotoxicity and the

induction of Leukaemia

Clastogenic damage

to chromosome

Metabolize

d in Liver

Lipophilic

Suppresses the

Central Nervous

System

Mobile-source air toxics: a critical review of the literature on exposure and health effects. Boston, MA, Health Effects Institute, 2007

U.S. Environmental Protection Agency. Integrated Risk Information System (IRIS) on Benzene. National Center for Environmental

Assessment, Office of Research and Development, Washington, DC. 2009.

Adverse effects on

the foetus

Bone-Marrow

Damage

US EPA and WHO has classified Benzene

as a Group A carcinogen.

~30% of the reacting benzene mass concentration can form SOA

(N.L.Ng et al., 2007)

hydrophilic hydrophobic

Volkamer et al., PCCP, 2002

Significant fraction of the benzenoid mass can partition to the aerosol

phase or coat onto existing aerosol particles => altering the water vapour

uptake properties of atmospheric aerosol => promote fog formation

SOA from Benzenoids: Implications for

aggravation of fog episodes

Total number of fire counts detected (≥ 80% confidence interval) in all the three years

(2012-2014) by MODIS satellite in the north west Indo-Gangetic Plain (black square box)

during (a) pre-paddy harvest period (06 September- 10 October) and (b) post-paddy

harvest period (11 October- 20 November). Blue triangle shows the location of the

measurement site (30.6670N, 76.7290E, 310 m a.s.l.).

Pre-harvest (06 Sep - 10 Oct)

(2012-2014)

Mohali

Post-harvest (11 Oct - 20 Nov)

(2012-2014)

Mohali

a) b)

B.P. Chandra and V. Sinha*,

Submitted , 2015

MODIS Fire counts during pre (blue dots) & post (red

dots) paddy harvest seasons (2012, 2013, 2014 )

Diel emission profiles during pre (blue dots) & post

(red dots) paddy harvest seasons (2012, 2013, 2014 )

B.P. Chandra and V. Sinha*,

Submitted , 2015

Emission ratio signatures during pre (blue dots) & post

(red dots) paddy harvest seasons (2012, 2013, 2014 )

B.P. Chandra and V. Sinha*,

Submitted , 2015

Mix

ing

rati

o (

pp

t)

Formation of isocyanic acid from precursor compounds

Roberts et al., PNAS, 2011

Photooxidation of amines:

CH3NH2 + OH CH2NH2 + H2O

CH2NH2 + O2 O2CH2NH2

O2CH2NH2 + NO OCH2NH2 + NO2

OCH2NH2 + O2 HC(O)NH2 (formamide) + HO2

HC(O)NH2 + OH C(O)NH2 + H2O

HC(O)NH + H2O

C(O)NH2 + O2 HNCO + HO2

HC(O)NH + O2 HNCO + HO2

Sarkar, Sinha et al., Atmos.

Chem. Phys. Discuss., 2015

Pathway for ambient photochemical formation of Toxic

Isocyanic acid

Alkyl

amines

Biomass

burning,

Animal

Husbandry

Formamide and

Acetamide

Isocyanic

acid

Exposure to >1 ppb of isocyanic acid

can cause cataracts, cardiovascular

diseases and rheumatoid arthritis

via protein carbamylation

Wang, Z., et al.,. Nat Med, 2007

Photo-

Chemical

Oxidation

Photo-

Chemical

Oxidation

Sarkar, Sinha et al., Atmos.

Chem. Phys. Discuss.,

2015

V. Sinha*,V. Kumar and C. Sarkar , Atmos Chem Phys , 14, 5921-5941, 2014

Impact of wheat residue fire emissions in the N.W. IGP

High ambient ozone sustained by crop residue fires

V. Kumar , C. Sarkar and V. Sinha* ,Submitted, 2015

Summary of Major Findings

1) Large cesspool of reactive, carcinogenic, toxic and reactive

gases are released from crop residue fires

2) These emissions perturb ambient chemical composition of air in

the region drastically and cause severe air pollution

3) The reactive gases and NOx cause enhanced photochemical

formation of ozone and isocyanic acid

4) High ozone exposure to winter crops in the N.W. IGP can be

reduced by mitigating the post harvest paddy fire emissions

5) Synergistic effect of all pollutants emitted and formed due to the

fires cause health risks burdening the healthcare system

ACKNOWLEDGEMENTS

Monthly average relative humidity(top panel), temperature( middle panel) and

peak daytime (12:00-14:00h) solar radiation(bottom panel)

Vertical bars represent monthly variability (10th and 90th percentile)

Summer/ Pre-monsoon Monsoon Post-monsoon

Ideal Site to Examine Impact of Extremes

on Atmospheric Chemistry

V. Kumar , C. Sarkar and V. Sinha* , Under Review in JGR (Atmos), 2015