Tropospheric Ozone Loss Processes:

Heterogeneous Reactions and SOA

Formation

Nidhi Verma
 Surface Ozone and PM2.5

250

200

Concentration (µg m-3)

150

100 NAAQ Standard = 60 µg m-3

50

0
Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec

Particulate matter can affect O3 concentration in two ways:

 Absorb or scatter a fraction of solar radiation causing change in photolysis rates,

and affecting O3 formation (Jacobson 1998; Castro et. al., 2001; Li et. al., 2011)

 Influence the tropospheric trace gas chemistry by providing surface for the
destruction reactions of ozone and NO2
Aerosols reduce photolysis coefficients of O3 (J[O3(1D)]) and NO2
(J[NO2]) and cause decrease in rate of formation of O3 (Li et. al., 2011).

O3+hv O2+O(1D) (290 nm<λ<329 nm)

NO2+hv NO+O(3P) (290 nm< λ <420 nm)

 Heterogeneous reactions affect O3 formation by:

• NO2 heterogeneous reaction

• N2O5 heterogeneous reaction
Disturbing the radical • NO3 heterogeneous reaction
and NOx cycle,

Direct removal
of O3 by
aerosols.
 HO˙ + NO
NO2 HR prevails where NOx conc. is high
HONO
+ HNO3 NO2
NO3 and N2O5 HRs O3
MNO3
At NOx sensitive regime as our HNO M+
campus site, the three HRs
3 O2
could proceed at a comparable
rate, and N2O5 HR have a
relatively heavy effect.

Xu et. al., 2012

250 y = -0.12x + 20.7
y = -1.2x + 198.3 25 (c)
R² = 0.32
Ozone (µg m-3)

R² = 0.50
200 20 R= -0.57
R=-0.71

NO2 (µg m-3)

150 15

100 10

50 5

0 0
0 50 100 150 0 50 100 150
PM2.5 (µg m-3 ) PM2.5 (µg m-3)

10 µg m-3 increase in PM2.5 concentration, causes reduction of 11.7 µg m-3of O3

and 1.2 µg m-3 of NO2
 Surface Ozone and carbonaceous aerosol

Carbonaceous Aerosol:
a) Organic Carbon (OC)
b) Elemental Carbon (EC)

Sources :
 OC consists of thousands of different individual organic species emitted
from both natural and anthropogenic sources
 EC is directly released by incomplete combustion.

60 54.5
Concentration (µgm-3)

50
40
30
15.7 18.3
20
10.2
10 2.8 3.2
0
Monsoon Winter Summer
OC EC
Sample Collection
Carbonaceous aerosol samples
 Collected on Quartz microfiber filters (Pallflex, Tissuquartz)
(47 mm)
 Duration of Sampling: 24 hours

 Flow rate: 16.6 liters/min.

Analysis

1.5 cm2 punch of the filter

paper is placed inside the
thermal chamber of the
OCEC analyzer

Thermal Carbon Aerosol Analyzer (Sunset Laboratory Inc.)

 • The CO2 formed is reduced to
• The punch is heated in four CH4 in Ni-firebrick methanator • Heated upto 900 C in fou
steps upto 870 ˚C at 500 ˚C Second phase or more steps
First phase is
under Pure He• Desorbed carbonaceous
under He/O2
• CH4 id detected with FID mixture • The CO2 measured in
vapours oxidised to CO2
• During First phase part of OC is second step is EC
(MnO2 as catalyst)
pyrolysed with formation of PC
Thermogram
 Loss of Surface O3 by OC
For eg. Reaction of Pyrene with O3
140
Winter y = -0.46x + 101
120
R² = 0.37
100
R= -0.61
80 O3 react
O3 ( µg m-3)

60
with PAHs
40 O3
20 O3
0
0 50 100 150
OC (µg m-3) O3
Organic
160 y = 1.02x + 78.8 carbon
140 Summer R² = 0.08
120 R= 0.28
100
O3 (µg m-3)

80
60
40
20
0
0 10 20 30 40
OC (µg m-3)
Ref. Cheng 2004

Winter to Summer ratio of PAH concentration is 1.6

(Dubey et. al., 2014).
 PAH concentration is inversely related to temperature (r= -0.65)
and an increase in particulate PAH was observed in winter.
 OC concentration was low in summer, about 1/3rd of that of in winter, this may be
reason of very weak correlation observed in summer.
 Carboxylic Acids

Sources:

Primary Anthropogenic emission

Primary Biogenic Emission
Photochemical transformation of precursors

Primary Anthropogenic Emission

• Biomass combustion, forest fires (Talbot et. al., 1990; Helas et. al., 1992)
• Vehicular Exhaust (Grosjean 1989, Kawamena, 2010)

Primary Biogenic Emission

• Emission of Formic acid from formicine ants
(Jonson and Dawson 1993): But it is not an important source
to Global troposphere
• Direct emission from vegetation (Servant et al., 1991)
Photochemical production of carboxylic acids from
precursors

O3 oxidation of olefins

The reaction proceeds by electrophilic addition of ozone on the unsaturated carbon-

carbon bond followed by decomposition of the trioxolane adduct to yield a carbonyl
and the Criegee biradical:

Trioxolane Adduct
Criegee biradical

Criegee biradical isomerizes to form corresponding acids

Reaction of criegee biradical with water vapour

The ozone-olefin reaction is expected to produce higher yield of organic acids at

high humidity.

Organic acids also formed by reaction of olefins with OH radical during daytime
(OH radical conc. is low during night-time) and NO3 radical during night-time
(NO3 photolyzes rapidly in sun-light)

The relative importance of three reactions can be estimated from the following reaction:
 Acid product Reaction rate constants, cm-3molecule-1s-1
Olefin Formic Acetic other kO3 (10-18) kOH (10-11) kNO3 (10-15)
Ethylene + 1.6 0.8 0.06
Propene + + 12.6 2.5 4.2
3-methyl1-pentene + iso-C5 - - -

1-pentene + n-C4 10.7 2.9 -

2-methyl-2-butene + 493 8.7 5100

1,3-butadiene + 8.4

2-methyl-1-butene + 6.5

1-butene + 12.6 2.9 5.4

For eg. For a typical day-time situation, Grosjean et.al.
[O3] = 100 ppb,
[OH] = 4*10-5 ppb
[NO3] = 0
For least reactive olefin, ethylene 66% removal will be made by OH radical and 33% by O3
For more reactive olefins eg. 2-methyl-2-butene 93% removal will be made by O3 while
7% by OH radical
Although, the room temperature rate constants for the reactions of O3 with some alkenes
are many orders of magnitude smaller than those for the corresponding OH reactions,
the fact that tropospheric ozone concentrations are so much larger makes these reactions
a significant removal process for the alkenes.
 Oligomers are formed from SCR and SOA Formation
this reaction mostly takes place in gas
phase

R- ˙ C HOO˙ Oligomers Oligomers

RO2 self reaction ROOR ROOR type

peroxide

R-CHO R-CHO
SOA nuclei
VOC R-OOH R-OOH
+ O3, OH (NO3)
R-OH R-OH

R-COOH R-COOH

High water content of aerosols

increase gas to particle conversion
• APM 550 Particulate Extraction • Dionex 1100 ion
Sampler
• At flow rate of 16.6 • 10 ml of deionised chromatograph
l/min for 24 hrs water • Eluent is 0.03
• 47 mm quatrz filter mM NaOH
paper • Ultrasonicated for 30
min
Sampling Analysis
 90 4
80 3.5
70 3
60

Temp (˚C)/RH (%)

2.5
50 Temp

Km/hr
2
40 RH
1.5 WS
30
20 1

10 0.5

0 0
Summer Monsoon Post Monsoon Winter

3.5 1.4
Acetate in pm 10 formate in pm 10
3 Acetate in pm 2.5 1.2 formate in pm 2.5

2.5 1

2 0.8

1.5 0.6

1 0.4

0.5 0.2

0 0
Summer Monsoon Post-monsoon Winter Summer Monsoon Post-monsoon Winter
Seasonal Variation of Acetate and Formate

Acetate Formate
 5.00
4 y = 0.0754x + 0.4101
y = 0.0314x + 0.2257 4.50 R² = 0.4219
3.5 R² = 0.4285 4.00 R= 0.65

Acetate(µg m-3)
R=0.65
Acetate conc. (µg m-3)

3 3.50

2.5 3.00
2.50
2
2.00
1.5
1.50
1
1.00
0.5 0.50
0 0.00
0 20 40 60 80 100 0.00 10.00 20.00 30.00 40.00 50.00
O3 conc. (µgm-3) EC (µg m-3)

5.00
0.9 4.50
0.8 4.00
y = 0.0077x - 0.0157
y = 0.0202x + 0.5093
Formate conc. (µg m-3)

0.7 R² = 0.5139 3.50

Acetate (µg m-3)

R= 0.72 R² = 0.3223
0.6 3.00
0.5 2.50
0.4 2.00
0.3 1.50
0.2 1.00
0.1 0.50
0 0.00
0 20 40 60 80 100 0.00 20.00 40.00 60.00 80.00 100.00 120.00 140.00 160.00
O3 conc. (µg m-3) OC (µg m-3)
Species AA FA O3 CO OC EC Temp RH WS

AA 1 0.78 0.65 0.40 0.57 0.65 0.48 0.71 -0.32

FA 1 0.72 0.24 0.29 0.15 0.61 0.69 -0.2

O3 1 -0.29 -0.54 -0.59 0.78 -0.47 0.21

CO 1 0.48 0.57 -0.24 0.34 -0.24

OC 1 0.67 -0.59 0.72 -0.51

EC 1 -0.67 0.63 -0.48

Temp 1 -0.89 0.55

RH 1 -0.42

WS 1
Thanks