The importance of VOCs in local and regional air quality: a few stories

Donald R. Blake Professor of Chemistry University of California, Irvine

June 20, 2012

Notice Nobel pin on Sherrys lapel

What to expect in WAS group

Laboratory analysis (shifts)

Response (mV)
10.0 20.0 30.0 40.0 50.0 0 0 mV 1.0 2.0 3.0 H-1211 4.0 CFC-11 5.0 CH3I 6.0 CH2Cl2 Methyl Nitrate 7.0 CHCl3 Ethyl Nitrate 8.0 9.0 10.0 3-Pentyl Nitrate / 2-Pentyl Nitrate 11.0 min 12.3 CHBr3 C2CHCl3 CHBrCl2 n-Propyl Nitrate C2Cl4 2-Butyl Nitrate i-Propyl Nitrate

Modifying chromatograms (shifts)

Time (min)

CFC-113

Importance of tropospheric ozone (O3)

3. Local and regional pollutant (photochemical smog)
adverse effects on humans, animals and plant life (>40 ppbv) formed by NOx-catalyzed oxidation of volatile organic compounds:
RH + OH R + O2 + M RO2 + NO NO2 + h O + O2 + M R + H2O RO2 + M NO2 + RO NO + O O3 + M

NOx-catalyzed oxidation of volatile organic compounds Ozone formation

RH = volatile organic compound (VOC), e.g. methane, isoprene, etc.

Results: Impact on O3 formation

Maximum Incremental Reactivity (MIR) scale
Measures a compounds ozone-forming potential Based on each compounds incremental reactivity number of O3 molecules formed per VOC atom added: [g-O3]/[g-VOC] O3 formation = MIR x [VOC] VOC CO Ethene m-Xylene o-Xylene Propene Mixing Ratio
(ppbv)

O3 Formation
(g-O3)

2300 11 2 2 2

145 91 78 44 42

Alkyl Nitrate Formation

Minor Pathway
Alkyl Nitrate

RONO2

Major Pathway
RO

NO
OH Hydrocarbon H2O

NO2 + h NO

NO + O(3P) O2

RH

O2

Alkylperoxy radical

ROO

HO2

ROOH

M + NO2 ROONO2

O3

ROO. ROOR

Ozone formation dependence on NOx and VOC concentrations

Whats the fuss about tropospheric ozone?

Bad to breathe Bad for crops and plants Death by a thousand cuts

LPG Source Samples

1993

Propane increased from <50% to 60%. Decrease in butanes, particularly i-butane . Large decrease in butenes (1-&i-butene, cis-2-butene, trans-2butene).
2006

Changes in composition of LPG are apparent in urban samples

NASA ARCTAS June-July, 2008

12 flights on the NASA DC-8 1651 whole air samples collected Flights in and around Los Angeles photochemistry and GHG emissions Flights in Canada for biomass burning

Benzene (pptv) vs CO (ppbv)

Toluene vs CO (solvents)

Propane vs CO (LPG)

HCFC-134a vs time (urban)

C2Cl4 vs time (solvents)

1,3-butadiene vs time (biomass burning)

Propyne vs time (biomass B)

Furan vs time (biomass B)

MTBE vs time (gasoline addative)

MAC vs MVK (isoprene oxidation)

2-pentylnitrate vs time (mixed)

Ethylnitrate vs methylnitrate (marine and photochem)

35 30 25

20

15

10

0 0 5 10 15 20 25 30 35

Results from a California Dairy Study: A Research Lesson

Donald Blake Professor of Chemistry University of California, Irvine

Sampling Campaign
Collaboration with other university Consisted of both ambient and flux chamber source samples
6 dairies were sampled Samples were collected at various locations and processes at the dairies

0.5 km

Open lot

Feed lane

Silage Pile

Bedding/Flush lane

End of flush lane

Solids Separator

Lagoon

Ambient sampling at source locations

Flux Chamber samples

Total surface area = 0.13 m2

Silage Piles

Acetaldehyde

Methanol

Ethanol

DMS Methyl acetate

1-propanol

Corn Silage pile Flux chamber

Ethyl Acetate

Sampling Campaign
Consisted of both ambient and flux chamber source samples
6 dairies were sampled Samples were collected at various locations and processes at the dairies

San Joaquin Valley grid study (hot tube science)

60 ambient samples 25 miles x 25 miles; all 8 counties covered

ARCTAS test flights

Low level flights through valley (1000ft)

San Joaquin Valley Grid Study

6th March 2008

Ethanol

Mixing ratio (pptv)

Stanislaus county

Merced county

Tulare county

Operation Blue Sky, Beijing 1999

Important Clothes

2002 flight around Hong Kong

Acknowledgements