Signature Alkane Ratios and Hydrocarbon Emissions Estimates for Western Kern County Oilfields

Davidson College SARP 2012 Dr. Don Blake and Greg Hartt

Kelvin Bates

Outline
Oil and gas in California Our relevant data Estimating emissions

Mapping infrastructure: alkane ratios The box model

Results Conclusions & Future Work Acknowledgements and sources

Oil and Gas in California

502,000 bbl oil/day

4th in the US 30% of CA consumption

900 million ft3 gas/day 10% of US refining Releases methane

(GHG) and other hydrocarbons (health effects, ozone formation)

Oil and Gas in California

Most concentrated
Natural gas fields Oil fields

oilfields in western Kern county

High emissions due to

concentration, seeps
Urgent need to assess

and reduce emissions

http://gif.berkeley.edu/westcarb/gallery.html

Our Data: Flight Paths

Research flight 4 Research flight 5

Our Data: Flight Samples

Our Data: Ground Samples

Our Data: Gregs Ground Samples

Our Data
Air samples Ground samples Gregs ground samples

i-/n-Pentane Ratio
2500

2000

i-pentane (pptv)

1500

SARP 2012: Red: flights Blue: ground

1000

500

0 200 400 600 800 1000

n-pentane (pptv)

i-/n-Pentane Ratio
Slope: 2.52 R2: 0.9726
3000

i-pentane (pptv)

Red: non-oil samples

2000

Slope: 0.8737 R2: 0.9788 Blue: Gregs oilfield samples Green: our oilfield samples Purple: near Chevron refinery (2011) Brown: flights over oil fields
0 500 1000 1500 2000 2500 3000

1000

n-pentane (pptv)

Gas wells

SARP 2009-2012 + Gregs oilfield samples

0.9

2.5

i-/n-pentane
Gas/oil wells

Oil fields

Seeps ? Chevron refinery

BOX MODEL
to estimate emissions from the western Kern county oilfields

0.9

2.5

i-/n-pentane

Building a Box Model

Box
Wind speed vent time Boundary layer height Length & width Mixing Ratios mg/m3

Background
Wind direction Mixing ratios mg/m3

[(Box conc.)-(Background conc.)] * Volume * Vents per year = Emissions per year

Building my Box Model

Box
3-4.5 mph winds 2.5-4 hour vent time Average PBL height: 4700 ft 15 km by 30 km rectangle Three runs: Feb, April, July 15-20 points

Background
Northeast of sample box 9-10 points

[(Box conc.)-(Background conc.)] * Volume * Vents per year = Emissions per year

Box Model Results

February Methane Ethane Propane Butanes Pentanes 80 7.0 7.0 4.5 3.2 April 91 8.4 7.6 5.0 3.3 July 160 8.1 7.9 5.0 2.7 Average Std. Dev. 110 7.83 7.5 4.83 3.07 43 0.74 0.46 0.29 0.32 %RSD 39% 9.5% 6.1% 6.0% 10.4%

Non-methane alkanes All C2+ hydrocarbons

29.8 32.1

29.9 31.6 in Gg/yr

27.7 28.2

29.1 30.6

1.2 2.1

4.1% 6.9%

Conclusions & Future Work

Identified an alkane ratio signature for oil

infrastructure emissions Used a simple but robust model to estimate western Kern county oilfield emissions
More sampling: bigger box; August-February; 13C analysis of hydrocarbon origin

Acknowledgements
Greg Hartt The WAS team Dr. Blake & the Blake lab Jessica Gilman, NOAA ESRL CALNEX & ARCTAS The SARP team, and support from NASA, NSERC, UND

Sources
Petron, G., et al. Hydrocarbon emissions characterization in the Colorado Front

Range: A pilot study. J. Geophys. Res. 2012, 117, D04304. Saito, T., et al. In situ measurements of butane and pentane isomers over the subtropical North Pacific. Geochem. J. 2004, 38, 397-404. Igari, S., et al. Pentane and hexane isomers in natural gases from oil and gas fields in Akita, Niigata, and Hokkaido, Japan: Determination factor in their isomer ratios. Geochem. J. 2007, 41, 57-63. Katzenstein, A., et al. Extensive Regional Atmospheric Hydrocarbon Pollution in the Southwestern United States. PNAS 2003, 100 (21) 11975-11979. Pozzer, A., et al. C3-C5 alkanes in the atmosphere: concentration, seasonal cycle and contribution to the atmospheric budgets of acetone and acetaldehyde. Atmos. Chem. Phys. Discuss. 2009, 9, 1939-1975. Simpson, I. J., et al. Characterization of trace gases measured over Alberta oil sands mining operations: 76 speciated C2-C10 volatile organic compounds (VOCs), CO2, CH4, CO, NO, NO2, NOy, O3 and SO2. Atmos. Chem. Phys. 2010, 10, 11931-11954.

Questions