References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-10-11931-2010

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

Simpson

I. J.

¹ Blake

N. J.

¹ Barletta

¹ Diskin

G. S.

² Fuelberg

H. E.

³ Gorham

¹ Huey

L. G.

⁴ Meinardi

¹ Rowland

F. S.

¹ Vay

S. A.

² Weinheimer

A. J.

⁵ Yang

¹ ² Blake

D. R.

Dept. of Chemistry, University of California-Irvine, Irvine, CA 92697, USA

NASA Langley Research Center, Hampton, VA 23681, USA

Dept. of Meteorology, Florida State University, Tallahassee, FL 32306, USA

School of Earth & Atmospheric Sciences, Georgia Institute of Technology, Atlanta, GA 30332, USA

National Center for Atmospheric Research, 1850 Table Mesa Dr., Boulder, CO 80305, USA

15 12 2010

10 23 11931 11954

This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

This article is available from http://www.atmos-chem-phys.net/10/11931/2010/acp-10-11931-2010.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/10/11931/2010/acp-10-11931-2010.pdf

Oil sands comprise 30% of the world's oil reserves and the crude oil reserves in Canada's oil sands deposits are second only to Saudi Arabia. The extraction and processing of oil sands is much more challenging than for light sweet crude oils because of the high viscosity of the bitumen contained within the oil sands and because the bitumen is mixed with sand and contains chemical impurities such as sulphur. Despite these challenges, the importance of oil sands is increasing in the energy market. To our best knowledge this is the first peer-reviewed study to characterize volatile organic compounds (VOCs) emitted from Alberta's oil sands mining sites. We present high-precision gas chromatography measurements of 76 speciated C2–C10 VOCs (alkanes, alkenes, alkynes, cycloalkanes, aromatics, monoterpenes, oxygenated hydrocarbons, halocarbons and sulphur compounds) in 17 boundary layer air samples collected over surface mining operations in northeast Alberta on 10 July 2008, using the NASA DC-8 airborne laboratory as a research platform. In addition to the VOCs, we present simultaneous measurements of CO2, CH4, CO, NO, NO2, NOy, O3 and SO2, which were measured in situ aboard the DC-8. Carbon dioxide, CH4, CO, NO, NO2, NOy, SO2 and 53 VOCs (e.g., non-methane hydrocarbons, halocarbons, sulphur species) showed clear statistical enhancements (1.1–397×) over the oil sands compared to local background values and, with the exception of CO, were greater over the oil sands than at any other time during the flight. Twenty halocarbons (e.g., CFCs, HFCs, halons, brominated species) either were not enhanced or were minimally enhanced (<10%) over the oil sands. Ozone levels remained low because of titration by NO, and three VOCs (propyne, furan, MTBE) remained below their 3 pptv detection limit throughout the flight. Based on their correlations with one another, the compounds emitted by the oil sands industry fell into two groups: (1) evaporative emissions from the oil sands and its products and/or from the diluent used to lower the viscosity of the extracted bitumen (i.e., C4–C9 alkanes, C5–C6 cycloalkanes, C6–C8 aromatics), together with CO; and (2) emissions associated with the mining effort, such as upgraders (i.e., CO2, CO, CH4, NO, NO2, NOy, SO2, C2–C4 alkanes, C2–C4 alkenes, C9 aromatics, short-lived solvents such as C2Cl4 and C2HCl3, and longer-lived species such as HCFC-22 and HCFC-142b). Prominent in the second group, SO2 and NO were remarkably enhanced over the oil sands, with maximum mixing ratios of 38.7 ppbv and 5.0 ppbv, or 383× and 319× the local background, respectively. These SO2 levels are comparable to maximum values measured in heavily polluted megacities such as Mexico City and are attributed to coke combustion. By contrast, relatively poor correlations between CH4, ethane and propane suggest low levels of natural gas leakage despite its heavy use at the surface mining sites. Instead the elevated CH4 levels are attributed to methanogenic tailings pond emissions. In addition to the emission of many trace gases, the natural drawdown of OCS by vegetation was absent above the surface mining operations, presumably because of the widespread land disturbance. Unexpectedly, the mixing ratios of α-pinene and β-pinene were much greater over the oil sands (up to 217 pptv and 610 pptv, respectively) than over vegetation in the background boundary layer (20±7 pptv and 84±24 pptv, respectively), and the pinenes correlated well with several industrial tracers that were elevated in the oil sands plumes. Because so few independent measurements from the oil sands mining industry exist, this study provides an important initial characterization of trace gas emissions from oil sands surface mining operations.

References 1

% vor jede Referenz Alboudwarej, H., Felix, J., Taylor, S., Badry, R., Bremner, C., Brough, B., Skeates, C., Baker, A., Palmer, D., Pattison, K., Beshry, M., Krawchuk, P., Brown, G., Calvo, R., Cañas Triana, J. A., Hathcock, R., Koerner, K. Hughes, T., Kundu, D., de Cárdenas, J. L., and West, C.: Highlighting heavy oil, Oilfield Rev., 34–53, 2006.

Apel, E. C., Calvert, J. G., Gilpin, T. M., Fehsenfeld, F. C., Parrish, D. D., and Lonneman, W. A.: The Nonmethane Hydrocarbon Intercomparison Experiment (NOMHICE): Task 3, J. Geophys. Res., 104(21), 26069–26086, 1999.

Apel, E. C., Calvert, J. G., Gilpin, T. M., Fehsenfeld, F., and Lonneman, W. A.: Nonmethane Hydrocarbon Intercomparison Experiment (NOMHICE): Task 4, ambient air, J. Geophys. Res., 108(D9), 4300, doi:10.1029/2002JD002936, 2003.

Atkinson, R.: Gas-phase tropospheric chemistry of organic compounds, J. Phys. Chem. Ref. Data, Monograph, 2, 1–216, 1994.

Atkinson, R.: Atmospheric chemistry of VOCs and NOx, Atmos. Environ., 34, 2063–2101, 2000.

Atkinson, R. and Arey, J.: Atmospheric degradation of volatile organic compounds, Chem. Rev., 103, 4605–4638, 2003.

Atkinson, R., Arey, J., Hoover, S., and Preston, K.: Atmospheric chemistry of gasoline-related emissions: Formulation of pollutants of potential concern, Draft for public comment, California Environmental Protection Agency, 2005.

Backer, W. S.: Contamination of drinking water by methyl tertiary-butyl ether (MTBE) and its effect on plasma enzymes, Sci. Res. Essays, 5(14), 1809–1812, 2010.

Baker, A. K., Beyersdorf, A. J., Doezema, L. A., Katzenstein, A., Meinardi, S., Simpson, I. J., Blake, D. R., and Rowland, F. S.: Measurements of nonmethane hydrocarbons in 28 United States cities, Atmos. Environ., 42, 170–182, 2008.

Barletta, B., Meinardi, S., Simpson, I. J., Khwaja, H. A., Blake, D. R., and Rowland, F. S.: Mixing ratios of volatile organic compounds (VOCs) in the atmosphere of Karachi, Pakistan, Atmos. Environ., 36, 3429–3443, 2002.

Barletta, B., Meinardi, S., Rowland, F. S., Chan, C.-Y., Wang, X., Zou, S., Chan, L. Y., and Blake, D. R.: Volatile organic compounds in 43 Chinese cities, Atmos. Environ., 39, 5979–5990, 2005.

Barletta, B., Meinardi, S., Simpson, I. J., Atlas, E. L., Beyersdorf, A. J., Baker, A. K., Blake, N. J., Yang, M., Midyett, J. R., Novak, B. J., McKeachie, R. J., Fuelberg, H. E., Sachse, G. W., Avery, M. A., Campos, T., Weinheimer, A. J., Rowland, F. S., and Blake, D. R.: Characterization of volatile organic compounds (VOCs) in Asian and north American pollution plumes during INTEX-B: identification of specific Chinese air mass tracers, Atmos. Chem. Phys., 9, 5371–5388, doi:10.5194/acp-9-5371-2009, 2009.

Benkovitz, C. M., Scholtz, M. T., Pacyna, J., Tarrasón, L., Dignon, J., Voldner, E. C., Spiro, P. A., Logan J. A., and Graedel, T. E.: Global gridded inventories of anthropogenic emissions of sulphur and nitrogen, J. Geophys. Res., 101(D22), 29239–29253, 1996.

Blake, D. R. and Rowland, F. S.: Continuing world-wide increase in tropospheric methane, 1978–1987, Science, 239, 1129–1131, 1988.

Blake, D. R. and Rowland, F. S.: Urban leakage of liquefied petroleum gas and its impacts on Mexico City air quality, Science, 269, 953–956, 1995.

Blake, N. J., Blake, D. R., Sive, B. C., Chen, T.-Y., Rowland, F. S., Collins Jr., J. E., Sachse, G. W., and Anderson, B. E.: Biomass burning emissions and vertical distribution of atmospheric methyl halides and other reduced carbon gases in the South Atlantic region, J. Geophys. Res., 101(D19), 24151–24164, 1996.

Blake, N. J., Blake, D. R., Simpson, I. J., Meinardi, S., Swanson, A. L., Lopez, J. P., Katzenstein, A. S., Barletta, B., Shirai, T., Atlas, E., Sachse, G., Avery, M., Vay, S., Fuelberg, H. E., Kiley, C. M., Kita, K., and Rowland, F. S.: NMHCs and halocarbons in Asian continental outflow during the Transport and Chemical Evolution over the Pacific (TRACE-P) field campaign:~Comparison with PEM-West B, J. Geophys. Res., 108(D20), 8806, doi:10.1029/2002JD003367, 2003.

Blake, N. J., Campbell, J. E., Vay, S. A., Fuelberg, H. E., Huey, L. G., Sachse, G., Meinardi, S., Beyersdorf, A., Baker, A., Barletta, B., Midyett, J., Doezema, L., Kamboures, M., McAdams, J., Novak, B., Rowland, F. S., and Blake, D. R.: Carbonyl sulfide (OCS): Large-scale distributions over North America during INTEX-NA and relationship to CO2, J. Geophys. Res., 113, D09S90, doi:10.1029/2007JD009163, 2008.

Borbon, A., Fontaine, H., Veillerot, M., Locoge, N., Galloo, J. C., and Guillermo, R.: An investigation into the traffic-related fraction of isoprene at an urban location, Atmos. Environ., 35, 3749–3760, 2001.

Burstyn, I., Senthilselvan, A., Kim, H.-M., Cherry, N. M., Pietroniro, E., and Waldner, C.: Industrial sources influence air concentrations of hydrogen sulfide and sulfur dioxide in rural areas of western Canada, J. Air Waste Manage., 57(10), 1241–1250, 2007.

Butler, J. H., Montzka, S. A., Clarke, A. D., Lobert, J. M., and Elkins, J. W.: Growth and distribution of halons in the atmosphere, J. Geophys. Res., 103(D1), 1503–1511, 1998.

Butler, J. H., King, D. B., and Lobert, J. M.: Oceanic distributions and emissions of short-lived halocarbons, Global Biogeochem. Cy., 21, GB1023, doi:10.1029/2006GB002732, 2007.

Buzcu, B. and Fraser, M. P.: Source identification and apportionment of volatile organic compounds in Houston, TX, Atmos. Environ., 40, 2385–2400, 2006.

Campbell, J. E., Carmichael, G. R., Chai, T., Mena-Carrasco, M., Tang, Y., Blake, D. R., Blake, N. J., Vay, S. A., Collatz, G. J., Baker, I., Berry, J. A., Montzka, S. A., Sweeney, C., Schnoor, J. L., and Stanier, C. O.: Photosynthetic control of atmospheric carbonyl sulfide during the growing season, Science, 322, 1085–1088, 2008.

Cetin, E., Odabasi, M., and Seyfioglu, R.: Ambient volatile organic compound (VOC) concentrations around a petrochemical complex and a petroleum refinery, Sci. Total Environ., 312(1–30), 103–112, 2003.

Choi, Y., Elliott, S., Simpson, I. J., Blake, D. R., Colman, J. J., Dubey, M. K., Meinardi, S., Rowland, F. S., Shirai, T., and Smith, F. A.: Survey of whole air data from the second airborne biomass burning and lightning experiment using principal component analysis, J. Geophys. Res., 108(D5), 4163, doi:10.1029/2002JD002841, 2003.

Colman, J. J., Swanson, A. L., Meinardi, S., Sive, B. C., Blake, D. R., and Rowland, F. S.: Description of the analysis of a wide range of volatile organic compounds in whole air samples collected during PEM-Tropics A and B, Anal. Chem., 73, 3723–3731, 2001.

Clerbaux, C., Cunnold, D. M., Anderson, J., Engel, A., Fraser, P. F., Mahieu, E., Manning, A., Miller, J., Montzka, S. A., Nassar, R., Prinn, R., Reimann, S., Rinsland, C. P., Simmonds, P., Verdonik, D., Weiss, R., Wuebbles, D., and Yokouchi, Y.: Long-lived compounds, Scientific Assessment of Ozone Depletion: 2006 Global Ozone Research and Monitoring Project, Report no. 50, Chapter 1, World Meteorological Organization, Geneva, 2007.

de Foy, B., Krotkov, N. A., Bei, N., Herndon, S. C., Huey, L. G., Martínez, A.-P., Ruiz-Suárez, L. G., Wood, E. C., Zavala, M., and Molina, L. T.: Hit from both sides: tracking industrial and volcanic plumes in Mexico City with surface measurements and OMI SO2 retrievals during the MILAGRO field campaign, Atmos. Chem. Phys., 9, 9599–9617, doi:10.5194/acp-9-9599-2009, 2009.

de Gouw, J. A., Te Lintel Hekkert, S., Mellqvist, J., Warneke, C., Atlas, E. L., Fehsenfeld, F. C. Fried, A., Frost, G. J., Harren, F. J. M., Holloway, J. S., Lefer, B., Lueb, R., Meagher, J. F., Parrish, D. D., Patel, M., Pope, L., Richter, D., Rivera, C., Ryerson, T. B., Samuelsson, J., Walega, J., Washenfelder, R. A., Weibring, P., and Zhu, X.: Airborne measurements of ethene from industrial sources using Laser Photo-Acoustic Spectroscopy, Environ. Sci. Technol., 43(7), 2437–2442, 2009.

Dehkissia, S., Larachi, F., and Chornet, E.: Catalytic (Mo) upgrading of Athabasca bitumen vacuum bottoms via two-step hydrocracking and enhancement of Mo-heavy oil interaction, Fuel, 83, 1323–1331, 2004.

Denman, K. L., Brasseur, G., Chidthaisong, A., Ciais, P., Cox, P. M., Dickinson, R. E., Hauglustaine, D., Heinze, C., Holland, E., Jacob, D., Lohmann, U., Ramachandran, S., da Silva Dias, P. L., Wofsy, S. C., and Zhang, X.: Couplings between changes in the climate system and biogeochemistry, in: Climate Change 2007: The Physical Science Basis. Contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change, edited by: Solomon, S., Qin, D., Manning, M., Chen, Z., Marquis, M., Averyt, K. B., Tignor, M., and Miller, H. L., Cambridge University Press, Cambridge, UK and New York, NY, USA, 2007.

Derwent, R. G., Simmonds, P. G., Greally, B. R., O'Doherty, S., McCulloch, A., Manning, A., Reimann, S., Folini, D., and Vollmer, M. K.: The phase-in and phase-out of European emissions of HCFC-141b and HCFC-142b under the Montreal Protocol: Evidence from observations at Mace Head, Ireland and Jungfraujoch, Switzerland from 1994 to 2004, Atmos. Environ., 41, 757–767, 2007.

Ehhalt, D. H. and Prather, M.: Atmospheric chemistry and greenhouse gases, in Climate Change 2001: The Scientific Basis, 245–287, Cambridge Univ. Press, New York, 2001.

Erickson, D. J., Rasch, P. J., Tans, P. P., Friedlingstein, P., Ciais, P., Maier-Reimer, E., Six, K., Fischer, C. A., and Walters, S.: The seasonal cycle of atmospheric CO2: A study based on the NCAR Community Climate Model (CCM2), J. Geophys. Res., 101(D10), 15079–15097, 1996.

Folberth, G. A., Hauglustaine, D. A., Lathière, J., and Brocheton, F.: Interactive chemistry in the Laboratoire de M�t�orologie Dynamique general circulation model: model description and impact analysis of biogenic hydrocarbons on tropospheric chemistry, Atmos. Chem. Phys., 6, 2273–2319, doi:10.5194/acp-6-2273-2006, 2006.

Forster, P., Ramaswamy, V., Artaxo, P., Berntsen, T., Betts, R., Fahey, D. W., Haywood, J., Lean, J., Lowe, D. C., Myhre, G., Nganga, J., Prinn, R., Raga, G., Schulz, M., and van Dorland, R.: Changes in Atmospheric Constituents and in Radiative Forcing, in: Climate Change 2007: The Physical Science Basis. Contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change, edited by: Solomon, S., Qin, D., Manning, M., Chen, Z., Marquis, M., Averyt, K. B., Tignor, M., and Miller, H. L., Cambridge University Press, Cambridge, UK and New York, NY, USA, 2007.

Fraser, P. J., Oram, D. E., Reeves, C. E., Penkett, S. A., and McCulloch, A.: Southern hemispheric halon trends (1978–1998) and global halon emissions, J. Geophys. Res., 104(D13), 15985–16000, 1999.

Fried, A., Diskin, G., Weibring, P., Richter, D., Walega, J. G., Sachse, G., Slate, T., Rana, M., and Podolske, J.: Tunable infrared laser instruments for airborne atmospheric studies, Appl. Phys. B, 92(3),~409–417, 2008.

Fuelberg, H. E., Harrigan, D. L., and Sessions, W.: A meteorological overview of the ARCTAS 2008 mission, Atmos. Chem. Phys., 10, 817–842, doi:10.5194/acp-10-817-2010, 2010.

Fuentes, J. D., Lerdau, M., Atkinson, R., Baldocchi, D., Bottenheim, J. W., Ciccioli, P., Lamb, B., Geron, C., Gu, L., Guenther, A., Sharkey, T. D., and Stockwell, W.: Biogenic hydrocarbons in the atmospheric boundary layer: A review, B. Am. Meteorol. Soc., 81(7),~1537–1575, 2000.

Gilman, J. B., Kuster, W. C., Goldan, P. D., Herndon, S. C., Zahniser, M. S., Tucker, S. C., Brewer, W. A., Lerner, B. M., Williams, E. J., Harley, R. A., Fehsenfeld, F. C., Warneke, C., and de Gouw, J. A.: Measurements of volatile organic compounds during the 2006 TexAQS/GoMACCS campaign: Industrial influences, regional characteristics, and diurnal dependencies of the OH reactivity, J. Geophys. Res., 114, D00F06, doi:10.1029/2008JD011525, 2009.

Gondwe, M., Krol, M., Gieskes, W., Klaassen, W., and de Baar, H.: The contribution of ocean-leaving DMS to the global atmospheric burdens of DMS, MSA, SO2, and NSS SO$_4^=$, Global Biogeochem. Cy., 17(2), 1056, doi:10.1029/2002GB001937, 2003.

Guenther, A., Geron, C., Pierce, T., Lamb, B., Harley, P., and Fall, R.: Natural emissions of non-methane volatile organic compounds, carbon monoxide, and oxides of nitrogen from North America, Atmos. Environ., 34, 2205–2230, 2000.

Guenther, A., Karl, T., Harley, P., Wiedinmyer, C., Palmer, P. I., and Geron, C.: Estimates of global terrestrial isoprene emissions using MEGAN (Model of Emissions of Gases and Aerosols from Nature), Atmos. Chem. Phys., 6, 3181–3210, doi:10.5194/acp-6-3181-2006, 2006.

Holopainen, J. K. and Gershenzon, J.: Multiple stress factors and the emission of plant VOCs, Trends Plant Sci., 15(3), 176–184, 2010.

Holowenko, F. M., MacKinnon, M. D., and Fedorak, P. M.: Methanogens and sulfate-reducing bacteria in oil sands fine tailings waste, Can. J. Microbiol., 46(10),~927–937, 2000.

Horowitz, L. W., Walters, S., Mauzerall, D. L., Emmons, L. K., Rasch, P. J., Granier, C., Tie, X., Lamarque, J.-F., Schultz, M. G., Tyndall, G. S., Orlando, J. J., and Brasseur, G. P.: A global simulation of tropospheric ozone and related tracers: Description and evaluation of MOZART, version 2, J. Geophys. Res., 108(D24), 4784, doi:10.1029/2002JD002853, 2003.

Hurst, D. F., Lin, J. C., Romashkin, P. A., Daube, B. C., Gerbig, C., Matross, D. M., Wofsy, S. C., Hall, B. D., and Elkins, J. W.: Continuing global significance of emissions of Montreal Protocol-restricted halocarbons in the USA and Canada, J. Geophys. Res., 111, D15302, doi:10.1029/2005JD006785, 2006.

Jacob, D. J., Field, B. D., Jin, E. M., Bey, I., Li, Q., Logan, J. A., Yantosca, R. M., and Singh, H. B.: Atmospheric budget of acetone, J. Geophys. Res., 107(D10), 4100, doi:10.1029/2001JD000694, 2002.

Jacob, D. J., Field, B. D., Li, Q., Blake, D. R., de Gouw, J., Warneke, C., Hansel, A., Wisthaler, A., Singh, H. B., and Guenther, A.: Global budget of methanol: Constraints from atmospheric observations, J. Geophys. Res., 110, D08303, doi:10.1029/2004JD005172, 2005.

Jacob, D. J., Crawford, J. H., Maring, H., Clarke, A. D., Dibb, J. E., Emmons, L. K., Ferrare, R. A., Hostetler, C. A., Russell, P. B., Singh, H. B., Thompson, A. M., Shaw, G. E., McCauley, E., Pederson, J. R., and Fisher, J. A.: The Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) mission: design, execution, and first results, Atmos. Chem. Phys., 10, 5191–5212, doi:10.5194/acp-10-5191-2010, 2010.

Jordan, C., Fitz, E., Hagan, T., Sive, B., Frinak, E., Haase, K., Cottrell, L., Buckley, S., and Talbot, R.: Long-term study of VOCs measured with PTR-MS at a rural site in New Hampshire with urban influences, Atmos. Chem. Phys., 9, 4677–4697, doi:10.5194/acp-9-4677-2009, 2009.

Kabir, E. and Kim, K.-H.: An on-line analysis of 7 odorous volatile organic compounds in the ambient air surrounding a large industrial complex, Atmos. Environ., 44, 3492–3502, 2010.

Karl, T., Apel, E., Hodzic, A., Riemer, D. D., Blake, D. R., and Wiedinmyer, C.: Emissions of volatile organic compounds inferred from airborne flux measurements over a megacity, Atmos. Chem. Phys., 9, 271–285, doi:10.5194/acp-9-271-2009, 2009a.

Karl, T., Guenther, A., Turnipseed, A., Tyndall, G., Artaxo, P., and Martin, S.: Rapid formation of isoprene photo-oxidation products observed in Amazonia, Atmos. Chem. Phys., 9, 7753–7767, doi:10.5194/acp-9-7753-2009, 2009b.

Katzenstein, A. S., Doezema, L. A., Simpson, I. J., Blake, D. R., and Rowland, F. S.: Extensive regional atmospheric hydrocarbon pollution in the southwestern United States, P. Natl. Acad. Sci., 100, 11975–11979, 2003.

Kesselmeier, J. and Staudt, M., Biogenic volatile organic compounds (VOC): An overview on emission, physiology and ecology, J. Atmos. Chem., 33, 23–88, 1999.

Kettle, A. J., Kuhn, U., von Hobe, M., Kesselmeier, J., and Andreae, M. O.: Global budget of atmospheric carbonyl sulfide: Temporal and spatial variations of the dominant sources and sinks, J. Geophys. Res., 107(D22), 4658, doi:10.1029/2002JD002187, 2002.

Kim, S., Huey, L. G., Stickel, R. E., Tanner, D. J., Crawford, J. H., Olson, J. R., Chen, G., Brune, W. H., Ren, X., Lesher, R., Wooldridge, P. J., Bertram, T. H., Perring, A., Cohen, R. C., Lefer, B. L., Shetter, R. E., Avery, M., Diskin, G., and Sokolik, I.: Measurement of HO2NO2 in the free troposphere during the Intercontinental Chemical Transport Experiment-North America 2004, J. Geophys. Res., 112, D12S01, doi:10.1029/2006JD007676, 2007.

Kindzierski, W. B. and Ranganathan, H. K. S.: Indoor and outdoor SO2 in a community near oil sand extraction and production facilities in northern Alberta, J. Environ. Eng. Sci., 5, S121–S129, 2006.

Ko, M. K. W., Poulet, G., Blake, D. R., Boucher, O., Burkholder, J. H., Chin, M., Cox, R. A., George, C., Graf, H.-F., Holton, J. R., Jacob, D. J., Law, J. S., Lawrence, M. G., Midgley, P. M., Seakins, P. W., Shallcross, D. E., Strahan, S. E., Wuebbles, D. J., and Yokouchi, Y.: Very short-lived halogen and sulfur substances, Scientific Assessment of Ozone Depletion: 2002 Global Ozone Research and Monitoring Project, Report no. 47, Chapter 2, World Meteorological Organization, Geneva, 2003.

Lu, N. and Rice, R. W.: Demand drivers and price supports for bioethanol use as fuel in the United States: A brief review, For. Prod. J., 60(2),~126–132, 2010.

McTaggart-Cowan, G. P., Rogak, S. N., Munshi, S. R., Hill, P. G., and Bushe, W. K.: The influence of fuel composition on a heavy-duty, natural-gas direct-injection engine, Fuel, 89, 752–759, 2010.

Meinardi, S., Simpson, I. J., Blake, N. J., Blake, D. R., and Rowland, F. S.: Dimethyl disulfide (DMDS) and dimethyl sulfide (DMS) emissions from biomass burning in Australia, Geophys. Res. Lett., 30(9), 1454, doi:10.1029/2003GL016967, 2003.

Millet, D. B. and Goldstein, A. H.: Evidence of continuing methylchloroform emissions from the United States, Geophys. Res. Lett., 31, L17101, doi:10.1029/2004GL020166, 2004.

Mintz, R. and McWhinney, R. D.: Characterization of volatile organic compound emission sources in Fort Saskatchewan, Alberta using principal component analysis, J. Atmos. Chem., 60(1), 83–101, 2008.

Montzka, S. A., Trainer, M., Goldan, P. D., Kuster, W. C., and Fehsenfeld, F. C.: Isoprene and its oxidation products, methyl vinyl ketone and methacrolein, in the rural troposphere, J. Geophys. Res., 98(D1), 1101–1111, 1993.

Montzka, S. A., Fraser, P. J., Butler, J., Cunnold, D., Daniel, J., Derwent, D., Connell, P., Lal, S., McCulloch, A., Oram, D., Reeves, C., Sanhueza, E., Steele, P., Velders, J. G. M., Weiss, R. F., and Zander, R.: Controlled substances and other source gases, Chapter 1, in Scientific Assessment of Ozone Depletion: 2002, Global Ozone Res. and Monitor. Proj., Vol. No. 47, World Meteorol. Org., Geneva, Switzerland, 2003.

Montzka, S. A., Calvert, P., Hall, B. D., Elkins, J. W., Conway, T. J., Tans, P. P., and Sweeney, C.: On the global distribution, seasonality, and budget of atmospheric carbonyl sulfide (COS) and some similarities to CO2, J. Geophys. Res., 112, D09302, doi:10.1029/2006JD007665, 2007.

Montzka, S. A., Hall, B. D., and Elkins, J. W.: Accelerated increases observed for hydrochlorofluorocarbons since 2004 in the global atmosphere, Geophys. Res. Lett., 36, L03804, doi:10.1029/2008GL036475, 2009.

Niinemets, Ü.: Mild versus severe stress and BVOCs: thresholds, priming and consequences, Trends Plant Sci., 15(3), 145–153, 2010.

Nowak, J. B., Davis, D. D., Chen, G., Eisele, F. L., Mauldin III, R. L., Tanner, D. J., Cantrell, C., Kosciuch, E., Bandy, A., Thornton, D., and Clark, A.: Airborne observations of DMSO, DMS, and OH at marine tropical latitudes, Geophys. Res. Lett., 28(11), 2201–2204, 2001.

O'Doherty, S., Cunnold, D. M., Manning, A., B. R. Miller, B. R., Wang, R. H. J., Krummel, P. B., Fraser, P. J., Simmonds, P. G., McCulloch, A., Weiss, R. F., Salameh, P., Porter, L. W., Prinn, R. G,. Huang, J., Sturrock, G., Ryall, D., Derwent, R. G., and Montzka, S. A.: Rapid growth of hydrofluorocarbon 134a and hydrochlorofluorocarbons 141b, 142b and 22 from Advanced Global Atmospheric Gases Experiment (AGAGE) observations at Cape Grim, Tasmania, and Mace Head, Ireland, J. Geophys. Res., 109, D06310, doi:10.1029/2003JD004277, 2004.

Paatero, P.: Least squares formation of robust non-negative factor analysis, Chemometr. Intell. Lab., 37, 15–35, 1997.

Parrish, D. D., Kuster, W., C., Shao, M., Yokouchi, Y., Kondo, Y., Goldan, P. D., de Gouw, J. A., Koike, M., and Shirai, T.: Comparison of air pollutant emissions among mega-cities, Atmos. Environ., 43(40), 6435–6441, 2009.

Penner, T. J. and Foght, J. M.: Mature fine tailings from oil sands processing harbour diverse methanogenic communities, Can. J. Microbiol., 56(6), 459–470, 2010.

Räisänen, T., Ryyppö, A., and Kellomäki, S.: Impact of timber felling on the ambient monoterpene concentration of a Scots pine (Pinus sylvestris L.) forest, Atmos. Environ., 42(28), 6759–6766, 2008.

Randerson, J. T., Thompson, M. V., Conway, T. J., Fung, I. Y., and Field, C. B.: The contribution of terrestrial sources and sinks to trends in the seasonal cycle of atmospheric carbon dioxide, Global Biogeochem. Cy., 11, 535–560, 1997.

Randerson, J. T., Field, C. B., Fung, I. Y., and Tans, P. P.: Increases in early season ecosystem uptake explain recent changes in the seasonal cycle of atmospheric at high northern latitudes, Geophys. Res. Lett., 26(17), 2765–2768, 1999.

Ras, M. R., Marcé, R. M., and Borrull, F.: Characterization of ozone precursor volatile organic compounds in urban atmospheres and around the petrochemical industry in the Tarragona region, Sci. Total Environ., 407(14), 4312–4319, 2009.

Redeker, K. R., Wang, N. Y., Low, J. C., McMillan, A., Tyler, S. C., and Cicerone, R. J., Emissions of methyl halides and methane from rice paddies, Science, 290, 966–969, doi:10.1126/science.290.5493.966, 2000.

Reimann, S., Calanca, P., and Hofer, P.: The anthropogenic contribution to isoprene concentrations in a rural atmosphere, Atmos. Environ., 34(1), 109–115, 2000.

Rogers, M. A. and Koons, C. B.: Generation of light hydrocarbons and establishment of normal paraffin preferences in crude oils, Adv. Chem., 103(3), 67–80, 1971.

Russo, R. S., Zhou, Y., White, M. L., Mao, H., Talbot, R., and Sive, B. C.: Multi-year (2004–2008) record of nonmethane hydrocarbons and halocarbons in New England: seasonal variations and regional sources, Atmos. Chem. Phys., 10, 4909–4929, doi:10.5194/acp-10-4909-2010, 2010.

Ryerson, T. B., Trainer, M., Angevine, W. M., Brock, C. A., Dissly, R. W., Fehsenfeld, F. C., Frost, G. J., Goldan, P. D., Holloway, J. S., Hübler, G., Jakoubek, R. O., Kuster, W. C., Neuman, J. A., Nicks Jr., D. K., Parrish, D. D., Roberts, J. M., Sueper, D. T., Atlas, E. L., Donnelly, S. G., Flocke, F., Fried, A., Potter, W. T., Schauffler, S., Stroud, V., Weinheimer, A. J., Wert, B. P., Wiedinmyer, C., Alvarez, R. J., Banta, R. M., Darby, L. S., and Senff, C. J.: Effect of petrochemical industrial emissions of reactive alkenes and NOx on tropospheric ozone formation in Houston, Texas, J. Geophys. Res., 108(D8), 4249, doi:10.1029/2002JD003070, 2003.

Schade, G. W. and Goldstein, A. H.: Increase of monoterpene emissions from a pine plantation as a result of mechanical disturbances, Geophys. Res. Lett., 30(7), 1380, doi:10.1029/2002GL016138, 2003.

Sharkey, T. D., Wiberley, A. E., and Donohue, A. R.: Isoprene emission from plants: Why and how, Annal. Botany, 101, 5–18, 2008.

Siddique, T., Fedorak, P. M., and Foght, J. M.: Biodegradation of short-chain $n$-alkanes in oil sands tailings under methanogenic conditions, Environ. Sci. Technol., 40, 5459–5464, 2006.

Siddique, T., Fedorak, P. M., MacKinnon, M. D., and Foght, J. M.: Metabolism of BTEX and naphtha compounds to methane in oil sands tailings, Environ. Sci. Technol., 41, 2350–2356, 2007.

Siddique, T., Gupta, R., Fedorak, P. M., MacKinnon, M. D., and Foght, J. M.: A first approximation kinetic model to predict methane generation from an oil sands tailings settling basin, Chemosphere, 72, 1573–1580, 2008.

Simpson, I. J., Blake, D. R., Rowland, F. S., and Chen, T.-Y.: Implications of the recent fluctuations in the growth rate of tropospheric methane, Geophys. Res. Lett., 29(10), 672–675, 2002.

Simpson, I. J., Wang, T., Guo, H., Kwok, Y. H., Flocke, F., Atlas, E., Meinardi, S., Rowland, F. S., and Blake, D. R.: Long-term amospheric measurements of C$_1$–C$_5$ alkyl nitrates in the Pearl River Delta region of southeast China, Atmos. Environ., 40, 1619–1632, 2006.

Sive, B. C.: Atmospheric nonmethane hydrocarbons: Analytical methods and estimated hydroxyl radical concentrations, Ph.D Thesis, University of California, Irvine, CA, 1998.

Sive, B. C., Varner, R. K., Mao, H., Blake, D. R., Wingenter, O. W., and Talbot, R., A large terrestrial source of methyl iodide, Geophys. Res. Lett., 34, L17808, doi:10.1029/2007GL030528, 2007.

Sprengnether, M., Demerjian, K. L., Donahue, N. M., and Anderson, J. G.: Product analysis of the OH oxidation of isoprene and 1,3-butadiene in the presence of NO, J. Geophys. Res., 107(D15), 4268, doi:10.1029/2001JD000716, 2002.

Stroud, C., Roberts, J. M., Goldan, P. D., Kuster, W. C., Murphy, P. C., Williams, E. J., Hereid, D., Parrish, D., Sueper, D., Trainer, M., Fehsenfeld, F. C., Apel, E. C., Riemer, D., Wert, B., Henry, B., Fried, A., Martinez-Harder, M., Brune, W. H., Li, G., Xie, H., and Young, V. L.: Isoprene and its oxidation products, methacrolein and methylvinyl ketone, at an urban forested site during the 1999 Southern Oxidants Study, J. Geophys. Res., 106, 8035–8046, 2001.

Talbot, R., Mao, H., Scheuer, E., Dibb, J., Avery, M., Browell, E., Sachse, G., Vay, S., Blake, D., Huey, G., and Fuelberg, H.: Factors influencing the large-scale distribution of Hg° in the Mexico City area and over the North Pacific, Atmos. Chem. Phys., 8, 2103–2114, doi:10.5194/acp-8-2103-2008, 2008.

Thurston, G. D. and Spengler, J. D.: A quantitative assessment of source contributions to inhalable particulate matter pollution in metropolitan Boston, Atmos. Environ., 19(1), 9–25, 1985.

100

Timoney, K. P. and Lee, P.: Does the Alberta tar sands industry pollute? The scientific evidence, Open Conservation Biol. J., 3, 65–81, 2009.

101

Vay, S. A., Anderson, B. E., Conway, T. J., Sachse, G. W., Collins, J. E., Blake, D. R., and Westberg, D. J.: Airborne observations of the tropospheric CO2 distribution and its controlling factors over the South Pacific Basin, J. Geophys. Res., 104(D5), 5663–5676, 1999.

102

Vay, S. A., Woo, J. H., Anderson, B. E., Thornhill, K. L., Blake, D. R., Westberg, D. J., Kiley, C. M., Avery, M. A., Sachse, G. W., Streets, D. G., Tsutsumi, Y., and Nolf, S. R.: The influence of regional-scale anthropogenic emissions on CO2 distributions over the western North Pacific, J. Geophys. Res., 108(D20), 8801, doi:10.1029/2002JD003094, 2003.

103

Warneke, C., McKeen, S. A., de Gouw, J. A., Goldan, P. D, Kuster, W. C., Holloway, J. S., Williams, E. J., Lerner, B. M., Parrish, D. D., Trainer, M., Fehsenfeld, F. C., Kato, S., Atlas, E. L., Baker, A., and Blake, D. R.: Determination of urban volatile organic compound emission ratios and comparison with an emissions database, J. Geophys. Res., 112, D10S47, doi:10.1029/2006JD007930, 2007.

104

Warneke, C., de Gouw, J. A., Del Negro, L., Brioude, J., McKeen, S., Stark, H., Kuster, W. C., Goldan, P. D., Trainer, M., Fehsenfeld, F. C., Wiedinmyer, C., Guenther, A. B., Hansel, A., Wisthaler, A., Atlas, E., Holloway, J. S., Ryerson, T. B., Peischl, J., Huey, L. G., and Case Hanks, A. T.: Biogenic emission measurement and inventories determination of biogenic emissions in the eastern United States and Texas and comparison with biogenic emission inventories, J. Geophys. Res., 115, D00F18, doi:10.1029/2009JD012445, 2010.

105

Watson, J. G., Chow, J. C., and Fujita, E. M.: Review of volatile organic compound source apportionment by chemical mass balance, Atmos. Environ., 35(9),~1567–1584, 2001.

106

Watts. S. F.: The mass budgets of carbonyl sulfide, dimethyl sulfide, carbon disulfide and hydrogen sulfide, Atmos. Environ., 34, 761–779, 2000.

107

Weinheimer, A. J., Walega, J. G., Ridley, B. A., Gary, B. L., Blake, D. R., Blake, N. J., Rowland, F. S., Sachse, G. W., Anderson, B. E., and Collins, J. E.: Meridional distributions of NOx, NOy, and other species in the lower stratosphere and upper troposphere during AASE II, Geophys. Res. Lett., 21, 2583–2586, 1994.

108

White, M. L., Russo, R. S., Zhou, Y., Mao, H., Varner, R. K., Ambrose, J., Veres, P., Wingenter, O. W., Haase, K., Stutz, J., Talbot, R., and Sive, B. C.: Volatile organic compounds in northern New England marine and continental environments during the ICARTT 2004 campaign, J. Geophys. Res., 113, D08S90, doi:10.1029/2007jd009161, 2008.

109

White, M. L., Russo, R. S., Zhou, Y., Ambrose, J. L., Haase, K., Frinak, E. K., Varner, R. K., Wingenter, O. W., Mao, H., Talbot, R., and Sive, B. C.: Are biogenic emissions a significant source of summertime atmospheric toluene in the rural Northeastern United States?, Atmos. Chem. Phys., 9, 81–92, doi:10.5194/acp-9-81-2009, 2009.

110

White, M. L., Zhou, Y., Russo, R. S., Mao, H., Talbot, R., Varner, R. K., and Sive, B. C.: Carbonyl sulfide exchange in a temperate loblolly pine forest grown under ambient and elevated CO2, Atmos. Chem. Phys., 10, 547–561, doi:10.5194/acp-10-547-2010, 2010.

111

Xiao, Y., Logan, J. A., Jacob, D. J., Hudman, R. C., Yantosca, R., and Blake, D. R.: Global budget of ethane and regional constraints on U.S. sources, J. Geophys. Res., 113, D21306, doi:10.1029/2007JD009415, 2008.

112

Yokouchi, Y., Osada, K., Wada, M., Hasebe, F., Agama, M., Murakami, R., Mukai, H., Nojiri, Y., Inuzuka, Y., Toom-Sauntry, D., and Fraser, P.: Global distribution and seasonal concentration change of methyl iodide in the atmosphere, J. Geophys. Res., 113, D18311, doi:10.1029/2008JD009861, 2008.

113

Zhang, Y. L., Guo, H., Wang, X. M., Simpson, I. J., Barletta, B., Blake, D. R., Meinardi, S., Rowland, F. S., Cheng, H. R., Saunders, S. M., and Lam, S. H. M.: Emission patterns and spatiotemporal variations of halocarbons in the Pearl River Delta region, southern China, J. Geophys. Res., 115, D15309, doi:10.1029/2009JD013726, 2010.