Air quality impacts of oil and gas development in the Bakken formation region

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1 Air quality impacts of oil and gas development in the Bakken formation region J. L. Collett, Jr. 1, A. Evanoski Cole 1, A. Prenni 2, D. Day 2, A. Sullivan 1, Y. Li 1, B. Sive 2, Y. Zhou 1, A. Hecobian 1, J. Hand 2, K. Gebhart 2, M. Schurman 1, W. Malm 2, and B. Schichtel 2 1. Atmospheric Science Department, Colorado State University, Ft. Collins, CO 2. NPS Air Resources Division/CIRA, Lakewood and Fort Collins, CO 1

2 Study Motivation Increases in U.S. oil and gas production may be relevant NO x emissions reductions substantially reduced PM 2.5 nitrate in much of U.S. Increasing winter nitrate, however, in some regions 2

3 Source: EPA Clean Air Markets Database Regional Power Plant Emissions Large decreases achieved in regional power plant emissions, but NO x emissions estimates for the basin suggest these are more than offset by growth in oil and gas emissions. Measured NO 2 concentrations in recent years have been flat or increasing. 3

4 Bakken winter 2012/13 and 2013/14 study Particle mass and speciation NO x, O 3, NH 3, HNO 3, SO 2,CH 4 Speciated VOCs 4

5 Summary of Pilot Study Results Concentration (µg m 3 ) Good news: O 3 concentrations were low, typical of rural sites Bad news: High particle concentrations Multi day episodes occur across study region Worst episodes in March during stagnant/recirculating air periods Primarily ammonium nitrate and ammonium sulfate Calcium Ammonium Nitrate Sulfate Theodore Roosevelt North Unit (THRO N) Fort Union (FOUN) /14/13 2/21/13 2/28/13 3/7/13 3/14/13 3/21/13 3/28/13 4/4/13 5

6 Did ammonia limit NH 4 NO 3 formation? NH 3 / (NH NH3 ) FOUS THRO N 0 2/14/13 2/21/13 2/28/13 3/7/13 3/14/13 3/21/13 3/28/13 4/4/13 Ammonia nearly depleted in Theodore Roosevelt National Park during episode 1, but not episode 2 Excess ammonia available both periods at Fort Union 1 2 6

7 Spatial patterns of methane and ethane 7 Methane elevated in oil and gas production and some other regions; ethane tied more directly to oil and gas

8 Light alkanes at all stationary sampling sites: Markers for oil and gas Concentrations elevated by ~an order of magnitude. Oil and gas impacts seen at all sites. 8

9 Bakken VOC concentrations in North Dakota Bakken Formation (this study) 1 NE Colorado, Denver-Julesburg Basin 2 Southwest Pennsylvania 3 Houston shipping channel, TX 4 Mexico City, upper=in city, lower=downwind 5 SW U.S., upper=sept. mean, lower=apr. mean context Mixing Ratio (ppbv) U.S. Cities range of means 1) Swarthout et al., 2013; 2) Swarthout et al., 2014, submitted; 3) Gilman et al., 2009; 4) Apel et al., 2010; 5) Katzenstein et al., 2003; 6) Baker et al., 2008 Ethane Propane i-butane n-butane i-pentane n-pentane Ethyne Benzene Toluene

10 Pentane isomer ratio as a source marker Constant i pentane to n pentane ratio suggests all sites are impacted by same source region during periods of high concentrations. i-pentane (ppbv) Rural/Urban n-pentane (ppbv) Oil and Gas R 2 = 1.00 Slope = 0.74 NE Colorado, Denver-Julesburg Basin Thompson Farm, Durham, NH (Oct.-May) Thompson Farm, Durham, NH (June-Sept.) Hickory, PA, Marcellus Shale Pittsburgh, PA Detroit, MI Natural Gas (Weld County, CO) Typical Urban Ratio THRO-NU FOUS MELA 10

11 Aerosol Composition, THRO N High particle concentrations in December, February, & March. Dominated by ammonium sulfate and ammonium nitrate. 11

12 Aerosol Composition at all Sites Increases in particle concentrations seen at all sites. 12

13 2 Day Back Trajectories from Low Concentration Days at Main Site 12/16/13 2/17/13 3/9/13 13

14 2 Day Back Trajectories from High Concentration Days at Main Site 12/22/13 2/15/14 3/6/14 2/13/14 14

15 Bakken VOC reactivity Alkanes dominate. OH reactivity, due to their abundance, despite their intrinsically low reactivity Nitration rates of alkanes provide a chemical clock for aging Bakken VOCs 15

16 Highest PM 2.5 Concentrations Correspond with Short VOC Lifetimes 16

17 Conclusions Decreases in NO x emissions from traditional sources have been offset by oil and gas development in the Bakken oil patch. Oil & gas production is a major regional source of light alkanes. During air stagnation, SO 2 and NO x accumulate and are oxidized to sulfuric and nitric acids. VOC clock suggests that PM episodes are associated with local emissions. Cold winter temperatures and available ammonia permit substantial NH 4 NO 3 formation. Sufficient ammonia is available to support additional PM formation if NO x emissions continue to grow. 17

18 Concentration (µg / m 3 ) Fort Union ammonia supply NH / N(-III) /29/13 12/6/13 12/13/13 12/20/13 12/27/13 1/3/14 1/10/14 1/17/14 1/24/14 1/31/14 2/7/14 2/14/14 2/21/14 2/28/14 3/7/14 3/14/14 3/21/14 NH 4 + NH 3 Median Sample Time

19 Bakken winter 2012/13 particle composition Concentration (µg m 3 ) Nitrite Chloride Sodium Potassium Magnesium Calcium Ammonium Nitrate Sulfate 20 Theodore Roosevelt North Unit (THRO N) Episode 1 Episode Fort Union (FOUN) Knife River (KNRI) Medicine Lake (MELA) Sampling Date

20 2013/14 study shows regional haze episodes, but lower peak concentrations Aerosol Concentration (µg m -3 ) 5 Ammonium 5 4 Nitrate Sulfate Main Site Fort Union Medicine Lake 11/29/13 12/6/13 12/13/13 12/20/13 12/27/13 1/3/14 1/10/14 1/17/14 1/24/14 1/31/14 2/7/14 2/14/14 2/21/14 2/28/14 3/7/14 3/14/14 3/21/14 Sample Time

21 Main Study Aerosol at Theodore Roosevelt NP MARGA Hourly Inorganic PM 2.5 AMS 5 Minute Organic PM 1 Aethalometer Black Carbon

22 Initial Motivation for the Study: Trends from IMPROVE data PM 2.5 and haze have increased since 2000, counter to national trends. 22

23 2013/14 Measurements Theodore Roosevelt NP PM 2.5 mass (15 min; 24 hr) Particle scattering (15 min) Aerosol composition Inorganic (24 hr, 1 hr PM 2.5 ; 15 min PM 1 ) Organic (24 hr; 1 min PM 1 ) Black carbon (15 min, 24 hr) Trace gases: NO x, NO y, NH 3, CO, O 3 (15 min) SO 2, NH 3, HNO 3 (1 hr, 24 hr) VOCs (grab samples throughout; limited PTR MS) Fort Union (weekly in January) Particle scattering (15 min) Aerosol composition Inorganic (24 hr) Trace gases: SO 2, NH 3, HNO 3 (24 hr) VOCs (grab samples 4 days/wk) Medicine Lake Particle scattering (15 min) Aerosol composition Inorganic (weekly) Trace gases: SO 2, NH 3, HNO 3 (weekly) VOCs (grab samples weekly) Mobile Measurements CH 4 (continuous) and VOCs 23

24 Pentane isomers as a source marker (Simpson et al., 2010) At low concentrations, greater contribution from background air or potentially Alberta oil sands. 24

25 2 day back trajectories 24 hr samples Elevated NO x, BC, and SO 2 25

26 2 day back trajectories 24 hr samples Low concentrations. Trajectories suggest little time in Bakken region. 26

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