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Upper Green River Basin Wyoming Winter Ozone Study WESTAR Oil and Gas Conference September 12, 2007 Cara Keslar Wyoming DEQ - Air Quality Division Introduction Background Ozone Monitoring Field Study Design Field Study Results Jonah 12:00 2/27/06 Background Hourly Average Ozone Concentrations February 2005, Jonah Study Periods Slide compliments of NOAA 2005 & 2006 Top 5 8-hour ozone concentrations Jonah Date ppm 02/03/05 0.098 02/26/05 0.089 Boulder Date ppm 02/20/05 0.089 02/03/05 0.081 Daniel South$ Date ppm 07/08/05 0.070 07/07/05 0.067 01/24/05 02/04/05 02/27/05 0.078 0.076 0.075 02/04/05 02/24/05 02/19/05 0.080 0.080 0.079 07/22/05 07/11/05 07/03/05 0.066 0.066 0.064 02/27/06 02/25/06 05/02/06 0.093* 0.081* 0.071 04/21/06 06/18/06 05/02/06 0.081 0.079 0.076 02/25/06 05/02/06 04/21/06 0.083 0.076 0.075 06/11/06 07/15/06 0.070 0.070 06/01/06 08/18/06 0.073 0.072 02/27/06 06/18/06 0.075 0.073 * Less than 75% data completeness $ Began operation in July 2005 Theories on Causes Monitoring error: Not Likely Checked certifications Additional 3rd party audits Elevated concentrations at multiple monitors Winter 2006 put Chemiluminescent ozone monitor at Jonah to check for VOC interference and found none Stratospheric Intrusion: Not Likely Tight inversion and stagnant conditions for several days Transport: Slight Possibility Other areas had not reported high wintertime conditions Theories on Causes (cont.) Locally Formed: Most Likely Precursors emitted in area Suspected tight inversion Stagnant conditions High Elevation, sunny, snow cover 2005 AQD Response to Ozone Events Concerns about elevated concentrations Potential for NAAQS violation Health effects on local public More development planned in SW Wyoming Requested proposals for a special study Ambient and Meteorological Field Study Modeling Study Emission Inventories Ozone Monitoring Field Study Ozone Monitoring Field Study 2005 & 2006 meteorological evaluation – forecasting High pressure aloft Light surface winds Snow cover Stable boundary layer UV reflectance Gather online data from other sources Total columnar ozone GOES temperature profiles Field Study - February and March 2007 Continuous Measurements Intensive Operating Periods (IOP) Continuous Measurements Continued and enhanced monitoring at Boulder, Jonah, and Daniel South CastNet continued collecting ozone data Airport operations Profiler Site Mesonet Meteorology Intensive Operating Periods (IOPs) Operational forecasts Elevated ozone events likely Trigger Intensive Operating Periods (IOPs) IOP Measurement Objectives Determine structure of atmosphere during high ozone events: How shallow is the inversion? What does the vertical ozone profile look like? What differences exist between Jonah, Boulder, Daniel? Determine spatial variability of ozone concentrations around Upper Green River Basin Determine VOC and Carbonyl concentrations IOP Measurements Tetheredsondes and VOC/Carbonyl at Boulder, Jonah and Daniel South Rawin/ozonesondes at Airport Mesonet Ozone Aircraft measurements 2007 Field Study Results Jonah Station and surrounding area 3/17/07 Station Mean 500 mb Wind Speeds Feb-Mar 2005, 2006 Feb-Mar 2007 Substantially stronger upper level winds during 2007 field study Mean Surface Temperatures Feb-Mar 2005, 2006 Feb-Mar 2007 Warmer temperatures during 2007 field study ppb Jonah 8-Hour O3 Consistently lower O3 in 2007 March Maximum Ozone Concentration Ozone (ppb) 140 120 100 Boulder Jonah Daniel 80 60 40 20 0 Hourly Max 8-Hourly Max 2005-2006 Hourly Max 8-Hourly Max 2007 Aerial Measurements 17 March Morning Flight NO titration and elevated PM under inversion Haystack Butte 17 March Afternoon Flight - Uniform O3 - Low PM - No inversion Boulder Rawinsonde/Ozonesonde 72 ppb O3 layer aloft O3 depletion below inversion Inversion Morning Afternoon No Inversion Ground-level Measurements Hourly Ozone at Selected Sites O3 at upwind location 60 Ozone (ppb) 50 40 30 Ozone depletion due to NO titration 20 10 Cora Jonah Simpsons Gulch 0 0 2 4 6 8 10 12 14 Hour(MST) 16 18 20 22 UV Albedo 0.9 Albedo UV Insolation 0.8 400 Daily Avg. 350 07:00 – 19:00 MST 0.7 Albedo 0.6 250 0.5 200 0.4 150 0.3 UV Insolation (W/m2) 300 2 March: Albedo = 0.81 (snow) 100 0.2 0.1 50 0.0 0 2/28 3/15 3/30 4/14 4/29 23 March: Albedo = 0.04 (bare ground) VOCs: Mean Concentration ppbC Total Identified 5000 4000 3000 2000 1000 0 Boulder Daniel Paraffins ppbC ppbC 3000 2000 1000 0 Boulder Daniel Jonah Jonah Olefins 40 30 20 10 0 Boulder Daniel Jonah Median VOC Concentrations: Top Six 120 100 Boulder Daniel Jonah 60 40 20 ne nt a nPe ne i-P en ta an ut i-B ta Bu n- e ne e an op Pr ha ne 0 Et ppbV 80 et h yl E M 2- cyc th et M lo en hy e he e l t thy xa er lh n t b ex e C uty an 3- yclo l et e M p h 2- eth ent er 2, Me ylh an 2- th e e D y xa im lh n et ep e hy ta lb ne n- uta M H ne et ex hy a 2- lcy To ne M clo lue et p n 2- hyl en e M -1 tan et he e hy x lp en e n- nta e H n ep e Be tan nz e en e M ppbV Median VOC Concentrations: Remainder of Top 21 8 7 6 5 4 3 2 1 0 Boulder Daniel Jonah Carbonyl Analysis 12 Samples at Each Site Not Detected 2,5Dimethylbenzaldehyde, Hexaldehyde, Isovaleraldehyde, m,o,pTolualdehyde, Propionaldehyde, Valeraldehyde, Sometimes Detected Buteraldehyde (roughly half of all samples), Crotonaldehyde (2 samples) Detected in all or nearly all samples Acetaldehyde, Acetone, Benzaldehyde, Formaldehyde Formaldehyde Max 9 Jonah Boulder Daniel 8 Mean 7 •Several formaldehyde sources near Jonah (high early morning concentrations) 6 ppbV 5 4 3 Tentative Conclusions: • Possibility of some midday photochemical production at Boulder Min 2 •Need more sampling! 1 0 0400-0700 0900-1200 Time (MST) 1400-1700 Summary Weather conditions associated with high ozone events in 2005-2006 did not occur during 2007 Warmer temperatures, lack of snow cover Morning surface inversions did not persist Observed “background” O3 in 50 – 55 ppb range Increases in NOx and reduced O3 at Jonah compared to 2005-2006 Need site downwind to observe results of O3 formation Need more information on VOC/carbonyl Lessons Learned Difficult to forecast high O3 events Lack of reliability, and low humidities limited usefulness of profilers Importance of local personnel to help with troubleshooting equipment, downloading data and coordinating logistics Recommendations for 2008 Field Study Start operations by mid-January Maintain wind & temperature obs at 8 mesonet sites (equipment has been purchased) Allow for potentially more IOPs by limiting cost of each Reduce number of mesonet sites with O3 Eliminate tethersondes Focus on aircraft for horizontal and vertical distributions of ozone, PM, temperature Simplify continuous upper air (SODAR or miniSODAR) Use leftover ozone/rawinsondes More VOC/carbonyl sampling Questions Cara Keslar Field Study Project Manager 307-777-8684 Darla Potter Acting Modeling Study Project Manager 307-777-7346