New AQAST Results from DISCOVER-AQ (and SEAC4RS) Field Analysis: Strat Intrusions (Texas. STL, 2013) & Oil-Natural Gas Activity (Colo, 2014) ANNE THOMPSON (NASA/GSFC) With B. N. Duncan, L. E. Ott (GSFC), Z. T. Fasnacht, D. W. Kollonige (UMD & UMD/ESSIC), H. S. Halliday, S. K. Miller (PSU). Thanks to J. Wilkins / J. Fishman, SLU AQAST9 STM, ST LOUIS, 6/2015

PRESENTATION UPDATE ON STRATOSPHERIC INTRUSIONS – Example from SEAC4RS/SEACIONS (Aug-Sept 2013) with sondes, GEOS-5 SI-O 3 tracer, AIRS RH. – Multiple ozone sources: J Wilkins Poster, 30 Aug 2013 St Louis sonde – Note: Sullivan et al: 6 Aug 2014 DAQ – lidar/sondes paper ready to submit (not shown here) UPDATE ON DISCOVER-AQ-2014/FRAPPE ANALYSES – Re-cap July-Aug 2014 field observations, eg NATIVE surface data – Further analysis of diurnal cycle in methane, CO 2, NO 2, NO/NO y – Benzene from Oil & Natural Gas (ONG) – strong, local, traceable to specific sources (Halliday paper in prep.) – Next Talk: Satellite, DISCOVER-AQ aircraft CH 4 Summary (D Kollonige)

All-Houston Overview- SEAC4RS & DISCOVER-AQ Sonde curtain displays considerable FT & UT/LS variability Signatures of stratospheric intrusions (SI) inferred from laminae, H 2 O-O 3 relation in sondes, aircraft tracers. AQAST8: SI investigated with GEOS-5 for 19 Aug & 24 Sept 13. AQAST9 - new GEOS-5 runs, satellite data. Next example = Sept 13 at Houston SEACIONS  |< -SEAC4RS & DAQ  |<-DISCOVER-AQ 19/8 24/ /9 24/9

SEAC4RS 1/DAQ: Houston SI, Sept /21 00Z 9/21 09Z 9/20 06Z Frontal passage on September 21 (Lower Left) led to SI GEOS-5 model with strat. O 3 tracer (Upper Right) shows SI over Houston (~30 N, white line) in troposphere. Impact to surface in tracer AIRS satellite RH (Lower Right)  stratospheric layer with RH < 20% from 800 hPa to top of profile SI present throughout troposphere with elevated ozone ~100 ppb, 22/9 sounding (Center) SI continued through 23 Sept before dissipation Subsequent SI 9/24-9/25 resulted from another front passing through on 9/24 SI

Concurrent Ozonesondes launches from 7 SE-US sites during SEAC4RS/SEACIONS Ozone Enhancements Due to Synoptic Meteorology Authors: Joseph L. Wilkins Jack Fishman, Benjamin de Foy, Anne Thompson, Gary Morris, Charles Graves, and Edward Hyer This work was supported in part from NASA Grant NNX11AJ63G to Saint Louis University through its AQAST Program. SEACIONS Data can be found at St. Louis, Mo Vertical Profiles Aug. 30, 2013 O 3 ppb (black) and RH % (green), Potential Vorticity 10^-6 pvu (blue), and FLEXPART-WRF CO BB tracer (shaded pbl (gray), pyro-cb (pink)). SEAC4RS 2 : 3 O 3 Enhancements in One Sounding Our key findings: SEAC4RS data allowed for identification of ~42 pyro-cb which produced considerable O3 plumes downwind over SE-US. Without the inclusion of pyro-cbs models will incorrectly place or miss pollution transport. 7 day aged air from western Wildfires + Stratospheric Air (8-11km ~50ppb) 5 day Aged Air from Wildfires + Stagnation (5-7km ~30ppb) Anthropogenic + local ag. fires less than 2 days old (1-4km ~10ppb). FLEXPART-WRF Pyro-cumulus FLEXPART-WRF Boundary Layer Emissions

PSU/GSFC NATIVE – Standard Gas (Ozone, CO, NO/NO 2 /NOY, SO 2 ) & Meteorol. Instruments & Sondes SAMPLING: 10 July-10 August 2014 HOSTED INSTRUMENTS – CH 4 LGR ANALYZER – GSFC, Hanisco – LICOR 7000 CO2 – LaRC, B Anderson – ENVIRON. SA NO2 – Szykman, Long (EPA) – Mini-MPL – Sigma Space & T Berkoff (LaRC).  BL Height, R. Hoff (UMBC) – Two Pandoras (Herman, UMBC/JCET) – Two Cimels (Holben, GSFC) – PT-RMS Quadrupole (Wisthaler, U Oslo) – Small Sensors (UC-Berkeley, CU-B) – MOPS - Baier & Brune (Penn State) PSU/GSFC NATIVE AT PLATTEVILLE

Methane & Other Trace Gases at Platteville P3-surface data in good agreement. Distinct day-night differences associated with PBL variation (effective day= ) lead to night-time pollutant buildup and complicate source interpretation Methane sources are complex: evidence from isotopes and correlations with other species not definitive – D-H more useful tracer than 13-C (A. Townsend-Small) but derived source (% Ag, % ONG) => 50/50 differs from tracer ratios at Platteville – Platteville CH 4 /CO 2 ratios suggest significant agricultural source but largest CH 4 spikes appear to be ONG (This analysis) Benzene ‘story’ (Halliday): Significant ONG source also strong diurnal pattern, strong propane, toluene, pentanes correlations

Diurnal Methane Mixing Ratio, Aircraft/Ground By Hour of Day Local Time (MDT) 0800/ / Halliday – similar pattern to Benzene & Other VOC. PBLH defines as ‘night”

Distinct Day-Night Patterns at Platteville from PBL Height Variability. Site in “Drainage Valley” with Denver -> NE Night Flow MPL (Hoff /Berkoff) & 40+ Platteville Sondes PBLH. Good agreement. “Day”= hr All diurnal cycles. Solid Red=median; Dashed red = 25, 75% range Methane Local Time CO CH 4, 0.05 ppmv bin

Complex Methane/CO2 Relationship. Platteville, 14 July-10 Aug Slopes < 0.04 imply more agricultural methane than ONG. More ONG methane at night but high NO2 (right) is not unambiguous marker. Will examine other VOC from PT-RMS at NATIVE, Platteville.  ONG Day Slope: Night Slope: CH 4 /CO 2 = Ag ( , in ppm). Color Scale = NO 2 in ppbv.

Diurnal Benzene Mixing Ratio, Aircraft/Ground By Hour of Day High benzene on the ground during early hours, low benzene measured over site by aircraft Benzene mixing ratios increase in the column as the day progresses, while ground benzene drops The column is well mixed with benzene by the midafternoon, ground benzene levels are low Local Time (MDT) 0800/ /

m = R 2 = 0.78 m = R 2 = 0.70 m = 0.88 R 2 = 0.37 m = R 2 = 0.27 AB Source Investigations using the Platteville Canister Samples Ethyne (Acetylene) – Traffic Combustion TracerPropane – Oil and Gas Production Tracer 35 whole air canister samples collected during P3 spirals over Platteville Pressurized 30 – 45 second canister samples Analyzed by Dr. Donald Blake (UCI) for VOCs PTR-MS Benzene ~ Canister Benzene: R 2 = m = Canister Benzene PTR-MS Benzene Ratios following - C. Thompson et al. (2014) Platteville Benzene ~ Ethyne: R 2 = 0.29 Benzene ~ Propane: R 2 = 0.73 Ratios following - C. Thompson et al. (2014) Platteville Benzene ~ Ethyne: R 2 = 0.29 Benzene ~ Propane: R 2 = 0.73

Directional Sources – Maxima CH 4 (L, Upper), C3H6 (L, Lower). Note: Source Map for ONG Production, No Feedlots NATIVE-Platteville Benzene Max (ppbv), Day/Night Methane Max (ppmv), Day/Night feedlots Facilities/Violations: echo.epa.gov

LOOKING AHEAD Complete writeup - SEACIONS Ozone STE Overview (AMT) Complete writeup – Platteville & A/C Benzene (HSH) Further Platteville methane surface analysis – use PTR/Canister VOC for tracers Characterization of Platteville night vs day chemistry differences – role of boundary-layer mixing. Modeling? Collaborations Welcome! Acknowledgments. Funding: AQAST, Tropospheric Chem Program (SEAC4RS), ACCDAM. Thanks to G. Pfister (FRAPPE), J. Crawford (DISCOVER-AQ), NOAA (Platteville Site), D. Blake

Outliers not shown CampaignDayNight Mean Median th th Max Ground Measurements of Benzene At Platteville using PTR-MS Day Night Day Night Day/Night defined by sun above/below horizon, data from NOAA solar calculator

Distinct Day-Night Patterns at Platteville from PBL Height Variability. Site in Drainage Valley Halliday: Compares MPL PBLH (Hoff Poster) & 40+ Platteville Sondes PBLH. Good agreement Isotopes from Amy Townsend- Small suggest CH4 source is a mixture of ONG and Ag. All diurnal cycles. Solid Red=median; Dashed red = 25, 75% range

Distinct Day-Night Patterns at Platteville from PBL Height Variability. Site in Drainage Valley MPL PBLH (Hoff /Berkoff) & 40+ Platteville Sondes PBLH. Good agreement All diurnal cycles. Solid Red=median; Dashed red = 25, 75% range Methane CO2 NOy

Day-Night CH 4 and CO 2 Contrasts at Platteville Transition from nighttime to daytime PBL (w/ MPL) used to separate Day-Night Platteville data. Higher concentrations, larger trace gas variability seen at night. Significant correlation between day/night CH 4 – CO 2 relationship. Nighttime: 2000 MDT (02 UTC) -> 0900 MDT (15 UTC)

Distinct Day-Night Trace Gas NO y at Platteville. Compare NO 2 (Szykman Environ-SA) – Binned by 0.5 ppbv

Wind/sources at Platteville: NO 2 /Med=Left; Max=Right

Benzene/Med=L Max=Right

Methane/Med=L Max=Right

SEAC4RS 1: Stratospheric Intrusion (SI) Update, 19 Aug On 17 Aug. frontal passage led to SI across central US. GEOS-5 model with stratospheric tracer (Upper Left, a) shows SI over Houston (~30 N, see white line) from ~ hPa AIRS satellite RH (Upper Right, b): Stratospheric layer as RH < 20% above 700 hPa SI observed at hPa in DC-8 descent to Houston (Lower Left, c) and in sounding where dry layer and O 3 is ~ 100 ppbv at 300 hPa; O 3 > 120 ppbv at 200 hPa (Lower Right, d) <- Yellow = 100% strat- ospheric air, with 30% strat- ospheric air at 300 hPa, 40% at hPa Intrusion Layer <- DC-8 high ozone, low CO, HCHO. Intrusion Layer <- Houston Ellington Field sounding Significance: Stratospheric O 3 Adds to “Smog” O 3 Burden