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) anne.m.thompson@nasa.gov

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, SLUAQAST9 STM, ST LOUIS, 6/2015

PRESENTATION

• UPDATE ON STRATOSPHERIC INTRUSIONS– Example from SEAC4RS/SEACIONS (Aug-Sept 2013) with sondes,

GEOS-5 SI-O3 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, CO2, NO2, NO/NOy

– Benzene from Oil & Natural Gas (ONG) – strong, local, traceable to specific sources (Halliday paper in prep.)

– Next Talk: Satellite, DISCOVER-AQ aircraft CH4 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, H2O-O3 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 = 22-23 Sept 13 at Houston

SEACIONS |< -SEAC4RS & DAQ |<-DISCOVER-AQ

19/824/922-23/9

24/9

SEAC4RS 1/DAQ: Houston SI, 22-23 Sept. 2013

9/21 00Z

9/21 09Z

9/20 06Z

• Frontal passage on September 21 (Lower Left) led to SI • GEOS-5 model with strat. O3 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/SEACIONSAuthors: Joseph L. Wilkins (jlwilkin9@slu.edu), 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 http://croc.gsfc.nasa.gov/seacions/

St. Louis, Mo Vertical Profiles Aug. 30, 2013O3 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 O3 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/NO2/NOY, SO2) & Meteorol. Instruments & Sondes

• SAMPLING: 10 July-10 August 2014• HOSTED INSTRUMENTS

– CH4 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=0900-2000) 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 CH4/CO2 ratios suggest significant agricultural source but largest

CH4 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)

0800/0900 1000 1100 1200 1300/1400 1500 1600

Halliday – similar pattern to Benzene & Other VOC. PBLH defines 0900-2000 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”=0900-2000 hr

All diurnal cycles. Solid Red=median;Dashed red = 25, 75% range

MethaneLocal Time

CO2

0 12 24

CH4, 0.05 ppmv bin

Complex Methane/CO2 Relationship. Platteville, 14 July-10 Aug 2014. 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: 0.005Night Slope: 0.012

CH4/CO2 = Ag (0.008-0.044, in ppm). Color Scale = NO2 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)0800/0900 1000 1100 1200 1300/1400 1500 1600

m = 0.011

R2 = 0.78

m = 0.011

R2 = 0.70

m = 0.88

R2 = 0.37

m = 0.797

R2 = 0.27

A B

Source Investigations using the Platteville Canister Samples

Ethyne (Acetylene) – Traffic Combustion Tracer Propane – 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: R2 = 0.9148

m = 1.007

11Canister BenzenePTR-MS Benzene

Ratios following - C. Thompson et al. (2014)

Platteville Benzene ~ Ethyne: R2 = 0.29 Benzene ~ Propane: R2 = 0.73

Ratios following - C. Thompson et al. (2014)

Platteville Benzene ~ Ethyne: R2 = 0.29 Benzene ~ Propane: R2 = 0.73

Directional Sources – Maxima CH4 (L, Upper), C3H6 (L, Lower). Note: Source Map for ONG Production, No Feedlots

NATIVE-PlattevilleBenzene 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

Campaign Day Night

Mean 0.530 0.327 0.802

Median 0.328 0.175 0.593

25th 0.138 0.101 0.348

75th 0.661 0.392 0.966

Max 29.27 22.3 29.27

Ground Measurements of Benzene At Platteville using PTR-MS

DayNight DayNight

Day/Night defined by sun above/below horizon, data from NOAA solar calculator http://www.esrl.noaa.gov/gmd/grad/solcalc/

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 CH4 and CO2 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 CH4 – CO2 relationship.

Nighttime: 2000 MDT (02 UTC) -> 0900 MDT (15 UTC)

Distinct Day-Night Trace Gas NOy at Platteville. Compare NO2

(Szykman Environ-SA) – Binned by 0.5 ppbv

Wind/sources at Platteville: NO2/Med=Left; Max=Right

Benzene/Med=LMax=Right

Methane/Med=LMax=Right

SEAC4RS 1: Stratospheric Intrusion (SI) Update, 19 Aug. 2013

• 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 ~750-300 hPa

• AIRS satellite RH (Upper Right, b): Stratospheric layer as RH < 20% above 700 hPa • SI observed at 500-600 hPa in DC-8 descent to Houston (Lower Left, c) and in sounding

where dry layer and O3 is ~ 100 ppbv at 300 hPa; O3 > 120 ppbv at 200 hPa (Lower Right, d)

<- Yellow = 100% strat- ospheric air, with 30% strat-ospheric air at 300 hPa, 40% at 500-600 hPa

Intrusion Layer

<- DC-8 high ozone, low CO, HCHO.

Intrusion Layer

<- Houston Ellington Field sounding

Significance: Stratospheric O3 Adds to “Smog” O3 Burden