NH3Monitoring in the Upper Green River Basin, WyomingJohn V. Molenar1H. James Sewell2JeffreyCollett3Cassie Archuleta1Mark Tigges1Florian M. Schwandner3Suresh Raja31 Air Resource Specialists, Inc2 Shell Exploration & Production Company3 Department of Atmospheric Science, Colorado State UniversityBackground image courtesy of: Dave Bell Photos • PO Box 1738 • Pinedale, WY 82941 ww.davebellphotos.com•Background: oil & gas developmentBackground:oil&gasdevelopmentin Upper Green River Basin•Monitoring & Laboratory Procedures•Results & InterpretationUpper Green River ValleyNestled between the high peaks of westernWyoming's Wind River, Gros Ventre andWyoming Ranges, the valley is home to:More than 100,000 big game animalsLargest mule deer herd in U.S.Continental America's longest big game migrationroute and a crucial link to the Greater YellowstoneEcosystem (GYE)Ecosystem(GYE)Largest publicly-owned big game winter range inthe GYEOne of the west's lastbest sage grouse habitatsand a world-class fisheryOne of the largest natural gas reserves in the U.S.

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## Miles198619992007Oil & Gas EmissionsParticulates – roads & disturbed landVOCs – drilling fluids, separation,dehydration,produced water,gas,p ,gventing, gas compressionNO–diesel drilling rigs gasxdieseldrillingrigs,gascompression, vehicles, flaringWRAP BART CALPUFF ModelingWRAPBARTCALPUFFModelingTh I t W k Ai Q lit M d li (IWAQM 1998)TheInteragencyWorkgroup onAirQualityModeling(IWAQM,1998)recommends three background values for CALPUFF modeling:05 bf f t dl d0.5ppbforforestedlands;1.0 ppb for arid lands; and10 ppb for grasslands.Most of the western U.S. Class Iareas are characterized by arid andforested lands,consequentlya1.0ppb background ammoniavalueqygwas selected for the WRAP RMC BART CALPUFF modeling.WRAP BART CALPUFF ModelingWRAPBARTCALPUFFModelingThe complex non-linear sulfate-nitrate-ammonia system is highlydependentgy pon availability of ammonia -NH3(g)SO2(g)↔H2SO4(g)NH3(g)+ H2SO4(g)↔(NH4)2SO4(p)NO2(g)↔HNO3(g)NH3(g)+ HNO3(g)↔NH4NO3(p)MonitoringPlanObjectives of the Upper Green River BasinA i Ai M it i P j tAmmoniaAirMonitoringProject•measure background ammonia (NH3)measurebackgroundammonia(NH3)concentration for one year for use in refinedvisibility analysesvisibilityanalyses• measure concentrations of other relatedgases and particles to provide informationgasesandparticlestoprovideinformationabout the local nitrogen budgettt t t id tif th i• attempttoidentifythe source regionsattributable to these gases and particulates.Monitoring ConstraintsMonitoringConstraints• sample at existingmonitoringsitegg• desire to use well known andt d li d l iacceptedsampling andanalysisprotocols• a priori assumption that NH3would be at low concentrations• cost

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# •Monitoring: Instrumentation• URG dual annular denuder system (Model 3000CA),mounted at a sample height of 1.5 meters• A dual channel URG denuder/filter pack sampler is usedto collect samples of ambient trace gas (ammonia, nitricid d it t ) d PMl i( iacid, andnitrate)andPM2.5aerosolspecies(ammonium,nitrate, and sulfate)•The prepared denuder/filter pack set is shipped to the siteTheprepareddenuder/filterpacksetisshippedtothesiteoperator on a weekly basis, who installs it into the URGsampler according to a defined twice-weekly schedule thatresults in alternating 3-day and 4-day integrated samplesresultsinalternating3dayand4dayintegratedsamples• The spent denuder/filter pack is shipped to theatmospheric science laboratory at CSU.atmosphericsciencelaboratoryatCSU.Ai Q lit St tiAir TemperatureFlow RecordersAirQualityStationAmmonia SamplerAirTemperatureController and MFCTemperature-Controlled Housingfor Denuders and FiltersShipping CaseforDenudersandFiltersController HousingPM2.5Size-Selective InletsLaboratory AnalysesLaboratoryAnalyses• The denuders are extracted immediatelyuponparrival at CSU and the extracts are refrigerateduntil further analysis• The filters are also unloaded immediately andstored frozen until extraction and analysis• Samples are analyzed by ion chromatographyon a monthly basis• Data is validated according to EPA protocolsand consist of concentrations inμg/m3 and ppbvandconsistofconcentrationsing/m3andppbvfor gases

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### April 200SR ltesus2.0NH3 (g)NH4 + (p)HNO3 (g)NO3 - (p)SO4 2-(p)1.01.5

n tration / ug m-3( )0.00.5 5

2 2 2 9 / 5 2 9 2 6 / 2 / 9 6 2 3 / 2 / 9 6 2 3 3 0 / 6 3 2 0 2 7 / 4 1 8 2 5 / 1 / 8 5 2 2 2 9 / 6 3 2 0 2 7 / 3 0 7 2 4 3 1 / 7 4 2 1 2 8 / 5 2 9 2 6 / 2 / 9 6 2 3 3 0 / 7 4 2 1 2 8 / 4 1 8

conce n 12/1 12/ 2 12/ 2 1 / 1/1 1/1 1/ 2 2 / 2 / 2/1 2/ 2 3 / 3 / 3/1 3/ 2 3/ 3 4 / 4/1 4/ 2 4/ 2 5 / 5/1 5/1 5/ 2 6 / 6 / 6/1 6/ 2 6/ 2 7 / 7/1 7/ 2 7/ 2 8 / 8/1 8/1 8/ 2 8/ 3 9 / 9/1 9/ 2 9/ 2 10 / 10/1 10/1 10/ 2 11 / 11 / 11/1 11/ 2 11/ 3 12 / 12/1 12/ 2 12/ 2 1 / 1/1 1/1date 2006-2008gas-particle partitioningNH4 + (p)NO3 (p)123

ug m- 3NH4+(p)NO3-(p)SO4 2- (p)NH3 (g)HNO3 (g)PM-10d

concentration /GAS-2 12/15 12/29 1/12 1/26 2/9 2/23 3/9 3/23 4/6 4/20 5/4 5/18 6/1 6/15 6/29 7/13 7/27 8/10 8/24 9/7 9/21 10/5 10/19 11/2 11/16 11/30 12/14 12/28 1/11 1/25startdate

# Monthly Average Concentrations

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-Neutralization•Convert mass to molar valuesConvertmasstomolarvalues•Ratio [NH+] / [NO-] + 2[SO2+]•Ratio[NH4]/[NO3]+2[SO4]• Then:ratio = 1 fully neutralizedratio < 1 acidic < 0.5 very acidicratio > 1 excess NH4+ratio>1excessNH4Monthly Average Ion Concentrations (μmole/m3)0 0250.030NO3-(p)SO42-(p)

es/m

30.0150.0200.025SO4(p)NH4+(p)

μ mol0.0050.0100.015Dec 06 Jan 07 Feb o7 Mar 07 Apr 07 May 07 Jun 07 Jul 07 Aug 07 Sep 07 Oct 07 Nov 07 Dec 07 Jan 08 Feb 08 Mar 080.0001.2

O 3

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+ / ( N O0 70.80.9Acidic SulfateOther Formof Nitrate ?Dec 06 Jan 07 Feb o7 Mar 07 Apr 07 May 07 Jun 07 Jul 07 Aug 07 Sep 07 Oct 07 Nov 07 Dec 07 Jan 08 Feb 08 Mar 08

rati o0.60.7Acidic SulfateEpisode ?AcidicSulfateEpisode ?All ionsvery low**05 ,---------------------------------------------------------~** **~-----------------.** 

# Boulder, Wyoming Particulate Ions**~ole/m**

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## Dec J a n 08 F e b M a r A p rMay, 2007 Sulfate Episode907080hourly bsphourly rhAverage Sulfate Ion

rh (%)5060702 5

b sp (Mm

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31 52.02.51020300 51.01.5May 10 May 11 May 12 May 13 May 14 May 15 May 16 May 17 May 18 May 19 May 20 May 21100.5Neutralization = 0.94Neutralization = 0.34Neutralization = 0.73

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## D J a n 0 7 F e b M a r A p r M a y Jun Jul Aug Se p O ct No v Dec J a n 08 F e b M a r A p rSource RegionsResidence Time AnalysisResidenceTimeAnalysis• Ammonia weighted back trajectories were used to identify thegeographic source areas most likely to contribute to the highestgeographicsourceareasmostlikelytocontributetothehighestmeasured ammonia days.• Trajectories were generated using the Hybrid-Single Particle LagrangianI t t d T j t (HYSPLIT) d l d l d b th N ti lIntegratedTrajectory(HYSPLIT)modeldevelopedbytheNationalOceanic and Atmospheric Administration’s (NOAA) Air ResourcesLaboratory (ARL). Detailed information regarding the trajectory modeland these data sets can be found on NOAA’s Web site(htt // l / d /h lit4 ht l)http://www.arl.noaa.gov/ready/hysplit4.html.• Three back trajectories were generated per day, including end times of0400,1200 and 2000 MST and end heights of 100 m. Each hourlypointg ypalong a 72-hour back trajectory paths was weighted with measuredammonia concentration corresponding to the end date of eachtrajectory. The ammonia values associated with each hourly point werethen summed and normalized into 1/4 degree horizontalgrid cells ofglatitude and longitude.

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Res i dence T i me ( % )

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• >0.3 2ConclusionsNHconcentrations are highly seasonally•3concentrationsarehighlyseasonallydependent. Ranging from near detectablelimits Dec-Feb, to peak values of 1.5 ppbd i thurngthe summer.•2007 average NHwas 0 24 ppb2007averageNH3was0.24ppb•Residence time analysis indicates that NH3istransported into the region primarily from thewest along the Snake River Valley andSouthwest along the Wasatch front.SouthwestalongtheWasatchfront.