InorganicGeochemistryofPennsylvaniaMarcellusFlowback WatersCarlS.KirbyDepartmentofGeologyDi tBUM llSh lI iti tirecor,arceusaeInitiativehttp://www geosc psu edu/ engelder/marcellus/http://www.geosc.psu.edu/~engelder/marcellus/marcellus.htmlAcknowledgments:MollyPritz’10forchemistrydataLukeSwenson‘11forConductivityresearchScottLunde’12andGarynTate‘12fordataminingBUEi lC(LF di )&PhotosfromNewYorkStateSGEISBUEnvironmentalCenter(LuceFoundation)&KatherineMabis McKennaFoundationDegenstein FoundationForumforPennsylvaniaHeartlandPresentedatUSEPAHydraulicFracturingWorkshopsArlingtonVAFebruary24,2011Bucknell MSIDatabasehttp://www.bucknell.edu/script/environmentalcenter/marcellus/default.aspxSlickwater+OilFieldBrine(+/dissolution)=Slickwater(+/dissolution)flowback water



# slick w Flow b

ater ack w aterOilfieldDiagramafterPritz,2010brineFlowback watermustbestored,t tddtht tdij tdranported,anenreaeorrenecedPhotosfromMollyPritz’10MarcelluscoresectionwithsaltblebsbeddingalongbeddingFromBlauch etal.,2009MarcellusFlowback WaterGeochemistryD tS•5BradfordCounty,PA,wellsDataSources:y,,•Datafromenergycompaniesprovidedtoaprivatewastewatertreatmentfacility•DatafromenergycompaniesprovidedtoaprivatewastewaterhaulerDid dbiDf•ataproveyenergycompanestothePAeptoEnv ProtectionasrequiredyearlybyForm26R(PADEP,2010)•DatafromareportpreparedfortheMarcellusShaleCoalition(Hayes,2009)•DatafromBlauchetal.,(2009).MarcellusFlowback WaterGeochemistry•Na/Ca/Cldominated•HighTDS,SpecificConductanceOfthhi hBS•enaveveryga,r•Mostareradioactive•LowMg,SO4•Near‐neutralpH•Endocrinedisruptors??OtherorganicsMarcellusfracwater hasdistinctiveNa/CaCl signature/Someofthefracwatersare1/3solids!DatacompiledbyMollyPritzMarcellusFlowback WaterGeochemistryVolumeofflowback waterversustimeofflowback fromMarcelluswells100000088%800000

o nsWellD(Horiz)WellE(Horiz)48%600000

f lowback, gall oWellE(Horiz)WellF(Horiz)WellG(Horiz)15%19%22%200000400000

Volume of fWellB(Vert)WellH(Vert)WellN(Vert)53%65%0200000020406080WellS(Vert)31%020406080Timeofflowback,daysDataarefromfourhorizontalandfourverticalwellsinHayes(2009)thathaddatafor0(injectedwater),1,5,14,and90‐dayflowback.200070000Salinityincreaseswithflowback time1000120014001600180030000400005000060000 t ion SO4, mg/L

r ation, mg/LNaCaClSO402004006008000100002000030000 Concentra t

Concent r0 5000 10000 15000Flowback,barrels100015002000

mg/LbaSrMgK05001000

Concentration,‐50000 5000 10000 15000Flowback,barrelsDatafromWellAinBlauchetal.(2009).PADEPSomeclearcorrelationswithTDSy = 0.0253x + 102.77R2 = 0.81778000Somelackenoughdataforcorrelationy = 0.5883x + 3967.5R2 = 0.90136000080000100000120000140000160000180000

o ncentration, mg/LCl2000300040005000600070008000

o Cuires/LGross Beta02000040000600000 50000 100000 150000 200000 250000 300000

C oTDS, mg/L-1000010000 50000 100000 150000 200000 250000 300000

,pic oTDS, mg/LSomemixedcorrelationswithTDSy = 0.0159x + 18.274R2 = 0.587400050006000

t ration, mg/LSr200002500030000

t ration, mg/LBa01000200030000 50000 100000 150000 200000 250000 300000

Concen ty = 0.036x + 361.74R2 = 0.28140500010000150000 50000 100000 150000 200000 250000 300000

Concen tTDS, mg/LTDS, mg/LVolatileDissolvedSolidsmaysuggestorganiccompoundsthatcancomplexmetalssuchasBa250000

/ LDissolvedSolids150000200000

t ration, mg /VolatileDissolvedSolidsFixedDissolvedSolids50000100000

o lids concen t012345

S ofDatacollectedWell,BradfordCountycollectedbyMollyPritzWesternPAAcidMineDrainagenWestern/CentralPAProducedWatersMarcellusFlowbackVenangoBrinen+10 20 30 40 50 60 70 80 90 100 110 120 130εSW140gSrChapman,Capo,Stewart,Kirby,2011AlkalinityGeochemicalmodeling(PHREEQCI)SIBariteConcOfSO2‐vsTemperatureGeochemicalmodeling(PHREEQCI)SIBarite,Conc.OfSO4vs.TemperaturepHSIGasesvsTGeochemicalmodeling(PHREEQCI)pH,SIGasesvs.TRadiationinflowback waters2000025000

, pCi/LNorthCentralPA,knownlocation,n=8privatewastewaterhauler,n=315000

a diation ,privatetreatmentfacility,n=7500010000

A lpha R a050000100000200000300000400000

Gross A0100000200000300000400000TotalDissolvedSolids,mg/L14000Radiationinflowback waters1200014000

/ LNorthCentralPA,knownLocation,n=8privatewastewaterhauler,n=3800010000

i on, pCi /privatetreatment,n=740006000

a Radiat i020000100000200000300000400000

oss Bet a0100000200000300000400000

GrTotalDissolvedSolids,mg/L450035004000226Ra228Ra250030003500

R a, pCi/L228Ra15002000

6 Ra/

228 R5001000

22 600 100000 200000 300000 400000TotalDissolvedSolidsmg/L,WillincreasesinstreamconductivitytelluswehaveaM ll“l k”?arceuseaNotconsistently.AMDandroadsaltcancausehighconductivity.CanwedistinguishMarcellus“leaks”fromthemwithconductivity?Cl‐Marcellus&roadsalt?Br–Marcellus?SO4– MineDrainage?PotentialLack‐of‐MixingProblems:PlacementofconductivitymetersSusquehannaRiverQ ti ?uestions?ActualandPotentialImpactsBucknell UniversityMarcellusShaleInitiativeGoals• Fund research in physical & social sciences, engineering, and humanities thatwill benefit all stakeholders.• Comprehensive, objective web-based clearinghouse for:• accurate and verifiable (i.e., peer-reviewed) scientific information• annotated non-scientific information from industry, regulatory agencies, printand web media, environmental groups, citizens’ groups• hyperlinked•organized• searchable• critically evaluated• Facilitate teaching and additional outreach effortsMarcellusShaleinOutcrophttp://www.geosc.psu.edu/~engelder/marcellus/marcellus.htmlOutline•What&WhereistheMarcellusFormation?•FormationoftheMarcellus&NaturalGas•HorizontalNaturalGasDrilling•LocationofDrillingActivityinPACharacterizationofwatersChemicalsignatureoffracwatersignaturefracwaterMonitoring?DischargeandconductivitywithtimeDischargevs.conductivitycurves– hysteresisMassbalancemodelingProblemsassociatedwithpoormixingActualandPotentialEnvironmentalImpactsPerspectiveCouldbeMarcellus‐influenced•Inadequatecoverage:8of99USGSgaging stationsinPAmeasureSC.Theseareonlargerstreams.•DataGaps:Twoyearsofhydrographsfrom9(7intheMarcellusregion)gaging stationsthatcollectSCdatashowedgapsinSCdatabetween4betweenand71%ofthetimeforindividualstations.•Hysteresis:PlotsofSCvs.Qforseveraltimeperiodsshowconsiderable&variablehysteresiseffectsdependentuponthestreamchosenandantecedenthydrologicconditions.6.1WaterResources•6.1.1WaterWithdrawals•6.1.1.1ReducedStreamFlow•6112DegradationofaStream’sBestUseNewYorkStateSGEISconsidersthefollowingpotentialenvironmentalimpacts•6.1.1.2DegradationofaStream sBestUse•6.1.1.3ImpactstoAquaticHabitat•6.1.1.4ImpactstoAquaticEcosystems•6.1.1.5ImpactstoDownstreamWetlands•6.1.1.6AquiferDepletion•6.1.1.7CumulativeWaterWithdrawalImpacts•6.1.2StormwaterRunoff•6.1.3SurfaceSpillsandReleasesattheWellPad•6.1.3.1Drilling•6.1.3.2HydraulicFracturingAdditives•6.1.3.3FlowbackWater•6.1.4GroundwaterImpactsAssociatedWithWellDrillingandConstruction•6.1.4.1Turbidity•6.1.4.2FluidsPumpedIntotheWell•6.1.4.3NaturalGasMigration•6.1.5HydraulicFracturingProcedure•6151WellboreFailure...WellboreFailure•6.1.5.2SubsurfacePathways•6.1.6WasteTransport•6.1.7CentralizedFlowbackWaterSurfaceImpoundments•6.1.8FluidDischarges•6.1.8.1TreatmentFacilities•6.1.8.1DisposalWells•6.1.9SolidsDisposal•6.1.9.1NaturallyOccurringRadioactiveMaterial(NORM)Considerations‐Cuttings•6.1.9.2CuttingsVolume•6.1.9.3CuttingsandLinerAssociatedWithMud‐Drilling•6.1.10PotentialImpactstoSubsurfaceNYCWaterSupplyInfrastructure•6.1.11DegradationofNewYorkCity’sDrinkingWaterSupplyNewYorkStateSGEISconsidersthefollowingpotentialenvironmentalimpacts6.2Floodplains6.XPrimaryandPrincipalAquifers6.3FreshwaterWetlands6.4EcosystemsandWildlife•6.4.1InvasiveSpecies•6.4.1.1Terrestrial•6.4.1.2Aquatic•6.4.2CentralizedFlowbackWaterSurfaceImpoundmentsNewYorkStateSGEISconsidersThefollowingpotentialenvironmentalimpacts6.5AirQuality•6.5.1RegulatoryAnalysis•6.5.1.1NOx‐InternalCombustionEngineEmissions•6512NaturalProductionFacilitiesSubpart(Glycol...NaturalGasProductionFacilitiesNESHAP40CFRPart63,SubpartHH(Glycol•Dehydrators)•6.5.1.3FlaringVersusVentingofWellsiteAirEmissions•6.5.1.4NumberofWellsPerPadSite•6.5.1.5EmissionsTables•6.5.1.6OffsiteGasGatheringStationEngine•6.5.1.7NaturalGasCondensateTanks•6.5.1.8PotentialEmissionofFracturingWaterAdditivesfromSurfaceImpoundments•6.5.2AirQualityImpactAssessment•6.6.1GreenhouseGases•6.6.2EmissionsfromOilandGasOperations•6.6.2.1VentedEmissions•6.6.2.2CombustionEmissions•6.6.2.3FugitiveEmissions663EiiCh t i ti•..mssonsSourceCharacterization•6.6.4EmissionRates•6.6.5DrillingRigMobilization,SitePreparationandDemobilization•6.6.6CompletionRigMobilizationandDemobilization•6.6.7WellDrilling•6.6.8WellCompletion•6.6.9WellProduction6.7CentralizedFlowbackWaterSurfaceImpoundmentslldlh l6.8NaturayOccurringRaioactiveMateriasintheMarcellusSae6.9VisualImpacts6.10Noise6.11RoadUse2ndLaw of Thermodynamics“Useful energy is lost in any physical or chemicaltransformation”It takes (fossil fuel) energy to produce energy, soeach added step makes a fuelless efficient than if itis used more directly.Greenhouse gasses – how many ft3of naturali l ( il l) d i kgasequivalent(oil,gas,coal) doesittaketoproduce 1 ft3of natural gas?Slickwater additiveshttp://www.dec.ny.gov/about/47291.htmlHorizontalDrillRigFracjobs8milliongallonsofwaterfromtake1‐milliongallonsstreams,reservoirs,GW,orreusedwaterPhotosfromMollyPritz’10DrillingActivitinPennsylvaniayMapbyCarlKirbyfromPennsylvaniaSpatialDataAccessinformationHowcan“leaks”occur?Hydraulicfracturingoperation,horizontalMarcelluswell,BradfordCounty,PAwww.donnan.comtiogagaswatch.blogspot.com/Transporttrucksforwater(above)andhydraulicfracturingacid(HCl)(below)BrinePitCourtesyofJ.HenryFairthroughMichelBoufadelSusquehannaRiverBasinCommissionRemoteWaterQualityMonitoringNetwork•Plan30monitoringstationsinPA&NY•T,pH,conductance,DO,turbidity,stageR lidbea‐tmeataonwewww.srbc.net/JuniataRiver,6‐dayperiodNotinMarcellusregion