Oil and Gas Produced WaterResearch Projects at USGSYousifK. Kharaka, *James K. Otton,U. S. Geological Survey, Menlo Park, California, USA*Lakewood, Colorado, USADOE/PERF MeetingNovember 1-4, 2005Financial support from DOE-NETLDrilling support from EPA-NRMRLOsage Nation Tribal AuthoritiesU.S. Army Corps of EngineersApplications software from WRDPrecipitationETInterflowOverland flowStreamInfiltrationGeneralized Concept ofPRMS/MODFLOWPRMS (surface layer)UZFPackageInfiltrationRechargeLosing streamGaining streamUnsaturatedzoneETInfiltrationRechargeLosing streamGaining streamUnsaturatedzoneETRechargeETGaining streamWellSubsurface outflowInflowAquiferMODFLOWProduced Water Research Projects at USGS1-OSPER sites, Oklahoma, Otton, Kharaka, others.2-National produced water geochemical data base, Otton,Breit, Kharaka&Rice.3-Organic and inorganic species in CBM produced water,Rice, Orem & Healy.4-E. Poplar Oil field, NE Montana, Thamke, Smith, others.5-Bemidji oil spill site, N Minnisota, Bekins, Herkelrath,Delin, others6-Produced water reclamation, Placeritaoil field,California, Kharaka, others.DOE/PERF MeetingNovember 1-4, 2005Distribution ofPetroleum wells inOklahoma, OsageCounty, & thestudy AreaOSPERsProject Investigators• USGS-WRD–Yousif Kharaka and staff-inorganic & organic aqueous geochemistry–Bill Herkelrathand staff-hydrology and modeling–Mike Godsy(EanWarren)-microbialecology, microbiogeochemistry–Tom Yanosky-treering geochemistry–Fran Hostetler-organic geochemistry–Marvin Abbott-site manager,GPS, GIS• USGS-GD–Jim Otton-geology and project management–Bob Zielinksi-inorganic solidgeochemistry, biogeochemistry–Cyndi Rice-inorganic solid geochemistry, CEC–Jim Cathcart-soil and bedrock mineralogy–Bruce Smith and others-geophysics•USGS-BRD–Bob Keeland-oak-tree ecology and tree-ring chronology• OSU–Joe Bidwell-lacustrineinvertebrate ecology and toxicology•USEPA-AdaResearch Lab–Don Kampbelland contractors-sitecharacterization/reclamation,–Geoprobesupport•Continuous productionfromshallowPennsylvanian sandstones since~1937.•Waterfloodedin mid-1950s.•Aerial photosshow sitewas reconfigured priorto Skiatookflooding in 1987,and afew pits were flooded offshore.•Old brine pit removed—New pit installedinearly1990s.•Soil &hayaddedto (3)salt scarred areas in 2000.Sampling Trips to the SitesMarch 2001---Source fluids from oil wells, GW, andSkiatook Reservoir. Surface pools at both sites.February 2002---~60 Geoprobe, auger and rotary wellsdrilled, cored, completed and sampled at and two sites.June 2002---Water level, conductance, and T measurements,followed by collection of ~40 water and a few oil samples.November 02---Drilling with geoprobeand sampling.March-April 03---Drilling (EPA auger) and sampling.January 2004---(9) deep wells (WRD air) at “A”, andsampling.May 2004---(4) deep (EPA auger) wells at “B”; sampling.February 2005---Water levels and sampling at both sites.September 2005---Weir discharges.OSPER "B"Site-TraverseD-D'204206OSPER "B"Site-TraverseD-D'204206208210212214216218220222224020406080100120140160180200Distance alongtraverse(meters)

A l titu d e (m e t e r s , a s l)BE-73BE-01BE-51BA-01BE-03BE-71BE-55BE-74BE-56BE-57BE-58BE-10BE-09BE-72BE-61BE-16TraverseD-D’EC=16,200Cl=3,280SO4=4,800EC=7,070Cl=1,090SO4=2,780EC=2,410Cl=346SO4=679V.E.~6.7EC=37,900Cl=13,300SO4=3,570EC=9,650Cl=2840SO4=1,020EC=15,500EC=14,100Cl=3,200SO4=4,260ElecricalConductance(μs/cm)Chloride(mg/L)Sulfate (mg/L)EC=12,200Cl=1,920SO4=4,530EC=7,330Cl=900SO4=3,050EC=8,770Cl=2,180SO4=1,740EC=12,600EC=20,500Cl=5,900SO4=4,400EC=38,200Cl=14,500SO4=1,150EC=13,400Cl=2,350SO4=4,600EC=36,100Cl=13,200SO4=252EC=28,000Cl=9,330SO4=61EC=15,900Cl=4,360SO4=2,420 1 0 , 0 0 0

10 , 0 00

1 0 , 0 0 0 

# 5

,

0

0

0

5, 00 0 

# 2

0

,

0

0

0

2 5

, 0 0 0 3 0 , 0 0 0 2 0 , 0 0 0



# 2

0

,

00

0EC=16,200Cl=3,280SO4=4,800EC=7,070Cl=1,090SO4=2,780EC=2,410Cl=346SO4=679V.E.~6.7EC=37,900Cl=13,300SO4=3,570EC=9,650Cl=2840SO4=1,020EC=15,500EC=14,100Cl=3,200SO4=4,260ElecricalConductance(μs/cm)Chloride(mg/L)Sulfate (mg/L)EC=12,200Cl=1,920SO4=4,530EC=7,330Cl=900SO4=3,050EC=8,770Cl=2,180SO4=1,740EC=12,600EC=20,500Cl=5,900SO4=4,400EC=38,200Cl=14,500SO4=1,150EC=13,400Cl=2,350SO4=4,600EC=36,100Cl=13,200SO4=252EC=28,000Cl=9,330SO4=61EC=15,900Cl=4,360SO4=2,420 1 0 , 0 0 0

10 , 0 00

1 0 , 0 0 0 

# 5

,

0

0

0

5, 00 0 

# 2

0

,

0

0

0

2 5

, 0 0 0 3 0 , 0 0 0 2 0 , 0 0 0



# 2

0

,

00

0SO4> ClCl> SO4

# 0 NBBBBBBBBBBBBBBBBBBBBBBBBBBBLegendOil-impactedsoilsSandstoneoutcropSlightlyto deeply erodedareasWannFormationOld redwoodtanksDrainagetraceTerrace edgeindeeply erodedareasArtifical fill, asphalticoiland weatheredoilClemCreek sandmemberLower shalemember,minor sandstonePennsylvanianLate Pleistocene/HoloceneColluvialgravelLayerAreaBCobblesand bouldersAeoliansand, silt, andclay,BPPPP?PNatural soilpedestalwithin deeplyerodedareaTreesTreesTreesTreesTreesTreesTreesGrass,forbs



# R o a dGrass,forbsGrass,forbsisolated treesGrass,forbs,isolated trees

x x

x x

x

x

x x x

x x x x

x x x x

x x

x x x x

xAE13AE14AE15AE16AE18AE17AA01AE01AE02AE19AA03AA02AA04AE04AE09AE10AE11AE12AE06AE07AE05AE08AE03AP-01SkiatookLake



# 5 0 1 0 0 f t

0 

# 3 0 m

2 0

1 0

0TRANSECT(Fig. 9)Geology MapUpper area (south)•gentle slope•tree kills from early(?) saltreleases•revegetatedwith grassesAsphalticpits•highly weathered oil•one pit contains relatively freshtank sludge(?)Lower area (north)•steeper slope•prominent saltscar (~2 m deep)•salt (& gypsum) at surfaceEM31conductivity mapfor the verticalmagnetic dipole4.5 m depth(Smith et al., 2003)A l titu d e , in m e te r s a b o v e se a le v e la-a’ traverse125150175200225Distancealongtraverse,inmeters26,100125150175200225Distancealongtraverse,inmeters26,100AE06AA10AE551820

2 , 0 0 0AE06AA10AE551820

2 , 0 0 0220225230AE07Southpits50-1002002052102150 255075100low:215.8 m(2/2003)Skiatook Lake levelshigh:219.1 m(3/2004)1670195010,800??TDS(mg/L)

1 0 , 0 00 2 , 0 0 0



# 1 0

, 0 0 0AA06AE51AA01AA02NorthSkiatookLakeDRYsaltscarerosionAE13AA61AA0416,10022,40047209,70019,10029,90011,3004810 

# 2 0

, 0 0 0

1 5

, 0 0 0 1 5, 000

1 0, 000220225230AE07Southpits50-1002002052102150 255075100low:215.8 m(2/2003)Skiatook Lake levelshigh:219.1 m(3/2004)1670195010,800??TDS(mg/L)

1 0 , 0 00 2 , 0 0 0



# 1 0

, 0 0 02002052102150 255075100low:215.8 m(2/2003)Skiatook Lake levelshigh:219.1 m(3/2004)1670195010,800??TDS(mg/L)

1 0 , 0 00 2 , 0 0 0



# 1 0

, 0 0 02002052102150 255075100low:215.8 m(2/2003)Skiatook Lake levelshigh:219.1 m(3/2004)1670195010,800??TDS(mg/L)

1 0 , 0 00 2 , 0 0 0



# 1 0

, 0 0 0AA06AE51AA01AA02NorthSkiatookLakeDRYsaltscarerosionAE13AA61AA0416,10022,40047209,70019,10029,90011,3004810 

# 2 0

, 0 0 0

1 5

, 0 0 0 1 5, 000

1 0, 000AA06AE51AA01AA02NorthSkiatookLakeDRYsaltscarerosionAE13AA61AA0416,10022,40047209,70019,10029,90011,3004810 

# 2 0

, 0 0 0

1 5

, 0 0 0 1 5, 000

1 0, 0004.21.70.31.46.90.11.21.09.94.2Tritium (in T.U.)Site A -a-a’ traverse (with tritium)[update 10/12/05]Solutes inaqueousExtractZielinski etal., 2003State of Oil DegradationGodsyet al., 2003Themicrobialpopulationsarequitedifferent at Sites A and BGodsyet al., 2003MethanogensAerobesFermentersDenitrifiersIronReducersSulfateReducersAerobesFermentersDenitrifiersIronReducersSulfateReducersMethanogensAB"A" SiteWeirStudy[Jan2004]020004000600080001000012000140001600018000200001600170018 00190020 0021 00220023 0024002500DateTime(DDHH)[Jan2004,cst]

C u m u lat ive C h lo r i d e lo ad ( g r a m s )0123456 C u m u lat i v e P r e cip it at i o n ( c m )ChloridePrecipitation05010015020025030035016-00:0017-00:0018-00:0019-00:0020-00:0021-00:0022-00:0023-00:0024-00:0025-00:00Date Time (DD-HH:MM) [Jan 2004, cst]

Di scharge (L/min)050010001500200025003000350040004500 El e c tri c a l Co nduc atan c e ( μ s/ c m )QECTotal saltload=28 kgSummary and Conclusions•Large amounts of produced water and associated oil have, and at‘B’, will continue to be released to ground surface.•General agreement between various methods for mapping the GWplumes.At OSPER ‘B’site:1)Three GW plumes ( up to 20,000 mg/l TDS), but minor organicsextend from brine pits & intersect Skiatook.2)GW plumes extend below a 10-25 ft shale bed; limits??Future PlansNatural attenuation; solute transport (overland &GW); remediation.*** Environmental Geosciences, 2005, v. 12, No. 2  http://ok.water.usgs.gov/skiatook/A national produced-watergeochemical data base, 2002byOtton, Breit, Kharaka&Rice.http://energy.cr.usgs.gov/prov/producedwater/htmlAnational produced-watergeochemistry databasehttp://energy.cr.usgs.gov/prov/producedwater.htmLos Angeles City OilFields, 1896VenocoOil Drill Siteat Century CityImportance of Protecting Ground Water•50% of drinking water in USA is from GW•95% of rural America is dependant on GW•21% of water withdrawals in USA are GW•GW use increased from 13 x 1010L/day in 1950 to 33x 1010L/day in 2000•Once GW is contaminated, remediation is very costlyor impossible1999 Coal Bed Methane Reserves2002 total=700; recoverable=100 TcfComposition of Water in Major BasinsBasinStateTypeTotal DissolvedpHSolids (mg/L)BlackAlNa-Cl-HCO3160-31,0005.4-9.9PowderWYNa-HCO3270-4,0006.7-8.0RatonCONa-HCO3530-6,000NDSan JuanCONa-HCO3-Cl410-170,0005.2-9.2UintaUTNa-HCO3-Cl6,350-43,0007.0-8.2Petroleum water: 5,000->350,000 mg/L TDS;Na-Cl&Na-Ca-ClWarriorNMMTRiverComposition of water from Powder River Basin CBM WellspH6.7 –8.4SAR5.6 –69TDS270 –4,000Chloride4.8 –130Sulfate<0.03 –530Bicarbonate290 –3,250Calcium1.8 –78Potassium3.1 –58Magnesium0.6 –46Sodium110 –1,000Iron2 –17,500Manganese1.4 –350Arsenic<0.2 –4.8Barium14 –2,540Cadmium<0.1Chromium<0.1 –1.8Lead<0.1 –0.43Mercury<0.005 –0.25Selenium<2Zinc<1 –80Rice and others, 2004(mg/L)(μg/L)Toxic Organic Compounds in Produced WatersConventional Oil and Gas Wells-DOC =5-1000 mg/L (as C)-Organic Acid anions = 1-10,000 mg/L (as acetate)-BTEX = ppb-20 mg/L-Phenols = ppb-15 mg/L-PAHs= ppb-10 mg/LPreliminary Results from CBM WellsWaters from wells in PRB & Gulf fell into three categories:-little or no organics present-high levels (ug/l) of N-and O-substituted aromatics-high levels of N-and O-substituted aromatics and PAH’s.-No acute hazard present—chronic exposure ??.Bill Orem, USGS, 2003Summary –Balkan Endemic Nephropathy-Well water from endemic villages in Romania andYugoslavia had higher abundances of extractable (andpotentially toxic) dissolved organic substances comparedto well water from nonendemic(control) villages.-Lignitesfrom endemic areas in Romania and Serbiayield a high abundance of dissolved organic substanceswhen leached with water or other polar solventscompared to other coals.Results of the 2000-2002 studies in Romania andYugoslavia support the Pliocene lignite hypothesis, andsuggest the possible involvement of toxic organiccompounds from coal in the etiology of BEN.Bill Orem, USGS, 2003Topics Discussed1-OSPER ‘A’& ‘B’sites, Osage County, OK.2-Chemical & isotopic compositions of source &ground waters at OSPER ‘A’&‘B’sites.3-Delineating the plume boundaries at OSPER ‘A’.4-Can produced water penetrate below thick shale unitat OSPER ‘B’.5-Processes--Mixing (brine, prec. & GW), ET &water-rock-bacterial interactions.6-Future plans & concluding remarks.Environmental Impacts fromPetroleum Exploration and ProductionHuge volumes of produced water and oil (~20 & 2 billionbbl/yr, resp.)—Disposal of PW & releases have causedsoil & ecosystem damage and surface & GW pollution.Produced water generally is highly saline, with toxicorganic and inorganic chemicals.Large number of wells drilled (~3.5 million).Drilling wells causes significant site disturbances and air,soil and water pollution.Large number of abandoned wells (~2.5 million)—Somehave caused GW pollution** .