Oil and Gas Produced 

Research Projects at U

Yousif K. Kharaka, *James 

U. S. Geological Survey, Menlo Park, Ca

*Lakewood, Colorado, USA

DOE/PERF Meeting

November 1-4, 2005

Financial suppDrilling suppoOsage Nation U.S. Army Co

Applications software fro

Precipitation

ET

Interflow

Ove

rland flow

Str

eam

Infiltration

Generalized Concept 

PRMS/MODFLOW

PRMS (surface layer)

U

Infiltration

R

U

nsaturate

d

zon

e

Infiltration

R

U

nsaturate

d

zon

e

Rech

a

rge ET

Gaining strea

m Well

Subsu

rface outflow

Inflow

Aquife

r

MODFLO

W
Produced Water Research Projec

1- OSPER sites, Oklahoma, Otton, Kharak2- National produced water geochemical dBreit, Kharaka

& Rice.

3- Organic and inorganic species in CBM pRice, Orem & Healy.4- E. Poplar Oil field, NE Montana, Tham5- Bemidji oil spill site, N Minnisota, BekinDelin, others6- Produced water reclamation, Placerita oCalifornia, Kharaka, others.

DOE/PER

Novemb
Distribution of 

Petroleum wells in Oklahoma, Osage County, & the study Area
OSPERs Project Investig

• USGS-WRD

– Yousif Kharaka and staff- inorganic & organic aque– Bill Herkelrath and staff- hydrology and modeling– Mike Godsy (Ean Warren)- microbial ecology, micr– Tom Yanosky- tree ring geochemistry– Fran Hostetler- organic geochemistry– Marvin Abbott- site manager, GPS, GIS

• USGS-GD

– Jim Otton- geology and project management– Bob Zielinksi- inorganic solid geochemistry, biogeo– 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 chrono

• OSU

– Joe Bidwell- lacustrine invertebrate ecology and tox

• USEPA- Ada Research Lab

– Don Kampbell and contractors- site characterization– Geoprobe support
• Continuous production from

shallow Pennsylvanian sandstones since ~

• Waterflooded in mid-1950s.• Aerial photos show site was reconfigured p

flooding in 1987, and a few pits were flood

• Old brine pit removed—New pit installed i• Soil & hay added to (3) salt scarred areas in 
Sampling Trips to the Si

March 2001--- Source fluids from oil wells

Skiatook Reservoir. Surface pools at both 

February 2002 --- ~60 Geoprobe, auger an

drilled, cored, completed and sampled at 

June 2002 --- Water level, conductance, an

followed by collection of ~40 water and a 

November 02 --- Drilling with geoprobe anMarch-April 03 ---Drilling (EPA auger) anJanuary 2004 ---

(9) deep wells (WRD air) 

sampling.

May 2004 --- (4) deep (EPA auger) wells aFebruary 2005 --- Water levels and sampliSeptember 2005 --- Weir discharges.
OSPER "B" Site - Traverse D-D'

204206

OSPER "B" Site - Traverse D-D'

204206208210212214216218220222224

0 20 40 60 80 100 120 

Distance along traverse (meters)

Altitude (meters,asl)

BE-73

BE-01 BE-51 BA-01BE-03BE-71 BE-55BE-74BE-56 BE-57 B

EC=16,200Cl=3,280SO4=4,800

EC=7,070Cl=1,090SO4=2,780

EC=2,410Cl=346SO4=679

V.E. ~ 6.7

EC=37,900Cl=13,300SO4=3,570

EC=9,65Cl=2840SO4=1,02

EC=15,500

EC=12,200Cl=1,920SO4=4,530

EC=7,330Cl=900SO4=3,050

EC=8,770Cl=2,180SO4=1,740

EC=12,600

EC=20,500Cl=5,900SO4=4,400

EC=38,200Cl=14,500SO4=1,150

10,000

10,000

5

,000

5,000 20

,000

25,000 30,000

EC=16,200Cl=3,280SO4=4,800

EC=7,070Cl=1,090SO4=2,780

EC=2,410Cl=346SO4=679

V.E. ~ 6.7

EC=37,900Cl=13,300SO4=3,570

EC=9,65Cl=2840SO4=1,02

EC=15,500

EC=12,200Cl=1,920SO4=4,530

EC=7,330Cl=900SO4=3,050

EC=8,770Cl=2,180SO4=1,740

EC=12,600

EC=20,500Cl=5,900SO4=4,400

EC=38,200Cl=14,500SO4=1,150

10,000

10,000

5

,000

5,000 20

,000

25,000 30,000

SO4 > 

Cl > S
0

N

B

B

B B

B B B B B

B

B

B

B

B B B B

B

B

B

B

B

B

B

B

B B

Legen

d

Oil-impacted soils

Sandstone outcrop

Slightly to deeply eroded areas

Wann Formation

Old redwood

Drainage tr

ace tanks

Terrace edge in

deeply eroded areas

Artifical fill, asphaltic 

oil and weathered oil

Clem Creek s

and member

Lower shale member, minor sandstone

Pennsylvanian

Late Pleistocene/Holocene

Colluvial

gravel

Layer

Area

C B obbles and boulders

Aeolian sand, silt, and clay, 

B

P

P

P

P

?

Natural soil pedestal 

P within deeply eroded

area

Trees

Trees

Trees

Trees

Trees

Trees

Trees

Grass,

forbs Road

Grass,

forbs

Grass,forbs 

isolated trees

Grass,forbs,

isolated trees

x

x

x

x

x

x

xx

x

x

x

x

x

x

x

x

x

x

x x

x

x

x

x

AE13

AE14

AE15

AE16

AE18

AE17

AA01

AE01

AE02

AE19 AA03

AA02

AA04

AE0

4

AE09 AE10

AE11

AE12

AE06

AE07

AE05

AE08

AE03

AP-01

Skiatook

Lake 50 100 ft

0 10 20 30 m

0

TR

A

N

S

E

C

T

(Fig. 9)

Upper a•

gentl

•

tree k

relea

•

reveg

Asphaltic pi

•

highly we

• one pit co

tank sludg

Lower ar•steeper •promine•salt (& g
EM31 

conductivity map 

for the vertical 

magnetic dipole 

4.5 m depth

(Smith et al., 2003)
A

ltitude, in meters above sea level

a-a’ traverse

125 150 

Distance along traverse, in meters

125 150 

Distance along traverse, in meters

AE06

AE55 AA10

1820

2,000

AE06

AE55 AA10

1820

2,000

220225230

AE07

South

pits

50-100

200205210215

0 25 50 75 100

low: 215.8 m (2/2003)Skiatook Lake levelshigh: 219.1 m (3/2004)

1670

1950

?? 10,800

TDS (mg/L)

10,000

2,000

10,000

AA01

AA02

DRY

salt scar er

AA04

22,400 

4720

11,300

4810

20,000

15,000

220225230

AE07

South

pits

50-100

200205210215

0 25 50 75 100

low: 215.8 m (2/2003)Skiatook Lake levelshigh: 219.1 m (3/2004)

1670

1950

?? 10,800

TDS (mg/L)

10,000

2,000

10,000

200205210215

0 25 50 75 100

low: 215.8 m (2/2003)Skiatook Lake levelshigh: 219.1 m (3/2004)

1670

1950

?? 10,800

TDS (mg/L)

10,000

2,000

10,000

200205210215

0 25 50 75 100

low: 215.8 m (2/2003)Skiatook Lake levelshigh: 219.1 m (3/2004)

1670

1950

?? 10,800

TDS (mg/L)

10,000

2,000

10,000

AA01

AA02

DRY

salt scar er

AA04

22,400 

4720

11,300

4810

20,000

15,000

AA01

AA02

DRY

salt scar er

AA04

22,400 

4720

11,300

4810

20,000

15,000

4.21.70.3

6.9

0.1

1.2

9.9

Tritium (in T.U.)

Site A - a-
Solutes in 

aqueous 

Extract

Zielinski et 

al., 2003
State of Oil Degrada

Godsy

et al., 2003
The microbial populations a

different at Sites A an

Godsy et al., 2003

Methanogens

Aerobes

Fermenters

Denitrifiers

Iron Reducers

SulfateReducers

Aer

Iron 

SulfateReducers

Methanogens

A B
"A" Site Weir Study [Jan 2004]

0

2000400060008000

100001200014000160001800020000

16 00 17 00 18 00 19 00 20 00 21 00 22 00 23 00 24 00 25 00

Date Time (DD HH) [Jan 2004, cst]

Cumulative Chloride load(grams)

0123456

Cumulative Precipitation(cm)

ChloridePrecipitation

0

50

100150200250300350

16-00:00 17-00:00 18-00:00 19-00:00 20-00:00 21-00

Date Time (DD-HH:MM

Discharge (L/min)

Total salt 

load=28 kg
Summary and Conclusi

• Large amounts of produced water and associa

‘B’, will continue to be released to ground sur

• General agreement between various methods 

plumes.

At OSPER ‘B’

site:

1) Three GW plumes ( up to 20,000 mg/l TDS), bu

extend from brine pits & intersect Skiatook.

2) GW plumes extend below a 10-25 ft shale bed; l

Future Plans

Natural attenuation; solute transport (overland &

*** Environmental Geosciences, 2005, v

http://ok.water.usgs.gov/skiatoo
A national produced-

geochemical data base

by

Otton, Breit, Kharaka

& 

http://energy.cr.usgs.gov/prov/produc

A national produced-water geochemis

http:

//energy.cr.us

gs.gov/prov/produce

Los A

F

Venoco Oil Drill Site 

at Century City

Importance of Protecting Grou

• 50% of drinking water in USA is from • 95% of rural America is dependant on • 21% of water withdrawals in USA are • GW use increased from 13 x 1010 L/da

x 1010 L/day in 2000

• Once GW is contaminated, remediation 

or impossible
1999 Coal Bed Methane Re

2002 total=700; recoverable=
Composition of Water in Maj

Basin

State Type Total Dissolved 

Solids (mg/L

)

Black

Al Na-Cl-HCO

3 160-31,000 

Powder WY Na-HCO

3 270-4,000 

Raton

C

O

Na-HCO

3 530-6,000 

San Juan CO Na-HC

O

3-Cl 410-170,00

Uinta

U

T

Na-HC

O

3-Cl

6,350-43,00

Petroleum water: 5,000->350,000 mg/L TDS;N

Warrior

NM

River MT
Composition of water from Powder River Ba

pH 6.7 –

8.4 SAR 

TDS 270 –

4,000 Chloride 

Sulfate

<0.03 – 530 Bicarbonate 

Calcium

1.8 –

7

8

Potassium 

Magnesium 0.6 –

4

6

Sodium 

Iron 2 – 17,500 ManganeseArsenic

<0.2 –

4.8 Barium 

Cadmium

<0.1

Chromium

Lead <0.1 –

0.43

Mercury 

Selenium <2 Zinc 

Rice an

(mg/L)

(μg/L)
Toxic Organic Compounds in Prod

Conventional Oil and Gas Wells- DOC =5-1000 mg/L (as C)- Organic Acid anions = 1-10,000 mg/L (as acet

- BTEX = ppb-20 mg/L- Phenols = ppb-15 mg/L- PAHs = ppb- 10 mg/LPreliminary Results from CBM Wells

Waters from wells in PRB & Gulf fell into thr

-little or no organics present-high levels (ug/l) of N- and O- substituted arom-high levels of N- and O- substituted aromatics -No acute hazard present—chronic exposure ?

Bill Orem
Summary – Balkan Endemic Ne

-Well water from endemic villages in Roma

Yugoslavia had higher abundances of extrpotentially toxic) dissolved organic substanto well water from nonendemic (control) v

-Lignites from endemic areas in Romania a

yield a high abundance of dissolved organiwhen leached with water or other polar socompared to other coals.

Results of the 2000-2002 studies in Romani

Yugoslavia support the Pliocene lignite hyposuggest the possible involvement of toxic orgcompounds from coal in the etiology of BEN

Bill Orem, U

Topics Discussed

1- OSPER ‘A’ & ‘B’ sites, Osage County, 2- Chemical & isotopic compositions of so

ground waters at OSPER ‘A’

& ‘B’ sites

3- Delineating the plume boundaries at OS4- Can produced water penetrate below thic

at OSPER ‘B’.

5- Processes--Mixing (brine, prec. & GW)

water-rock-bacterial interactions.

6- Future plans & concluding remarks.
Environmental Impacts 

Petroleum Exploration and P

 Huge volumes of produced water and oil 

bbl/yr, resp.) —Disposal of PW & releasesoil & ecosystem damage and surface & G

 Produced water generally is highly saline

organic and inorganic chemicals.

 Large number of wells drilled (~3.5 millio Drilling wells causes significant site distu

soil and water pollution.

 Large number of abandoned wells (~2.5 m

have caused GW pollution**.