Frio Site, Texas - IAEA KHARAKA... · 2006: Frio ―Blue‖ Pilot site Power plants Industrial sources rend he Frio Houston 20 miles Regional Setting of Pilot Site Significance

Pilot sitePilot site

Power plantsPower plants

Industrial

sources

Industrial

sources

High sand tr

end

in the F

rio

Houston

20 miles

Regional Setting of Pilot Site

Significance

to US carbon program:

Potential to

upscale to impact

US releases

International Symposium on Isotopes in Hydrology,

Marine Ecosystems, and Climate Change Studies Session 2: Carbon Dioxide Sequestration and

Related Aspects of the Carbon Cycle ----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

Environmental impacts of geologic sequestration

of CO2: Mobilized toxic organic compounds Yousif K. Kharaka, Pamela Campbell, R. Burt Thomas

U. S. geological Survey, Menlo Park, California, USA

IAEA, Monaco, March 29, 2011

Frio Site,

Texas

Topics Discussed

• What is CO2 storage/sequestration? Is it necessary?

• Nature, distribution and interactions of organic

compounds in brine produced with oil and natural gas.

• Partitioning of organics between brine, CO2 and organic

matter, including oil.

• Supercritical CO2 is an excellent solvent for organics,

including BTEX and PAHs.

• Results from Frio (TX), Cranfield (MS) & other field

experiments.

• Major geochemical & environmental issues for CO2

sequestration; implications of results on organics to date.

Kentisch and Buckheit, Science, 2006

The New Number 1 Emitter

World energy use, 1980-2030. IEA, 2007

IEA, November, 2006

2009 total global CO2

emissions = 30.3 Gt

Projections of Future Changes in Climate IPCC-2007

Best estimate for low scenario

(B1) is 1.8°C (likely range is

1.1°C to 2.9°C), and for high

scenario (A1FI) is 4.0°C (likely

range is 2.4°C to 6.4°C).

Arctic summers ice-free 'by 2013'The 16 September 2007 record low falls below the previous minimum set on 20 September

2005, by an area the size of Texas and California combined, or nearly five UKs. US (NSIDC).

4.3 million sq km

http://www.globalwarmingart.com/wiki/

Sea_Level_Rise_Maps_Gallery

Florida, USA

Some of the consequences of

Global Warming

Ocean acidification

pH from 8.1 to 8.0

Impact on coral

reefs and oceanic

ecosystems.

Sea-level rise by 2100

IPCC (2007)=40 cm

Carlson (2009)=100 cm

This is not an accident, but rather is part of a global

pattern of projections of precipitation change.

Poles and

tropical

oceans get

wetter.

Subtropics

get drier.

Most of

conterminous

US falls

somewhere in

between.

Rio de Janeiro Mudslides, Floods Kill 349 People Mudslides and floods in Rio de Janeiro state have killed at least 349 people, including three firefighters, and left about 2,700 homeless as houses are swept by dirt, rocks and water http://www.businessweek.com/news/2011-01-13

Brisbane flood bill to hit $5bn BRISBANE'S clean-up bill is expected to top $5 billion as the waters recede and the city takes stock. http://www.perthnow.com.au/news/top-stories

Snow covered street in New York January 12, Reuters

Extreme weather conditions

http://www.businessweek.com/news/2011-01-13/rio-de-janeiro-mudslides-floods-kill-349-people.html



http://www.apimages.com/

http://www.apimages.com/

http://www.perthnow.com.au/news/top-stories/brisbane-flood-bill-to-hit-5bn/story-e6frg12l-1225987556538?from=public_rss



Carbon Capture and Storage (CCS)• Capture:

– Separation of 5 -15 % CO2 in flue gas from N2

• Transportation:– CO2 is piped to the injection site

• Geological storage:– Liquefied CO2 is injected into porous formations at depths of 1-4 km

– (P and T > critical point, = 500 to 700 kg/m3)

– CO2 displaces existing fluid (water, oil, gas).

– Storage formation must be sealed by overlying low-permeability formation (mudstone, shale, evaporite).

– Seal integrity to retain buoyant and reactive CO2 phase.

– Allow measurement, monitoring, and verification (MMV).

– Storage volume large enough for commercial project.

Development of a Probabilistic Assessment

Methodology for Evaluation of Carbon Dioxide Storage

Robert Burruss, Sean Brennan, Philip Freeman, Matthew Merrill, Leslie Ruppert, Mark

Becker, William Herkelrath, Yousif Kharaka, Christopher Neuzil, Sharon Swanson, Troy

Cook, Timothy Klett, Philip Nelson, and Christopher Schenk

1- Methodology developed by the USGS for evaluation of the resource potential for

storage of CO2 in the subsurface of the United States as authorized by the Energy

Independence and Security Act (Public Law 110–140, 2007).

2- Based on USGS assessment methodologies for oil and gas resources created and

refined over the last 30 years.

3- The resource that is evaluated is the volume of pore space in the subsurface in the

depth range of 3,000 to 13,000 feet that can be described within a geologically defined

storage assessment unit consisting of a storage formation and an enclosing seal

formation.

4- Units are divided into physical traps (PTs), which are oil and gas reservoirs, and the

surrounding saline formation (SF). Storage resource is determined separately for these

two types of storage.

5- Monte Carlo simulation methods are used to calculate a distribution of the potential

storage size for individual PTs and the SF. To estimate the aggregate storage resource

of all PTs, a second Monte Carlo simulation step is used to sample the size and number

of PTs. USGS Open-File Report 2009–1035

In some regions there is

mismatch between largest

sources and largest oil and

gas traps

Therefore, we need new

infrastructure, either CO2 pipelines

or new PP at storage locations

1000 MW coal PP emits 8 Mtonne/y

50 yr project = 400 Mtonne

correct for subsurface density,

convert to barrels:

4.0 BBOe at reservoir P & TFrio site

Yaqing Fan, 2006

Issues of storage of CO2 A- Huge volumes of CO2 require storage for long time;

CO2 will displace huge volumes of formation brine.

B- CO2 becomes toxic in air at concentrations >5%.

C- At subsurface conditions, CO2 is SC, buoyant, and is a corrosive acid when dissolved in water.

D- CO2 is an excellent solvent for toxic organics, including BTEX, phenols and PAHs.

Storage Forms

1- CO2 as supercritical fluid (T=31°C; P= 74 bar) has a density lower than water; buoyancy transport (hydrodynamic and residual trapping).

3- CO2 is moderately soluble in brine lowering pH, becoming reactive to minerals, pipes, and forming aqueous species like H2CO3, HCO3

- & CO3

-2 (solution trapping)

3- Precipitates as carbonate minerals (calcite, dolomite, magnesite and siderite) (mineral trapping).

CO2 Storage – Underway or Proposed

Source: Peter Cook, CO2CRC, AU

Cranfield

Z

Frio Brine Pilot Site • Injection intervals: Oligocene

fluvial and reworked sandstones, porosity 24-34%, permeability 2.5-4.4 Darcys

• Steeply dipping 11 to 16o

• Seals several thick shales

• Depth 1,500 and 1,657 m

• Brine-rock system, no hydrocarbons

• 150 and 165 bar, 55 -65°C, supercritical CO2

Hovorka, 2007

Oil production

Fresh water (USDW) zone

protected by surface casing

Injection zones:

First experiment

2004: Frio ―C‖ & ―B‖

Second experiment

2006: Frio ―Blue‖

Pilot sitePilot site

Power plantsPower plants

Industrial

sources

Industrial

sources

High sand trend

in the F

rio

Houston

20 miles

Regional Setting of Pilot Site

Significance

to US carbon program:

Potential to

upscale to impact

US releases

Surface sampling

(swab) & Kuster

injection (C) &

Observation (B) wells

Jan 23-27, 2006

Surface sampling

(N2) & Kuster

injection (C) &

observation (B) wells

April 4-6, 2005

U-tubeobservation wellOct 29-Nov 3, 2004

U-tubeobservation wellOct 4-7, 2004

surface sampling

(N2), Kuster

injection &

observation wells

Jul 23-Aug 2, 2004

MDT tool

(Schlumberger)

injection wellJune 3, 2004

Sampling toolSampling site Sampling date

Surface sampling

(swab) & Kuster

injection (C) &


Jan 23-27, 2006

Surface sampling

(N2) & Kuster

injection (C) &


April 4-6, 2005



surface sampling

(N2), Kuster

injection &

observation wells

Jul 23-Aug 2, 2004

MDT tool

(Schlumberger)



Frio I CO2 Field sampling

U-tube observation wellMarch 20, 2007

U-tube and Kusterobservation &

injection wellOct 9-10, 2006

U-tubeobservation &

injection wellsSep 25-Oct 2, 2006

surface sampling

(N2), Kuster

injection &

observation wellsSep 6-12, 2006


Frio II CO2 Field samplingTracers added to the Frio fluids

1- Dye tracers, fluoresciene & rhodamine WT; 2- perfluorocarbon tracers;

3- SF6; 4- noble gases; 5- tagged CH4




U-tubeobservation &


surface sampling

(N2), Kuster

injection &






Tracers added to Frio Fluids

1- Dye tracers, fluoresciene &

Rhodamine WT.

2- Perfluorocarbon gases (PFTs).

3- SF6

4- Noble gases.

5- Tagged CH4.

Surface sampling

(swab) & Kuster

injection (C) &


Jan 23-27, 2006

Surface sampling

(N2) & Kuster

injection (C) &


April 4-6, 2005



surface sampling

(N2), Kuster

injection &

observation wells

Jul 23-Aug 2, 2004

MDT tool

(Schlumberger)



Surface sampling

(swab) & Kuster

injection (C) &


Jan 23-27, 2006

Surface sampling

(N2) & Kuster

injection (C) &


April 4-6, 2005



surface sampling

(N2), Kuster

injection &

observation wells

Jul 23-Aug 2, 2004

MDT tool

(Schlumberger)



Frio I CO2 Field sampling




U-tubeobservation &


surface sampling

(N2), Kuster

injection &









U-tubeobservation &


surface sampling

(N2), Kuster

injection &






Tracers added to Frio Fluids

1- Dye tracers, fluoresciene &

Rhodamine WT.

2- Perfluorocarbon gases (PFTs).

3- SF6

4- Noble gases.

5- Tagged CH4.

5.5

5.7

5.9

6.1

6.3

6.5

6.7

6.9

4-Oct-04 5-Oct-04 6-Oct-04 7-Oct-04 8-Oct-04

pH

0

500

1000

1500

2000

2500

3000

3500

Alk

alin

ity

HC

O3 (

mg

/L);

EC

(x

10

mS

/cm

)

pH

HCO3

EC

Frio I chemical data from observation well during CO2 injection

Frio II - Observation Well; U-tube

3.5

4.0

4.5

5.0

5.5

6.0

6.5

7.0

7.5

9/25/06 9/26/06 9/27/06 9/28/06 9/29/06 9/30/06 10/1/06 10/2/06 10/3/06

pH

0

100

200

300

400

500

600

700

800

900

1000

Ob

se

rva

tio

n W

ell T

ub

ing

Pre

ss

ure

(P

SIA

)

in-line pH

bench pH

Tubing pressure

Ball Check

Valve

Inlet filter: 40 cm sintered

stainless steel

Tee

Coupling

Sliding End Packer

Sample Tubing

Drive Tubing

Ball Check

Valve

Inlet filter: 40 cm sintered

stainless steel

Tee

Coupling

Sliding End Packer

Sample Tubing

Drive Tubing

Frio I (Fe & Mn)

― ‖

― ‖

― ‖

― ‖

― ‖

― ‖

0

200

400

600

800

1000

1200

10/4/04 10/5/04 10/6/04 10/7/04 10/8/04

0

4

8

12

16

20

0

200

400

600

800

1000

1200

10/04 2/05 6/05 10/05 2/06

0

4

8

12

16

20

Mn

(m

g/L

)

11

0

200

400

600

800

1000

1200

10/4/04 10/5/04 10/6/04 10/7/04 10/8/04

0

4

8

12

16

20

0

200

400

600

800

1000

1200

10/04 2/05 6/05 10/05 2/06

0

4

8

12

16

20

Mn

(m

g/L

)

0

200

400

600

800

1000

1200

10/4/04 10/5/04 10/6/04 10/7/04 10/8/04

0

4

8

12

16

20

0

200

400

600

800

1000

1200

10/04 2/05 6/05 10/05 2/06

0

4

8

12

16

20

Mn

(m

g/L

)

0

200

400

600

800

1000

1200

10/4/04 10/5/04 10/6/04 10/7/04 10/8/04

0

4

8

12

16

20

0

200

400

600

800

1000

1200

10/4/04 10/5/04 10/6/04 10/7/04 10/8/04

0

4

8

12

16

20

0

200

400

600

800

1000

1200

10/04 2/05 6/05 10/05 2/06

0

4

8

12

16

20

Mn

(m

g/L

)

11

Eh-pH diagram for selected Fe species

Important Mineral-Water-Gas Interactions in Frio

CO2 (gas) + H2O H2CO 3o ------ (1)

H2CO3o HCO3

- + H+ ------ (2)

CO2 (gas) + H2O + CaCO3 Ca++ + 2HCO3- ------ (3)

H+ + CaCO3 Ca++ + HCO3- ------ (4)

H+ + FeCO3 Fe++ + HCO3- ------ (5)

4Fe(OH)3 + 8H2CO3 4Fe++ + 8HCO3- + 10H2O + O2 ------ (6)

2Fe(OH)3 + 4H2CO3 + H2 2Fe++ + 4HCO3- + 6H2O ------ (7)

Feo + 2H2CO3 Fe++ + 2HCO3- + H2 ------ (8)

2H+ + CaMg(CO3) 2 Ca++ + Mg++ + 2HCO3- ------ (9)

0.4H+ + Ca.2Na.8Al1.2Si2.8O8 + 0.8CO2+ 1.2H2O

.2Ca++ + .8NaAlCO3(OH)2 + 0.4Al(OH)3+2.8SiO2 -- (10)

Kharaka et al.,

2009.

-2.5

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

-24 0 24 48 72 96 120 144 168 192 216

Elapsed Hours after CO2 Injection

Fe/Z

n (

wt)

0

50

100

150

200

250

300

350

d56F

e

56Fe

Fe/Zn

-2.5

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

48 72 96 120 144 168 192 216 240 264 288 312 336


Fe/Z

n (

wt)

0

50

100

150

200

250

300

350

d56F

e

56Fe

Fe/Zn

d56Fe range for 2 7/8‖

carbon steel tubing

Sta

rt

inje

ction

Pre-injection samples

15-19 days prior

Elapsed days after CO2 injection

0 1 2 3 4 5 6 7 8 13 14

d56Fe

FRIO-II, September, 6 – October 9, 2006

Fe/Zn from pipes: 20-45 x 103

-2.5

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

-24 0 24 48 72 96 120 144 168 192 216


Fe/Z

n (

wt)

0

50

100

150

200

250

300

350

d56F

e

56Fe

Fe/Zn

-2.5

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

48 72 96 120 144 168 192 216 240 264 288 312 336


Fe/Z

n (

wt)

0

50

100

150

200

250

300

350

d56F

e

56Fe

Fe/Zn


carbon steel tubing

Sta

rt

inje

ction


15-19 days prior

Elapsed days after CO2 injection

0 1 2 3 4 5 6 7 8 13 14

d56Fe


Fe/Zn from pipes: 20-45 x 103

-2.5

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

-24 0 24 48 72 96 120 144 168 192


Fe/M

n (

wt)

0

10

20

30

40

50

60

70

80

90

100

d56F

e

56Fe

Fe/Mn

-2.5

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

48 72 96 120 144 168 192 216 240 264 288 312 336


Fe/M

n (

wt)

0

10

20

30

40

50

60

70

80

90

100

d56F

e

56Fe

Fe/Mn


carbon steel tubing

Sta

rt

inje

ctio

n


15-19 days prior

Elapsed days after CO2 injection0 1 2 3 4 5 6 7 13 14

d56Fe


Fe/Mn from pipes 63-91

-2.5

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

-24 0 24 48 72 96 120 144 168 192


Fe/M

n (

wt)

0

10

20

30

40

50

60

70

80

90

100

d56F

e

56Fe

Fe/Mn

-2.5

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

48 72 96 120 144 168 192 216 240 264 288 312 336


Fe/M

n (

wt)

0

10

20

30

40

50

60

70

80

90

100

d56F

e

56Fe

Fe/Mn


carbon steel tubing

Sta

rt

inje

ctio

n


15-19 days prior


d56Fe


Fe/Mn from pipes 63-91

-2.5

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

-24 0 24 48 72 96 120 144 168 192

Elapsed Days after CO2 Injection

Fe

(m

g/L

)

0

200

400

600

800

1000

1200

d56F

e

56Fe

Fe

Frio II

-2.5

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

0 24 48 72 96 120 144 168 192 216 240 264 288 312 336


Fe

(m

g/L

)

0

200

400

600

800

1000

1200

d56F

e

56Fe

Fe


carbon steel tubing

Sta

rt inje

ction


15-19 days prior


d56Fe

-2.5

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

-24 0 24 48 72 96 120 144 168 192


Fe

(m

g/L

)

0

200

400

600

800

1000

1200

d56F

e

56Fe

Fe

Frio II

-2.5

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

0 24 48 72 96 120 144 168 192 216 240 264 288 312 336


Fe

(m

g/L

)

0

200

400

600

800

1000

1200

d56F

e

56Fe

Fe


carbon steel tubing

Sta

rt inje

ction


15-19 days prior


-2.5

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

-24 0 24 48 72 96 120 144 168 192


Fe

(m

g/L

)

0

200

400

600

800

1000

1200

d56F

e

56Fe

Fe

Frio II

-2.5

-2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

0 24 48 72 96 120 144 168 192 216 240 264 288 312 336


Fe

(m

g/L

)

0

200

400

600

800

1000

1200

d56F

e

56Fe

Fe


carbon steel tubing

Sta

rt inje

ction


15-19 days prior


d56Fe


I

Benson & Cook, 2005;

IPCC, 2005

A- Huge volumes of CO2 require storage for long time; CO2 will displace huge

volumes of formation water.

B- CO2 is non toxic, but will displace air & is buoyant and reactive in the subsurface.

Storage Forms1- CO2 as supercritical fluid (T=31°C; P= 74 bar) has a density lower than water;

buoyancy transport (hydrodynamic & residual trapping).

2- CO2 is moderately soluble in brine lowering pH and forming aqueous species like

H2CO3, HCO3- and CO3

—2 (solution trapping).

3- Precipitates as carbonate minerals (calcite, dolomite, magnesite & siderite) (mineral trapping).

Storage of CO2

0 20 40 60 80 100 120 140 1602

3

4

5

6

7

pH

pCO2 (bars)

pH

-12

-10

-8

-6

-4

-2

0

2

4pH values at:

surface

T & P

eq. calcite

calcite

albite, low

dolomite

goethite

siderite

G

(kca

l/mol

e)

Computer SimulationsTo understand

gas-water-mineral

Interactions and

multi phase fluid transport

Benson & Cook, 2005

100 75 50 25 0 25 50 75 100

Frio II "blue" sand [06FCO2-212]

(observation well; pre-injection)

100 75 50 25 0 25 50 75 100

Frio I "C" sand [04FCO2-218]

(observation well, pre-injection)

100 75 50 25 0 25 50 75 100

[milliequivalents/liter, normalized to 100%]

pH = 6.7; TDS = 93,800 mg/L

pH = 6.6; TDS = 92,200 mg/LpH = 6.03; TDS = 92,600 mg/L

pH = 6.7; TDS = 101,600 mg/L

Cl Cl

Cl Cl

SO4

SO4SO

4

HCO3

HCO3

HCO3

Mg

HCO3

SO4

MgMg

Mg

Ca

CaCa

Na

Na

Na

Ca

Na

Frio I "C" sand [04FCO2-337]

(observation well; post injection)

100 75 50 25 0 25 50 75 100

Frio "B" sand [05FCO2-110]

(observation well)

Audigane et al. (2008)

Benson & Cook (2005)

Brine/CO2 volume ratio at reservoir conditions

18O shift18O shift Brine/CO 2Date* Brine CO 2 volume ratio

10-5-04 0 0

10-6-04 0.37 32 43

10-6-04 0.69 32 23

10-6-04 0.77 32 21

10-6-04 1.22 32 13

10-7-04 2.24 32 7.1

11-3-04 1.43 32 11

11-3-04 1.74 32 9.1

4-4-05 11.2 22 0.97

5-4-05 11.7 22 0.93

6-4-05 11.9 22 0.92


10-5-04 0 0

10-6-04 0.37 32 43

10-6-04 0.69 32 23

10-6-04 0.77 32 21

10-6-04 1.22 32 13


10-5-04 0 0

10-6-04 0.37 32 43

10-6-04 0.69 32 23

10-6-04 0.77 32 21

10-6-04 1.22 32 13

10-7-04 2.24 32 7.1

11-3-04 1.43 32 11

11-3-04 1.74 32 9.1

4-4-05 11.2 22 0.97

5-4-05 11.7 22 0.93

6-4-05 11.9 22 0.92

d18

OfCO2 - d

18O

iCO2

Xbrine/XCO2 = _______________________

(1)

d18

OiH2O - d

18O

fH2O

The isotopic mass balance equation for a closed

system and no isotopic exchange with minerals

is given by: (Clark and Fritz, 1997):

where the superscripts ―i‖ and ―f‖ are the initial

and final δ values for brine and CO2, and X is

the atomic oxygen in the subscipted component.

Kharaka et al., 2006

-11

-10

-9

-8

-7

-6

-5

-4

-3

-2

-1

0

0 10 20 30 40 50 60 70 80 90 100

CO2 (%)

d1

3C

(C

O2

)

production wells [3/09]



F2

F3

Jackson Dome

Mixing line

Jackson Dome

Tuscaloosa

Mixing with C-isotopes

Concentrations of DOC in Frio I brine

Frio I

1

10

100

1000

7/1/04 10/9/04 1/17/05 4/27/05 8/5/05 11/13/05 2/21/06

Date

DO

C (

mg

/L)

IW - pre CO2

OW - pre CO2

OW U-tube(10/5-10/7/04)-pre BT

OW U-tube(10/5-10/7/04)-post BT

OW U-tube(10/29-11/3/04)

IW post CO2 (4/4-4/5/05)

OW "B" post CO2 (4/5-4/6/05)

Kuster

IW (1/06)

OW "B" (1/06)

?

0.00

1.00

2.00

3.00

4.00

5.00

6.00

7.00

8.00

9.00

10.00

0 500 1000 1500 2000 2500 3000 3500

HCO3

DO

C

OW-pre

IW-pre

slugtest

OW-pre BT

OW-post BT

OW-10/9

OW-K 10/9/06

OW-11/2/06

IW-U

IW-K

Frio II

Organics in Oil-Field Water

(mg/L)

Frio DOC (6/04-4/05)

0

1

10

100

1000

Jun-04 Aug-04 Oct-04 Dec-04 Feb-05 Apr-05

DO

C (

mg

/L)

DOC injection w ell

DOC observation w ell C-sand

DOC observation w ell B-sand

Organics in Produced Water

(mg/L)

0.7Ground Water

7Surface Water

5-1000Produced Water

MeanDOC

0.7Ground Water

7Surface Water


MeanDOC

Kharaka & Hanor, 2004

1.23 – HYDROXY BENZOIC ACID

0.22 – HYROXY BENZOIC ACID

44 – METHYL BENZOIC ACID

5BENZOIC ACID

24 – METHYL PHENOL

10,000

60

10

20

ACETATE & OTHER ACID

ANIONS

BTEX

PAHs

PHENOL





5BENZOIC ACID


10,000

60

10

20


ANIONS

BTEX

PAHs

PHENOL

Kharaka & Hanor, 2007 Classes & Importance of Dissolved Organic Species

(1) Hydrocarbons; (2) Organic acid anions; & (3) Toxic Organics

(2-A) Mineral Diagenesis (Kharaka and Hanor, 2007, and many references listed)

1- They act as proton donors for a variety of pH-dependent reactions.

2- They act as pH and Eh buffering agents

3- They form complexes with cations (Ca, Mg) and metals such as Al, Fe, Pb and Zn; catalysis.

(3-A) High environmental and health impacts of toxic organics, especially BTEX , phenols and PAHs.

1- May be present in brines at 10s of mg/L

2- High toxicity--MCL at low ppb levels

2- Partition into & potential to leak with the super critical CO2 into GW .

Sampling well

24-3

29-3

29-1

29-6

29-5

29-9

29-2

29-7

26-1

25-2

24-2

29-4

27-1

48-1

28-2

28-1

29-12

29-10

Injector 29-10 29-12 29-2 29-7 29-4

69 587

26-1 25-2 24-2 27-1 28-1 48-1

Injection volume byMar/09 (103 metric ton) 110 62 52 53 48 45 56 28

Injector 0 0.5 1.0 1.5 km

DAS

0 125 250 km

Jackson Dome

Denbury Resources International

Cranfield oil field, MS

CO2 injection for EOR, and

into saline aquifer (DAS)

Polycyclic Aromatic Hydrocarbons - PAHs

PAHs – semi-volatile organic compounds,

16 of PAHs are designated by

the EPA as priority pollution. Occur in

oil, coal, tar deposits and produced as

by-products of fuel burning.

Alkylated PAHs-methyl groups are

removed during incomplete

combustion. PAH toxicity and solubility

are structurally dependent on isomers

displaying differential charactersitics.

Phenols- including o-, m-,

and p-cresol. High solubility

in water, not extremely

hazardous, product of coal

Oxidation.

Comparison of solubility of benzene, phenol and some PAHs in supercritical CO2 (400 bar and 50°C) and ambient water (25°C, 1 bar)

Compounds Solubility in SCC (g/kg) Solubility in water (g/kg) benzene miscible 1.8 phenol ~95a 82000b naphthalene 120 3.2×10–4 phenanthrene 11 1.3×10–3 pyrene 1.2 1.4×10–4 chrysene 0.02 2×10–6 perylene 0.005 4×10–7 benzo[a]perylene 0.002 3×10–7 Zheng et al., 2010

Mole fraction solubility of PAHs in SC CO2

Miller & Hawthorne, 1996

22

compound MW S (mol/L

water)

Kow

naphthalene 128 8.7 E-04 2300

phenanthrene 178 3.5 E-05 37153

anthracene 178 3.5 E-07 34673

pyrene 202 6.8 E-07 134896

n-octadecane 254 8.3 E-09

benzene 78 2.3 E-02 130

toluene 92 5.6 E-03 490

phenol 94 8.9 E-01 28

Solubility and Octanol/Water coefficients of a selected

group of phenols, PAHs, n-alkanes and BTEX compounds

(key facors in determining environmental beahvior and impact)

Organics in Cranfield brine

Organics in Cranfield brine

• 50% of drinking water in USA is from GW

• 95% of rural America is dependant on GW

• GW use increased from 13x1010 L/day in 1950 to 33x1010 L/day in 2000

• Once GW is contaminated, remediation is very costly or impossible

Importance of Protecting Ground Water

Greenpeace International, 2008Emily Rochon (lead author)

Cross section of the Frio Formation showing injection and monitoring wells, C- and B-sands, shale layers, and perforation zones.

B perforated for subsurface monitoring

After Hovorka, 2007

Near surface monitoring

Soil CO2, PFTs, and shallow

groundwater wells

No leakage detected

B perforated for subsurface monitoring

Date

1/1/04 5/1/04 9/1/04 1/1/05 5/1/05 9/1/05 1/1/06 5/1/06

d13C

DIC

(p

er

mil)

-40

-35

-30

-25

-20

-15

-10

-5

0

Injection well

Monitoring well

Frio I - d18

O vs Time

-12

-10

-8

-6

-4

-2

0

2

7/8/04 10/6/04 1/4/05 4/4/05 7/3/05 10/1/05 12/30/05 3/30/06

d1

8O

(p

erm

il) "C" sand

"B" sand

Chemical Composition of Frio GasesFrio formation water at saturation with CH4

Gas1‖C‖

2‖C‖

3―B‖

4"B"

He 0.0077 0 0.01 0.012

H2 0.040 0.19 0.92 0.30

Ar 0.041 0 ND 0.061

CO2 0.31 96.8 2.86 0.22

N2 3.87 0.037 1.51 2.46

CH4 93.7 2.94 94.3 96.8

C2H6+ 1.95 0.005 0.12 0.13

Gas1‖C‖

2‖C‖

3―B‖

4"B"

He 0.0077 0 0.01 0.012

H2 0.040 0.19 0.92 0.30

Ar 0.041 0 ND 0.061

CO2 0.31 96.8 2.86 0.22

N2 3.87 0.037 1.51 2.46

CH4 93.7 2.94 94.3 96.8

C2H6+ 1.95 0.005 0.12 0.13

Perfluorocarbon tracers (PFT)(Phelps et al., 2006).

Wells et al., 2007 (AG, v. 22, p. 996-1016)

W. Pearl Queen field, NM (2090 t CO2) Leakage at 0.009% per year

PDCH concentrations

measured over 54 days

Experts Criticize Evidence Used to

Diagnose a Suspected Leak at One

of the World's Largest CO2 Storage

Sites [Weyburn-Midale in Canada]

Citing a lack of information, scientists

argue a consultant's conclusion that

Saskatchewan's Weyburn oil field is

leaking greenhouse gas is unfounded

By Mike Orcutt | January 20, 2011 |

Cenovus uses [8,000 tons/day of] CO2,

which arrives via pipeline from [a synfuel coal

plant] in North Dakota, for enhanced oil

recovery—a technique in which the

greenhouse gas (GHG) is injected into an oil

reservoir to coax out extra oil. Much of the

CO2 (around 18 million metric tons as of July

2010) is then stored 1.5 kilometers

underground in a depleted reservoir, where it

is supposed to stay trapped. The

International Energy Agency (IEA) GHG

Weyburn–Midale CO2 Monitoring and

Storage Project, a research group affiliated

with the Paris-based agency has spent the

past decade studying CO2 injection and

storage at Weyburn, the goal being to

"deliver the framework necessary to

encourage implementation of CO2 geological

storage on a worldwide basis," according to

the group's web site.

http://www.scientificamerican.com/author.cfm?id=2548

http://www.scientificamerican.com/article.cfm?id=enhanced-oil-recovery

http://www.scientificamerican.com/article.cfm?id=enhanced-oil-recovery

http://www.iea.org/

http://www.iea.org/

http://www.iea.org/

http://www.ptrc.ca/weyburn_overview.php

Illustration of a typical CCS operation and potential CO2 leakage pathways to shallow groundwater (Zheng et al., 2010).

Injection of Supercritical CO2

CO2 storage formation

Computed spatial distribution of benzene mass fraction in SCC & GW after 3.5 yrs (Zheng et al., 2010)

Contamination of groundwater from leakage of CO2 with benzene

pH ZERT - "B" wells - water samples

5.5

6.0

6.5

7.0

7.5

07/07 07/10 07/13 07/16 07/19 07/22 07/25 07/28 07/31 08/03 08/06 08/09 08/12 08/15

pH

.

well 1B

well 2B

well 4B

well 5B

CO2 start

CO2 stop

7/18 rain2.4cm7/19 rain2.8cm8/7 rain.56cm8/8 rain1.6cm

alkalinityZERT - "B" wells - water samples

200

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

07/07 07/10 07/13 07/16 07/19 07/22 07/25 07/28 07/31 08/03 08/06 08/09 08/12 08/15

alk

alin

ity

(m

g/L

as

HC

O3

@ p

H 4

.5)

.

well 1B

well 2B

well 4B

well 5B

CO2 start

CO2 stop

7/18 rain2.4cm7/19 rain2.8cm8/7 rain.56cm8/8 rain1.6cm

ZERT Results

ZERT - "B" Shallow Water Wells (as of 8/14/08)

400

600

800

1000

1200

1400

1600

1800

7/7 7/9 7/11 7/13 7/15 7/17 7/19 7/21 7/23 7/25 7/27 7/29 7/31 8/2 8/4 8/6 8/8 8/10 8/12 8/14

Ele

ctr

ica

l co

nd

uc

tiv

ity

(in

-sit

u a

t s

cre

en

; m

icro

S/c

m)

1B

2B

3B

4B

5B

3B no water

CO2

stop 8/7

CO2

Starts 7/9

• To mitigate global warming resulting from increases in atmospheric GHG concentrations, CCS is necessary as part of a portfolio of mitigation options.

• Organic compounds, especially short chained aliphatic acid anions are present in high concentrations in water produced with oil and gas , and must be considered in CO2-brine- mineral interactions.

• Supercritical CO2 is an excellent solvent for some toxic organics, including BTEX , phenols and PAHs.

• Results from field tests show mobilization of organics following CO2 injection, even in aquifers with no petroleum .

• Need for detailed site characterization and a comprehensive MMV programs are needed to minimize environmental impacts, including contaminating USDW with mobilized toxic organics.

• Much more work needed to understand the partitioning of organics into CO2, brine, oils, gases, as well as their transport and fate in the subsurface.

Kharaka et al., 2009, Applied Geochemistry, v. 24, p. 1106-1112.

Kharaka and Hanor, 2007, Treat. on Geoch, J.I. Drever (ed), v. 6, p. 1-48, Elsevier.

Summary and Conclusions

Arts, et al., 2008

Bickle, 2009

Injection

started 1996 at

: 1 MT/yr

Utsira sand:

Poorly

consolidated,

1-3 Darcy.

CO2 flows

through the

shale layers

Sleipner site

Norway

Importance of Dissolved Organic Species (A) Mineral Diagenesis (Kharaka and Hanor, 2007, and

many references listed)

1- They act as proton donors for a variety of pH-dependent

reactions.


3- They form complexes with cations (Ca, Mg) and metals

such as Al, Fe, Pb and Zn; catalysis.

(B) They can be used as proximity indicators in petroleum

exploration (Kartsev, 1974; Carothers and Kharaka, 1978)

(C) They serve as possible precursors for natural gas

(Kharaka et al., 1983; Drummond and Palmer, 1986).

(D) Environmental and health impacts of toxic organics,

including BTEX , phenols and PAHs.

H2CO3o HCO3

- + H+ ------ (1)

CH3COOH CH3COO- + H+ ------ (2)

H2C2O4 C2O4- - + 2H+ ------ (3)

Total alkalinity = ∑HCO3- + ∑2CO3

- - + ∑CH3COO- + ∑HC2O4-

+ ∑2C2O4- - + ∑OH- + ∑HS- + --- Carothers and Kharaka, 1978

Temperature and CO2 records

400 350 300 250 200 150 100 50 now

Thousands of year before present

(Siegenthaler et al., 2005; Lüthi et al., 2008, NOAA)

20

-2-4-6-8

-10

Tem

pera

ture

change (

oC

)

400

350

300

250

200

Carb

on D

ioxode (

ppm

v)2010 = 390 ppmCO2 Higher levels and

more rapid increase

A scientist holding an ice core—a

sample taken from polar ice caps

or mountain glaciers.

Ice cores reveal clues about

climate changes in Earth’s past.

Compound 06FCO2-232 06FCO2-309 06FCO2-326 06FCO2-355 06FCO2-361 Grease Extract

ng/liter ng/liter ng/liter ng/liter ng/liter ng/mg grease

Naphthalene 139 870 114 467 0 1

1 Methylnaphthalene 54 559 312 244 0 3

2 Methylnaphthalene 151 434 271 268 0 2

Biphenyl 43 185 103 101 0 2

Dimethylnaphthalenes 1481 2234 1161 1857 0 20

Acenaphthylene 0 65 57 50 0 0

Acenaphthene 211 156 100 175 0 0

Trimethylnaphthalenes 92 0 106 0 70

Fluorene 732 366 657 394 0 0

dibenzothiophene 111 86 70 117 0 0

Phenanthrene 1099 591 549 958 0 44

Anthracene 0 0 0 0 0 0

Methylphenanthrenes 0 0 0 0 0 267

3,6-dimethylphenanthrene 0 0 0 0 0 470

Fluoranthene 13 20 18 21 0 0

Pyrene 16 33 3 51 0 0

Benzo[a]anthracene 0 0 0 0 0 0

Chrysene 0 0 0 0 0 0

PAH Concentrations in Frio II samples

Analyses by W. Orem

Ninth Annual Conference on Carbon Capture & Sequestration

• Na-Ca-Cl brine

• TDS ~152,000 mg/L

• pH ~5.5 surface; ~4.7-5.0 @ 3000 psi

• EC ~170-175 mS/cm

• T ~ 120 °C; ~340 bar

Fingerprint Spider diagram - 38 samples,

including Denbury production wells

DAS -F2 & F3 Wells (12 samples)

Cranfield - F2, F3 and Denbury production wells

1

10

100

1000

10000

100000

Na K Mg Ca Sr Mn Fe HCO3

Lower Tuscaloosa Formation - brine chemistry

(mg/L) stdev % variation

Li 8.3 1 12%

K 312 44 14%

Na 41953 751 2%

Mg 1195 76 6%

Ca 13467 606 5%

Sr 739 35 5%

Mn 18 1 6%

Fe 103 18 17%

Cl 92900 1734 2%

Br 461 22 5%HCO3 370 93 25%

B 52 4 8%

Ba 81 21 26%

SO4 25 27 108%

TDS 151977 2395 1.6%

Gas chemistry (ORNL)

• ~85-90 % CH4

• ~2.5-5 % C2 & higher

• 3.5-6 % CO2 (13C ~-10 permil)

• minor H2S

Jackson Dome – CO2 injectate

~99 % CO2 (13C = -2.9 permil)

0

50

100

150

200

1 2 3

mg

/L

sampling time 1 with inhibitor; sampling times 2 and 3 - no inhibitor

DOC and ACETATE concentrations - CRANFIELD, MS Oil Wells - APRIL 2010

DOC well 29-1

ACET well 29-1

DOC well 29-9

ACET well 29-9

DOC well 29-3

ACET well 29-3

Impacts in the Pacific Coastline

California Wine Industry: Unwelcome Changes?

• Climate change affects managed ecosystems like vineyards and

farms just as it affects natural ecosystems

• Future warming unlikely to help wine growers in California’s

premium wine regions: some areas projected to become ―marginal‖

by 2100

National Academy of Sciences

National Academy of Engineering

Institute of Medicine

National Research Council

Estimated Costs of CO2 Capture, Transport,

and Geological Storage (2007 US$/t CO2)

CCS system component Cost range (US$)

Capture: Fossil fuel power plants $20-95/t CO2 net captured

Capture: Hydrogen and ammonia

production or gas-processing plant$5-70/t CO2 net captured

Capture: Other industrial sources $30-145/t CO2 net captured

Transport: Pipeline $1-10/t CO2 transported

Storage: Deep geological formation $0.5-10/t CO2 net injected

Source: IPCC (2005); Rubin, 2008

• 50% of drinking water in USA is from GW

• 95% of rural America is dependant on GW

• GW use increased from 13x1010 L/day in 1950 to 33x1010 L/day in 2000

• Once GW is contaminated, remediation is very costly or impossible

Importance of Protecting Ground Water

0

50

100

150

200

1 2 3

mg

/L

sampling time 1 with inhibitor; sampling times 2 and 3 - no inhibitor

DOC and ACETATE concentrations - CRANFIELD, MS Oil Wells - APRIL 2010

DOC well 29-1

ACET well 29-1

DOC well 29-9

ACET well 29-9

DOC well 29-3

ACET well 29-3

Concentration (mg/L) References

Acid Anion Reported Likely (Max. reported)

Oxalate 494 10 1

Malonate 2540 100 1

Succinate 63 100 4

Glutarate 95 100 5

Adipate 0.5 10 4

Pimelate 0.6 10 4

Suberate 5.0 10 4

Maleic 26 50 1

(1) McGowan and Surdam (1988); (2) Surdam et al., (1984)

(2) McGowan and Surdam (1990b); (4) Kharaka et al. (1985);

(5) Kharaka et al. (1997). Source: Kharaka et al., 2000

Dicarboxylic Acid Anions

Concentration (mg/L) References

Acid Anion Reported Likely (max. reported)

Formate 174 10 1

Acetate 10000 5000 2

Propionate 4400 2000 1

Butyrate 682 500 3

Valerate 371 200 3

Caproate 107 100 4

Enanthate 99 100 1

Caprylate 42 100 1

Organic Acid Anions

Concentrations of DOC in Frio I brine

Frio I

1

10

100

1000

7/1/04 10/9/04 1/17/05 4/27/05 8/5/05 11/13/05 2/21/06

Date

DO

C (

mg

/L)

IW - pre CO2

OW - pre CO2

OW U-tube(10/5-10/7/04)-pre BT

OW U-tube(10/5-10/7/04)-post BT

OW U-tube(10/29-11/3/04)

IW post CO2 (4/4-4/5/05)

OW "B" post CO2 (4/5-4/6/05)

Kuster

IW (1/06)

OW "B" (1/06)

?

0.00

1.00

2.00

3.00

4.00

5.00

6.00

7.00

8.00

9.00

10.00

0 500 1000 1500 2000 2500 3000 3500

HCO3

DO

C

OW-pre

IW-pre

slugtest

OW-pre BT

OW-post BT

OW-10/9

OW-K 10/9/06

OW-11/2/06

IW-U

IW-K

Frio II

Organics in Oil-Field Water

(mg/L)

Frio DOC (6/04-4/05)

0

1

10

100

1000

Jun-04 Aug-04 Oct-04 Dec-04 Feb-05 Apr-05

DO

C (

mg

/L)

DOC injection w ell

DOC observation w ell C-sand

DOC observation w ell B-sand

Organics in Produced Water

(mg/L)

0.7Ground Water

7Surface Water


MeanDOC

0.7Ground Water

7Surface Water


MeanDOC





5BENZOIC ACID


10,000

60

10

20


ANIONS

BTEX

PAHs

PHENOL





5BENZOIC ACID


10,000

60

10

20


ANIONS

BTEX

PAHs

PHENOL

Kharaka & Hanor, 2007 Classes & Importance of Dissolved Organic Species

(1) Hydrocarbons; (2) Organic acid anions; & (3) Toxic Organics

(2-A) Mineral Diagenesis (Kharaka and Hanor, 2007, and many references listed)

1- They act as proton donors for a variety of pH-dependent reactions.


3- They form complexes with cations (Ca, Mg) and metals such as Al, Fe, Pb and Zn; catalysis.

(3-A) High environmental and health impacts of toxic organics, especially BTEX , phenols and PAHs.

1- May be present in brines at 10s of mg/L

2- High toxicity--MCL at low ppb levels

2- Partition into & potential to leak with the super critical CO2 into GW .

Mono & dicarboxylic acid

anions in oil field brines

Kharaka et al., 1988

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