Isotope Techniques for Discriminating Methane Sources

8th International Petroleum & Biofuels Environmental Conferenc Houston, TX, November 8-10, 2011
Julie K. Sueker, Ph.D., P.H., P.E., ARCADIS, Lakewood, CO Boyce L. Clark, Ph.D., P.Hg., ARCADIS, Baton Rouge, LA George H. Cramer, P.G., ARCADIS, Baton Rouge, LA

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Overview
Why use methane forensics? Methane generation mechanisms Methane forensic techniques Geochemistry Isotopes Geophysics Statistics Case study Storage cavern natural gas release
Methane bubbles in swamp
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Methane Forensics
Methane derived from numerous sources Potential methane release site may have multiple unrelated methane sources Methane forensic techniques used in various settings to differentiate methane sources

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Methane Generation Mechanisms

Thermogenic
Coal bed and oil & gas formations

Biogenic
Methanogenesis swamp gas and drift gas Acetate fermentation landfill gas

USGS

Abiogenic
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Geochemical Techniques
Light hydrocarbon gas composition
Thermogenic versus biogenic

Composition of other gases (CO2, O2, H2, Ar, He, etc.)

Gas source, migration pathway
Methane / Ethane
100000 10000 1000 Mixing 100 10

Groundwater geochemistry
Differentiate water types

Biogenic Gas Composition

Trace CH4 generation pathway

Identify formation/produced water

Thermogenic Gas Composition

0.01 0.1 1 10

1 0.001

Carbon Dioxide / Methane

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Geochemical Techniques
10000

Ca-Cl Type

1000

Concentration (meq/L)

100 Cations Anions

Surface Water Well A Well B Formation Water

Na-Cl Type
10

Ca-CO3 Type

0.1 Ca
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Mg

Na + K

Cl

SO4

CO3

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What are Isotopes?

Atoms of same element with differing masses
same # of protons, different # of neutrons

e-

e-

ep n n
Tritium 3H, T

p
Hydrogen 1H

p
n
Deuterium 2H, D

Lighter

Heavier

Sum of protons and neutrons is the atomic mass

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Isotope Techniques
Stable carbon and hydrogen isotopes of methane Carbon-14 (14C) of methane

Other isotopic tracers, e.g., 87Sr/86Sr, H and O of water

Landfill Gas Swamp and Marsh Gas Drift Gas Thermogenic Gas Fossil
~23,000 Years ~11,500 Years ~5,700 Years

Modern

25
14C

50

75

100

125

150

Activity as Percent Modern Carbon

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Stable Isotope Signatures

-100 -150

d2H CH4 ()

-200

Biogenic Gas
("Swamp Gas")

Thermogenic Gas
("Natural Gas", Coal Bed Methane)

-250

-300

Biogenic Gas
("Landfill Gas")

-350 -100

-90

-80

-70

-60 -50 d13C CH4 ()

-40

-30

-20

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Case Study
Storage Cavern C

Storage Caverns A & B

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Theoretical Migration Pathways

0

500 ft

150

350

Overburden

395

500

Cap Rock

700

1,000

Salt Dome
2,000

Cavern B

Cavern A

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3,300

Storage Cavern C

Storage Caverns A & B

Legend Relief Vent

Bubbles
Abandoned Gas Wells 12 Southern Vent

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Prepared at the request of counsel As of 1-28-04

Geochemical Data
100000 10000

Biogenic Gas Composition

Methane / Ethane

1000

Mixing
100

10

Thermogenic Gas Composition

1 0.001

0.01

0.1 Carbon Dioxide / Methane

10

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Isotope Data All Samples

(up to one year of sample collection with several repeat locations)
-140

All Samples
Southern Vent
-155

Cavern C

Cavern Gas
Caverns A&B

d2H Methane (per mil)

-170

-185

-200

Biogenic
-215 -70 -65 -60

Thermogenic

-55

-50

-45

-40

-35

d13C Methane (per mil)

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Isotope Data Southern Vent

(one location, many samples)
-145 Cavern C -150 d2H Methane (per mil)

-155

-160 Cavern A Cavern B

132 189

-165
47 145 139 63 41 70 118

153 114 77

159 125 84 105 90 98 218

-170

202

174

385 244

-175 -50.6

-50.4

-50.2

-50

-49.8

-49.6

-49.4

-49.2

-49

-48.8

d13C Methane (per mil)

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Area of Surface Expression of Gas (Bubbles)

Estimated Extent of Subsurface Gas

Storage Cavern C

Storage Caverns A & B

Legend Relief Vent Vents -No Gas Bubbles-Match

Bubbles-No Match

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Abandoned Gas Wells 16 Southern Vent

Prepared at the request of counsel As of 1-28-04

Methane Forensic Techniques

Cost effective and definitive investigation tool

Highest standard of environmental forensics practice Establish baseline conditions

Evaluate extent of gas migration
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Questions?

Mother Goose and Grimm 2001 Grimmy, Inc. Dist. By Tribune Media Services. All rights reserved.

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Imagine the Result

Julie K. Sueker, PhD, PH, PE 303.231.9115 x112 Julie.Sueker@arcadis-us.com

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