Fred Baldassare, P.G.

Sr. Geoscientist Christopher Laughrey, Sr. Geosciences Advisor, Weatherford Laboratories,

Mark McCaffrey, Ph.D., Sr. Technical Advisor, Weatherford Laboratories, John Harper, Ph.D., Mgr., Geologic Resources, PA Geological Survey

Prepared for

September 28, 2011

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Stray gas incidents can manifest as non-threatening or as serious to public health and safety…

…incidents have occurred long before contemporary Marcellus gas well drilling

Methane in the shallow subsurface as a dissolved gas in groundwater or in the gas phase is not unusual in many aquifer systems in the northern Appalachian basin. The origin may be: 1) natural condition, 2) result of legacy conditions, 3) due to recent activity To determine the source of a stray gas incident, there is no silver bullet, no desk top model… …Alleged stray gas migration incidents require investigation at the site specific level to determine origin and source. Conclusions must be supported by multiple lines of evidence.

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1) Molecular & Isotopic compositions for > 2000 gas samples obtained during drilling of contemporary Marcellus

formation gas wells

2) Historical evidence including gas shows documented in well completion reports and well records on file with PA

Geological Survey & published data from previous investigations

3) Molecular & Methane Isotopic compositions for

background groundwater water quality of local and regional aquifer systems

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Study Objective: determine the occurrence and identify the origin of natural gases in Quaternary through Devonian age strata within our study area in the N. Appalachian basin…this objective was accomplished comprehensively by evaluating different data types:

• Study Results: relative to aquifer systems: - Microbial, thermogenic, and mixed microbial/thermogenic gases occur in the aquifer systems (pre-contemporary Marcellus fm. well drilling) - Thermogenic gas of different thermal maturities occurs in the Catskill/Lock Haven formations across our study area - In certain areas of the basin in NE PA, isotope data reveals reversals (δ13C1>δ13C2>δ13C3) throughout stratigraphic section, & universally in the Marcellus formation - The different data types are corroborative.

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Five County Study Area In N.E. Pennsylvania

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General Stratigraphy – NE Pennsylvania

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Upper Devonian wells were determined searching the IHS well database for wells TD’d in the Catskill, Lock Haven, Bradford or Venango. Marcellus wells were filtered from the PADEP database reported w/production from the Marcellus as of June 2011.

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LEGEND Upper Devonian Wells

Marcellus Fm Wells Upper Devonian Bedrock

Geologic formations at the surface in our study area produce commercial volumes of natural gas west of our study area

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Interpretations are from seismic surveys not stratigraphy or structure

Various researchers have determined by examination of stable hydrogen and carbon isotopes of methane and C2+ hydrocarbons that there are common hydrogen and carbon isotopic compositions for thermogenic gas associated with coal and natural gas, drift gas, and other near-surface microbial gases (Craig, 1953; Coleman and others, 1977; Deines, 1980; Schoell, 1980; Rice and Claypool, 1981; Schoell, 1983; Whiticar,1986; Wiese and Kvenvolden, 1993; Coleman, 1994; Baldassare and Laughrey, 1997; Kaplan and others, 1997; and Rowe and Muehlenbachs, 1999, Osborn and McIntosh, 2010).

The isotopic and compositional variations in natural gas can be described in terms of: 1) processes during the formation of gases (bacterial fermentation, maturation of organic matter) and 2) processes during secondary migration (mixing of primary gases). The carbon and hydrogen isotopic compositional ranges of methane from different sources are based on the genetic classification scheme of Schoell (1980) Stable carbon & hydrogen isotope compositions are expressed as the ratio of 12C to 13C and 2H/1H of the sample compared with that of the international standards…expressed in the following notation as per mil. Properly interpreted, isotope geochemistry provides powerful geochemical evidence to constrain gas origin, and focus the investigation.

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I s o t o p e G e o c h e m i s t r y Carbon & Hydrogen Isotopes

International standards: carbon: Pee Dee Belemnite (“PDB”) hydrogen: Standard Mean Ocean Water (“SMOW”)

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Mudgas Isotope Geochemistry

Our database for this study includes > 2,000 gas samples analyzed & interpreted for

molecular & isotopic composition from

>150 Marcellus gas wells

Isotope analyses for mudgases are accomplished using online continuous

flow, or GC-IRMS systems with a precision of +/- 0.3 to 0.4 on 13C and +/- 5 for 2H

When combined with geographic and

stratigraphic data, the mudgas isotope data provide important depth specific

background isotope compositions of gases that occur in the strata which can be

diagnostic for investigations of potential stray gas migration incidents.

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Shallow gas shows encountered in aquifer system during drilling of Marcellus fm. Wells

Gases are thermogenic in origin

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Shallow gas shows encountered in aquifer system during drilling of Marcellus fm. Wells

Gases are thermogenic in origin

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Shallow gas shows encountered in aquifer system during drilling of Marcellus fm. wells

Gases are thermogenic in origin

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0 - 1000 ft. Mean (‰) Median (‰) 45 ptsδ13C1 -44.077 -46.000δ13C2 -41.594 -41.900δDC1 -223.200 -223.000

0 - 2000 ft. Mean (‰) Median (‰) 91 ptsδ13C1 -42.776 -44.200δ13C2 -40.877 -40.600δDC1 -226.471 -223.000

2000 - 5000 ft. Mean (‰) Median (‰) 172 ptsδ13C1 -37.218 -36.200δ13C2 -39.835 -40.050δDC1 -195.363 -178.000

> 5000 ft. Mean (‰) Median (‰) 1407 ptsδ13C1 -32.642 -33.100δ13C2 -38.582 -39.300δDC1 -163.305 -162.000

Isotopic results reveal distinct thermogenic gases that are somewhat correlative with depth

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> 11.4 per mil difference in δ13C1 0-1,000’ vs. >5,000’

> 3 per mil difference in δ13C2 0-1,000’ vs. >5,000’

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Seal

Upper Devonian Catskill/Lock Haven

Marcellus fm.

Marcellus fm. gas well Bradford County, PA

Marcellus fm. gas well Bradford County, PA

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Marcellus fm. gas well Tioga County, PA

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Marcellus fm. gas well Tioga County, PA

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Representative gas shows for Catskill/Lock Haven from completion

reports of Upper Devonian &

Marcellus wells

Source: well completion reports on file w/PA Geological Survey

Catskill/Lock Haven is the aquifer system

in many areas of NE. Pennsylvania

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Well completion reports with documented shallow gas shows

Source: well completion reports on file w/PA Geological Survey

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Water supplies with background dissolved phase and gas phase methane – (pre-contemporary Marcellus fm. well drilling)

Methane was found as a background condition in water supply wells in all counties of our study area

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Background δ13C1 and δDC1 compositions for dissolved phase and gas phase methane (pre-contemporary Marcellus fm well drilling activity)

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Mixed Gases

Our data reveals shallow microbial gas and mixed microbial/thermogenic

gas in glacial drift/bedrock in the western part of our study area, and thermogenic gas of different thermal maturities in the shallow section of the Upper Devonian strata in the eastern part of our study area

Microbial, thermogenic, and mixed microbial/thermogenic gases occur in the aquifer systems (pre-contemporary Marcellus fm. well drilling)

Thermogenic gas of different thermal maturities occurs in the Catskill/Lock

Haven formations across our study area Distinct thermogenic gases evident throughout the Devonian system

In certain areas of the basin in NE PA, isotope data reveals reversals

(δ13C1>δ13C2>δ13C3) throughout section, & universally in the Marcellus formation

Isotope rollover…origin currently at debate, important because its presence

may define exploration “sweet spots” containing over pressure and increased gas production rates.

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