A PowerPoint presentation supposedly obtained by the LA Times that concludes nearby Marcellus Shale drilling and fracking likely caused methane migration in some area residents' water wells. The presentation contains data that supposedly originates with the EPA, although the EPA is not referenced anywhere in the document, nor is the document attributed to the EPA (nor footnoted). Therefore, the source of the document is suspect unless/until the EPA confirms that this document originated from their offices.

1. Determining the origin of methane
and its effect on the aquifer.

2. Agenda
 Geologic history
 Methane characteristics
 The ratio of carbon isotopes in methane.
 The unique ratio of hydrocarbons in the Marcellus
F iFormation
 Identifying the age of the methane.
 Th ff t th d d illi h th if  The effects methane and drilling have on the aquifer
and trend over time.
 Conclusions Conclusions.

3. EnvironmentEnvironment
of Deposition
Middle Devonian
(385 MA)

4. Osborn S G et al. PNAS 2011;108:8172‐8176

5. h h l h d b d dMethane is the principal hydrocarbon detected in
all stray natural gas migration incidents
 Exposure limit (gas phase): TLV‐TWA: 1,000 ppm (ACGIH, 10/2009)
 Methane (CH4) is the simplest paraffin hydrocarbon gas
 Methane is generated by microbial & thermogenic processes
 Flammable, colorless, odorless.
 Specific gra it 0 (NTP) air  Specific gravity: 0.555 (NTP) air = 1
 Explosive range: 5‐15% in ambient air
 Solubility in water: 26‐32 mg/l (1 atm.)y 3 g/ ( )
 Non toxic, no ingestion hazard
 Simple asphyxiant, explosion hazard
Methane can migrate as free gas or dissolved in the groundwater

6. Isotopic Balance
 Researchers have determined that there are common carbon
& hydrogen isotopic compositions or signatures for
thermogenic gas associated with coal & natural gas, drift gas,
So by collecting numerous gas samples of
known origin a database has been
d l d d fi i ti f
g g g g
and other near surface microbial gases .
 Natural carbon is nearly all isotope 12, with 1.11 percent being
isotope 13
developed and fingerprinting of gas
samples may performed.
isotope 13.
 Organic material contains less C‐13, because bacteria
/photosynthesis preferentially selects C‐12 over C‐13. p y p y 3
 Oil and natural gas typically show a C‐12 to C‐13 ratio similar
to that of the biological materials from which they are to have
originated originated.

7. Sh l GShale Gas
 Increasing formation  Increasing formation
temperature leads to diagnostic
methane/ethane and isotopic
ratios
The normal sequence of carbon isotopic compositions is:ratios
 Tight gas shales such as the
Marcellus often have uniquely
diagnostic isotopic reversals
δ13C methane (C1) < δ13C ethane (C2) < δ13C propane (C3) and < δ13C butane (C4)
δ13C1 < δ13C2 < δ13C3 and < δ13C4
diagnostic isotopic reversals
(e.g. δ13C‐CH4 heavier than
δ13C‐C2H6)
In the Marcellus they are fully reversed ‐ δ13C1 > δ13C2 > δ13C3
Also hydrogen isotopic compositions (δ2H) of C1 and C2 are also reversed.
 Uniquely identifiable when
paired with additional proxies
(e.g. noble gases)

8. I t G h i tIsotope Geochemistry
Easily Distinguishes:
 Molecular: Methane/Ethane
 Isotopic: Carbon and
Biogenic vs. Thermogenic
(e.g. Schoell, 1983; Coleman et al, 1991;
Baldassare and Laughrey, 1998)
Hydrogen isotopes (δ13C‐CH4,
δ2H‐CH4, δ13C‐C2H6)
 N bl G
Distinguishing different
thermogenic gases
(e.g. Schoell et al, 1983; Jenden et al, 1993;
 Noble Gases Revesz et al, 2010; Tilley et al, 2010)
? What’s best for distinguishing
thermally mature gases?y g

9. 13 C fractionation
2 H fractionation
% argon
2 H fractionation
% argon
‐29
‐160
% nitrogen

10. HW04
HW02zHW05
HW12
HW17
HW24
HW02
HW14
HW06
HW08a
HW12
HW01

11. Sample Quality ‐ degassing?Sample Quality degassing?
ideal

13. Three Patterns of Contamination
1. Short term (< 1 year) disruption to the aquifer
caused by drilling.
( ) di i i i 2. Long term (> 3‐4 year) disruption or contamination
of the aquifer caused by drilling/fracking, releases or
other situationsother situations.
3. Natural Background Conditions with high levels
of metals and anions.

14. Type 1: Short Term Disruption

15. HW04Gas Well Activity
HW04
1000
1200
25000
30000
35000
Baker Wells ‐ 1,300 ft to SSE
Spud ‐ Baker 1 11 Aug. 2008
‐ Baker 2 11 Dec. 2009
Methane isotope sample probably
plots outside Marcellus Shale age
zone. (interestingly the gas
appears older, maybe deeper than
Marcellus Shale)
400
600
800
5000
10000
15000
20000
0
200
4
‐10000
‐5000
0
5
10‐Aug‐08 26‐Feb‐09 14‐Sep‐09 2‐Apr‐10 19‐Oct‐10 7‐May‐11 23‐Nov‐11g 9 4 p 9 p 9 y 3
Methane_ug_l Eh in Mv
Linear (Methane_ug_l) Linear (Eh in Mv)
Normal range of Eh in groundwater
is 200 to ‐100 Mv. Freshwater
streams 300 to 500 Mv.
9 pH
6
7
8
9 p
4
5
12‐May‐08 28‐Nov‐08 16‐Jun‐09 2‐Jan‐10 21‐Jul‐10 6‐Feb‐11 25‐Aug‐11
Analysis_Ph_ph_Units

16. 80018000 HW‐7
600
700
12000
14000
16000
l
Gas Well Activity
Baker Wells ‐ 1,300 ft to SSE
Spud ‐ Baker 1 11 Aug. 2008
‐ Baker 2 11 Dec. 2009
400
500
8000
10000
12000
Methane in ug/l
100
200
300
2000
4000
6000
00
2000
9‐Sep‐08 28‐Mar‐09 14‐Oct‐09 2‐May‐10 18‐Nov‐10 6‐Jun‐11 23‐Dec‐11
M h l Eh M M /l Li (M h l) Li (Eh M ) Li (M /l)Methane_ug_l Eh Mv Manganese ug/l Linear (Methane_ug_l) Linear (Eh Mv) Linear (Manganese ug/l)
8
8.5
pH
7
7.5
12/18/2008 3/28/2009 7/6/2009 10/14/2009 1/22/2010 5/2/2010 8/10/2010 11/18/2010 2/26/2011 6/6/2011 9/14/2011 12/23/2011

17. 45014000 HW17
350
400
45
12000
4
250
300
8000
10000
g/l
& Mnin ug/l
Methane isotope
sampling indicate
Marcellus Shale age
100
150
200
4000
6000
Methane in mg
Eh in Mv
Marcellus Shale age
gas at this data point
.
0
50
100
0
2000
M
Eh Mv Mn ug/l Methane ug/l Eh Trend Methane Trend
G ll S d i
Note incomplete data set
Gas Well Date Spud Distance to HW17
Lewis 5/28/2008 670 ft.
Ely 4H & 6H 3/27/2008 1,360 ft.
Costello 1 7/16/2008 1,350 ft.

18. 50045
HW1 ‐ Hubert
300
400
30
35
40
Methane isotope
sampling indicate
Marcellus Shale age
gas at this data point
g/l
200
300
20
25
30
Eh in Mv
Gesford 3 spud
July 28, 2008
Methane in mg
0
100
5
10
15
M
‐1000
16‐Dec‐08 16‐Apr‐09 16‐Aug‐09 16‐Dec‐09 16‐Apr‐10 16‐Aug‐10 16‐Dec‐10 16‐Apr‐11 16‐Aug‐11 16‐Dec‐11
Methane mg/l Eh in Mv Methane Trend Eh Trend
HW1 lacked data for nearly all constituents,
particularly for the years 2009‐2010

19. Type 2: Long Term Disruption

20. 45030 Gesford 2
HW8
Methane isotope sample
Methane and Manganese
300
350
400
20
25
Remediation of well
on April 1, 2009
Methane isotope sample
plots outside Marcellus
Shale age zone.
Gesford 2
Spud Sept. 23, 2008
Stimu Nov‐ Dec 2008
100
150
200
250
10
15
0
50
0
5
29‐Oct‐08 17‐May‐09 3‐Dec‐09 21‐Jun‐10 7‐Jan‐11 26‐Jul‐11 11‐Feb‐12
Methane in mg/l Mn in ug/l Linear (Methane in mg/l) Linear (Mn in ug/l)Methane in mg/l Mn in ug/l Linear (Methane in mg/l) Linear (Mn in ug/l)
7
8
9
605
705
pH ‐ Eh
2
3
4
5
6
7
205
305
405
505
0
1
5
105
29‐Oct‐08 17‐May‐09 3‐Dec‐09 21‐Jun‐10 7‐Jan‐11 26‐Jul‐11 11‐Feb‐12
Eh in Mv Analysis_Ph_ph_Units Linear (Eh in Mv) Linear (Analysis_Ph_ph_Units)

22. Gas is Gas
0
500
Interbedded
sandstone,
siltstone
Gas is Gas
 Thermogenic gas is present
throughout the upper Devonian
1,000
Catskill
& shale
g pp
formations. Drilling creates
pathways, either temporary or
permanent, that allows gas to
migrate to the shallow aquifer
1,500
2,000
Sandstone
surface
migrate to the shallow aquifer
near surface.
 Shallower (non Marcellus) gas
may also include higher amounts
2,500
Gas shows
h beneath s
may also include higher amounts
of H2S which can have a greater
impact on groundwater.
 In some cases these gases
3,000
3,500
interbedded
siltstone and
shale
Depth
 In some cases, these gases
disrupts groundwater quality
4,000
From Gesford 2 Well Record and Completion Report
4,500
5,000
Tully Limestone
Gas show

23. 600
700
18.00
20.00
Maye ‐HW 14
Mn x 10,000
Eh in mV
Mn_mg_l
Methane ‐ mg/l
‐Postdrill‐
Mn 62 ug/l
TSS 35.5 mg/l
TDS 127 mg/l
Methane isotope
sampling indicate
Marcellus Shale age
600
700
18,000.00
20,000.00
‐HW 14
‐Postdrill‐
Mn 62 ug/l
TSS 35.5 mg/l
TDS 127 mg/l
Fe 3 38 mg/l
Methane isotope
sampling indicate
500
600
14.00
16.00
g
Fe 3.38 mg/l
Cl‐ 12.7 mg/l
Major rain event
10" 7 9 Sept 2011
gas at this data point
.
500
600
14,000.00
16,000.00
Mn x 10,000
Fe 3.38 mg/l
Cl‐ 12.7 mg/l
Marcellus Shale age
gas at this data point
.
G W ll A i i
400
12.00
Predrill
10 7‐9 Sept 2011
400
12,000.00 Eh trend
h d
Gas Well Activity
Baker Wells 1,100 ft. east
Spud ‐ Baker 1 11 Aug. 2008
‐ Baker 2 11 Dec. 2009
300
8.00
10.00 ‐Predrill‐
Mn ‐ na
TSS <5 mg/l
TDS 149mg/l
Fe 0.03mg/l
Cl‐ 7.9mg/l
300
8,000.00
10,000.00 methane trend
200
4.00
6.00
200
4,000.00
6,000.00
‐Predrill‐
Mn ‐ na
TSS <5 mg/l
0
100
0.00
2.00
100
2,000.00
TSS <5 mg/l
TDS 149mg/l
Fe 0.03mg/l
Cl‐ 7.9mg/l
00.00

24. 12040
HW‐2
80
100
120
30
35
40
l
Mn
Methane isotope
sampling indicate
Marcellus Shale age
40
60
15
20
25
Methane mg/
Mn
ug/l
Stimulation
30 Sept. 09
Completion
12 Sept. 2008
g
gas at this data point
.
1.80
12.50
3.20
0
20
0
5
10
Arsenic ug_l
Manganese_ug_l
Methane mg l
Costello 1V 2V
Spud Date: 7/26/08 8/19/08
C D / / 8 / / 8 l d Methane_mg_lComp Date 9/12/08 11/11/08
Stim Date 9/30 /09 1/10/09
Note incomplete data set

25. 70300
HW6
Gesford 3 & 9 remediation
Methane isotope sampling
indicate Marcellus Shale
age gas at this data point
50
60
150
200
250
v
May 23 & 24, 2010
age gas at this data point
10x ug/l
30
40
50
100
150
Eh in Mv
Gesford 3 spud
July 28, 2008
mg/l As
10
20
‐50
0
y
Methane
0‐100
Eh in Mv Methane mg/l Arsenic ug/lEh in Mv Methane mg/l Arsenic ug/l
7
9
11
5
7
9‐Jul‐08 9‐Jan‐09 9‐Jul‐09 9‐Jan‐10 9‐Jul‐10 9‐Jan‐11 9‐Jul‐11 9‐Jan‐12
pH

26. 70300
HW6
50
60
150
200
250
Mv
As 10x
30
40
50
100
150
Eh in M
ane mg/l
Graph Cautions:
Data was selected on basis of the most representative of well conditions .
Due to incomplete data description, in some cases data may not be
representative of the well or the data was not plotted. Due to this
10
20
‐50
0
Meth
ug/l
uncertainty, trend may differ with different data use.
0‐100
9‐Jul‐08 9‐Jan‐09 9‐Jul‐09 9‐Jan‐10 9‐Jul‐10 9‐Jan‐11 9‐Jul‐11 9‐Jan‐12
Eh in Mv Methane mg/l Arsenic ug/l Linear (Eh in Mv) Power (Methane mg/l)
7
9
11
5
7
9‐Jul‐08 9‐Jan‐09 9‐Jul‐09 9‐Jan‐10 9‐Jul‐10 9‐Jan‐11 9‐Jul‐11 9‐Jan‐12
pH

27. Type 3: Naturally Occurring
Contamination

28. 350
400
16000
18000
HW47 ‐
No isotope
250
300
12000
14000
Mv&
in ug/l
l
No isotope
sample collected
150
200
8000
10000
Eh in M
Arsenic
Methane in mg/l
Post 1
No 20 0
100
150
4000
6000
Arsenic ug/l
M
Nov. 11, 2010
0
50
0
2000
Arsenic ug/l
Methane ug/l
Eh in Mv
When no data is plotted,
no data was available.

29. Conclusions
 Methane is released during the drilling and perhaps during the fracking
process and other gas well work.
 Methane is at significantly higher concentrations in the aquifers after gas  Methane is at significantly higher concentrations in the aquifers after gas
drilling and perhaps as a result of fracking and other gas well work.
 The methane migrating into the aquifer is both from the shallower
( ) f ti d ld M ll Sh l ( d h (younger age) formations and older Marcellus Shale (and perhaps even
older formations).
 Methane and other gases released during drilling (including air from the
drilling) apparently cause significant damage to the water quality.
 In some cases the aquifers recover (under a year) but, in others cases the
damage is long term (greater than 3 years).damage is long term (greater than 3 years).