Determining the origin of methane and its effect on the aquifer. Agenda ? Geologic history ? Methane characteristics ? The ratio of carbon isotopes in methane. ? The unique ratio of hydrocarbons in the Marcellus Formation F i ? Identifying the age of the methane. ? Th ff t th The effects methane and drilling have on the aquifer d d illi h th if and trend over time. ? Conclusions Conclusions. I Environment ofDepoflflon Middle Devonian (385 MA) h h lh d b d d Methane 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 Specific gravity: 0.555 (NTP) air = 1 (NTP) air ? 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 Isotopic Balance ? Researchers have determined that there are common carbon So by collecting numerous gas samples of & hydrogen isotopic compositions or signatures for known origin a database has been thermogenic gas associated with coal & natural gas, drift gas, g g g g developed and fi d l d d fingerprinting of gas i ti f and other near surface microbial gases . samples may performed. ? Natural carbon is nearly all isotope 12, with 1.11 percent being isotope 13. isotope 13 ? Organic material contains less C-13, because bacteria p y p y 3 /photosynthesis preferentially selects C-12 over C-13. ? 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 Sh l G Shale Gas ? Increasing formation temperature leads to diagnostic methane/ethane and isotopic The normal sequence of carbon isotopic compositions is: ratios ?13C methane (C1) < ?13C ethane (C2) < ?13C propane (C3) and < ?13C butane (C4) ? Tight gas shales such as the Marcellus often have uniquely C2 < ? 13 C3 and < ? 13 C4 ? 13 C1 < ? 13 diagnostic isotopic reversals In the Marcellus they are fully reversed - ?13C1 > ?13C2 > ?13C3 (e.g. ?13C-CH4 heavier than ?13C-C2H6) Also hydrogen isotopic compositions (?2H) of C1 and C2 are also reversed. ? Uniquely identifiable when paired with additional proxies (e.g. noble gases) I t G h it Isotope Geochemistry Easily Distinguishes: ? Molecular: Methane/Ethane ? Isotopic: Carbon and Hydrogen isotopes (?13C-CH4, ?2H-CH4, ?13C-C2H6) ? N bl G Noble Gases ? Biogenic vs. Thermogenic (e.g. Schoell, 1983; Coleman et al, 1991; Baldassare and Laughrey, 1998) ? Distinguishing different thermogenic gases (e.g. Schoell et al, 1983; Jenden et al, 1993; Revesz et al, 2010; Tilley et al, 2010) ? What's best for distinguishing thermally mature gases? y g I gLHsoTEce ANALYSIS REPORT Lab 235438 Job 17407 Sample Namemumber: 13 fractionatioa Date Sampled: Container: Dissolved Gas Bottle Fieldrsite Name: ASTA 2 fractlonatlon Location: Formationmepth: Sampling Point: Dale 2!03f2012 0 cumpanem Cherlnical 5:0 $0 mo. Carbon Monoxide -- nd Hydrogen Sulfide -- na Helium 0.0112 Hydrogen -- nd Argon -- o.e2e -29 Oxygen -- 0.60 "160 Nitrogen -- 40.72 Carbon Dioxide 0.094 Methane -- 5106 -29.30 -1 60.6 Ethane -- 0.637 Ethylene -- nd 1'11t1'0ge1'1 Propane -- nd Propylene 0.0001 lao-butane -- nd N-bulane -- nd lso-pemane nd N-pentane - -- nd He:-canes -- nd water -64.6 -9.66 Total dry 60deg 1 4.?psia, calculated: 590 Specific gravity. calculated: 0.736 :53 CH4 -1ee-~ Water well samples I. Dissolved methane in water wells in gas--extraeti-an areas" within 1 km ef nearest gas well ilsetepie Signatures shewn based en figure Dsbern et aI..2i]11} DEE reductiian overlying HW HWP4 r'"n Ii' Upperanri Middie ?HWi'11iferriientaticin -se -50 -an -an al-as EH4 ran. !amp|e Quality - degassing? 100 I ideat . 0 EPA Samples 0 egassing/ Fra '0nati0n[Methane] Air Saturated Water Atmospheric Eh (V) 1.2 WATER 1 bar 1.4.3.5: -:12 5. Pl!' 414- bar -011:: +l]_Er +l]_Er +fl_-4 +fl_3 Eh In -11.1 -11-2 413 -114 -11-5 3 4 5 Fe++ Hn++ scnlubles ~'apH 7" Ffil Hfil Three Patterns of Contamination 1. Short term (< 1 year) disruption to the aquifer caused by drilling. 2. Long term (> 3-4 year) disruption or contamination ( ) di i i i of the aquifer caused by drilling/fracking, releases or other situations. other situations 3. Natural Background Conditions with high levels of metals and anions. Type 1: Short Term Disruption Gas Well Activity Baker Wells - 1,300 ft to SSE Spud - Baker 1 11 Aug. 2008 35000 - Baker 2 11 Dec. 2009 30000 HW04 Methane isotope sample probably plots outside Marcellus Shale age zone. (interestingly the gas appears older, maybe deeper than Marcellus Shale) 25000 20000 1200 1000 800 15000 600 10000 5 5000 4 400 0 200 -5000 -10000 10-Aug-08 g 0 26-Feb-09 9 14-Sep-09 4 p 9 2-Apr-10 p 19-Oct-10 9 Methane_ug_l Eh in Mv Linear (Methane_ug_l) 7-May-11 y Linear (Eh in Mv) 23-Nov-11 3 Normal range of Eh in groundwater is 200 to -100 Mv. Freshwater streams 300 to 500 Mv. p pH 9 8 7 6 5 4 12-May-08 28-Nov-08 16-Jun-09 2-Jan-10 21-Jul-10 Analysis_Ph_ph_Units 6-Feb-11 25-Aug-11 HW-7 18000 16000 700 Gas Well Activity Baker Wells - 1,300 ft to SSE Spud - Baker 1 11 Aug. 2008 - Baker 2 11 Dec. 2009 14000 Methane in ug/l l 800 12000 600 500 10000 400 8000 300 6000 200 4000 100 2000 0 9-Sep-08 Methane_ug_l M h l 0 28-Mar-09 Eh Mv Eh M 14-Oct-09 2-May-10 Manganese ug/l M /l 18-Nov-10 Linear (Methane_ug_l) Li (M h l) 6-Jun-11 Linear (Eh Mv) Li (Eh M ) 23-Dec-11 Linear (Manganese ug/l) Li (M /l) pH 8.5 8 7.5 7 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 HW17 14000 4 450 45 400 12000 10000 300 8000 M Methane in mg g/l Methane isotope sampling indicate Marcellus Shale age gas at this data point . 6000 250 200 150 4000 100 2000 50 0 0 Eh Mv Mn ug/l Gas Well G ll Date Spud S d Distance to HW17 i Lewis 5/28/2008 670 ft. Ely 4H & 6H 3/27/2008 1,360 ft. Costello 1 7/16/2008 1,350 ft. Methane ug/l Eh Trend Methane Trend Note incomplete data set Eh in Mv & Mn in ug/l 350 HW1 - Hubert 45 500 40 Methane isotope sampling indicate Marcellus Shale age gas at this data point 30 300 25 20 Gesford 3 spud July 28, 2008 200 100 15 10 0 5 0 16-Dec-08 -100 16-Apr-09 16-Aug-09 16-Dec-09 Methane mg/l 16-Apr-10 16-Aug-10 Eh in Mv 16-Dec-10 16-Apr-11 Methane Trend HW1 lacked data for nearly all constituents, particularly for the years 2009-2010 16-Aug-11 Eh Trend 16-Dec-11 Eh in Mv M Methane in mg g/l 35 400 Type 2: Long Term Disruption HW8 30 25 Gesford 2 Spud Sept. 23, 2008 Stimu Nov- Dec 2008 Gesford 2 Remediation of well on April 1, 2009 Methane and Manganese Methane isotope sample plots outside Marcellus Shale age zone. 450 400 350 20 300 250 15 200 10 150 100 5 50 0 29-Oct-08 0 17-May-09 3-Dec-09 Methane in mg/l 21-Jun-10 7-Jan-11 Mn in ug/l 26-Jul-11 Linear (Methane in mg/l) 11-Feb-12 Linear (Mn in ug/l) pH - Eh 705 9 8 7 6 5 4 3 2 1 0 605 505 405 305 205 105 5 29-Oct-08 17-May-09 Eh in Mv 3-Dec-09 Analysis_Ph_ph_Units 21-Jun-10 7-Jan-11 Linear (Eh in Mv) 26-Jul-11 Linear (Analysis_Ph_ph_Units) 11-Feb-12 {Bangle W6 0 Gas is Gas Gas is Gas 500 1,000 ? Thermogenic gas is present ? Shallower (non Marcellus) gas may also include higher amounts of H2S which can have a greater impact on groundwater. 1,500 Depth h beneath s surface throughout the upper Devonian g pp formations. Drilling creates pathways, either temporary or permanent, that allows gas to migrate to the shallow aquifer near surface. Interbedded sandstone, siltstone & shale Catskill Sandstone 2,000 2,500 Gas shows 3,000 interbedded siltstone and shale 3,500 ? In some cases these gases In some cases, these gases disrupts groundwater quality 4,000 4,500 From Gesford 2 Well Record and Completion Report Gas show Tully Limestone 5,000 20.00 20,000.00 18.00 18,000.00 16.00 16,000.00 14.00 14,000.00 12.00 12,000.00 10.00 10,000.00 8.00 8,000.00 700 700 -Postdrill- -Postdrill- Mn 62 ug/l Mn 62 ug/l TSS 35.5 mg/l TSS 35.5 mg/l TDS 127 mg/l TDS 127 mg/l Fe 3 38 mg/l Fe 3.38 mg/l Fe 3.38 mg/l Cl- 12.7 mg/l Cl- 12.7 mg/l Gas Well Activity G W ll A i i Baker Wells 1,100 ft. east Spud - Baker 1 11 Aug. 2008 - Baker 2 11 Dec. 2009 -Predrill- Predrill Mn - na TSS <5 mg/l TDS 149mg/l Fe 0.03mg/l Cl- 7.9mg/l 6.00 6,000.00 4.00 4,000.00 2.00 2,000.00 0.00 0.00 Maye -HW 14 Mn x 10,000 -HW 14 Mn x 10,000 Eh in mV Methane isotope sampling indicate Methane isotope Marcellus Shale Methane - mg/l sampling indicate age g gas at this data point Marcellus Shale age . gas at this data point . Mn_mg_l 600 600 500 500 Major rain event 10 7 9 Sept 2011 10" 7-9 Sept 2011 Eh trend 400 methane trend h d 300 200 -Predrill- Mn - na TSS <5 mg/l TDS 149mg/l Fe 0.03mg/l Cl- 7.9mg/l 400 300 200 100 100 0 0 HW-2 40 120 35 100 Methane isotope sampling indicate Marcellus Shale age g gas at this data point . Methane mg/l 30 25 20 15 Completion 12 Sept. 2008 80 Mn ug/l 60 Stimulation 30 Sept. 09 40 10 20 12.50 5 3.20 1.80 0 0 Arsenic ug_l Costello Spud Date: Comp Date C D Stim Date 1V 7/26/08 9/12/08 / / 8 9/30 /09 2V 8/19/08 11/11/08 / / 8 1/10/09 Manganese_ug_l Note incomplete data set l d Methane mg l Methane_mg_l Methane isotope sampling indicate Marcellus Shale age gas at this data point Gesford 3 & 9 remediation May 23 & 24, 2010 250 60 200 Eh in Mv 70 50 150 40 100 30 Gesford 3 spud 50 July 28, 2008 y 20 0 -50 10 -100 0 Eh in Mv Methane mg/l Arsenic ug/l 11 9 7 5 9-Jul-08 9-Jan-09 9-Jul-09 9-Jan-10 9-Jul-10 pH 9-Jan-11 9-Jul-11 9-Jan-12 Methane mg/l As 10x ug/l HW6 300 HW6 70 250 60 Eh in Mv 200 150 100 50 50 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 uncertainty, trend may differ with different data use. 0 30 20 10 -50 -100 9-Jul-08 40 0 9-Jan-09 Eh in Mv 9-Jul-09 Methane mg/l 9-Jan-10 9-Jul-10 9-Jan-11 Linear (Eh in Mv) Arsenic ug/l 9-Jul-11 9-Jan-12 Power (Methane mg/l) 11 9 7 5 9-Jul-08 9-Jan-09 9-Jul-09 9-Jan-10 9-Jul-10 pH 9-Jan-11 9-Jul-11 9-Jan-12 Meth ane mg/l As 10x ug/l 300 Type 3: Naturally Occurring Contamination HW47 - 18000 400 16000 350 No isotope sample collected 14000 M Methane in mg/l l 12000 250 10000 200 Eh in M & Mv Arsenic in ug/l 300 8000 Post 1 Nov. 11, 2010 No 20 0 150 6000 100 4000 50 2000 Arsenic ug/l Methane ug/l 0 0 When no data is plotted, no data was available. Eh in Mv 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 drilling and perhaps as a result of fracking and other gas well work. ? The methane migrating into the aquifer is both from the shallower (younger age) formations and older Marcellus Shale (and perhaps even ( ) f ti d ld M ll Sh l ( d h 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).