Life in the Frac Pit:The Microbiology of Unconventional Shale Gas

Extraction

John F. Stolz

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Unconventional Natural Gas Production Since 2000

Bcf/d

http://www.propublica.org/images/articles/methane/methane_graphic_475px_090424.gif

Simplified Steps In Hydraulic Fracturing

1. Water, sand and additives are pumped at extremely high pressures down the wellbore.

2. The liquid goes through perforated sections of the wellbore and into the surrounding formation, fracturing the rock and injecting sand or proppants into the cracks to hold them open.

3. Experts continually monitor and gauge pressures, fluids and proppants, studying how the sand reacts when it hits the bottom of the wellbore, slowly increasing the density of sand to water as the frac progresses.

4. This process may be repeated multiple times, in “stages” to reach maximum areas of the wellbore. When this is done, the wellbore is temporarily plugged between each stage to maintain the highest water pressure possible and get maximum fracturing results in the rock.

5. The frac plugs are drilled or removed from the wellbore and the well is tested for results.

6. The water pressure is reduced and fluids are returned up the wellbore for disposal or treatment and re-use, leaving the sand in place to prop open the cracks and allow the gas to flow.

http://www.hydraulicfracturing.com/Process/Pages/information.aspx

Dallas Ft Worth Airport

EUR (estimated ultimate recovery/well)Haynesville - 6.5 BcfeFayetteville - 2.4 BcfeBarnett - 2.65 Bcfe

Marcellus - 4.4 Bcfe

http://shale.typepad.com/

http://www.declineoftheempire.com/2010/04/a-miracle-in-the-marcellus-shale.html

IP Rate 3.5 mmcf/d1yr decline 75%

Jonah, Wyoming (Green River Basin)

Roan Plateau, ColoradoDISH Texas

Bradford County PA

Half of PA state forest leased

15,393+ permits, 7,425 drilled

Marcellus Drilling in PA

http://www.dep.state.pa.us/dep/deputate/minres/oilgas/2011PermitDrilledmaps.htm

*Non-Marcellus Permits issues -2239/Wells drilled -954

2012 (actual): 2,656 permits, 1,347 wells(permits filed and wells drilled slowed in latter part of 2012)

Symbol Description Sites

Red New since 2010 67

Yellow Present in 2010 & 2012 185

Orange Site restored since 2010 9

Green Site replanted since 2010 12

Washington County PAAugust 2012

143 households surveyed

33 households sampled

57 samples analyzed

Findings:56 respondents indicated changes in water quality or quantity

Color and smell most common

25 homes with Manganese above SMCL

Only 2 homes with total coliforms,1 home with both TC and E.coli

Contamination included Na, Ca, Mg, Sr, Ba, Cl, Br, Fe, Mn, and methane

Monterey Shale15.4 Billion barrels

USC study2.8 million jobs4.5 billion in tax

http://oilshalegas.com/montereyshale.html

Marcellus FactsNumber of permits (2005 through 2013) - 15,393Nnumber of wells (2005 through 2013) – 7,425Typical well pad acreage 4-6 Typical amount of drill cuttings 1,000 tonsTypical amount of water per stimulated well 3-5 million gallonsTypical amound of proppant (sand) 3 million poundsTypical amount of water in an impoundment: 10 acres, 15 million gallons*Typical amount of chemicals in frac fluid 500,000 gallons (0.5 X 1 million)

Typical Marcellus well produces ~5,200 Mcf/dTypical Decline rate 75% in the first yearEstimated Ultimate Recovery – 4.4 BcfeCurrent commodity price is $5.63 per million BTU (or thousand cf or Mcf)

TDS in flow back (produced) water: : 60,000 – 550,000 mg/L

*acre foot contains 325,851 gallons of water50 acre feet contain 16,292,550 gallons1030 BTU = 1 cubic foot

Fracking Ingredients

In the “old days”, wells would be fracked with diesel. Today a combination of surfactants, biocides, gelling and organics are used.

Stimulation Chemicals (http://www.talismanusa.com/what_we_do/fracturing-a-well.html)

Below is a list of the typical chemicals used on Marcellus Shale wells completed by Universal Well Services, Inc. along with their function and typical loadings.

FRP-121- FRP-121 is a granulated anionic polyacrylamide based friction reducer used to reduce the friction pressure in surface lines and down the well casing during pumping operations. The typical loading for FRP-121 is 3-5 lb/1000 gal throughout the entire treatment.

Flomax 70- Flomax 70 is a nonionic micro-emulsion surfactant used to increase the recovery of injected water into a well. It has a typical loading of 2 gpt. Flomax 70 can be run throughout the entire treatment or just during the first portion of the job.

EC6116A- EC6116A is a bromine based biocide used to quickly kill organisms encountered in oilfield operations. The typical loading for EC6116A is 0.25 gpt throughout the entire treatment.

Scalehib 100- Scalehib 100 is a liquid polymer based scale inhibitor used to control the precipitation of calcium carbonate, calcium sulfate, barium sulfate and strontium sulfate. The typical loading for Scalehib 100 is 55 gallons injected during the pad.

Water for Fracking (Monongahela River)

The Impoundment

Drilling Deeper

Courtesy B. Donnan, www.marcellus-shale.us

The Frac Job

The Refinery

8/29/12

The Produced Water

Emissions from Condensate Tanks

TO-15 analysis was done on each canister with a total of 73 componentstested for. The results, although not quantitative, found that the air surrounding the four condensate banks had measurable concentrations (e.g., above reporting limits) of dichlorofluoromethane, chloromethane, n- butane, n-hexane, n-heptane, toluene, and xylenes. In addition, the air surrounding one bank had measureable amounts of acetone as well as benzene, chloroform, cyclohexane and methyl ethyl ketone. It also had the highest concentration of n-butane measured (60 ug/m3 for canister 1 and 75 ug/m3 for canister 2). Another also had measurable amounts of benzene, chloroform, and cyclohexane as well as methyl ethyl ketone, while another had measurable amounts of trichlorofluoromethane.

Series # Chloride Bromide Sulfate

FB01 87.9 25.2 450.9

FB02 38278.9 192.0 489.2

FB03 49088.4 233.4 575.6

FB04 47285.3 219.7 562.1

FB05 47431.1 244.0 595.5

FB06 46813.3 242.9 602.4

FB07 53580.3 260.2 567.6

FB08 54137.8 251.5 561.7

FB09 54808.0 296.6 588.8

FB10 58589.9 316.6 602.1

FB11 59795.9 308.9 603.3

FB12 60836.7 352.7 660.8

FB13 65843.7 323.3 587.9

FB14 69910.5 339.2 604.8

FB15 73837.9 360.8 624.0

FB16 74116.3 362.1 611.7

FB17 75931.0 373.2 633.7

FB18 75859.3 356.8 622.6

FB19 77605.7 379.9 613.8

FB20 79845.9 383.0 571.6

FB21 81831.6 256.3 383.8

FB22 77635.4 392.4 538.7

FB23 75376.7 420.8 556.9

FB24 78273.8 442.1 581.3

ICS Analyses of Flow Back/Produced Water Series

Table 1: Anion data for impoundment water, coal mine effluent, and freshwater stream water Field Sample Field Sample Field Sample Field Sample Field Sample

Impoundment

Water Impoundment

Water Coal Mine Effluent

Freshwater Stream

Freshwater Stream

Unit Sample #1 Sample #2 Sample #3 Fonner Run Bates RunConductivity uS cm‐3 102,864 61,477 6,400 387 476

pH 5.38 5.67 7.53 7.91 7.67 Sulfate mg/L 8.64 10.21 3,826 25.07 24.46 Nitrate mg/L ND ND 1.81 0.11 0.58 Bromide mg/L 255 226 14.25 ND ND Chloride mg/L 30,683 27,700 1,241 1.29 6.00 Arsenic ug/L BDL BDL BDL BDL BDL

ND - not detected BDL - below detection limit

ICP-MS of selected ions from flowback and produced water (mg/L)

Element FB sample, ppm (5x dilution) IMP, ppm (5x dilution) Li 10.23 37.52 B 0.0019 4.72Be 154.68 bdl Na 40080.28 15907.95Mg 544.36 582.63 Al 0.004 0.027Si 23.66 12.08 P 0.237 0.316K 3440.28 194.23 Ca 5262.58 5613.82Ti bdl 0.167 V bdl bdlCr 0.035 bdl Mn 1.93 3.11Fe 30.56 3.80 Co bdl bdlNi bdl bdl Cu 0.132 0.004Zn 0.299 0.110 As 0.079 0.005Se 0.035 0.032 Sr 369.35 804.58Mo 0.316 0.011 Ag 0.373 bdlCd 0.0006 bdl Sn 0.0201 naSb 0.013 bdl Ba 4.17 103.55Tl 0.0304 bdl Pb 0.0528 0.017S 302.95 11.93

Comparison of Flowback Water and Impoundment Water Analyzed by ICP-OES

Changes in microbial composition over time (Mohan et al., 2013)

Mohan et al., 2013

Mohan et al., 2013

Recyling impoundment in Amwell, PA

Aeration needed to control anaerobic bacterial growth

Courtesy B. Donnan, www.marcellusCourtesy B. Donnan, www.marcellus--shale.usshale.us

Google EarthGoogle Earth

Impoundment composition

Cl: 31,000-52,000 mg/LBr: 340-805 mg/L

Na: 14,000 mg/LSr: 800-2245 mg/LBa: 109-185 mg/LLi: 30-78 mg/LAs: 500-800 ug/L

Phase contrast microscope images of enrichment biofilms A) Lone Pine B) SWPA

A.

B.

Frac Medium (1000 mL)60 g NaCl1.2 g KCl8 g CaCl21 g NH4 Cl1 g MgCl20.5 g KH2PO4

150 mg BaCl2100 mg FeCl22.75 g SrCl2 * 6H2O4.2g NaHCO3

strain LP

Salinivibrio costicola subsp. costicola DSM 11403; NCIMB 701

Salinivibrio costicola subsp. alcaliphilus DSM 16359

Salinivibrio siamensis

Salinivibrio costicola subsp. vallismortis DSM 8295

Salinivibrio proteolyticus DSM 19052

Enterovibrio coralii DSM 19135

Enterovibrio nigricans

Pseudoalteromonas mariniglutinosa DSM 15203; NCIMB 1770

Pseudoalteromonas prydzensis DSM 1423210072

65

100

5741

89

0.02

Bacillus firmus strain XP8 (JN863907)

SWP-clone

Bacillus firmus strain J22N (JX490066)

Bacillus firmus strain SEP-5 (KF22890)

Bacillus firmus strain GY-30 (KC774008)

Bacillus firmus strain SAH2 (KC431017)

87

4371

0.002

Conclusions

1.Flowback and Produced water are multi-phased (particulate/aqueous/organic) fluids that are characteristically high in total dissolved solids (TDS).

2.The major constituents as detected barium, boron, calcium, chloride, fluoride, iron, potassium, lithium, sodium, strontium, magnesium, manganese

3.We have formulated a medium with high TDS that mimics the inorganic constituents of the produced water.

4.Enrichment cultures from both flowback and impoundent water were clearly salt requiring (e.g., halophilic) with strains of Halomonas taeanensis, Marinobacterium rhizophilum, Nitrincola lacisaponensis, Arcobacter halophilus, and Arcobacter nitrofigilis

5.Strains of Bacillus firmus (SWPA) and Salinivibrio costicola (LP) where isolated and characterized. Both were found to tolerate a wide range of salt concentrations (up to 120 g/L) and pH .

6.These results suggest that the fluids associated with Marcellus Shale (e.g, flow back, produced, and impoundment waters) select for and are populated by halophilic and extremely halotolerant microbial species.

Biogas: methanogenesis from food waste, agriculture (beef cattle, dairy, chicken, swine), human.

Acknowledgements

Stolz LabTetiana Kondratyuk*Lucas Eastham*Jennifer Rutter*Samir JoshiOliver Dugas

U PittsburghDan Bain

FundingHeinz EndowmentsColcom Foundation

ICP-OES provided by Thermo Fisher (Richard Jack)

Special Thanks to the landowners, testing lab, and Kelvin Gregory (CMU) for providing samples