### Paul Jehn The Ground Water Protection Council www.gwpc.orgIn 2010, U.S. shale gas production reached 4.87 Tcf (23 percent of total U.S. natural gas production), compared with 0.39 Tcf in 2000. This shows both the rapid growth and absolute importance of the shale gas resource to the United States. Rising production from shale gas resources has been credited with both lower natural gas prices and declining dependence on imported natural gas. As is often the case with resource development, shale gas production also has raised local environmental concerns, largely centering on the amount of water used in the fracturing process and the need to handle, recycle, and treat fracturing fluids in a manner that addresses the risk of spills that can potentially affect water quality. EIA's Annual Energy Outlook 2011 Reference case also reflects the growing importance of U.S. shale gas. It projects that shale gas will account for about 46 percent of U.S. natural gas production in 2035
. http ://www.eia.doe.gov/todayinenergy/detail.cfm?id=811 

### All land use activities have the potential to impact groundwater  

### Many land use activities use similar chemicals and compounds  

### Some of these chemicals and compounds can occur naturally 

### Chemicals used in HydroFrac operations  

### Geochemistry of the formation to be HF  

### Geochemistry of the USDW  

### Chemicals used in homes and nearby industry  

### Chemicals and compounds common to all of the above  

### Baseline and trend monitoring  

### Indicator chemicalsCompound Percent PPM Surfactant 0.0850 850 KCl 0.0600 600 Gelling Agent 0.0560 560 Scale Inhibitor 0.0430 430 pH Adjusting Agent 0.0110 110 Breaker 0.0100 100 Crosslinker 0.0070 70 Iron Control 0.0040 40 Corrosion Inhibitor 0.0020 20 Biocide 0.0010 10 Acid 0.1230 1230 Friction Reducer 0.0880 880 

### Surfactant: Glycol Ether  

### Gelling Agents: Benzene, Ethyl Benzene, Xlyenes , Toluene, Methyl Tert

- Butyl Ether  

### Biocides: Polynuclear Aromatics and Polycyclic Organics  

### Clay Stabilizers: Methanol  

### Crosslinkers : Formic Acid, Ammonium Chloride  

### Zirconium Nitrate and Sulfate  

### Buffers: Acetic Acid  

### Acidizing Treatment: Methanol 

### Acid  

### Iron Control Agent  

### Corrosion Inhibitor  

### Bactericide  

### Scale Inhibitor  

### Friction Reducer See PDF file for more detail 

### Uranium (10

- 100ppm, U 4+, 

### U 6+) 

### , Zinc, Iron, Sr , Cl , Na, Ca , Ba, As, Co, Pb , Cr, V  

### High TDS , Specific Conductance
 

### For more information on the geochemistry of the Marcellus Shale see: http://connect.sierraclub.org/app/render/go.asp x?g=9664c52f

-f718

- 4790

- 810a

- 667acb1aaf42&xsl=tp_SocialObjects_ObjectType _SIERRA_CLUB_ONLINE_COMMUNITIES_RESOURCE S_PUBLIC.xslt&id=9664C52F

- F718

- 4790

- 810A

- 667ACB1AAF42&cons_id=&ts=1303506080&sig nature=d8b40fb3068d36e7062d5d1d5815ca86 

### NORM 

### NORM occurs naturally throughout our environment from the sun and deep space, in our bodies, the food we eat, the places we live and work, and the ground we live on. Certain industrial processes, however, can cause NORM to accumulate at concentrations greater than natural background levels. The petroleum industry is one of several industries that generate large volumes of NORM

- bearing wastes. The petroleum industry, is one of several industries that generate large volumes of NORM

- bearing wastes. The sources of most of the radioactivity in petroleum industry wastes are the isotopes formed from the radioactive decay of uranium

- 238 (U

- 238) and thorium

- 232 (Th

- 232), which are naturally present in the subsurface formations from which oil and gas are extracted. The primary radionuclide of concern in NORM wastes is radium
- 226 of the U

- 238 decay series
. Radium
- 228 of the Th

- 232 decay series also occurs in NORM waste, but usually at lower concentrations. Other radionuclides of concern include those that form from the decay of Ra
- 226 and Ra
- 228.• Units

– μRoentgen/ hr (radiation exposure)

– μRem/ hr (also units of Sv or sieverts) (human dosage)

– pCi /g (concentration per mass)

– pCi /m

– Rads (also units of grays)

– μ = micro = millionth

– p = pico = billionthRadium is concentrated in scale and sludge when precipated with Ba

- , Sr

- , or Ca

- SO4
http://www.rrc.state.tx.us/environmen tal/publications/norm/NORMRRCsemin ar04.pdfRadium radionuclides emit alpha and beta particles as well as gamma rays. The radiation emitted from a Radium 226 atom is 96% alpha particles and 4% gamma rays. The alpha particle is the most dangerous particle associated with NORM. Alpha particles are helium nuclei. Alpha particles travel short distances in air, of only 2-3 centimeters and cannot penetrate through a dead layer of skin on the human body. However, alpha particles are "bone seekers" due to Radium possessing a high affinity for Chloride ions. In the case that Radium atoms are not expelled from the body, they concentrate in areas where Chloride ions are prevalent, such as bone tissue. The half
-life for Radium 226 is approximately 1620 years, and will remain in the body for the lifetime of the human; a significant length of time to cause damage. Beta particles are high energy electrons or positrons. They are in the middle of the scale in terms of ionizing potential and penetrating power, being stopped by a few millimeters of aluminum foil. This radiation is a small portion of the total emitted during Radium 266 decay. Radium 228 emits 100% beta particles, which are also a concern for human health through inhalation and ingestion. Beta particles are electrons or positrons and can travel farther than alpha particles in air. The gamma rays emitted from Radium 226, accounting for 4% of the radiation are harmful to humans with sufficient exposure. Gamma rays are highly penetrating and some can pass through metals, so Geiger counters with a scintillation probe are used to measure gamma ray exposures when monitoring for NORM. 

### The petroleum industry waste streams most likely to contain elevated radium concentrations include produced water, scale, and sludge. Radium, which is slightly soluble, can be mobilized in the liquid phases of a subsurface formation and transported to the surface in the produced water stream. As the produced water is brought to the surface, some of the dissolved radium precipitates out in solid form. Most commonly, the radium coprecipitates with barium sulfate, a hard and relatively insoluble scale deposit; however, it also can coprecipitate to form other complex sulfates and carbonates.

### Measurement of total radioactivity with a hand

- held radiation detection instrument permits rapid assessment of a site for NORM contamination , but site cleanup criteria and waste disposal options are based on actual concentrations of radium isotopes. Some specialized field instruments permit rapid estimates of the concentration of radium isotopes, but such estimates require confirmation by careful laboratory analysis of selected subsets of samples
. Radium concentrations are generally reported as picocuries/gram ( pCi /g) of solid material or picocuries/liter ( pCi /L) of water or air. A picocurie equals 2.22 disintegrations

- per- minute (dpm ). 

### Geothermal Energy Production Wastes  

### Oil and Gas Production Wastes  

### Coal Ash  

### Mining Wastes: uranium, fertilizer, aluminum

◦ http://www.epa.gov/radiation/tenorm/sources.htm l#summary

-tablehttp://www.epa.gov/radiation/tenor m/sources.html#summary

-table 

### http://norm.iogcc.state.ok.us / 

### U.S. Department of Energy, Office of Fossil Energy http ://www.fe.doe.gov/  

### American Petroleum Institute http ://api

- ec.api.org /  

### Nuclear Regulatory Commission http ://www.nrc.gov/  

### U.S. Environmental Protection Agency http://www.epa.gov/radiation/tenorm /  

### Interagency Steering Committee on Radiation Standards http://www.iscors.org /  

### International Commission on Radiological Protection http://www.icrp.org /  

### U.S. Geological Survey

-- NORM Fact Sheet http://pubs.usgs.gov/fs/fs

- 0142

- 99/fs

- 0142

- 99.pdf

### Can methane be use as an indicator for impacts to groundwater from HF operations? 

### CH 4  

### Colorless, odorless gas  

### Principal component of natural gas  

### The firedamp of coal mines is chiefly methane  

### Anaerobic bacterial decomposition of plant and animal matter, such as occurs under water, produces marsh gas, which is also methane
.

 Ref: http://scifun.chem.wisc.edu/chemweek/methane/methane.htmlMethane gas occurs naturally in groundwater aquifers in most geological sedimentary basins worldwide, including here in Alberta. Methane gas exists in a dissolved state in groundwater underground and will “bubble out” when pumped to the surface. For those on private water well supplies, spurting taps is a common result of this phenomenon
. Alberta Environment oversees a network of over 250 groundwater monitoring wells spread across the province. A monitoring program was initiated in 2006 to better understand the quality of groundwater in Alberta. The monitoring wells are tested for a variety of water quality parameters, including methane gas. A total of 126 wells have been accessed for gas sampling to date. Wells will be sampled every few years to monitor long

-term trends. http ://environment.alberta.ca/02883.html 

### Out of the 126 wells visited, 38 wells contained appreciable concentrations of methane gas (>3000 ppmv), 32 wells contained minor concentrations (<3000 ppmv) and 56 wells contained no measurable amounts of gas. M any wells with methane gas lie outside the coalbed methane development areas in Alberta and many wells with no gas lie within coalbed methane development areas
. http://environment.alberta.ca/02883.html

### In many places, groundwater naturally contains significant concentrations of methane. High concentrations of methane, sometimes at explosive levels, are known to occur in both NY and PA, and elsewhere (Osborn 2010; WV USGS 2006). This makes the mere detection of methane in private water wells an inadequate test for determining whether gas drilling has caused water contamination.

### Typical Composition of Natural Gas  

### Methane CH4 70

- 90%  

### Ethane C2H6 0

- 20%  

### Propane C3H8  

### Butane C4H10  

### Carbon Dioxide CO2 0

- 8%  

### Oxygen O2 0

- 0.2%  

### Nitrogen N2 0

- 5%  

### Hydrogen sulphide H2S 0

- 5%  

### Rare gases A, He, Ne, Xe trace 

### Methane gas can be biogenic or thermogenic depending on its origin.  

### Biogenic methane is produced by subsurface bacteria and is a common natural source of methane gas in groundwater aquifers used for water well supplies;  

### Thermogenic methane gas is produced at greater depths through high pressure and temperature processes and is characteristic of deep oil & gas reservoirs that conventional energy wells tap into; and  

### CBM gas tends to fall somewhere between these two components. Biogenic  Thermogenic Two distinct processes produce hydrocarbon gas: biogenic and thermogenic degradation of organic matter. Biogenic gas is formed at shallow depths and low temperatures by anaerobic bacterial decomposition of sedimentary organic matter. In contrast, thermogenic gas is formed at deeper depths by:  (1) thermal cracking of sedimentary organic matter into hydrocarbon liquids and gas (this gas is co

- genetic with oil, and is called "primary" thermogenic gas ), and  (2) thermal cracking of oil at high temperatures into gas ("secondary" thermogenic gas) and pyrobitumen
.  Biogenic gas is very dry (i.e., it consists almost entirely of methane). In contrast, thermogenic gas can be dry, or can contain significant concentrations of "wet gas" components (ethane, propane, butanes) and condensate (C 5+ hydrocarbons).Various data analyses can be used in conjunction to help determine whether gas in a monitoring well is of biogenic or thermogenic origin, or a mixture of the two. Methane gas typically contains a small amount of ethane. The proportion of methane to ethane in a gas can help determine its origin. Biogenic gas typically contains above 1000 times more methane than ethane. In addition, isotope data can also be used to help determine whether a gas is biogenic or thermogenic . Carbon isotope ratios have been reported for monitoring wells containing concentrations of methane gas above 3000 ppmv. Isotope values tend not to be reliable below this concentration.
 http://environment.alberta.ca/02883.htmlhttp://environment.alberta.ca/02883.h tml

### Thermogenic gas components (methane, ethane, propane) generated at a given thermal maturity contain, on average, isotopically heavier carbon than do the corresponding gas components generated at a lower thermal maturity. Relationships between gas isotopic compositions and source maturity have been calibrated, allowing the vitrinite reflectance equivalent (VRe) of the gas source to be estimated from the gas geochemistry (Faber, 1987; Berner and Faber, 1988; Berner, 1989). Biogenic methane, on average, contains isotopically lighter carbon (i.e., is more depleted in 13C) than thermogenic methane. Biogenic gas is also drier than many thermogenic gases. Ranges of gas composition corresponding to (i) bacterial gas, (ii) thermogenic, oil
-associated gas, (iii) dry, post-mature thermogenic gas, and (iv) gas of mixed biogenic/ thermogenic origin have been defined, facilitating the interpretation of gas compositional data (e.g., Schoell , 1983, 1988; Faber et al., 1992; Whiticar, 1994). In cases where gas seeps may be derived from biogenic decomposition of anthropogenic wastes ("landfill" gases), other tracers, such as 14C and tritium can be used to distinguish landfill gases from older biogenic gases unassociated with anthropogenic waste (Coleman, 1995).

### These techniques involve measurement of stable isotopes of carbon (C) and hydrogen (H) within methane (CH4) and related compounds , such as carbon dioxide (CO2), water (H2O), ethane (C2H6) and other hydrocarbons . The goal of this type of monitoring is to aid water well owners who wish to distinguish methane contamination that arises naturally from contamination resulting from nearby drilling activities http://wri.eas.cornell.edu/index_18_2774977203. pdf 

### While stable isotope monitoring can provide valuable information in the event of water contamination , it also has significant limitations. Conclusive results generally require extensive and coordinated sampling, incorporation of additional data related to geology, hydrology, and chemistry, and expertise in data interpretation
. For more information on Isotopes see http://wri.eas.cornell.edu/index_18_2774977203. pdf

### “Diagnosing methane contamination in groundwater and private drinking water wells is possible with the help of isotopic analyses. However, it is not necessarily an easy task, and can be limited by significant uncertainty.” http://wri.eas.cornell.edu/index_18_27749772 03.pdf

### Trend Monitoring, Pre

- Frac Baseline, Post Frac Analysis and Indicator Chemicals Major cations and anions  pH  Specific Conductance  Total Dissolved Solids  Nitrates  Dissolved methane  Benzene , Toluene, Ethyl benzene, Xylene (BTEX)/ Diesel Range Organics (DRO)/ Gasoline Range Organics (GRO)  VOC’s and Semi

-VOC ‘s  Total Petroleum Hydrocarbons or Oil & Grease ( HEM)  Arsenic  Barium  Calcium  Chromium  Iron  Magnesium 

### Selenium  

### Boron  

### Sodium  

### Chloride  

### Potassium  

### Bicarbonate  

## Dissolved Methane  

## NORM 

### If free gas or a dissolved methane concentration level greater than two (2) milligrams per liter (mg/l) is detected in a water well, gas compositional analysis and stable isotope analysis of the methane (carbon and deuterium) should be performed to determine gas type. 

### If the test results indicate biogenic gas, no further isotopic testing is necessary.  

### If the test results indicate thermogenic or a mixture of thermogenic and biogenic gas additional isotopic analysis should be performed to determine the source of the gas. 

### State Public Water Supply Records  

### State Monitoring Networks  

### State Permit Compliance Data  

### State Oil and Gas Agencies  

### US EPA: STORET http://www.epa.gov/STORET/  

### USGS: http://water.usgs.gov/owq/ 

### Baseline monitoring is necessary

◦ Is there data to show trends in data before the HF operation?  

### Post HF monitoring

◦ First level

 Methane

 NORM 

### RBDMS Water http://www.gaschem.com/determ.html  Berner, U., and E. Faber, 1988, Maturity related mixing model for methane, ethane and propane, based on carbon isotopes: Org. Geochem ., v. 13, p. 67

- 72.  Coleman, D. D., C.

- L. Liu, K. C. Hackley, and S. R. Pelphrey, 1995, Isotopic Identification of Landfill Methane: Environmental Geosciences, v. 2, p. 95

- 103
.  Faber, E., W. J. Stahl, and M. J. Whiticar, 1992, Distinction of bacterial and thermogenic hydrocarbon gases, in R. Vially, ed., Bacterial Gas, Paris, Editions Technip , p. 63

- 74.  Rice, D. D., 1993, Biogenic gas: controls, habitats, and resource potential, in D. G. Howell, ed., The Future of Energy Gases

- U.S. Geological Survey Professional Paper 1570, Washington, United States Government Printing Office, p. 583

- 606.  Schoell , M., 1983, Genetic characterization of natural gases: AAPG Bulletin, v. 67, p. 2225

- 2238.  Schoell , M., 1988, Multiple origins of methane in the earth: Chemical Geology, v. 71, p. 1

- 10.  Whiticar, M. J., 1994, Correlation of natural gases with their sources, in L. B. Magoon , and W. G. Dow, eds., The Petroleum System, From Source to Trap, AAPG, p. 261

- 283
.  http:// wri.eas.cornell.edu/index_18_2774977203.pdf The Role of Isotopes in Monitoring Water Quality Impacts Associated with Shale Gas Drilling