Sunday, October 5, 2014

ARE THE LAND AND WATER RESOURCES SAFE FROM HYDRAULIC FRACTURING ACTIVITIES?



ARE THE LAND AND WATER RESOURCES SAFE FROM HYDRAULIC FRACTURING ACTIVITIES?
The simple answer is of course, no.  There is no human activity that is completely safe for the land and water resources:  from domestic wastewater generation, handling and disposal, to drilling for oil and gas, to oil transportation through tankers or pipelines, to chemical manufacturing, to mining and mining waste, and so on, there are risks and consequences associated with every activity, including broken pipes, improperly designed or constructed wells or equipment, human errors, noise pollution, dust, carcinogenic crystalline frac sand, radioactive wastewater and solid waste, heavy truck traffic, and so on.  The 2010 BP Deepwater Horizon oil spill in the Gulf of Mexico comes to our mind as a prime example of an activity that can create havoc to the land and water resources through human error and/or criminal conduct.  We believe that the key to safeguarding our resources is to understand what we are doing, the individual process components involved and to take steps to minimize the risk.
Perhaps many of you have seen the images of the toppled fracking tanks (Figure 1) and other infrastructure during the Colorado floods in Weld County or the dumping of fracking fluids in unlined pits in California (Figure 2) and began to question the environmental risk (and as result the potential liability to the insurer or the insured) created by such activities.  This blog attempts to answer some of these concerns.


Figure 1.  Overturned holding tanks in Colorado following flooding of the fracking fields.



Figure 2.  Illegal discharge of fracking fluids into an unlined pit in California.  The drilling company was fined over $60,000.

As more attention is paid by the public to incidents of contamination of the land and water resources by hydraulic fracturing, it is clearly becoming obvious that there is significant dispute regarding the effects of such activities on the human health and environment.  These disputes arise because there is not much information available, in the form of comprehensive long-term studies, on the effect of the hydraulic fracturing activities on the groundwater and surface water resources.  The key problem is that alleged incidents of oil or gas migration require investigations at the site-specific level and evaluation and synthesis of multiple data types to determine the source of the stray gas; this is an expensive proposition considering the length of the monitoring wells and the required sampling.   Thus so far the parties are just sniping at each other and we are merely waiting for more environmental incidents to happen for further regulation or other scrutiny to take place.
WHAT IS HYDRAULIC FRACTURING?
Hydraulic Fracturing (also known as “hydrofracking, or “fracking”) has received considerable public attention due to recent drilling activity in the Marcellus Shale in the Appalachian region, the Barnett Shale in Texas, and the Bakken Shale in North Dakota and Montana.  Hydraulic fracturing, along with horizontal drilling and the increased price of oil products, has made previously-inaccessible natural gas and petroleum resources in “tight” or “unconventional” reservoirs producible in economic quantities.  The application of these technologies has greatly expanded U.S. oil and natural gas production over the past ten years.
Hydraulic fracturing produces fractures in the rock formation through which the natural gas or oil can flow.  Wells may be drilled vertically thousands of feet below the land surface and may include horizontal or directional sections extending thousands of feet.
Fractures are created by pumping large quantities of fluids (water, sand and chemical additives) at high pressure down a perforated well casing and into the target rock formation.  Ninety-nine percent (99%) of the hydraulic fracturing fluid commonly consists of water and sand.  The sand helps keep the fractures open for the oil or gas to freely flow.  A number of chemical additives (about one percent of the volume of the fracking fluid) are also added to the subsurface to reduce friction, prevent iron, scale and corrosion and to control bacteria from clogging the formation. These fractures can extend several hundred feet away from the wellbore.  Figure 3.

                                             Figure 3.  Fracking Schematic

During the completion phase of an oil/gas well, fresh water is used to fracture the shale formation.  A typical multi-stage fracking process uses at least 100,000 barrels of fresh water.  When this water “flows back” it is salty and may contain the injected chemicals plus naturally occurring materials such as brines, metals, radionuclides, and hydrocarbons.  The flowback water must be transported away from the drilling site and disposed of in a permitted disposal well.  The need for disposal of flow-back water occurs only during the drilling of a new well, however flow-back water disposal is often the second-largest expense of drilling a new well.
Water that comes to the surface during the normal oil or gas production process is naturally occurring briny water that is generated from deep within the earth along with the oil and gas.  This water is called “produced water”.  The need to dispose of “produced water” is on-going and continues throughout the life of the oil/gas well.
The flowback and produced waters are typically stored on site in tanks or pits before treatment, disposal or recycling.  In many cases, it is injected underground for disposal.  In areas where that is not an option, it may be treated and reused or processed by a wastewater treatment facility and then discharged to surface water.
Other activities that are part of the oil and gas production include, but are not limited to: increased water usage, deforestation, dust, heavy truck traffic, blasting, sights and heavy flood lights on a 24/7 operation, flaring and venting of the gases, compressor stations for compression of the natural gas, storm water runoff, dehydrators, condensate tanks and other storage, erosion of the cleared areas, high pressure venting noises, loud gas flaring that emits pollutants into the air, and so on.
There have many debates surrounding the regulatory exemptions for hydraulic fracturing. It has been noted that if not for the exemption for hydraulic fracturing in the Energy Policy Act of 2005 or the RCRA exemption that exempts oil and gas waste from being designated as a hazardous waste, underground injection would have included fracking operations, and the EPA would have had the power to further regulate it as well as enforcing disclosure requirements.  Some say that these exemptions not only create inadequate regulations but also provide incentives for gas and oil companies to use chemicals that may increase the risks of exposure to local communities.  On the other side of this, the oil and gas industry, Congress, and some environmental groups support the idea that states, with greater knowledge about the local economic and ecological landscape, should control the regulatory specificities of fracking.
FRACKING ACTIVITIES THAT CAN RESULT IN CONTAMINATION OF THE ENVIRONMENT
The biggest by far problem is that many of these hydraulic fracking activities are exempt from federal regulations or are loosely regulated regarding the handling of hazardous or otherwise contaminated fluids or waste byproducts.  The states are mainly responsible for regulating these activities.  Highly sophisticated state regulators such as the NJDEP in New Jersey have placed a moratorium on fracking; other states should take a hint from New Jersey.  We believe that it is important to ensure that the practice will not harm health, safety, air, land, water or water security, considering the significant amounts of water required fro fracking.
·         Oil and natural gas wells flow back water throughout their production lifespan, which produces a constant and known demand for disposal.
·         The high pressures used to crack the rocks can create fractures that can extend half a mile or more.
·         The drilling companies add biocides, surfactants, flocculants, corrosion inhibitors, acids, etc. into the production fluid to prevent the swelling of the formation clay (the shale) and the self-sealing of the wells.  Many of these additives are not regulated or known.
·         The pit liners can tear or the pits overflow due to hard to control fluids or piping/fittings brake resulting in spillages. See Figure 3.
·         The spill containment facilities maybe undersized or located in flood plains.
·         Very little attention has been placed on the short-circuiting of the fracking fluids through existing boreholes or through natural faults.
·         The shale formation is not known (i.e., mapped) with much certainty, as the oil and gas industry typically claims.  These rock formations have faults that are not known and where the fracking fluids can enter and contaminate the subsurface.
·         Very significant truck traffic, noise, lights, dust, compressor noise, flaring, air emissions, and so on.

                                 Figure 4.  Lining and pit holding capacity issues

The point we want to make is that accidents happen in every process.  Hydraulic fracking is no exception and impacts to the environment have already occurred and are bound to occur in the future.  Both the proponents and the opponents need to get together to develop procedures that minimize the damage to the human health and the environment when sudden or accidental releases occur or releases caused by recklessness, negligence or other human errors.
Gas Sources
Methane and other light hydrocarbon gases may originate through a number of different mechanisms depending on the geologic environment.  These gases are formed by the decomposition of organic matter in the absence of oxygen.  In general, the gas formation processes may generally be classified as either biogenic or thermogenic.  The biogenic gas is concentrated at the shallower depths, with gradation with depth to thermogenic origin.  This classification of the gas origin is important in determining the fate and transport of the gas during fracking activities as it results in different gas composition, different stable isotopic signature and different source.  Determination of the stable-carbon isotopic composition and the stable-hydrogen isotopic composition generally makes it possible to distinguish methane formed in natural gas from methane formed in landfills, or in coalbed gas or in glacial drift gas or in shale gas. 
Heavy isotopes get left behind during the process of methane formation. Methane molecules formed both thermogenically and bacteriogenically contain more light H and C relative to the source material from which the methane was made (such as acetate, or organic material within the shale). The amount of fractionation that has occurred is denoted with the symbol “δ”.  It should be noted however that the processes of mixing of the various types of gases, migration of gas in the subsurface and bacterial oxidation all have the potential to impede a clear diagnosis of methane gas origin (i.e., whether it came from thermogenic gas due to fracking) or it is a shallower bacterial-produced methane.
Potential Migration Pathways
Further investigation is necessary to determine mechanisms of aqueous and gas phase transport in the area of investigation. However, at least three mechanisms can be postulated at this time. The first mechanism is aqueous and/or gas transport via boreholes due to insufficient or inadequate cement outside production casing.  
The second mechanism is fracture fluid excursion from thin discontinuous tight sandstone units into sandstone units of greater permeability. This would be accompanied by physical displacement of gas-rich solutions in both tight and more permeable sandstone formations.
A third mechanism is that the process of hydraulic fracturing generates new fractures or enlarges existing ones above the target formation, increasing the connectivity of the fracture system.
In all three transport pathways, a general correlation (spatial relationships ultimately determined by fault and fracture systems in addition to lithology) would exist between proximity to gas production wells and concentration of aqueous and gas phase constituents in ground water.
It is helpful to sample groundwater wells prior to and during development of the shale gas wells.  Only periodic sampling will help establish if groundwater wells already containing entrained dissolved gas become contaminated with gas from an adjacent oil and gas well.
What Chemical Additives Are Used
As previously noted, chemicals perform many functions in a hydraulic fracturing job.  Although there are dozens to hundreds of chemicals which could be used as additives, there are a limited number which are routinely used in hydraulic fracturing.  The following is a list of the chemicals used most often.  This chart is sorted alphabetically by the Product Function to make it easier for you to compare to the fracturing records .
Chemical Name
CAS
Chemical Purpose
Product Function
Hydrochloric Acid
007647-01-0
Helps dissolve minerals and initiate cracks in the rock
Acid




Glutaraldehyde
000111-30-8
Eliminates bacteria in the water that produces corrosive by-products
Biocide
Quaternary Ammonium Chloride
012125-02-9
Eliminates bacteria in the water that produces corrosive by-products
Biocide
Quaternary Ammonium Chloride
061789-71-1
Eliminates bacteria in the water that produces corrosive by-products
Biocide
Tetrakis Hydroxymethyl-Phosphonium Sulfate
055566-30-8
Eliminates bacteria in the water that produces corrosive by-products
Biocide




Ammonium Persulfate
007727-54-0
Allows a delayed break down of the gel
Breaker
Sodium Chloride
007647-14-5
Product Stabilizer
Breaker
Magnesium Peroxide
014452-57-4
Allows a delayed break down the gel 
Breaker
Magnesium Oxide
001309-48-4
Allows a delayed break down the gel 
Breaker
Calcium Chloride
010043-52-4
Product Stabilizer
Breaker




Choline Chloride
000067-48-1
Prevents clays from swelling or shifting
Clay Stabilizer
Tetramethyl ammonium chloride
000075-57-0
Prevents clays from swelling or shifting
Clay Stabilizer
Sodium Chloride
007647-14-5
Prevents clays from swelling or shifting
Clay Stabilizer




Isopropanol
000067-63-0
Product stabilizer and / or winterizing agent
Corrosion Inhibitor
Methanol
000067-56-1
Product stabilizer and / or winterizing agent
Corrosion Inhibitor
Formic Acid
000064-18-6
Prevents the corrosion of the pipe
Corrosion Inhibitor
Acetaldehyde
000075-07-0
Prevents the corrosion of the pipe
Corrosion Inhibitor




Petroleum Distillate
064741-85-1
Carrier fluid for borate or zirconate crosslinker
Crosslinker
Hydrotreated Light Petroleum Distillate
064742-47-8
Carrier fluid for borate or zirconate crosslinker
Crosslinker
Potassium Metaborate
013709-94-9
Maintains fluid viscosity as temperature increases
Crosslinker
Triethanolamine Zirconate
101033-44-7
Maintains fluid viscosity as temperature increases
Crosslinker
Sodium Tetraborate
001303-96-4
Maintains fluid viscosity as temperature increases
Crosslinker
Boric Acid
001333-73-9
Maintains fluid viscosity as temperature increases
Crosslinker
Zirconium Complex
113184-20-6
Maintains fluid viscosity as temperature increases
Crosslinker
Borate Salts
N/A
Maintains fluid viscosity as temperature increases
Crosslinker
Ethylene Glycol
000107-21-1
Product stabilizer and / or winterizing agent.  
Crosslinker
Methanol
000067-56-1
Product stabilizer and / or winterizing agent.  
Crosslinker




Polyacrylamide
009003-05-8
“Slicks” the water to minimize friction 
Friction Reducer
Petroleum Distillate
064741-85-1
Carrier fluid for polyacrylamide friction reducer
Friction Reducer
Hydrotreated Light Petroleum Distillate
064742-47-8
Carrier fluid for polyacrylamide friction reducer
Friction Reducer
Methanol
000067-56-1
Product stabilizer and / or winterizing agent.  
Friction Reducer
Ethylene Glycol
000107-21-1
Product stabilizer and / or winterizing agent.  
Friction Reducer




Guar Gum
009000-30-0
Thickens the water in order to suspend the sand
Gelling Agent
Petroleum Distillate
064741-85-1
Carrier fluid for guar gum in liquid gels
Gelling Agent
Hydrotreated Light Petroleum Distillate
064742-47-8
Carrier fluid for guar gum in liquid gels
Gelling Agent
Methanol
000067-56-1
Product stabilizer and / or winterizing agent.  
Gelling Agent
Polysaccharide Blend
068130-15-4
Thickens the water in order to suspend the sand
Gelling Agent
Ethylene Glycol
000107-21-1
Product stabilizer and / or winterizing agent.  
Gelling Agent




Citric Acid
000077-92-9
Prevents precipitation of metal oxides
Iron Control
Acetic Acid
000064-19-7
Prevents precipitation of metal oxides
Iron Control
Thioglycolic Acid
000068-11-1
Prevents precipitation of metal oxides
Iron Control
Sodium Erythorbate
006381-77-7
Prevents precipitation of metal oxides
Iron Control




Lauryl Sulfate
000151-21-3
Used to prevent the formation of emulsions in the fracture fluid
Non-Emulsifier
Isopropanol
000067-63-0
Product stabilizer and / or winterizing agent.  
Non-Emulsifier
Ethylene Glycol
000107-21-1
Product stabilizer and / or winterizing agent.  
Non-Emulsifier




Sodium Hydroxide
001310-73-2
Adjusts the pH of fluid to maintains the effectiveness of other components, such as crosslinkers 
pH Adjusting Agent
Potassium Hydroxide
001310-58-3
Adjusts the pH of fluid to maintains the effectiveness of other components, such as crosslinkers 
pH Adjusting Agent
Acetic Acid
000064-19-7
Adjusts the pH of fluid to maintains the effectiveness of other components, such as crosslinkers 
pH Adjusting Agent
Sodium Carbonate
000497-19-8
Adjusts the pH of fluid to maintains the effectiveness of other components, such as crosslinkers 
pH Adjusting Agent
Potassium Carbonate
000584-08-7
Adjusts the pH of fluid to maintains the effectiveness of other components, such as crosslinkers 
pH Adjusting Agent




Copolymer of Acrylamide and Sodium Acrylate
025987-30-8
Prevents scale deposits in the pipe
Scale Inhibitor
Sodium Polycarboxylate
N/A
Prevents scale deposits in the pipe
Scale Inhibitor
Phosphonic Acid Salt
N/A
Prevents scale deposits in the pipe
Scale Inhibitor




Lauryl Sulfate
000151-21-3
Used to increase the viscosity of the fracture fluid
Surfactant
Ethanol
000064-17-5
Product stabilizer and / or winterizing agent.  
Surfactant
Naphthalene
000091-20-3
Carrier fluid for the active surfactant ingredients
Surfactant
Methanol
000067-56-1
Product stabilizer and / or winterizing agent.  
Surfactant
Isopropyl Alcohol
000067-63-0
Product stabilizer and / or winterizing agent.  
Surfactant
2-Butoxyethanol
000111-76-2
Product stabilizer
Surfactant
One of the problems associated with identifying chemicals is that some chemicals have multiple names.  For example Ethylene Glycol (Antifreeze) is also known by the names Ethylene alcohol; Glycol; Glycol alcohol; Lutrol 9; Macrogol 400 BPC; Monoethylene glycol; Ramp; Tescol; 1,2-Dihydroxyethane; 2-Hydroxyethanol; HOCH2CH2OH; Dihydroxyethane; Ethanediol; Ethylene gycol; Glygen; Athylenglykol; Ethane-1,2-diol; Fridex; M.e.g.; 1,2-Ethandiol; Ucar 17; Dowtherm SR 1; Norkool; Zerex; Aliphatic diol; Ilexan E; Ethane-1,2-diol  1,2-Ethanedio.
This multiplicity of names can make a search for chemicals somewhat difficult and frustrating. However, if you search for a chemical by the CAS number it will return the correct chemical even if the name on the fracturing record does not match. For example if the fracturing record listed the chemical Hydrogen chloride and you searched for it by name using a chemical search site you may not get a result. But if you search for CAS # 007647-01-0 it might return Hydrochloric acid which is another name of Hydrogen chloride. Therefore, by using the CAS number you can avoid the issue of multiple names for the same chemical.
Multiple names for the same chemical can also leave you with the impression that there are more chemicals than actually exist.  If you search the National Institute of Standards and Technology (NIST) ‡ website the alternate names of chemicals are listed. This may help you identify the precise chemical you are looking for. The NIST site also contains the CAS numbers for chemicals. NIST is only one of many websites you can use to locate additional information about chemicals. You can also search the following websites using the chemical name or CAS number:
OSHA/EPA Occupational Chemical Database ‡
The Chemical Database ‡
EPA Chemical Fact Sheets ‡


METROPOLITAN’S GAS MIGRATION INVESTIGATION AND REMEDIATION EXPERIENCE

·         Investigated methane impacts at residential water supply wells near a gas production well in Pennsylvania.  The methane gas was found emitting from a well in the vicinity of a gas well, posing an explosion and health hazard.  Metropolitan performed a detailed review of the regional and site specific geology, the construction of the gas well, and performed a detailed review of the fracking and waste handling operations.  The investigation revealed that the well was located on top of coal seams; the coal seams would emit the coal-bed methane.  Isotopic analyses and detailed composition analyses of the gases from the water well, the gas production well and the coal seams indicated that the gas present in the water well was of similar composition to that from the coal seams and different from the gas produced at the gas well.  The conclusions were that the gas well was not the source of the methane inside the water supply well.  We also proposed and implemented a mitigation strategy for the methane in the residential water supply well.
·         Investigated methane impacts at residential water supply wells near a gas production well in New York.  Metropolitan performed a detailed review of the regional and site specific geology, the construction of the gas well, and performed a detailed review of the fracking and waste handling operations.  We also performed a video inspection of the water supply well and determined that it was installed through coal beds.  The coal seams would emit the coal-bed methane.  Isotopic analyses and detailed composition analyses of the gases from the water well, the gas production well and the coal seams indicated that the gas present in the water well was of similar composition to that from the coal seams and different from the gas produced at the gas well.  The conclusions were that the gas well was not the source of the methane inside the water supply well.
·         Metropolitan provided litigation support for a large number of litigation cases involving methane gas migration and  intrusion, toxic vapor gas migration and intrusion and petroleum hydrocarbon contamination involving refineries, bulk fuel oil terminals, gas service station sites, oil and gas exploration sites and brownfield sites.
·         Designed, installed and operated hundreds of methane and vapor gas recovery or remediation systems at landfills, industrial sites and brownfield sites.
·         For a confidential gas company, served as a testifying expert on issues related to alleged groundwater contamination from hydraulic fracturing activities.  Work included reconstruction of baseline groundwater condition prior to gas operations, tracking sources of organic and inorganic compounds in groundwater, and tracking sources of dissolved and gaseous methane using stable isotopes.
·         For gas production companies, designed and implemented forensic field programs to differentiate native gas from storage gas using composition and isotope analysis.
·         For gas companies, investigated sources of natural gas bubbling in residential water wells.  Used chemical fingerprinting including gas composition and isotope analysis to determine the origin of the gas in the water wells.
·         For a gas company in California and Pennsylvania, investigated storage gas migration from a storage field.  Using forensic and sampling results, calculated the percentage of storage gas vs native gas in a number of gas wells located near the leaking field.
·         Performed numerous field investigations to determine sources of methane in soil and water wells underneath newly constructed houses near brownfield sites.


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