Tag Archives: Natural Resource Development

Any human development that extracts a natural resource.

Hydraulic Fracturing Impacts to Groundwater in Wise County Texas

The increased production of shale gases nationwide has often resulted in complaints by homeowners in some areas that their drinking water wells have been contaminated by nearby hydraulic fracturing activity. As regular readers of this blog know, I have been reviewing the recently released studies by the Environmental Protection Agency (EPA) which attempt to determine in four different areas of the country whether hydraulic fracturing for oil and gas (hydrofracturing or fracking for short) has been the cause of water well contamination. This blog post reviews the EPA’s “Retrospective Case Study in Wise County, Texas: Study of the Potential Impacts of Hydraulic Fracturing on Drinking Water Resources.”

Northern Texas and southern Oklahoma have had traditional oil and gas development areas for nearly a hundred years. Hydraulic fracturing of the Barnett Shale in these areas has brought a boom of new gas development. Hydraulic fracturing started in the Barnett Shale earlier than in most other areas where shale gas formations are located and it really ramped up around the middle part of the last decade.

The EPA selected Wise County in northern Texas for one of their “retrospective” studies. EPA calls them “retrospective” because they are trying to determine, after the fact, whether hydrofracturing activities caused water well contamination. A herculean feat, since there is usually a lack of data on the groundwater in the areas being studied before hydraulic fracturing took place. There were complaints in three different locations in Wise County of drinking water contamination after hydrofracturing. Wise County is just north of Dallas/Fort Worth. Having spent some time in Texas, the area is what I think most people imagine a Texas landscape to look like – flat with lots of cows and lots of oil wells. It is a pretty rural place and most people depend on groundwater for water supply. They have an excellent aquifer in this area of Texas. It is called the Trinity Aquifer and it is kind of famous among us water folk. It is a prolific aquifer producing large quantities of fresh to slightly salty water. It’s used not only for private wells but for municipal wells and industrial wells too. It has been extremely over pumped and the water table has been lowered pretty seriously. In Wise County the Trinity Aquifer is about 700 to 1000 feet below the surface, while the Barnett Shale is 7000 to 8000 feet below the surface – quite a distance between the two.

One of the three areas where there were complaints of water well contamination was near a small lake next to a gas well pad where a fish kill had occurred. The complaint was a concern with the odor and taste of the water. Two other areas had complaints of odor and corrosion of appliances. One of those two areas also had complaints of the water tasting salty. To determine if there had been an impact on the wells, EPA had to rely pretty much on old fashioned water quality work. The reason was that in testing the water wells for organic chemicals used in hydrofracturing there were no contaminants EPA could link back to the shale gas development, nor was there enough methane gas in the water wells to even analyze to determine whether its isotopic signature for the constituents of methane (Hydrogen and Carbon) were similar to that of the Barnett Shale. Methane can form in groundwater from natural bacteria decomposing organic material and the very low methane levels seen in the water wells tested in Wise County were the same as wells in the Trinity aquifer elsewhere. EPA considered the methane in the Wise County wells as normal for the area and not an indication of contamination from methane in the deeper gas formation.

As I’ve explained in previous posts, scientists can use the ratios of different isotopes of an element to determine how and where the isotope originated. For this study, EPA looked at the isotopic signatures for the isotopes of water – hydrogen and oxygen – and strontium. Of the 16 water wells EPA sampled in Wise County, 13 had the same isotopic signature for hydrogen, oxygen and strontium as that generally found in the Trinity aquifer, but 3 wells in one location were significantly different. In fact these 3 wells became really the source of EPA’s interest. Two of these wells were from the location where homeowners complained of a salty taste to the water. The other well tested was a water supply well in the same area. The supply well was not just drilled into the Trinity aquifer but had been left open in rock formations above the Trinity to draw as much water from various aquifers large and small in order to provide a substantial amount of water. When EPA started their water quality parameter investigation of these three wells, they found water in the two homeowner wells to be different from the water in the supply well.

The water types in most of the wells in all three locations with groundwater complaints were either a sodium bicarbonate or calcium bicarbonate, except in the location with the three wells that EPA was now beginning to consider impacted; there about 20 % of the water type was sodium chloride type water. We know sodium chloride as salt. Hence the salty taste. EPA was able to assemble a number of historical water datasets from the area. EPA also looked at the current water quality in other wells in the area to determine background. When scientists talk about background for water, they are referring to the regular, run of the mill, day to day water quality for groundwater in an area. In other words they are looking to establish the waters present natural chemical composition.

The water from the two potentially impacted homeowner wells had significantly different pH and specific conductance from the historical water data. Specific conductance is a measurement of water’s ability to conduct an electric current. High specific conductance means there are a lot of ions in the water. A lot of ions basically mean there are a lot of dissolved solids in the water. The two wells had higher chloride, bromide, sulfate, potassium, magnesium, sodium, strontium, barium, and boron than historical water data. You get the picture. EPA was now beginning to think that the two homeowner wells had been impacted by brine.  Although the supply well was different in some aspects from background, it was not similar to the water quality issues that the two homeowner wells had.

EPA then looked around for the possible cause of brine intruding into these two homeowner wells. They noted a lot of possibilities, but whittled them down to brine from the Barnett shale or another deep formation coming up through either natural fissures in rock, a historic well or maybe a new well that wasn’t cased properly; leaks from surface impoundments being used to store formation water from the Barnett shale or reserve pits being used to hold cuttings from the borehole of a gas well; a nearby injection well for disposing of brines from the Barnett shale which are brought up during drilling and production; or leachate from a closed landfill within a mile of the wells.

In determining the source, EPA looked at various ratios of one constituent to another. These ratio comparisons have been developed by various researchers to determine if there has been brine entry into a freshwater aquifer. Yes there have been years of studies by those crazy water scientists looking at ratios of the amount of chlorides over the sum of anions in water compared to total dissolved solids; ratios of the amount of chloride to bromide and chloride to iodide; and the amount of potassium over rubidium compared to potassium. I am not kidding you here; people spend their days researching this stuff and coming up with curves in order to compare water samples to various brines. There are curves for brines from the Barnett Shale and other oil and gas formations, curves for road salt, curves for landfill leachate. And these fun loving water scientists put together what they call mixing curves. How much water from the Barnett Shale, landfill leachate, etc. would result in what changes to freshwater. You can put your home well water on the mixing curve and see from where any sort of brine might have come. EPA did the comparison of water from the two homeowner wells and brine from the Barnett Shale and found it to fall on the mixing curve. EPA’s conclusion was that the brine intrusion into the homeowner’s wells was from the Barnett Shale. And the supply well, where did it fall? It apparently looked more like landfill leachate.

How could brine from the Barnett Shale have intruded into these two homeowners wells? EPA couldn’t say and with good reason. This was a “retrospective” study. There was no water quality work done before hydrofracturing began in the area or prior to the installation of the brine injection well. So EPA could make no specific conclusions.

I think it is becoming increasingly clear. EPA says impacts to groundwater quality from hydrofracturing do not occur often. However EPA has now found a number of cases where they have concluded that there are impacts. But the source of the impacts cannot always be readily determined because of the lack of groundwater quality characterization and water well sampling prior to and after hydraulic fracturing activity. If we see new regulation in the next few years as a result of EPA’s studies, I am hoping it will be a requirement for good water quality studies before and after hydraulic fracturing.

Southwest Pennsylvania Case Study of Hydraulic Fracturing Impacts on Groundwater

The Environmental Protection Agency’s (EPA) “Retrospective Case Study in Southwest Pennsylvania: Study of the Potential Impacts of Hydraulic Fracturing on Drinking Water Resources” is a work of nuance and intrigue. An exciting read. Well maybe not to everyone, but for me, it was science done at its best. The scientists used a multiple line theory of investigation to track down the cause of complaints of contaminated water in homeowner’s wells in southwest Pennsylvania. The complaints were similar. After hydraulic fracturing for gas in the Marcellus Shale had occurred nearby, homeowners found water from their wells turbid and odiferous. Their water tasted bad plus it left unsightly stains.

The EPA, as regular readers of this blog know, has been conducting “retrospective” studies of areas with significant complaints of groundwater impacts from hydraulic fracturing to determine if there was actually an impact to people’s drinking water wells and how it might have occurred. The study in southwest Pennsylvania was conducted in Washington County which is a short drive from Pittsburgh. I have visited Washington County and it is a pretty, rolling hill, rural sort of place that has a long history of coal mining and oil and gas development. The first oil well was drilled there sometime in the late 1800’s. Most people get their drinking water from the Monongahela River, but about a quarter of the residents are using groundwater. The groundwater there is pretty shallow, about 50 to 160 feet below the surface and the Marcellus Shale is pretty deep, about 5000 to roughly 7500 feet. The groundwater is generally pretty good, if you are going to drink groundwater. Most domestic wells are primarily producing a nice calcium bicarbonate type water and a lesser number of wells produce a sodium bicarbonate or calcium sulfate type. The problem with groundwater in Washington County is that it has a lot of naturally occurring iron and manganese. The groundwater also has naturally occurring methane gas. Remember methane is one of the components of natural gas but it can also be produced by bacteria as they decompose organic matter.

First, to determine if people’s drinking water wells had been contaminated by hydraulic fracturing fluid, the EPA analyzed for 133 organic compounds commonly used in hydraulic fracturing fluid. This doesn’t mean that companies are using 133 different chemicals every time they conduct hydraulic fracturing. Usually they use less than 10, but the chemical content of the fluid can vary depending on what the company is trying to achieve. So you’ve got to do a full analysis. I am happy to report that EPA found no organic contaminants they could trace to hydraulic fracturing in anybody’s water well.

EPA also analyzed the water for 102 other constituents including metals, stable isotopes, radionuclides, and your basic water quality constituents such as calcium, sodium, chloride and the like. Since there was no smoking gun of organic contamination from hydraulic fracturing in the wells, EPA looked at the results of stable isotope analysis, specifically the stable isotope signatures for the components of water in the drinking water wells – which we all know to be hydrogen and oxygen. The Marcellus Shale has water as well as gas. It is a brine type of water with lots of dissolved solids and other constituents such as sodium, chloride and bromide which make it briny. The brine is called formation or produced water and comes up oil and gas wells during hydrofracturing (remember this tidbit because we’ll come back to it later). Anyway the hydrogen and oxygen stable isotopes of the Marcellus brine and other deep rock formations are very different from shallow groundwater. If there was any movement of the formation water along with hydrofracturing fluid into shallow groundwater, it would show up in these analyses. Even a small amount of this briny fluid entering shallow groundwater would significantly change the stable isotope signature of hydrogen and oxygen in the drinking water wells. Again no bullet holes or dead bodies were found. Hydrogen and oxygen isotopes in people’s drinking water were the same as shallow groundwater in similar aquifers where no hydrofracturing has ever occurred.

Not to be deterred in their investigatory work, the EPA then looked at the stable isotopes of methane. As I mentioned earlier, methane is a component of natural gas and it is also formed by bacterial decomposition of organic material (these are commonly referred to as biogenic methane). The later is very common and occurs in wetlands and other places where you don’t have a lot of free oxygen, such as a groundwater well. Methane, which is composed of carbon and hydrogen, has very distinct stable isotope signatures for those components depending on whether it was produced at depth in an oil and gas formation or at the surface in a groundwater well. Unfortunately there were only two wells sampled that had sufficient methane in the water to analyze for stable isotopes. One sample showed clearly that it was biogenic methane; the other sample was less clear.

So EPA conducted a more definitive stable isotope test. This test was for what is called: dissolved inorganic carbon. Methane is considered organic carbon. There is another carbon that is associated with calcite in the rock formation. Calcite is what makes up limestone. It is calcium carbonate. As it moves along in an aquifer, the carbon in carbonate is oxidized, which results in the formation of carbon dioxide. When the carbon dioxide enters a water well (or other oxygen depleted location) the bacteria love it and use it to make biogenic methane, resulting in enriched inorganic carbon. Dissolved inorganic carbon produced this way has a very distinct isotopic signature compared to the inorganic carbon you find in the brine from the Marcellus Shale. The isotopic signature for dissolved inorganic carbon in the two wells tested was the same as other shallow groundwater in similar rock formations where no hydraulic fracturing has taken place and was totally different from the signature of dissolved inorganic carbon from the Marcellus. Evidence of contamination of people’s drinking water wells from hydrofracturing failed to appear.

Strontium isotope analysis of drinking water also failed to show impact from hydrofracturing. The radionuclide radium was then looked at because the Marcellus brine has some pretty extraordinary levels of both radium 226 and 228. Again there was nothing unusual in the drinking water wells to show impacts to groundwater from hydrofracturing.

The interesting find EPA made was simply using good old fashioned water quality data. EPA had several sets of historical water quality data from the area that had been collected decades before hydraulic fracturing even occurred in Washington County. EPA looked at such mundane water quality constituents as chloride, bromide, sodium and calcium and found that two springs in the southern part of Washington County exhibited some strange behavior during the collection of the 3 sets of samples EPA took over a year and a half period. The springs initially had elevated chloride and calcium levels exceeding both historical groundwater data and other groundwater data from wells EPA had sampled. Even more mysterious, those spurious high numbers decreased during the next two sampling rounds. It looked like the type of data you get when sampling groundwater after a spill. EPA looked around for what might be causing such an anomaly. It didn’t take long to find that both springs were close by and downgradient from an impoundment and reserve pit which had been used during the construction and hydrofracturing of a gas well. Remember the tidbit I told you to about where the briny formation water comes back up the hole during hydrofracturing and well production. The surface impoundment was used to store this water. So finally, here was a culprit. There was an extremely limited effect, since it was local and didn’t impact anyone’s personal water well. But obviously the use of a surface impoundment in this particular case caused leaching into groundwater and impacts to the two springs.

So if EPA couldn’t find any suspects from all of this incredible sleuthing, what did they say caused all of the homeowner’s water quality problems after hydraulic fracturing of the Marcellus Shale in southwest Pennsylvania? Here the EPA kind of failed me. They went into the territory of speculation. It is a good speculation though. It’s based on scientific literature and a good knowledge of groundwater reactions. Being water scientists, the EPA investigators looked at the water complaints, saw that there was a lot of naturally occurring iron and manganese in the groundwater and used their noggins to deduce that staining, taste and odor issues were probably a result of high levels of iron and manganese in the water.  In fact, when they tested the water for iron and manganese, they ran both a filtered and an unfiltered sample. The unfiltered sample was much higher for both of these constituents in the water, which leads them to believe the increased turbidity was the result of a lot of undissolved iron and manganese particulates entering the water wells. What was causing the sudden turbidity? EPA made note in their report that other studies have shown the drilling process for an oil and gas well produces a lot of vibrations and that has resulted in mobilization of iron and other rock constituents, like manganese, into water wells resulting in a lot of turbidity in those wells. So there you go, no contamination from hydraulic fracturing in southwest Pennsylvania, but possibly just poor water quality as the result of the drilling of the gas well. Little consolation for the homeowners who had to put up with foul taste and having their laundry stained, but thank goodness they aren’t drinking something really foul from the hydrofracturing fluid.

 

The Mercury Cycle

I thought a long time about the title of this post. At first I wanted to name it “Up in the Air” then I thought maybe “What Goes Up Must Come Down and Then Go Up Again”. But I stuck with the dull title of “The Mercury Cycle” because it is a clear presentation of how mercury acts in the environment. Everybody has heard of cycles: the cycle of life, the lifecycle of a product, lifecycle management, the lunar cycle. Well mercury has a cycle too. The mercury cycle is like a merry go round that never stops.

Before I write about the mercury cycle, I need to discuss metal species. Everybody has heard of species: plants have them, animals have them. We talk about the human species. Well metals have species too, but it is different. When scientists talk about metal species they are often talking about their oxidation state. We have to look back at our basic knowledge gained over the years, whether from a classroom or a Discovery channel special. You know everything is made up of atoms and those atoms are made up of electrons, protons and neutrons. You’ll maybe not remember but the electrons are the ones that are kind of special and exchange themselves to other atoms. Oxidation means that an atom is losing electrons. There is a complimentary process called reduction used to describe the other atom that is gaining the electrons. These exchanges go on at the molecular level too (remember molecules are a bunch of atoms). Mercury has only a few of these types of species. They include elemental mercury that hasn’t undergone any electron exchange and then the mercurous and mercuric forms of mercury which have lost electrons. Mercuric is the mercury that is most common. You will see it described as Hg (II). Hg is the periodic symbol for mercury by the way. People also talk about metal species when a metal bonds with another element. Again it is those crazy electrons who also share themselves between two elements. Mercury bonds with a lot of different elements, especially other metals. But when it comes to the mercury cycle, the species in which scientists are most interested are the ones where mercury bonds with sulfur and carbon. These mercury species are things like mercury sulfide and when you throw in a little hydrogen with some carbon you get your methylated mercury, including methylmercury, ethylmercury, dimethylmercury and so on. People refer to mercurous and mercuric forms of mercury and mercury sulfide as inorganic mercury. People refer to the methylated mercury as organic mercury.

Okay enough for basic chemistry. That is as far as I am going on that subject. It is a lot more complex but I wanted to tell you about metal species because they will play a role in the mercury cycle story.

The story begins with the release of mercury into the atmosphere. This can come from natural sources since mercury is everywhere in the environment to some extent. It is part of the earth. It is in our rocks and therefore our soils and when soils are eroded mercury goes into our streams and out to the oceans. So there is a natural occurrence of mercury in the environment. As mentioned in a previous post, mercury vaporizes at pretty low temperatures. Heat it up to like 357 degrees Centigrade and it boils. It has, I believe, the lowest boiling point for a metal. So natural mercury is being released to the atmosphere all the time, but at really, really low levels. Now add in your average human being who is interested in being warm in the winter, cool in the summer; who is in need of medical care; wants to put the trash out instead of letting it fill the house; and wants to be able to have nice white clothes and a safe drinking water supply free of bacteria. In other words, a person interested in living a modern existence. Now you start getting man-made sources of mercury in the atmosphere through the burning of coal, medical and trash incinerators, and chlor-alkali plants that are producing chlorine and other chemicals associated with the modern existence.

Mercury in the atmosphere is mostly in three forms: gaseous elemental mercury, the mercuric form, and particulates. The elemental form of mercury can be oxidized in the atmosphere, which results in even more of the mercuric form. Here’s the “what goes up must come down” portion of this post. Mercury comes down in the rain and snow. This is what is known as wet deposition. Mercury also just falls out of the air. Sure there is gravity involved but as usual it’s a lot more complicated. I’m not going into it, because I would have to explain Brownian motion and whole lot of other things. Just know that it is occurring and that it is called dry deposition.

The mercury falls on the ground and in the water. Mercury has a variety of things it can do.  In the ground it can get tied up in the soil thanks to all that organic matter. Or it can run off into the water or percolate down into the groundwater. If the soil is eroded, mercury can enter surface water that way too. Or it can enter surface water directly through wet or dry deposition.

Now that mercury has entered the environment from man-made and natural sources it can immediately get back into the mercury cycle and return to the atmosphere, it can get frozen into a great big glacier, it can get all tied up with the organic material in soil, it can float around in the water (although mercury is not very soluble), or it can settle down in the sediment. When it settles down in the sediment, mercury can undergo methylation if the right conditions exist. The methylation process results in methylmercury. Remember methylmercury is the bad stuff. Methylmercury is taken up by algae and bacteria then ingested by invertebrates living down there in the gunk. Algae and invertebrates are eaten by fish. Methylmercury is accumulated in fish tissue. Birds, animals and people eat fish. Not all birds, animals and people, but osprey, eagles, minks, otters and people along the coasts and lakes are usually chowing down on them. Hey I found a fish in my back yard that an osprey must have dropped! The ants were eating it, so you could probably include insects too.

Fish

There has been a lot of research going on in the past few years on how methylmercury is formed in the environment, but one of the interesting things I have read about is that methylation and demethylation can be going on in the same water body. So mercury is not tied up for all time as methylmecury but can get right back into the mercury cycle.

Now you have the low down on the mercury cycle – not a like a uni-cycle or a motorcycle – but a cycle that needs balance none the less. If humans continue to add to the mercury cycle, there could be a terrible wreck.

Supreme Court Makes Decision on the Environmental Protection Agency’s Mercury Air Toxics Standards Regulations

You don’t often find anything amusing about Supreme Court decisions. They are usually laced with stuffy legal language on prior court decisions and how it applies to a case, but every once in a while you can get a good laugh. And that is the case in the June 29, 2015 Supreme Court decision on Michigan et al. versus the Environmental Protection Agency (EPA). You may recall that this case is a result of a bunch of state governments and industry groups suing the EPA over the Mercury Air Toxics Standards Regulations issued back in February of 2012.

The regulations basically imposed pollution controls on power plants to reduce mercury emissions. The lawsuit was over the fact that the EPA didn’t consider the costs of health and environmental benefits achieved by the regulation versus the cost to industry for complying with the regulation. The cost of the regulation to industry was estimated at $9.6 billion a year. The EPA only conducted a partial cost benefit for reduction of mercury that established a yearly benefit of $4 to 6 million a year. Additional benefits for reduction of sulfur dioxide and particulates would occur as a result of the pollution controls and those were estimated to be $39 to 90 billion a year. But the EPA didn’t use those figures or any others in determining under their Clean Air Act authority that they should regulate power plant mercury emissions.

In deciding the case, the Supreme Court looked at the Clean Air Act which says: the EPA must conclude “regulation is appropriate and necessary” after studying hazards to public health posed by power plant emissions. The Court found that the agency considered regulation “appropriate” because mercury poses a risk to health and the environment and because pollution controls exist to reduce mercury. The agency also found the regulations “necessary” because other Clean Air Act regulations did not eliminate the risk of mercury. The Court held that the EPA interpreted the Clean Air Act unreasonably when it deemed cost irrelevant to the decision to regulate, because the Clean Air Act specifically required power plants to be treated differently from other sources (other sources don’t require a cost benefit analysis to regulate). The Clean Air Act specifically required a cost study for the regulation of power plants.

The Supreme Court decided that the EPA must consider cost, including the cost of compliance, before deciding whether the Mercury Air Toxics Standards Regulation is appropriate and necessary. But the Court said it is up to EPA to decide how to account for cost.

Good grief! All this decision does is “kick the can down the road.” Now the EPA must go back and do the full calculations of the regulations benefits. EPA even stated in the regulations that their calculation of $4 to $6 million was only a partial cost analysis based on IQ loss of recreational fishermen who caught and ate mercury contaminated fish. EPA acknowledged that this was a small subset of the overall benefits of reducing mercury. Now the EPA will have to engage in a much longer and more expensive cost analysis. The analysis will have to show the economic benefits to not only human health but the environment as well. That includes impacts to wildlife like ospreys and eagle, minks and otters, and the many other animals that eat a lot of fish. They will have to look at reproductive and other impacts to the fish themselves. EPA will also have to look at subsistence populations who regularly eat fish and to the population at large who are eating fish from mercury impacted waters. And will the decision to regulate based on the cost benefit study change? I doubt it. If you start looking at impacts to wildlife and fisheries including reduction of recreational uses of streams with consequent losses to local economies and impacts to the fishing industry, well you are going to get an enormous figure. Add on top of that the cost of the side health benefit for the easier to calculate reductions in sulfur dioxide and particulates and I would expect the annual benefits to be in maybe the trillion dollar range.

I thought to myself, surely these state governments and industry groups thought about this in advance before they took this case all the way to the Supreme Court. Of course this is all handled by the lawyers and they may not know much about the cost calculation of damages to health and the environment, but they have scientists on staff who should be very well aware. That’s when I started laughing. Of course they must have known. Maybe all they were doing in taking this case to court was fishing for a delay in implementation of the regulations.

Stray Gas from Hydraulic Fracturing for Natural Gas in Northeast Pennsylvania

Stray natural gas is common in northeast Pennsylvania. It existed before hydraulic fracturing for gas began in the area. The Marcellus Shale is the main rock formation from which natural gas is being extracted, but all the formations above the Marcellus also have natural gas. The Lockhaven and Catskill are the main drinking water formations that people in the area drill into for water supply and are located several thousand feet above the Marcellus Shale. There is plenty of water monitoring data showing natural gas already existed in the water supply formations before hydrofracturing occurred in the area. But between 2009 and 2011, the Pennsylvania Department of Environmental Protection investigated somewhere around 90 complaints of stray gas in domestic water wells. Obviously something new was happening.

When I envision stray gas, I always get this picture in my head of stray cats. You leave the door open one day and your cat slips out. It becomes a stray, living in the woods, killing songbirds for food, trespassing into people’s backyards, and generally making a nuisance of itself. Stray natural gas is really the same thing, you don’t do such a good job cementing your casing and you leave the door open for natural gas to come up the sides of the casing, it enters into groundwater rock formations and sometimes travels through natural fractures in the rock, it slips into people’s water wells and sometimes their basements, it can cause groundwater in the well to become discolored and turbid as iron and other minerals precipitate out of the water, and it generally makes a nuisance of itself because after all natural gas can explode.

The Environmental Protection Agency selected Northeast Pennsylvania for one of their five “Retrospective Studies.”  The selections were made based on complaints of water well contamination in areas that were undergoing hydraulic fracturing for oil and gas. The study being “retrospective” was designed to determine through various chemical tests whether the Environmental Protection Agency could determine if the gas in people’s water wells in northeast Pennsylvania came from hydrofracturing activities in the area.

Based on the Environmental Protection Agency’s research, two main water types are being used for water supply in the study area. There is a nice calcium bicarbonate water in the upland areas and in the river valleys a sodium chloride or sodium bicarbonate type water. Geologists in the area have proposed that rivers followed weaker naturally fractured rock to form the valleys. The geologists further theorize that brines from lower rock formations moved upward through these highly fractured rocks underneath the valleys into the shallower drinking water formations, hence the chloride and sodium. Methane is common in the valley groundwater both in wells and in springs but is uncommon in the upland wells.

The main line of evidence that hydraulic fracturing in the area is the cause of stray gas in water wells comes from stable isotope work conducted by the Environmental Protection Agency and others. In a previous post I mentioned that stable isotopes have a signature. Remember from high school or college science: atoms have electrons, neutrons, and protons. So let’s take carbon as an example, it has 6 neutrons and 6 protons. That is called carbon 12. Get it, six and six is twelve. Okay, about one percent of carbon has 7 neutrons and 6 protons. It is called carbon 13. Since it has one less neutron, carbon 12 is lighter and reacts a little quicker in chemical bonding than its heavy brother. So various compounds that contain carbon have different amounts of carbon 13 to 12 based on their origin. These ratios are expressed in parts per thousand and give a signature that can be used in this case to determine the origin of methane.

Methane, a component of natural gas, is a compound of carbon and hydrogen. Hydrogen also has a stable isotope signature. Methane can be produced by bacteria in surface water. Methane in natural gas and methane produced by bacteria have two different carbon and hydrogen signatures. Methane is just one component of natural gas. Other components include ethane, propane and butane which are also compounds of carbon and hydrogen. And guess what? Each component of natural gas has a very specific ratio of carbon isotopes in relation to the other components for most of the oil and gas deposits around the world. Except in gas shales like the Marcellus where the ratio is reversed. If you got this reversal of the methane and ethane isotopic signatures in water wells, you would know immediately from where the gases originated. The problem is that there is usually not enough ethane found in water wells to analyze.

Okay enough for our background science. The Environmental Protection Agency tested 36 drinking water wells over a one and a half year period. They did three rounds of sampling and analysis. All wells sampled were within a mile of a hydraulic fracturing site. In addition to stable isotopes, the drinking water was tested for chemicals used in hydrofracturing fluid. The good news is that no drinking water wells tested were found to have hydrofracturing chemicals in them.

Some of the 36 drinking water wells the Environmental Protection Agency tested had natural gas that originated in deep rock formations. Three wells had isotopic signatures of natural gases from rock formations above the Marcellus and five had isotopic signatures of possibly the Marcellus or other deep rock formations. What is the cause of the movement of the stray gas? The Environmental Protection Agency cites a 2012 report by the Groundwater Protection Council that blames inadequate cementing of the casing that allowed gas to move from depth into shallower formations. However, the Environmental Protection Agency says that without having been able to sample the water wells before the hydraulic fracturing occurred in the area, it is difficult to determine exactly what the impacts have been to drinking water in the area.

It sounds to me like there is a strong need for groundwater assessment and sampling before hydraulic fracturing is conducted in an area instead of having to ferret out environmental impacts after the fact. The Environmental Protection Agency cites a study in Northeast Pennsylvania done by an oil and gas company prior to fracturing a well 800 feet from a drinking water well. Multiple rounds of sampling were conducted before and after the hydrofracturing occurred. Data showed a 7 fold increase in methane and a 1000 fold increase in ethane in the drinking water well after the hydraulic fracturing took place. Isotopic testing showed the gas entering the drinking water well came from deep gas bearing rocks but not the Marcellus itself. Little consolation to the homeowner I suspect who probably didn’t care where the gas came from, just that it hadn’t been there prior to hydrofracturing.

Can Hydraulic Fracturing for Oil and Gas Cause Groundwater Contamination?

Can hydraulic fracturing for oil and gas cause groundwater contamination? This is the question I have been waiting to find out from the U.S. Environmental Protection Agency’s hydrofracturing scientific investigation and studies. Of course if you have a spill, there is always the potential for contamination. But does the actual process of inducing fractures through injecting water and chemical additives under pressure down a well actually cause contamination, either from the hydrofracturing fluid or natural gas migrating into the groundwater. I’ve read through the Environmental Protection Agency’s “Draft Assessment of the Potential Impacts of Hydraulic Fracturing for Oil and Gas on Drinking Water Resources.” I didn’t have to read all 998 pages, just the Executive Summary and the Chapter on Injection. The answer is there are documented cases where the hydrofracturing process itself has contaminated groundwater. Incidences, as the Environmental Protection Agency has stated before, are rare. The evidence comes primarily from the case studies that the Environmental Protection Agency conducted. They have released the case studies as well as the Draft Assessment and I plan to take a look at the case studies in the next few weeks and provide more information on how they determined contamination did or did not come from the hydrofracturing process.

The Environmental Protection Agency always does a good job on their reports. The Draft Assessment is an excellent compilation of the scientific literature on the subject. They have summarized dozens of published research papers. As you can imagine, there has been a lot of recent research in the area of hydraulic fracturing and its possible impact on drinking water. The Draft Assessment also looks at data on well construction and practices. This data was gathered through a survey of service companies that perform hydraulic fracturing for oil and gas companies. The Environmental Protection Agency used the collected data to determine what practices are being used to protect groundwater. As advertised in the Study Plan for the current report, a numerical model was conducted and has been published in the scientific literature. I hope to get a copy of that in the next few months and take a look at it.

The Environmental Protection Agency also gives a litany of possible ways natural gas and chemicals from fracturing fluid could enter the groundwater. These include everything from poor cementing of the casing protecting groundwater to casing failure during hydrofracturing. You could say that the Environmental Protection Agency has validated Murphy’s Law: anything that can go wrong will go wrong.

Right now the Draft Assessment is undergoing review. With the amount of scientific literature quoted in the report, the review needs to be conducted before I write anything further on the Assessment Report as interpretations made in the report may change. So I’m going to concentrate on reviewing and writing about the case studies while that process is ongoing.

The U.S. Environmental Protection Agency Announces the Release of the “Draft Assessment of the Potential Impacts of Hydraulic Fracturing for Oil and Gas on Drinking Water Resources”

The Environmental Protection Agency finally released their “Draft Assessment of the Potential Impacts of Hydraulic Fracturing for Oil and Gas on Drinking Water Resources” last Thursday June 4, 2015. They held two webinars on Friday about the contents of the report. If you’ve been reading this blog for a while, you knew that the report was due for release, you’ve also gotten the background on what the Environmental Protection Agency has been studying and why. If you are a new reader of this blog, go back and check out previous posts. The posts will give you information on the studies the Environmental Protection Agency has been conducting.

I was excited to see the report come out even though it is 998 pages and I am committed to reading the whole thing. In addition, the Environmental Protection Agency published a bunch of new scientific papers on hydrofracturing. So I will be reading up for a while on all this new scientific information. I will be posting about the contents of the report so you can get the in-depth information without having to read the whole 998 pages yourself. The Environmental Protection Agency will be accepting comments until August 28, 2015.

The Environmental Protection Agency said that their studies found no widespread contamination of drinking water resources by hydraulic fracturing. That is a pretty strong statement. However, The Environmental Protection Agency also stated their studies have identified vulnerabilities that need to be addressed by state regulators when permitting hydraulic fracturing wells. So it was a good news, bad news sort of message. Look for future posts on this blog about the report results.

 

Global Man-made Mercury Contributions to the Atmosphere

I had a conversation the other day with a friend of mine who is an environmental attorney. I was telling her about the Environmental Protection Agency’s regulations to reduce mercury emissions from coal burning power plants. Her area of legal expertise is not air regulation so it was news to her that the Environmental Protection Agency had written and issued the regulations. Actually her area of expertise is international environmental law. She asked me a very logical question coming from someone who has a global perspective. What portion of global emissions is coming from the U.S. compared to countries like China who burn lots more coal than the U.S. and who have about zilch in the way of emission controls. I said mercury emissions from the U.S. are pretty small in comparison to the industrializing countries like China and on top of that the largest mercury air emissions are actually coming from small gold mining operations in Africa and South America. Yes, can you believe it? It is the 21st century and yet these mostly unregulated and often illegal mining operations are still using mercury to produce gold.

Go back to my previous blog post on “Where is All This Mercury Coming From?” and take a look at the chart showing mercury emissions over the last couple of hundred years. You will notice a big old slug of mercury air emissions between the years of 1850 to 1884. Those were the years of the Gold Rush. If you are an American, you will probably have studied the Gold Rush in school. The famous location where it all started was Sutter’s Mill on the South Fork of the American River in Coloma, California. James Marshall’s discovery of gold in the South Fork at Sutter’s Mill in 1848 is an iconic event in American History and Sutter’s Mill is now a California State Park. The event set off gold fever in the U.S. and thousands of people migrated west to try their luck at getting rich by mining gold. History books even have a name for these migrants – the 49ers. Yes, San Francisco named their football team after a bunch of gold miners.

As we have seen, mercury is a unique metal with some highly unusual properties. One of these properties is that it binds readily with other metals in what is called an amalgam. The 49ers learned pretty quickly that mercury was the perfect way to extract gold from the river sediments and the rock and soils they washed out of the Sierra hillsides through hydraulic mining. They washed the gold through mercury lined sluices and over mercury coated metal plates the size of houses. Mercury from these gold extraction processes can still be found today in the American River. Fortunately the use of mercury in gold extraction was replaced by another toxic favorite – cyanide. Cyanide has its problems but at least it degrades rapidly. Mercury is forever.

I took a look at the United Nations Environment Programme report “Global Mercury Assessment 2013: Sources, Emissions, Releases and Environmental Transport.” According to the report, small gold mining operations are now the largest source of man-made mercury emissions. The U.N. has calculated contributions from world-wide mercury sources to annual mercury emissions. The numbers in the report are from 2010. In 2010 global estimates were 1960 tons of mercury released into the air. Seven hundred and twenty seven tons of the mercury came from small gold mining operations. That is 37 percent of all mercury emissions. Worldwide in 2010 only 475 tons of mercury came from burning coal in power plants. Sure that is a big figure too. Twenty four percent of all annual emissions in 2010 came from power plants. It is the second biggest source.

Here’s the answer to my friend the environmental attorney. The whole of North America (remember Canada and Mexico are included in with the U.S.) only contributed 60.7 tons or 3.1 percent of mercury to the global atmosphere. That is from all sources, not just power plants. Even the European Union contributed more mercury to the atmosphere (4.5 percent). What about China. There were not specific numbers for China in the U.N. report, but Asia contributed nearly 50 percent of the global mercury emissions. East and Southeast Asia were 40 percent and South Asia was 8 percent.

Mercury in Coal

I got an email from a reader. They wanted to know why coal has so much mercury in it. In reality coal doesn’t have that much mercury in it. The problem is that you are burning the coal and releasing the mercury into the atmosphere.

Interestingly enough, the smarty-pants at the U.S. Geological Survey have been analyzing coal for years. They have an entire database of coal samples from all over the country. Admittedly, it is somewhat skewed to samples of coal from the eastern United States, but it is the best collection out there.

Mercury is one of the elements for which the Geological Survey has been analyzing the coal samples. Their database includes about 7000 samples of coal. The ranges for mercury in coal are from .003 parts per million to 1.753 parts per million. Eighty percent of coal samples are less than .25 parts per million. The mean coal content is .17 parts per million. (Remember mean is the average – all the mercury values for samples in the database are added up and divided by the number of samples.) Parts per million are milligrams per kilogram. These are very tiny numbers. And that is not even the coal that is going to the power plants. A lot of coal is “cleaned” before it goes to the power plant. Utilities want a good burning coal without a lot of ash and sulfur, so after coal is mined it is often sent through a cleaning process to reduce these unwanted attributes. Ash and sulfur are unwanted because the United States Environmental Protection Agency has regulations to reduce particulates (ash) and sulfur. You don’t want to breathe particulates because they are linked to respiratory problems and you don’t want to have sulfur in the atmosphere. Remember acid rain? Yes sulfur is the big contributor to that problem. The Geological Survey says that 37 percent of mercury is removed by coal cleaning.

When the Environmental Protection Agency wrote their regulations on reducing mercury at power plants, they didn’t rely on the Geological Survey’s database. They conducted a study back in 2010 on mercury content of coals delivered to power plants. I didn’t go looking for this study. The Geological Survey says that the Environmental Protection Agency’s mean mercury content for coal delivered to power plants is .12 parts per million. A bit less than the .17 parts per million the Geological Survey had for their database. The Geological Survey attributed the difference primarily to coal washing and the fact their database had more eastern coal which is higher in mercury than many western coals. Interestingly, the Geological Survey analysis of their database showed Northern Appalachian and Southern Appalachian eastern coals to have the highest mercury content of U.S. coals.

The Geological Survey is doing a lot of research on where mercury resides in coal. I personally thought this was interesting because it was something new to me, so I wanted to share it with you. Pyrite is the source of most of the mercury in coal. You may know pyrite by the term fool’s gold. It is an iron sulfide and often has trace metals like mercury associated with it. Mercury in coal can also be bound to the organic carbon in coal, it can be sort of diffuse as elemental mercury, and it can be part of other minerals found in coal.

Here’s another interesting fact from the Geological Survey. Their database also includes about 1600 coal samples from 57 other countries around the world including China. They looked at the mean mercury content of those samples and found it was 0.16 parts per million, about the same as the mean mercury content of coals in the United States.

Anyway I digress from the main point of my post here which is coal is not teeming with mercury, in fact not any more so than say soils. The same Geological Survey has analyzed soils from all over the country. One of the elements they have analyzed for is mercury. They looked at three different depths of soil. Just looking at the top 5 centimeters of soil, mercury levels ranged from non detectable by current analytic methods to 3.55 parts per million. Soils in the middle part of the U.S. were lower than the soils on the east and west coasts. Again these are really tiny numbers. But we don’t burn soil.

What is EPA Testing Water Wells for in their Case Studies?

This post is part of a series on EPA’s Hydraulic Fracturing Study. Previous posts will give you more detail on the specific case studies EPA is conducting and you may want to read them prior to reading this post.

EPA is running a number of standard water quality tests as part of their water well sampling for their case studies. These tests characterize the water. Standard measures for water are things like temperature, pH, Total Dissolved Solids (you’ll see this referred to as TDS), specific conductivity, alkalinity, turbidity, dissolved oxygen, oxidation/reduction potential, ferrous iron, and hydrogen sulfide.  EPA will also be looking at existing water quality data collected for the case study areas by government agencies whose business is to characterize water resources. Your average person only generally knows they have hard water, or too much lime that leaves a ring in their bathtub, or their water smells like rotten eggs. They don’t know if they have a bicarbonate or alkaline water, or low dissolved oxygen, or hydrogen sulfide. But your water scientist will. These are water characteristics that they use to describe water. Get one of these water scientists at a dinner party and they will be telling you how your favorite European mineral water gets its taste. EPA’s water scientists will look for changes in water quality characteristics or unusual test data and deduce if something may be going on in the well they are testing.

EPA is testing a large number of chemicals that hopefully aren’t characteristic of your average drinking water. These are mostly chemicals associated with the components of hydrofracturing fluid. Hydrofracturing fluid is generally over 98 percent water but the remaining 2 percent is composed of additives that help the engineer get the oil and gas out of the rock and into the oil and gas well. The additives EPA is testing for are chemicals such as glycols, acids, surfactants, volatile and semi-volatile organic compounds. Volatile organics are things like toluene and styrene. Semi-volatile organics are things like 1,2,4-trichlorobenzene. These are not good to drink.

There are also natural substances commonly found in the flowback water that are removed from the rock during the fracturing process. Some of these are being tested for as well. These are arsenic, manganese and iron. And EPA is testing for chloride and bromide which are characteristic of the flowback water as well. If you have been reading this series of posts on hydrofracturing you will remember that EPA has concerns about adequate treatment of chloride and bromide from flowback water at Publically Owned Treatment Works. Natural organic material is also being tested. And EPA is testing for methane, ethane, and propane which are all components of natural gas.

Finally EPA is testing for: stable isotopes of the components of water, which we know are hydrogen and oxygen; stable isotopes of hydrogen and carbon, which you may not know are the components of methane; and strontium. The easiest explanation of why EPA is analyzing for them is because stable isotopes have different ratios depending on how they were produced and where they came from.

This is kind of an aside, but did you know certain companies who require their products to contain a specific proprietary ingredient that only they make often check stable isotopic ratios of their product manufactured by contractor entities? Why? To see if the contractors are using the proprietary ingredients! They can tell by the stable isotopic ratio.

In EPA’s case they are looking at what the usual stable isotopic ratios are for water, methane and strontium in the case study area. If EPA’s well samples in the case study area then show differences from what the normal isotopic ratios are, it is an indication something might have been introduced. In other words it is an indicator of contamination.

Oh wait I forgot, EPA is also testing for NORM. Remember that from an earlier post? It is the naturally occurring radioactive material.

All in all this is a lot of testing and it will be done at several EPA laboratories.  EPA should have a very good picture of whether water in people’s wells has been contaminated and it should help them draw some conclusions on potential sources of the contamination.