Methane in the Water

Posted in: Fracking, Misc Water Issues, United States Water News, Water Contamination
Tags: , ,

Photo credit: Jeff Danner

Article courtesy of Jeff Danner | August 24, 2014 | Chapelboro (Part I) Chapelboro (Part II) | Shared as educational material

In recent weeks, there have been many reports in both the local and national media regarding a study published by Duke University showing elevated methane levels in drinking water wells located near fracking operations in New York and Pennsylvania. In my opinion, these reports do not provide sufficient information for the reader/viewer/listener to evaluate the fundamental question, “How worried should I be?” In this two-part series, I will attempt to provide a comprehensive answer to that question. To do so, I am going to have to delve a bit deeper into technical details than normal. However, with fracking coming to the Tar Heel State, I think it is important for this issue to be addressed accurately and comprehensively. So pour yourself a fresh cup of coffee and let’s get to it.

Let me start with a one-paragraph primer on fracking. First, a drilling company locates an underground deposit of natural gas, which is a mixture composed primarily of methane along with small amounts of ethane, propane, and butane. Next, the company drills down to the depth of the gas deposit and protects the well bore with steel piping encased in a layer of concrete. From the bottom of the vertical well, horizontal holes are drilled in several directions. Then a high-pressure slurry of water, sand, and chemicals is pumped into the horizontal holes, fracturing adjacent rocks. Fracturing the rocks allows the natural gas in the deposit to migrate to the vertical well bore, and subsequently to be brought up to the surface. Many of the chemicals used in the fracking process are highly toxic. (1)

As we consider the issues discussed below, an appreciation for depth will be helpful. Water wells for drinking and agriculture are almost always less than 1,000 feet deep, because that is where the water is. Fracking wells tend to be much deeper, 2,000 to 20,000 feet, because that is where the natural gas is. The separation in depth between underground aquifers and fracking operations is a critical parameter in trying to avoid water contamination. If fracking occurs at depths which are too close to aquifers, then cracks can extend from the fracking zone into the aquifer and allow fracking chemicals to contaminate the water. I have previously written about a case of this occurring in Wyoming. The physics of fracking suggest, at least to me, that the separation in depth between an aquifer and any fracking activity should be at least 1,000 feet.

The graph above, from the Duke University study, shows methane concentrations for water wells as a function of distance from fracking operations. The data clearly show that water wells closer to fracking operations have higher concentrations of methane. This graph contains a lot of information and implications, and, thus, raises a number of questions which I will attempt to answer below.

What is the source of the methane?

The two most common sources of methane in ground water are bacteria in the soil and natural gas deposits. Drilling companies frequently raise the possibility of multiple possible sources in order to suggest that methane found in ground water may not be related to their activities. However, it is actually quite easy to determine the origin of methane found in a water well. When bacteria are going about their business, they make methane and only methane. In contrast, methane from natural gas, which is produced by the decomposition of ancient organic matter deep underground, is accompanied by other decomposition products such as ethane, propane, and butane. Since the water in the wells from the Duke study contains these other hydrocarbons along with methane, there is little doubt that the methane they found was from natural gas.

Did the methane reach the underground aquifers due to fracking?

As you look at the graph above, the answer seems to obviously be “yes.” However, drilling companies have claimed that the methane may have infiltrated local aquifers prior to the fracking operations and that since the Duke study does not have baseline data collected prior to drilling, causation has not been established.

While the assertions from the drilling companies are defensible on the surface, they don’t stand up to scrutiny. Consider that all of the water wells in the Duke study are over the same shale formation that bridges the New York/Pennsylvania border. If methane in that zone was naturally migrating into the aquifers, one would expect that nearly all of the wells would be contaminated. To accept the drilling companies’ explanation that their activities are not related to the water contamination, one would also have to accept that somehow they have only drilled near to previously contaminated aquifers and that the aquifers in areas where they have yet to drill have somehow avoided the onslaught of naturally migrating methane. The odds of the drilling companies’ theories being correct are infinitesimally small.

The explanation posited by the Duke researchers is that methane is reaching the aquifers adjacent to the fracking wells by leaking through cracks in steel piping and concrete casings around the vertical well bores. I find this explanation to be far more compelling.

Is methane toxic?

The short answer is no.  Methane is essentially inert and will not undergo chemical reactions except at very high temperatures. Therefore, any methane dissolved in water that you drink will pass through your body without causing any harm. Further, as flatulence can contain up to 10% of it, methane is not unfamiliar to your gastrointestinal system.

Is methane a harbinger of other pollutants?

The essence of this question is, “If methane can migrate from the fracking zone to the aquifer, can harmful fracking chemicals such as benzene do so as well?” To explain why the answer to this question is “not necessarily,” we need to talk a little chemistry.

Methane consists of a single carbon atom in the middle attached to four hydrogen atoms. Since the four hydrogen atoms are arranged symmetrically, methane is non-polar. What this means is that the electrons within a methane molecule are evenly distributed, which results in the characteristic that methane molecules tend not to stick to each other or to anything else. Methane is also a very small molecule. Since it is small and doesn’t stick to anything, methane can worm its way through very small cracks and fissures.

Molecules which are polar have a much more difficult time migrating from place to place underground. As an example, let’s consider water (H20), a molecule about the same size as methane. In the case of water, the two hydrogens are not symmetrically arrayed around the central oxygen atom. As a result, part of a water molecule is electron rich while the remainder is electron deficient. This has the effect of making water molecules act like little magnets such that they stick to each other and many other things, like soil and rock. So it has a much harder time migrating underground.

The chemicals used in the fracking process are both much larger than methane and tend to be polar like water, limiting their ability to migrate. Therefore, the fact that an aquifer has been infiltrated by methane is not a particularly strong indicator that fracking chemicals will soon arrive.

To sum up Part I, what we know so far is:

  • fracking operations allow methane from natural gas deposits to reach drinking water aquifers;
  • methane itself is not toxic; and
  • methane in the water does not necessarily mean that other fracking chemicals will also contaminate aquifers.

This is the conclusion of a two-part series of the implications and potential hazards of methane contamination of drinking water wells due to fracking. Part I explained how we know that fracking allows methane to infiltrate drinking water aquifers, and reviewed the associated toxicity implications. For the purposes of this week’s column, the key point to know is that a recent Duke University study demonstrated that drinking water wells near to fracking operations in New York and Pennsylvania had methane concentrations of up to 70 mg/L, a level many times greater than normal. Since methane, the primary component of natural gas, is quite flammable, the question I will address this week is what level of methane contamination in drinking water wells represents a fire or explosion hazard.

In order to evaluate the potential hazards stemming from methane contamination of water wells, we need to discuss some thermodynamics.(2) Methane is a flammable gas, but like all flammable gases, it can only burn in air at certain concentrations. If the concentration is too low, there is not enough fuel to sustain a fire. If the concentration is too high, there is not enough oxygen. (Essentially, the methane crowds out the oxygen.) For methane to burn when mixed with air, its concentration must be between 5 and 15%, which are known as the lower and upper flammability limits. Therefore, in order to avoid a methane fire or explosion, we need to avoid creating a vapor mixture with 5-15% of methane in air. This is almost always accomplished by keeping the methane concentration at less than 5%.

Now that we know what concentrations of methane-air mixtures are flammable, the next question for us is, “How much methane must be dissolved in my well water such that a flammable mixture of methane and air can be created?” To answer this question we need to discuss the vapor liquid equilibrium (VLE) for methane and water shown below.

Photo credit: Jeff Danner

The X axis on this graph shows concentrations of methane dissolved in water in milligrams per liter (mg/L).  The Y axis shows the percent methane in the air above the liquid. The diagonal line represents the conditions when the liquid and vapor are in equilibrium with one another. I will explain what that means using the example below.

Start on the X axis and find 5 mg/L of dissolved methane. If you move straight up from there, you will hit the diagonal line at 2.5% methane in the vapor. What this means is that if I make a solution of 5 mg/L of methane in water and put it in a closedcontainer, methane will evaporate out of the liquid until the vapor concentration reaches 2.5%. The reverse is also true. If I were to start with pure water and introduce a vapor mixture of 5% methane above it, methane from the vapor will dissolve into the water until a concentration of 5 mg/L is reached. At these conditions, the vapor and the liquid are in equilibrium which means that methane evaporates from the water at the same rate that is dissolving back in from the gas. This is what equilibrium means in this context.

Now that we know how the VLE graph works, let’s consider the data for 10 mg/L of dissolved methane, a concentration just high enough that the DOI recommends mitigation. In this case we see that a vapor concentration of 5% methane would be created in a closed container. As we discussed above, 5% is the lower flammability limit for methane. Since a 10 mg/L solution of methane in water has the potential to create a flammable vapor mixture above it, the DOI uses 10 mg/L as the lower limit for its action level range.

Consider again the example of water with 10 mg/L of dissolved methane, but this time let’s put it in an open container. In this case, methane evaporating from the water into the vapor space above can waft away. In most circumstances, it will float away at a rate faster than it can evaporate from the water. Therefore, the vapor space above the water cannot build up a concentration of 5% methane – the lower flammability limit – and thus cannot burn or explode. Additionally, over time in an open system, eventually nearly all of the methane initially dissolved in the water will be gone.

The issue of closed versus open areas or containers is vital to evaluating the potential hazards of methane-contaminated water wells. The first place to look for fire and explosion risks in a home water system are closed spaces where methane vapor can accumulate. In a typical home water well and supply system there are two potential trouble spots: the well head and the pressure tank. The diagram below of a typical home water well system should help illustrate the potential problems.

Photo credit: Jeff Danner

When installing a water well, you start by digging a 4-6” diameter hole into the ground until you find the water table, typically 100-500 feet in this neck of the woods. The top portion of the large hole is protected with a steel and/or concrete casing to prevent it from collapsing. At the top of the casing there is a cap called the well head. Then a pump is placed near to the bottom of the well which pumps water up to the surface through a thin (1-2”) pipe which runs up through the well casing to just below the ground surface and then into your house.(3) Once inside your house it feeds a pressure tank which has a flexible bladder inside. The bladder supplies pressure which allows water to flow to the faucets, showers, toilets, and appliances in the house. When the pressure in the bladder drops due to water use, a pressure switch turns on the well pump, refilling the bladder, until the pressure goes back up and then the pump is turned back off.

The most likely place for methane to accumulate in this system is at the top of the well casing below the well head. Methane in the aquifer can evaporate and rise up in the space outside of the thinner water delivery pipe. In circumstances where the aquifer contains more than 10 mg/L of methane, the presence of a flammable mixture below the well head is quite likely. On occasion, well head fires and explosions have been reported when the well head is opened in the course of maintenance activity. This potential hazard can be mitigated by installing a vent on the well head to let the methane escape and float away. Note that while this will prevent the formation of an explosive atmosphere, it creates an open pathway for the methane, a potent greenhouse gas, to enter the atmosphere.

The second potential place for methane to accumulate is in the vapor space of the bladder inside the pressure tank. As we learned in our discussion of the VLE diagram, when the concentration of methane builds in the vapor space, more and more of it will dissolve into the liquid. This dissolved methane will escape into the house when you use your faucets, showers, and toilets. This is the mechanism purported to be behind the famous scene in the movie Gasland when a man lights a fire in his kitchen sink. Because the sink is an open rather than closed environment, it is difficult (but not impossible) to create a flammable mixture of methane vapor in the sink. But having methane accumulate in your pressure tank can create a possible fire hazard, and attempting to mitigate this situation seems to be the prudent course of action.

Fortunately, it is not difficult to prevent the accumulation of methane it the bladder of the pressure tank. Unfortunately, the solution is expensive. The way to remove the methane is to have the well pump first deliver the water to an unpressurized, vented tank outside the house. The methane in the water will evaporate and exit through the vent of this tank. This process can be sped up by bubbling air through the water. Then the now methane-free water from this tank must be pumped into the bladder of the pressure tank to service the house. The extra tank, pump, and associated valving and controls for this design are not cheap!

As I have outlined, the fire and explosion risks of methane-contaminated well water can be addressed by venting the well head and adding extra tanks, pumps, and bubblers, at least in theory. But the real world often does not care too much about theory. Since the aquifers in North Carolina are not currently contaminated with methane, our wells generally don’t include these safeguards. When fracking does begin here and methane starts to infiltrate our drinking water, I believe that it is unrealistic to assume that these safeguards will be installed in all, or even a substantial portion, of the wells. Who would pay for it?

Furthermore, let’s step back for a moment and consider what is really happening here.  First, the drilling companies are creating a pathway for methane from underground natural gas deposits to reach the aquifers. Then if we make the changes to our water systems I described above in order to prevent fire and explosion hazards, we will be venting methane into the atmosphere!

This is not an acceptable situation. If you cannot demonstrate that you can extract natural gas without getting methane into our water, you should not be allowed to frack.

Want to Donate?
Please contact us for gifts in kind - Mail your check to: P.O. Box 545934, Surfside, Fl 33154