A recent study published in the “Analytical Chemistry” journal suggests surfactant chemicals found in fracking fluid samples were no more toxic than substances in household items.

Imma Ferrer, chief scientist at the mass spectrometry laboratory and co-author of the paper, and Thurman stand next to an Agilent Model 6540 LC/QTOF-MS that was used to determine the fracking components. Source: Michael Thurman

The analysis is the first of its kind, says Michael Thurman, lead author of the paper and a co-founder of the Laboratory for Environmental Mass Spectrometry at the University of Colorado Boulder’s College of Engineering and Applied Science.

Thurman and his research team tested samples from Colorado, Louisiana, Nevada, Pennsylvania and Texas. The surfactants they analyzed make up a portion of the chemicals many oil and gas companies add to fracking fluids, which can also include anti-bacterial agents and corrosion inhibitors. Surfactants reduce the surface tension between water and oil, allowing more oil to be extracted from fractured shale underground.

A large concern stemming from the fracking boom questions the impact of fracking fluids on the environment. Thurman recently spoke with National Driller about the significance of the findings and how they play into those fears.

Q. What did you find out about the chemical contents of fracking fluids through your research and how big a deal is it?

A. “What we found out was that the surfactants, which are the soaps and detergents that are applied in the fracking solution — their purpose is to help bring the oil and gas back up. So they lubricate the rock formation. So that class of compounds are called surfactants and they’re about 20 percent of the material that’s going down the well. We found two major classes of compounds and we identified them. One is called polyethylene glycol, or PEG, and the other is called linearalkyl ethoxalates. Those are two classes and within each class we identified from 50 to several hundred different compounds within that, and we did this using a technique called accurate mass spectrometry.”

“The significance [of the findings] is this: People are concerned about the toxicity of the chemicals that are going down the well. So our goal was to figure out what are the compounds and once we knew that, then you have some idea from the published scientific literature whether these compounds are toxic or not. So for example, on the toxic side something called alkylphenol ethoxalates, called APEs, have been suggested that they are used in the fracking process … In the paper there were eight samples that were analyzed. The APEs did not show up in the samples and then we found these other two classes of compounds, which are much more environmentally friendly in that, for example, with PEGs they are used in soaps, they are used in pharmaceuticals, they’re used in cosmetics. So these are things we’re putting on our skin, or used as a laxative. PEG is a very potent laxative. So that’s the PEGs. The other class, which are the linear alkyl ethoxalates (LAEs), are one of the major ingredients used in dish soap. So if you wash your dishes by hand, that’s the material that you squirt in there. So from a toxicity level these would be at the lowest levels, versus the APEs.”

Q. Aside from surfactants, are there other chemicals in fracking fluids that could be good or bad for the environment?

A. “There’s at least five different groups. The next one that comes to mind is the biocides. These are organic compounds, usually, that are put down the well to prevent bacterial growth within the well. The word biocide means that it kills bacteria so that’s something that you would not want to ingest, for example. There’s others too. There’s things called polyacrylamides and this is an interesting one. It’s a class that’s used as a friction-reducing compound. And if you eat popcorn … the inside of the bag of the popcorn is coated with polyacrylamides to prevent the oil of the popcorn from going through the paper bag. So here’s an example of a material that’s used in fracking that’s also used in the food industry … So it’s an interesting problem. I think what’s happening, although I’ve not directly talked with the people making these solutions yet, is that there’s an effort being made to make [the chemicals] as less toxic as possible.”

Q. What does the culmination of your research imply? If the chemicals in fracking fluids are similar to those in household products, can concerns about potential environmental harm from fracking waste be laid to rest?

A. “Here’s the thing, is that usually in science — I’ve been an environmental scientist now for 35 years and usually in the beginning scientists would go out and do research and then maybe 10 or 15 years later the public would find out about it. Things have changed now and, probably, it’s because of our need for information. We have all of these ways of finding things out. We have the Web, we have the Internet, we have all these sources of information. So people are finding out about environmental issues before the scientists have even analyzed anything. Fracking is the first example where I’ve seen this. There’s been so much in the news about it and yet there’s been very few scientific papers. Ours is the first to look at the organic chemicals in the flowback water, published with this technique, which is LC/MS.”

“… In spite of all of this interest in fracking and all of the concern, we’re just now getting some basic data about what’s going down the well and whether it’s toxic or not. So it’s too early to tell all of the effects, but this is the first positive side. But there’s another important aspect here … The second thing is this: These compounds are good tracers of the fracking water itself. So let’s say that you have a well that’s nearby a fracking operation and you’re concerned that maybe some of those chemicals have gotten into your well. These are the kind of compounds that we can easily determine to see if, in fact, it has. So they are tracers and that’s yet another application of work. But there’s many aspects to fracking. There’s air pollution, there’s the natural hydrocarbons, there’s the oil, the gas — especially methane.”

“It’s complicated. That’s the issue. And what happens is we want to simplify a complicated problem and that’s not easy to do.”

Q. How and from where did you obtain the fluid samples? Is it necessary for fracking companies to disclose their fluid chemical properties to you for research to be carried out?

A. “One of the reasons the scientists have been a bit slow at this is it’s difficult to get the samples. They are private samples. It’s not like you can go out to the South Platte River or the nearest lake and collect a water sample and come back and analyze it. You have to get permission from whoever is drilling the well and also the owner because it’s a two part operation. The owner of the well may not be the person who’s putting down the fracking materials. For example, Halliburton drills the wells but somebody else owns the property. So you have to go through the process of collaboration. Initially that’s what we did. Two of the co-authors on the paper are from Colorado State University and they had a project with Halliburton. So they agreed to give the samples, the samples came to CSU and then they were sent to us. So in a second-hand way we got it through them. That was two or three samples. Then, here at the University of Colorado, we have a project and that’s with the collaboration also with a local drilling company. So we received samples from them. The third one was Colorado School of Mines had a project and so we received a sample from them. I got a hold of contacts at the EPA and they had some, not flowback waters, but what are called produced waters, which means that the well has been in operation for several years and there’s water coming out of the well. So we had samples from them. So really it’s a potpourri of samples. For that reason, you have to be careful about interpreting it too far. That’s why I’m so anxious to get as many samples as possible.”

Q. What do these findings mean for the oil and gas industries?

A. “I think they know the kinds of compounds they’re adding. It’s proprietary information. Each well site, though, could be a little bit different. So I think for them one advantage is we have the tools to identify what’s going down the wells, which if there’s any litigation involved, that could be very important. I have one example in Wyoming there is a site that I know has been under some kind of litigation for like three years. I tried to get a water sample from there a year-and-a-half or two years ago, and because it was under litigation they said, ‘No, we won’t give any samples from this area.’ So there’s one thing because our tool is a fingerprint of what’s in the sample. So, for example, if there were more than one well and different companies were putting in the wells, we could fingerprint whose flowback water it is. Now that could be a very important tool for them.”

Q. What do these findings mean for the groundwater industry?

A. “Because we’re identifying approximately 15 to 20 percent of what’s going down the well, I think that means that we have a handle now on a chunk of the organic matter that’s going down the well, that could contaminate the groundwater let’s say if it was a drinking water operation.”

“The average guy out there drilling the well — if the well foams, you should look into what’s going on. You shouldn’t see water foaming out of the well. If that starts happening, that’s what surfactants do. If you pump a well hard, let’s say a shallow groundwater well, and it starts to foam then you should stop and take a look at it because there could be an interaction. That’s the practical side because at 700 ppm surfactants will foam a lot, and that’s the concentration that’s in these flowback waters.”

Q. Are there any unanswered questions in your research that you hope to fill in moving forward?

A. “The most important one is to see if this is a widespread phenomenon, are these the surfactants that are being used everywhere. That requires a lot more samples, so that’s our next project.”

Q. From your perspective, what are best practices for oil & gas drilling companies practicing hydraulic fracturing?

A. “I think there are some companies that are producing what are called green fracking solutions and I think that it would be a good idea for the drillers to look into seeing what are those compounds and, in fact, is it a big advantage or not. That’s what I would suggest.”
 

Valerie King is associate editor of National Driller.