The LCGC Blog: Research on Polarizing Environmental Topics Requires More Than Just Analytical Chemistry

On Thursday afternoon at Pittcon 2018, I participated in a session titled “Advances in Environmental Analytical Chemistry: Impacts on Modern Petroleum Production Monitoring and Oil Spill Science,” which was organized by Ryan Rodgers of the National High Magnetic Field Laboratory at Florida State University. I received the honorary co-organizer title, but Ryan was the one who initiated the effort, pulled it together, and saw it through to successful fruition.

It was an excellent session, featuring Imma Ferrer from University of Colorado, Frank Dorman from the Pennsylvania State University, and me speaking about analytical methodology to study the potential environmental impacts of unconventional oil and gas extraction (including hydraulic fracturing, or “fracking”), as well as wastewater characterization and treatment. Further talks from Christopher Reddy of Woods Hole Oceanographic Institute and Matthew Tarr of the University of New Orleans expanded the discussion into the characterization, the environmental impacts of, and the environmental effects (for example, photodegradation) on oil spills.

As you can imagine, the level of analytical science was very high. All of these researchers are considered leaders in the field. However, what was interesting were some of the non-analytical chemistry take-home messages gleaned from the discussion.

The topics addressed in the session are all highly polarizing. Scientists whose work on topics related to the environmental effects of unconventional drilling or oil spills can be subjected to praise or ridicule from those with extreme views, depending on the nature of their findings, and the conclusions they draw from them. Scientists must walk the fine line of objectivity, where the middle ground is a lonely place (1). Here, at the Collaborative Laboratories for Environmental Analysis and Remediation (CLEAR) at U.T. Arlington, we say we are just in the right place if both sides are at different times either praising or trying to debunk our work. All comments that try to question the objectivity of our work need to be addressed head-on to protect its integrity, but there is a lot more to the story. Before you can report the research, you have to actually do the research, and some steps or considerations in that process might be initially overlooked.

Clearly, one who is an expert in analytical chemistry, even if they have some significant breadth related to their experience in environment chemistry, cannot conduct such in-depth research on their own. All of the professors indicated the importance of assembling a team of collaborators, including various industry supporters, to address such a complex topic. Analytical chemists need biologists, hydrogeologists, biochemists, statisticians, oceanographers, and many others to decipher the meaning of the analytical results and to help draw conclusions. Obligatory acknowledgment slides in the talks were necessarily extensive to attribute credit to work by a large number of stakeholders who made the research possible.

Take a few steps back. Before any work can be done, we need to obtain samples. One thing is clear-researchers dressed in personal protective equipment in the field will draw attention from bystanders. The researchers may design an agenda to collect some number of samples in a day, but it is difficult to judge the potential for expediency when it is likely that they will be bombarded at each site with questions from onlookers. It takes a special person both to have the know-how to collect samples from a site and to be able to explain the objectives of the research in a responsible, informative, and unbiased fashion. Often, the bystanders will already have some preconceived notions about the value of the research, which could be positive or negative. We joke, but in Texas, we have found that personal protective equipment augmented with a little camouflage and a Texas A&M hat will be met with greater hospitality than other attire. All joking aside, our visits to homeowners for sample collection have been met with everything between the extremes of hugs from deeply worried individuals, to a shotgun in the face with the curt request to get off the property in 90 seconds or less.

Timing the sampling is not easy either. All presenters spoke a bit about serendipity and the role of coincidence in obtaining some of their most valuable samples. Certainly, response to an oil spill requires quick action and coordination. All of the research questions addressed had some aspect of industry uncertainty. Serendipity can often be in the form of, “I know a guy who knows a guy” who might be able to get you a sample. Major advances in the environmental analyses shown were often a result of partnerships forged over extensive interactions between academia and industry. Following some previous work (2), we expounded on the necessity to have insight from industry to time the sampling so that it best coincided with the processes under investigation. We were happy to have this lead, in our case, to an ongoing collaboration with Apache Corporation and its scientists to perform a variety of environmental monitoring efforts in west Texas, as well as laboratory experiments related to assessing the performance and safety of hydraulic fracturing chemicals (3). Others have forged similar essential relationships with industry partners to advance their science.

Once you have the sample, how do you analyze it? Crude oil, wastewater, and even groundwater are extremely complex samples. Standard methods, such as those promulgated by the U.S. Environmental Protections Agency (EPA), may be good for some general analyses, but often the specific targets (and the presence of many unknowns) require new methods to be developed. The focus of those methods may be on increased coverage of analytes, accommodation of smaller sample sizes, throughput, effective combination of targeted and untargeted determinations, or achieving the necessary sensitivity and specificity in the presence of complex sample backgrounds. Many of the components of interest can be proprietary to the industry, making it difficult to know what to look for.

Liquid chromatography (LC) and gas chromatography (GC) (especially on-line comprehensive multidimensional gas chromatography [GCxGC]) were featured prominently to study samples such as nonionic surfactants in oilfield-produced wastewater, Archean biomarkers in crude oil, and trace contaminants in drinking water. The power of Fourier transform–ion cyclotron resonance mass spectrometry (FT-ICR-MS) was shown to be essential for elucidating crude oil transformation products from photoxidation processes. Because many results of the studies will be heavily scrutinized, validation and quality control steps and data are of paramount importance. Often you get just one shot at the analysis of each sample; in most cases, the samples have a limited shelf-life. Simply designing the laboratory analysis workflow and timing, sometimes in the face of hundreds of samples to be analyzed, can be no small feat. Again, many people and different tasks need to be coordinated. More than once, the essential nature of robust and reliable instrumentation brought the presenters to praise important partnerships with instrument manufacturers.

Although complex samples need to be addressed with novel methods, there is a desire to reduce research-based methods to routine use. Through continual use (and continual quality control), the robustness and reliability of the methods and instrumentation can be established. This approach is essential to building a reliable foundation for each ongoing research enterprise. At CLEAR, we continue to develop new methods, but we rely on the data obtained for our established legacy methods to provide depth, context, and reliability to results from the new approaches.

Several years ago, I would have held the stance that environmental analysis was fairly boring. How complicated can water be? I am not ashamed to say that was a naïve view. It is clear from our research and related research by others on similar topics that much more work in these areas is needed. Standard methods cannot solely accommodate the growing list of targets and the multitude of unknowns associated with complex samples taken from the interface between the petroleum industry and the environment. New and reliable analytical methods are always needed, and prior standard methods can be used to glean best practices in their development. I am not alone in my current feeling that these are exciting research areas; we need more people engaged in these topics so that we can ensure appropriate environmental stewardship in the face of enormous and multifaceted petroleum operations-and we need to be able to work closely with industry in a collaborative manner to be the most effective with our efforts.           

References

1. K.A. Schug, The LCGC Blog. May 11, 2016. http://www.chromatographyonline.com/middle-ground-unconventional-oil-and-gas-development-aka-fracking-lonely-place

2. Z.L. Hildenbrand, D.D. Carlton Jr., B.E. Fontenot, J.M. Meik, J. Walton, J.B. Thacker, S. Korlie, C.P. Shelor, A.F. Kadjo, A. Clark, S. Usenko, J. Hamilton, P. Mach, G. Verbeck IV, P. Hudak, and K.A. Schug, Sci. Tot. Environ.562, 906–913 (2016).

3. K.A. Schug, The LCGC Blog. Dec. 7, 2016. http://www.chromatographyonline.com/lcgc-blog-partnering-monitor-effects-fracking

Kevin A. Schug is a Full Professor and Shimadzu Distinguished Professor of Analytical Chemistry in the Department of Chemistry & Biochemistry at The University of Texas (UT) at Arlington. He joined the faculty at UT Arlington in 2005 after completing a Ph.D. in Chemistry at Virginia Tech under the direction of Prof. Harold M. McNair and a post-doctoral fellowship at the University of Vienna under Prof. Wolfgang Lindner. Research in the Schug group spans fundamental and applied areas of separation science and mass spectrometry. Schug was named the LCGC Emerging Leader in Chromatography in 2009 and the 2012 American Chemical Society Division of Analytical Chemistry Young Investigator in Separation Science. He is a fellow of both the U.T. Arlington and U.T. System-Wide Academies of Distinguished Teachers.