Jenna L. Luek

Organic compounds in hydraulic fracturing fluids and wastewaters: A review

High volume hydraulic fracturing (HVHF) of shale to stimulate the release of natural gas produces a large quantity of wastewater in the form of flowback fluids and produced water. These wastewaters are highly variable in their composition and contain a mixture of fracturing fluid additives, geogenic inorganic and organic substances, and transformation products. The qualitative and quantitative analyses of organic compounds identified in HVHF fluids, flowback fluids, and produced waters are reviewed here to communicate knowledge gaps that exist in the composition of HVHF wastewaters. In general, analyses of organic compounds have focused on those amenable to gas chromatography, focusing on volatile and semi-volatile oil and gas compounds. Studies of more polar and non-volatile organic compounds have been limited by a lack of knowledge of what compounds may be present as well as quantitative methods and standards available for analyzing these complex mixtures. Liquid chromatography paired with high-resolution mass spectrometry has been used to investigate a number of additives and will be a key tool to further research on transformation products that are increasingly solubilized through physical, chemical, and biological processes in situ and during environmental contamination events. Diverse treatments have been tested and applied to HVHF wastewaters but limited information has been published on the quantitative removal of individual organic compounds. This review focuses on recently published information on organic compounds identified in flowback fluids and produced waters from HVHF.

Halogenated Organic Compounds Identified in Hydraulic Fracturing Wastewaters Using Ultrahigh Resolution Mass Spectrometry

Large volumes of water return to the surface following hydraulic fracturing of deep shale formations to retrieve oil and natural gas. Current understanding of the specific organic constituents in these hydraulic fracturing wastewaters is limited to hydrocarbons and a fraction of known chemical additives. In this study, we analyzed hydraulic fracturing wastewater samples using ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) as a nontargeted technique to assign unambiguous molecular formulas to singly charged molecular ions. Halogenated molecular formulas were identified and confirmed using isotopic simulation and MS-MS fragmentation spectra. The abundance of halogenated organic compounds in flowback fluids rather than older wastewaters suggested that the observed molecular ions might have been related to hydraulic fracturing additives and related subsurface reactions, such as through the reaction of shale-extracted chloride, bromide, and iodide with strong oxidant additives (e.g., hypochlorite, persulfate, hydrogen peroxide) and subsequently with diverse dissolved organic matter. Some molecular ions matched the exact masses of known disinfection byproducts including diiodoacetic acid, dibromobenzoic acid, and diiodobenzoic acid. The identified halogenated organic compounds, particularly iodinated organic molecules, are absent from inland natural systems and these compounds could therefore play an important role as environmental tracers.

Picocyanobacteria and deep-ocean fluorescent dissolved organic matter share similar optical properties

Marine chromophoric dissolved organic matter (CDOM) and its related fluorescent components (FDOM), which are widely distributed but highly photobleached in the surface ocean, are critical in regulating light attenuation in the ocean. However, the origins of marine FDOM are still under investigation. Here we show that cultured picocyanobacteria, Synechococcus and Prochlorococcus, release FDOM that closely match the typical fluorescent signals found in oceanic environments. Picocyanobacterial FDOM also shows comparable apparent fluorescent quantum yields and undergoes similar photo-degradation behaviour when compared with deep-ocean FDOM, further strengthening the similarity between them. Ultrahigh-resolution mass spectrometry (MS) and nuclear magnetic resonance spectroscopy reveal abundant nitrogen-containing compounds in Synechococcus DOM, which may originate from degradation products of the fluorescent phycobilin pigments. Given the importance of picocyanobacteria in the global carbon cycle, our results indicate that picocyanobacteria are likely to be important sources of marine autochthonous FDOM, which may accumulate in the deep ocean.

Sulfate Reduction in Sediments Produces High Levels of Chromophoric Dissolved Organic Matter

Sulfate reduction plays an important role in altering dissolved organic matter (DOM) in estuarine and coastal sediments, although its role in the production of optically active chromophoric DOM (CDOM) and a subset of fluorescent DOM (FDOM) has not been previously investigated in detail. Freshwater sediment slurries were incubated anaerobically with added sulfate and acetate to promote sulfate-reducing bacteria. Ultraviolet visible (UV-Vis) absorbance and 3-dimensional excitation emission matrix (EEM) fluorescence spectra were measured over a five weeks anaerobic dark incubation period. Parallel Factor Analysis (PARAFAC) of FDOM determined components that increased significantly during dark and anaerobic incubation matching three components previously considered of terrestrially-derived or humic-like origin published in the OpenFluor database. The observed FDOM increase was strongly correlated (R2 = 0.96) with the reduction of sulfate. These results show a direct experimental link between sulfate reduction and FDOM production, which impacts our understanding of coastal FDOM sources and early sediment diagenesis. As 3D fluorescence techniques are commonly applied to diverse systems, these results provide increasing support that FDOM can have many diverse sources not consistently captured by common classifications such as “humic-like” fluorescence.

Temporal dynamics of halogenated organic compounds in Marcellus Shale flowback

The chemistry of hydraulic fracturing fluids and wastewaters is complex and is known to vary by operator, geologic formation, and fluid age. A time series of hydraulic fracturing fluids, flowback fluids, and produced waters was collected from two adjacent Marcellus Shale gas wells for organic chemical composition analyses using ultrahigh resolution mass spectrometry. Hierarchical clustering was used to compare and extract ions related to different fluid ages and many halogenated organic molecular ions were identified in flowback fluids and early produced waters based on exact mass. Iodinated organic compounds were the dominant halogen class in these clusters and were nearly undetectable in hydraulic fracturing fluid prior to injection. The iodinated ions increased in flowback and remained elevated after ten months of well production. We suggest that these trends are mainly driven by dissolved organic matter reacting with reactive halogen species formed abiotically through oxidizing chemical additives applied to the well and biotically via iodide-oxidizing bacteria. Understanding the implications of these identified halogenated organic compounds will require future investigation in to their structures and environmental fate.

Author Correction: Sulfate Reduction in Sediments Produces High Levels of Chromophoric Dissolved Organic Matter

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