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

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

Investigating the Sorption of Pharmaceutical and Personal Care Products on High-Density Polyethylene and Polypropylene Microplastics

The term “microplastics” refers to plastic particles with a diameter of 5mm or less. Microplastics are capable of sorbing organic contaminants to concentrations magnitudes higher than the surrounding water. One such contaminants class is a group of pharmaceuticals and personal care products (PPCPs). As of now, very little information is known about the sorption behavior of PPCPs on microplastics; therefore, to better understand the interaction between PPCPs and microplastics, their sorption behavior must be studied. The goal of this project is to explore and evaluate the sorption behavior of polar and ionizable PPCPs onto microplastics. The PPCPs in this study were: diphenhydramine, an antihistamine, venlafaxine hydrochloride, an antidepressant, and N, N-diethylmeta-toluamide (DEET), which is an insect repellant.NSF, Sea Gran

Chemodiversity of dissolved organic matter in the Amazon Basin

Regions in the Amazon Basin have been associated with specific biogeochemical processes, but a detailed chemical classification of the abundant and ubiquitous dissolved organic matter (DOM), beyond specific indicator compounds and bulk measurements, has not yet been established. We sampled water from different locations in the Negro, Madeira/Jamari and Tapajós River areas to characterize the molecular DOM composition and distribution. Ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) combined with excitation emission matrix (EEM) fluorescence spectroscopy and parallel factor analysis (PARAFAC) revealed a large proportion of ubiquitous DOM but also unique area-specific molecular signatures. Unique to the DOM of the Rio Negro area was the large abundance of high molecular weight, diverse hydrogen-deficient and highly oxidized molecular ions deviating from known lignin or tannin compositions, indicating substantial oxidative processing of these ultimately plant-derived polyphenols indicative of these black waters. In contrast, unique signatures in the Madeira/Jamari area were defined by presumably labile sulfur- and nitrogen-containing molecules in this white water river system. Waters from the Tapajós main stem did not show any substantial unique molecular signatures relative to those present in the Rio Madeira and Rio Negro, which implied a lower organic molecular complexity in this clear water tributary, even after mixing with the main stem of the Amazon River. Beside ubiquitous DOM at average H ∕ C and O ∕ C elemental ratios, a distinct and significant unique DOM pool prevailed in the black, white and clear water areas that were also highly correlated with EEM-PARAFAC components and define the frameworks for primary production and other aspects of aquatic life

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

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

Sargassum sp. Act as a Large Regional Source of Marine Dissolved Organic Carbon and Polyphenols

Dissolved organic carbon (DOC) plays critical roles in marine carbon cycling, but its sources and sinks remain uncertain. In this study, we monitored DOC exudation rates of Sargassum natans under visible light (lambda > 390 nm) and solar radiation. DOC release rates ranged from 7 to 10 mu g C g(biomass)(-1) hr(-1) (wet weight) under visible light, but increased to 23 to 41 mu g C g(biomass)(-1) hr(-1) when exposed to natural sunlight. Results indicate that DOC released by Sargassum could amount to 0.3 to 1.2 Tg C/year, potentially contributing significantly to the marine DOC pool in the Gulf of Mexico and Western North Atlantic. We employed the Folin-Ciocalteu phenolic content method, nuclear magnetic resonance (NMR) spectroscopy, and ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to characterize the diverse pool of organic compounds exuded from Sargassum. Results from these complementary methods showed that Sargassum release large quantities of phlorotannins, a class of polyphenols that have very similar properties to terrestrial DOC. These phlorotannins and their oxygenated phenolic derivatives exhibit a high hydrogen deficiency and functionalization (i.e., 4 to 6 oxygen atoms per aromatic ring), representing 5 to 18% of the released DOC isolated by solid phase extraction. Thus, Sargassum is the largest biological source of open ocean polyphenols recorded to date. The amount of polyphenolic DOC released by Sargassum challenges previous beliefs that all polyphenols found within the oceans are remnants of terrestrial organic matter, although the stability of phlorotannins and their derivatives needs to be further evaluated

Chemodiversity of dissolved organic matter in the Amazon Basin

Regions in the Amazon Basin have been associated with specific biogeochemical processes, but a detailed chemical classification of the abundant and ubiquitous dissolved organic matter (DOM), beyond specific indicator compounds and bulk measurements, has not yet been established. We sampled water from different locations in the Negro, Madeira/Jamari and Tapajós River areas to characterize the molecular DOM composition and distribution. Ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) combined with excitation emission matrix (EEM) fluorescence spectroscopy and parallel factor analysis (PARAFAC) revealed a large proportion of ubiquitous DOM but also unique area-specific molecular signatures. Unique to the DOM of the Rio Negro area was the large abundance of high molecular weight, diverse hydrogen-deficient and highly oxidized molecular ions deviating from known lignin or tannin compositions, indicating substantial oxidative processing of these ultimately plant-derived polyphenols indicative of these black waters. In contrast, unique signatures in the Madeira/Jamari area were defined by presumably labile sulfur- and nitrogen-containing molecules in this white water river system. Waters from the Tapajós main stem did not show any substantial unique molecular signatures relative to those present in the Rio Madeira and Rio Negro, which implied a lower organic molecular complexity in this clear water tributary, even after mixing with the main stem of the Amazon River. Beside ubiquitous DOM at average H ∕ C and O ∕ C elemental ratios, a distinct and significant unique DOM pool prevailed in the black, white and clear water areas that were also highly correlated with EEM-PARAFAC components and define the frameworks for primary production and other aspects of aquatic life

Actin: its cumbersome pilgrimage through cellular compartments

In this article, we follow the history of one of the most abundant, most intensely studied proteins of the eukaryotic cells: actin. We report on hallmarks of its discovery, its structural and functional characterization and localization over time, and point to present days’ knowledge on its position as a member of a large family. We focus on the rather puzzling number of diverse functions as proposed for actin as a dual compartment protein. Finally, we venture on some speculations as to its origin

The Stubenberg meteorite—An LL6 chondrite fragmental breccia recovered soon after precise prediction of the strewn field

On March 6, 2016 at 21:36:51 UT, extended areas of Upper Austria, Bavaria (Germany) and the southwestern part of the Czech Republic were illuminated by a very bright bolide. This bolide was recorded by instruments in the Czech part of the European Fireball Network and it enabled complex and precise description of this event including prediction of the impact area. So far six meteorites totaling 1473 g have been found in the predicted area. The first pieces were recovered on March 12, 2016 on a field close to the village of Stubenberg (Bavaria). Stubenberg is a weakly shocked (S3) fragmental breccia consisting of abundant highly recrystallized rock fragments embedded in a clastic matrix. The texture, the large grain size of plagioclase, and the homogeneous compositions of olivine (Fa31.4) and pyroxene (Fs25.4) clearly indicate that Stubenberg is an LL6 chondrite breccia. This is consistent with the data on O, Ti, and Cr isotopes. Stubenberg does not contain solar wind-implanted noble gases. Data on the bulk chemistry, IR spectroscopy, cosmogenic nuclides, and organic components also indicate similarities to other metamorphosed LL chondrites. Noble gas studies reveal that the meteorite has a cosmic ray exposure (CRE) age of 36 ± 3 Ma and that most of the cosmogenic gases were produced in a meteoroid with a radius of at least 35 cm. This is larger than the size of the meteoroid which entered the Earth's atmosphere, which is constrained to <20 cm from short-lived radionuclide data. In combination, this might suggest a complex exposure history for Stubenberg.PostprintPeer reviewe