Resin-coated proppants (RCPs) are used in hydraulic fracturing of oil and gas wells to improve well performance; however, these proppants could be a cause for environmental concern if they are disposed of improperly. In this study, we investigate the water-leachable organic and inorganic constituents from proppants collected from surficial releases of RCPs in southeastern New Mexico. Significant concentrations of nonvolatile dissolved organic matter (>100 mg C/L) and phenolic compounds (>50 mg phenol/L) were identified in one of the proppant leachates, with further gas chromatography-mass spectrometry analysis identifying isomers of bisphenol F, a known endocrine disruptor analogous to bisphenol A, as the main organic constituents within this leachate. Fluorescence excitation-emission matrices analyses of proppant leachates identified several peaks associated with phenolic compounds, similar to previously studied oilfield wastewaters. Precursors of polyurethane production, including the inhalation sensitizer methylene diphenyl diisocyanate, were identified in the leachate from another proppant sample. An understanding of leachable compounds from RCPs is vital to management of environmental contamination from surficial releases, protecting the public and industry workers from associated hazards, and identifying the sources of organic compounds in oilfield wastewaters.

Methylmercury (MeHg) production is controlled by the bioavailability of inorganic divalent mercury (Hg(II)i ) and Hg-methylation capacity of the microbial community (conferred by the hgcAB gene cluster). However, the relative importance of these factors and their interaction in the environment remain poorly understood. Here, metagenomic sequencing and a full-factorial MeHg formation experiment were conducted across a wetland sulfate gradient with different microbial communities and pore water chemistries. From this experiment, the relative importance of each factor on MeHg formation was isolated. Hg(II)i bioavailability correlated with the dissolved organic matter composition, while the microbial Hg-methylation capacity correlated with the abundance of hgcA genes. MeHg formation responded synergistically to both factors. Notably, hgcA sequences were from diverse taxonomic groups, none of which contained genes for dissimilatory sulfate reduction. This work expands our understanding of the geochemical and microbial constraints on MeHg formation in situ and provides an experimental framework for further mechanistic studies.

Human health effects can arise from unregulated manual disassembly of electronic waste (e-waste) and/or hydraulic fracturing fluid spills. There is limited literature on the effects of e-waste and hydraulic fracturing wastewater exposure on the male reproductive system. Thus, this proof-of-concept study begins to address the question of how wastewater from two potentially hazardous environmental processes could affect sperm quality. Therefore, three groups of eight-week-old adult mice were exposed (5 d/wk for 6 wks) via a mealworm (Tenebrio molitor and Zophabas morio) feeding route to either: (1) e-waste leachate (50% dilution) from the Alaba Market (Lagos, Nigeria); (2) West Virginia hydraulic fracturing flowback (HFF) fluid (50% dilution); or, (3) deionized water (control). At 24-hours (hr), 3 weeks (wk), or 9-wk following the 6-wk exposure period, cohorts of mice were necropsied and adverse effects/persistence on the male reproductive system were examined. Ingestion of e-waste leachate or HFF fluid decreased number and concentration of sperm and increased both chromatin damage and numbers of morphological abnormalities in the sperm when compared to control mice. Levels of serum testosterone were reduced post-exposure (3- and 9-wk) in mice exposed to e-waste leachate and HFF when compared to time-matched controls, indicating the long-term persistence of adverse effects, well after the end of exposure. These data suggest that men living around or working in vicinity of either e-waste or hydraulic fracturing could face harmful effects to their reproductive health. From both a human health and economic standpoint, development of prevention and intervention strategies that are culturally relevant and economically sensitive are critically needed to reduce exposure to e-waste and HFF-associated toxic contaminants.

Subsurface microbial (biogenic) methane production is an important part of the global carbon cycle that has resulted in natural gas accumulations in many coal beds worldwide. Laboratory studies suggest that complex carbon-containing nutrients (e.g., yeast or algae extract) can stimulate methane production, yet the effectiveness of these nutrients within coal beds is unknown. Here, we use downhole monitoring methods in combination with deuterated water (D2O) and a 200-liter injection of 0.1% yeast extract (YE) to stimulate and isotopically label newly generated methane. A total dissolved gas pressure sensor enabled real-time gas measurements (641 days preinjection and for 478 days postinjection). Downhole samples, collected with subsurface environmental samplers, indicate that methane increased 132% above preinjection levels based on isotopic labeling from D2O, 108% based on pressure readings, and 183% based on methane measurements 266 days postinjection. Demonstrating that YE enhances biogenic coalbed methane production in situ using multiple novel measurement methods has immediate implications for other field-scale biogenic methane investigations, including in situ methods to detect and track microbial activities related to the methanogenic turnover of recalcitrant carbon in the subsurface.

Mercury (Hg) contamination has been a persistent concern in the Florida Everglades for over three decades due to elevated atmospheric deposition and the system's propensity for methylation and rapid bioaccumulation. Given declines in atmospheric Hg concentrations in the conterminous United States and efforts to mitigate nutrient release to the greater Everglades ecosystem, it was vital to assess how Hg dynamics responded on temporal and spatial scales. This study used a multimedia approach (water and biota) to examine Hg and methylmercury (MeHg) dynamics across a 76-site network within the southernmost portion of the region, Everglades National Park (ENP), from 2008 to 2018. Hg concentrations across matrices showed that air, water, and biota from the system were inextricably linked. Temporal patterns across matrices were driven primarily by hydrologic and climatic changes in the park and no evidence of a decline in atmospheric Hg deposition from 2008 to 2018 was observed, unlike other regions of the United States. In the Shark River Slough (SRS), excess dissolved organic carbon and sulfate were also consistently delivered from upgradient canals and showed no evidence of decline over the study period. Within the SRS a strong positive correlation was observed between MeHg concentrations in surface water and resident fish. Within distinct geographic regions of ENP (SRS, Marsh, Coastal), the geochemical controls on MeHg dynamics differed and highlighted regions susceptible to higher MeHg bioaccumulation, particularly in the SRS and Coastal regions. This study demonstrates the strong influence that dissolved organic carbon and sulfate loads have on spatial and temporal distributions of MeHg across ENP. Importantly, improved water quality and flow rates are two key restoration targets of the nearly 30-year Everglades restoration program, which if achieved, this study suggests would lead to reduced MeHg production and exposure.

Balkan endemic nephropathy (BEN) is a chronic tubulointerstitial nephropathy affecting residents of rural farming areas in many Balkan countries. Although it is generally believed that BEN is an environmental disease caused by multiple geochemical factors with much attention on aristolochic acids (AAs), its etiology remains controversial. In this study, we tested the hypothesis that environmental contamination and subsequent food contamination by polycyclic aromatic hydrocarbons (PAHs) and phthalate esters are AA toxicity factors and important to BEN development. We identified significantly higher concentrations of phenanthrene, anthracene, diethyl phthalate (DEP), dibutyl phthalate (DBP), and benzyl butyl phthalate (BBP) in both maize and wheat grain samples collected from endemic villages than from nonendemic villages. Other PAHs and phthalate esters were also detected at higher concentrations in the soil samples from endemic villages. Subsequent genotoxicity testing of cultured human kidney cells showed an alarming phenomenon that phenanthrene, DEP, BBP, and DBP can interact synergistically with AAs to form elevated levels of AA-DNA adducts, which are associated with both the nephrotoxicity and carcinogenicity of AAs, further increasing their disease risks. This study provides direct evidence that prolonged coexposure to these environmental contaminants via dietary intake may lead to greater toxicity and accelerated development of BEN.

The widespread application of directional drilling and hydraulic fracturing technologies expanded oil and gas (OG) development to previously inaccessible resources. A single OG well can generate millions of liters of wastewater, which is a mixture of brine produced from the fractured formations and injected hydraulic fracturing fluids (HFFs). With thousands of wells completed each year, safe management of OG wastewaters has become a major challenge to the industry and regulators. OG wastewaters are commonly disposed of by underground injection, and previous research showed that surface activities at an Underground Injection Control (UIC) facility in West Virginia affected stream biogeochemistry and sediment microbial communities immediately downstream from the facility. Because microbially driven processes can control the fate and transport of organic and inorganic components of OG wastewater, we designed a series of aerobic microcosm experiments to assess the influence of high total dissolved solids (TDS) and two common HFF additives-the biocide 2,2-dibromo-3-nitrilopropionamide (DBNPA) and ethylene glycol (an anti-scaling additive)-on microbial community structure and function. Microcosms were constructed with sediment collected upstream (background) or downstream (impacted) from the UIC facility in West Virginia. Exposure to elevated TDS resulted in a significant decrease in aerobic respiration, and microbial community analysis following incubation indicated that elevated TDS could be linked to the majority of change in community structure. Over the course of the incubation, the sediment layer in the microcosms became anoxic, and addition of DBNPA was observed to inhibit iron reduction. In general, disruptions to microbial community structure and function were more pronounced in upstream and background sediment microcosms than in impacted sediment microcosms. These results suggest that the microbial community in impacted sediments had adapted following exposure to OG wastewater releases from the site. Our findings demonstrate the potential for releases from an OG wastewater disposal facility to alter microbial communities and biogeochemical processes. We anticipate that these studies will aid in the development of useful models for the potential impact of UIC disposal facilities on adjoining surface water and shallow groundwater.

The Permian Basin, straddling New Mexico and Texas, is one of the most productive oil and gas (OG) provinces in the United States. OG production yields large volumes of wastewater that have complex chemistries. These OG wastewaters pose unknown environmental health risks, particularly in the case of accidental or intentional releases. Starting in November 2017, at least 39 illegal dumps of OG wastewater were identified in southeastern New Mexico, part of the Permian Basin, releasing ~4,000 barrels of fluid onto desert soils. To evaluate the impacts of these releases, we analyzed changes in soil geochemistry and microbial community structure at 5 sites by comparing soils from within OG wastewater dump-affected zones to corresponding unaffected (control) soils. Soil geochemistry for all dump samples differed from unaffected samples, reflecting the residual salts and hydrocarbons left behind by the OG wastewater release (e.g., enriched in sodium (Na), chloride (Cl), and bromide (Br)). Microbial community analysis, using Illumina 16S iTag sequencing, revealed significant differences (p<0.01) between communities in dump and control zones. Further, soils from dump areas had significantly (p<0.01) lower alpha diversity, and differences in phylogenetic composition. Dump-affected soil samples showed an increase in taxa with halophilic capabilities, such as those affiliated with Marinobacteraceae, Halomonadaceae, and Halobacteroidaceae, suggesting that the high salinity of the dumped OG wastewater was a strong selective pressure for microbial communities. Taxa with capabilities to metabolize hydrocarbons were also detected in the dump-affected soil sample communities. Overall, this study elucidates changes in desert soil geochemistry and microbial community dynamics due to OG wastewater exposure.

Since 2009, unconventional natural gas development (UNGD) has significantly increased in Appalachia’s Marcellus Shale formation. Elevations of fine particulate matter <2.5 µm (PM2.5), have been documented in areas surrounding drilling operations during well stimulation. Furthermore, many communities are experiencing increased industrial activities and probable UNGD air pollutant exposures. Recent studies have associated UNGD emissions with health effects based on distances from well pads. In this study, PM2.5 filter samples were collected on an active gas well pad in Morgantown, West Virginia, and three locations downwind during hydraulic stimulation. Fine particulate samples were analyzed for major and trace elements. An experimental source identification model was developed to determine which elements appeared to be traceable downwind of the UNGD site and whether these elements corresponded to PM2.5 measurements. Results suggest that 1) magnesium may be useful for detecting the reach of UNGD point source emissions, 2) complex surface topographic and meteorological conditions in the Marcellus Shale region could be modeled and confounding sources discounted, and 3) well pad emissions may be measurable at distances of at least 7 km. If shown to be more widely applicable, future tracer studies could enhance epidemiological studies showing health effects of UNGD-associated emissions at ≥15 km.

The present study investigated the possibility of microbial transformations of coal to gas (biogasification) as an alternative to conventional coal mining because this approach has the potential to be less expensive, cleaner, and provide greater access to deeper coal resources. Biogasification is often associated with low rank coal such as lignite and subbituminous coal that has produced enough coalbed methane to be commercially viable in the United States and Australia. However, little work has been done to analyze the potential of biogasification in higher rank coal. For this purpose, bioassay using a wetland-derived consortium and a coal-derived consortium were used to analyze coal samples from Pakistan belonging to different ranks (lignite to semi-anthracite). Among all samples a low volatile bituminous coal produced the maximum methane 34.95 mu mol CH4/g coal with the wetland-derived microbial consortium, followed by subbituminous coal (30.18 mu mol CH4/g coal). Lower methane levels were recorded with the coal-derived consortium, with subbituminous coal yielding the highest concentration (25.1 mu mol CH4/g coal). Methane levels appeared to be increasing on the last measurement indicating the coal-derived consortium was slower than the wetland-derived consortium but could still catalyze biogasification in higher rank coals. Quantitative polymerase chain reaction analysis for mcrA functional genes indicated that the microbial community members that produce methane (methanogens) varied during the incubations. Energy conversion efficiency of different strategies (other biological and underground coal gasification processes) was also compared and discussed. This study was the first to compare bioassay using consortia of microbes non-indigenous and indigenous to coal and indicate the potential of biogasification from many different coalbeds across Pakistan. (C) 2020 Elsevier Ltd. All rights reserved.

The organic composition of produced waters (flowback and formation waters) from the middle member of the Bakken Formation and the Three Forks Formation in the Williston Basin, North Dakota were examined to aid in the remediation of surface contamination and help develop treatment methods for produced-water recycling. Twelve produced water samples were collected from the Bakken and Three Forks Formations and analyzed for non-purgeable dissolved organic carbon (NPDOC), acetate, and extractable hydrocarbons. NPDOC and acetate concentrations from sampled wells from ranged from 33-190 mg per liter (mg/L) and 16-40 mg/L, respectively. Concentrations of individual extractable hydrocarbon compounds ranged from less than 1 to greater than 400 μg per liter (μg/L), and included polycyclic aromatic hydrocarbons (PAHs), phenolic compounds, glycol ethers, and cyclic ketones. While the limited number of samples, varying well production age, and lack of knowledge of on-going well treatments complicate conclusions, this report adds to the limited knowledge of organics in produced waters from the Bakken and Three Forks Formations.

The lower Eagle Ford Group (LEFG) is one of the most productive continuous hydrocarbon plays in the United States but few associated produced waters data and minimal interpretation have been published. This effort focuses on results from compositional and isotopic data from 39 produced water samples collected from horizontal wells producing from the LEFG in south central Texas. The depth of the LEFG increases by approximately 1 km across the study area, from northwest (2.9 km) to southeast (3.9 km). Associated increases in calculated reservoir temperature (125-165 degrees C), development of reservoir over-pressuring (400-800 bars total pressure), and increased thermal maturity (heavy oil to gas condensate) also occur along this trend. Produced water salinity starts at nearly 100 g/L in the shallowest samples and decreases linearly with depth to < 35 g/L. Comparison of Br/Cl and Sr-87/Sr-86 data between LEFG produced waters and the Louann salt, suggests that halite recycling is the mechanism generating salinities greater than seawater. Decreasing salinity with depth and thermal maturity in the Gulf Coast Basin have previously been shown to be a result of release of inter-layer water during smectite to illite conversion. The produced water samples show increasing delta O-18 and decreasing delta H-2 with depth, which is attributed temperature-dependent isotope fractionation of O and H exchange between seawater and clays and calcite with increasing temperature. Multiple sources of data indicate that the waters in the LEFG are not connate, but rather entered the unit prior to smectite-illite conversion. Presence of allochthonous water in many major tight oil and shale gas plays in the U.S., including the LEFG, suggests there is an unknown mechanism allowing for water flow into low permeability reservoirs.

The position of tidal wetlands at the land-sea interface makes them especially vulnerable to the effects of nutrient discharges and sea level rise (SLR). Experimental studies of coastal wetland nutrient additions report conflicting results among and within habitats, highlighting the importance of site-specific factors, and how spatial and temporal scaling modulates responses. This suite of influences as SLR accelerates creates a "Gordian Knot" that may compromise coastal habitat integrity. We present eight testable hypotheses here to loosen this knot by identifying critical modulators about nutrient form, soil type and porosity, physiochemical gradients, and eco-evolutionary responses that may control the impacts of nutrient enrichment on coastal wetland sustainability: (1) the delivery and form of the nutrient shapes the ecosystem response; (2) soil type mediates the effects of nutrient enrichment on marshes; (3) belowground responses cannot be solely explained by phenotypic responses; (4) shifting zones of redox and salinity gradients modulate nutrient enrichment impacts; (5) eco-evolutionary processes can drive responses to nutrient availability; (6) nutrient enrichment leads to multiple changed ecosystem states; (7) biogeography trumps a plant's plastic responses to nutrient enrichment; and, (8) nutrient-enhanced wetlands are more susceptible to additional (and anticipated) anthropogenic changes. They provide a framework to investigate and integrate the urgently needed research to understand how excess nutrients threaten the sustainability of coastal wetlands, and wetlands in general. While there is no single 'right way' to test these hypotheses, including a combination of complex and simple, highly-replicated experiments is essential.

The Florida Everglades has one of the most severe methylmercury (MeHg) contamination issues in the USA, resulting from factors including high rates of atmospheric mercury (Hg) deposition and sulfate inputs from agricultural lands. Sulfate loading stimulates microbial sulfate reduction and production of toxic and bioaccumulative MeHg. Controls on regional Hg emissions have been successful in reducing Hg deposition and MeHg production in wetlands in other areas, but this has not been the case for the Everglades as the Hg deposited here appears to come from unknown global sources of emissions. We posit that reductions in sulfate loading to the Florida Everglades can be an effective alternative approach used to reduce MeHg production. This study tested this hypothesis (1) by evaluating temporal trends in MeHg concentrations in response to a reduction in sulfate loading at a site in central Water Conservation Area (WCA) 3 and (2) using ecosystem-scale models to predict the effects of reductions in sulfate loading on sulfate concentrations in surface water and MeHg Risk. At the WCA site, we report a decline in sulfate concentrations (from about 9 mg/L in the late 1990s to levels of < 1 mg/L by 2001) due to changes in water delivery as part of Everglades restoration. Concurrent with the decline in sulfate, declines in MeHg concentrations in surface water and fish and wading bird tissues were observed at this site. These results suggest the efficacy of reducing MeHg production and bioaccumulation in the ecosystem through a reduction in sulfate loading. A previously developed model was used to predict the effects of reductions in sulfate loading (97%, 33%, and 10% reduction scenarios) on sulfate concentrations in surface water and MeHg Risk in the Everglades. The model identified areas of the ecosystem where MeHg Risk is most sensitive to the reductions in sulfate loading. Results show that reductions of > 33% in sulfate loading will significantly benefit the Everglades by reducing MeHg Risk.

Scenarios modeling can be a useful tool to plan for climate change. In this study, we help Everglades restoration planning to bolster climate change resiliency by simulating plausible ecosystem responses to three climate change scenarios: a Baseline scenario of 2010 climate, and two scenarios that both included 1.5 °C warming and 7% increase in evapotranspiration, and differed only by rainfall: either increase or decrease by 10%. In conjunction with output from a water-use management model, we used these scenarios to drive the Everglades Landscape Model to simulate changes in a suite of parameters that include both hydrologic drivers and changes to soil pattern and process. In this paper we focus on the freshwater wetlands; sea level rise is specifically addressed in prior work. The decreased rainfall scenario produced marked changes across the system in comparison to the Baseline scenario. Most notably, muck fire risk was elevated for 49% of the period of simulation in one of the three indicator regions. Surface water flow velocity slowed drastically across most of the system, which may impair soil processes related to maintaining landscape patterning. Due to lower flow volumes, this scenario produced decreases in parameters related to flow-loading, such as phosphorus accumulation in the soil, and methylmercury production risk. The increased rainfall scenario was hydrologically similar to the Baseline scenario due to existing water management rules. A key change was phosphorus accumulation in the soil, an effect of flow-loading due to higher inflow from water control structures in this scenario.