Selenium Adsorption onto Iron Oxide Layers beneath Coal-Mine Overburden Spoil.

A field experimental study to determine the feasibility of sequestering dissolved selenium (Se) leached from coal-mine waste rock used an iron (Fe)-oxide amendment obtained from a mine-drainage treatment wetland. Thirty lysimeters (4.9 × 7.3 m), each containing 57.7 t (1.2-1.8 m thickness) of mine-run carbonaceous shale overburden, were installed at the Hobet mine in southeastern West Virginia. The fine-grained Fe-oxide was determined to be primarily metal oxides (91.5% ferric and 4.37% aluminous), with minor (<3%) SO and Ca, perhaps as gypsum. The mineralogy of the Fe was goethite, although residual ferrihydrite may have been present. Various thicknesses of this amendment (0.0064, 0.057, 0.229, and 0.457 m, plus a zero-amendment control) were used, ranging from 0 to 2.2% weight percent of the spoil. The control and each treatment were replicated six times to estimate uncertainty due to compositional and hydrological variation. Infiltration of rainfall created leachate that drained to individual batch-collection tanks that were sampled 46 times at approximately 2-wk intervals from 2010 to 2012. Basal Fe-oxide layers in the three highest amendment categories removed up to 76.1% selenium (in comparison to unamended piles) from leachate by adsorption. Only lysimeters with very thin Fe-oxide layers showed no significant reduction compared with unamended piles. Reproducibility of replicates was within acceptable limits for amended and unamended lysimeters. Results indicate that in situ amendment using Fe-oxide obtained from treatment of mine water can sequester Se by adsorption on surfaces of goethite and possibly also ferrihydrite. This process is demonstrated to substantially reduce dissolved Se in leachate and improve compliance with regulatory discharge limits.

Microbial communities reveal impacts of unconventional oil and gas development on headwater streams.

The demand for natural gas has led to the development of techniques used to access unconventional oil and natural gas (UOG) resources, due to the novelty of UOG, the potential impacts to freshwater ecosystems are not fully understood. We used a dual pronged approach to study the effects of UOG development on microbial biodiversity and function via a laboratory microcosm experiment and a survey study of streams with and without UOG development within their watersheds. The microcosm experiment simulated stream contamination with produced water, a byproduct of UOG operations, using sediment collected from one high water-quality stream and two low water-quality streams. For the survey study, biofilm and sediment samples were collected from streams experiencing varying levels of UOG development. In the microcosm experiment, produced water decreased microbial aerobic and anaerobic CO2 production in the high water-quality stream sediment but had a positive effect on this microbial activity in the lower water-quality stream sediments, suggesting habitat degradation alters the response of microbes to contaminants. Results from the stream survey indicate UOG development alters stream water temperature, chemistry, sediment aerobic and anaerobic CO2 production, and microbial community biodiversity in both sediments and biofilms. Correlations among UOG associated land use, environmental, and microbial variables suggest increases in light availability and sediment delivery to streams, due to deforestation and land disturbance, impact stream microbial communities and their function. Consistent changes in the relative abundance of bacterial taxa suggest microorganisms may be good indicators of the environmental changes associated with UOG development. The observed impacts of UOG development on microbial community composition and carbon cycling could have cascading effects on stream health and broader ecosystem function.

Toxicity of hydraulic fracturing wastewater from black shale natural-gas wells influenced by well maturity and chemical additives.

Hydraulic fracturing of deep shale formations generates large volumes of wastewater that must be managed through treatment, reuse, or disposal. Produced wastewater liberates formation-derived radionuclides and contains previously uncharacterized organohalides thought to be generated within the shale well, both posing unknown toxicity to human and ecological health. Here, we assess the toxicity of 42 input media and produced fluid samples collected from four wells in the Utica formation and Marcellus Shale using two distinct endpoint screening assays. Broad spectrum acute toxicity was assessed using a bioluminescence inhibition assay employing the halotolerant bacterium Aliivibrio fischeri, while predictive mammalian cytotoxicity was evaluated using a N-acetylcysteine (NAC) thiol reactivity assay. The acute toxicity and thiol reactivity of early-stage flowback was higher than later produced fluids, with levels diminishing through time as the natural gas wells matured. Acute toxicity of early stage flowback and drilling muds were on par with the positive control, 3,5-dichlorophenol (6.8 mg L-1). Differences in both acute toxicity and thiol reactivity between paired natural gas well samples were associated with specific chemical additives. Samples from wells containing a larger diversity and concentration of organic additives resulted in higher acute toxicity, while samples from a well applying a higher composition of ammonium persulfate, a strong oxidizer, showed greater thiol reactivity, predictive of higher mammalian toxicity. Both acute toxicity and thiol reactivity are consistently detected in produced waters, in some cases present up to nine months after hydraulic fracturing. These results support that specific chemical additives, the reactions generated by the additives, or the constituents liberated from the formation by the additives contribute to the toxicity of hydraulic fracturing produced waters and reinforces the need for careful consideration of early produced fluid management.

Water chemistry-based classification of streams and implications for restoring mined Appalachian watersheds.

We analyzed seasonal water samples from the Cheat and Tygart Valley river basins, West Virginia, USA, in an attempt to classify streams based on water chemistry in this coal-mining region. We also examined temporal variability among water samples. Principal component analysis identified two important dimensions of variation in water chemistry. This variation was determined largely by mining-related factors (elevated metals, sulfates, and conductivity) and an alkalinity-hardness gradient. Cluster analysis grouped water samples into six types that we described as reference, soft, hard, transitional, moderate acid mine drainage, and severe acid mine drainage. These types were statistically distinguishable in multidimensional space. Classification tree analysis confirmed that chemical constituents related to acid mine drainage and acid rain distinguished these six groups. Hard, soft, and severe acid mine drainage type streams were temporally constant compared to streams identified as reference, transitional, and moderate acid mine drainage type, which had a greater tendency to shift to a different water type between seasons. Our research is the first to establish a statistically supported stream classification system in mined watersheds. The results suggest that human-related stressors superimposed on geology are responsible for producing distinct water quality types in this region as opposed to more continuous variation in chemistry that would be expected in an unimpacted setting. These findings provide a basis for simplifying stream monitoring efforts, developing generalized remediation strategies, and identifying specific remediation priorities in mined Appalachian watersheds.

Bias in determining aluminum concentrations: Comparison of digestion methods and implications on Al management.

Aluminum is an important aquatic contaminant due to its ubiquity, toxicity and low regulatory discharge limits. Aluminum is mobilized in mining related, acidic drainage and is commonly a regulated pollutant. However, while aquatic toxicity studies and toxicity criteria are based on dissolved aluminum(Ald), discharge levels are, for statutory reasons, based on total recoverable aluminum (Alt). The rationale for using total recoverable aluminum recognizes the potential for the release of exchangeable, toxic cations or dissolution of metastable metal flocs in the event the discharge enters an acidic receiving stream. The digestion methods used in determining total recoverable metals are not meant to dissolve aluminosilicate clay particles but we found that they do, resulting in positively biased total recoverable aluminum values. This study explored the interaction between total suspended solids (TSS) and total recoverable aluminum using three digestion methods to evaluate which method introduced the least bias. Using field collected water and sediment samples from two coal mine drainage sites in Central West Virginia, three total recoverable digestion methods (USEPA Method 200.7, M1; USGS In-Bottle method, M2; and a Modified In-Bottle method, M3) were used to determine total recoverable aluminum across a range of total suspended solids concentrations. Baseline simulation experiments were conducted at pH 2.5, 3.5, 4.5 and 5.5 at different total suspended solids concentrations. Results indicated that dissolved aluminum did not respond to increasing total suspended solids concentrations while determined total recoverable aluminum increased with total suspended solids, indicating varying degrees of clay dissolution and, thus bias in the total recoverable aluminum concentration. While all three digestion methods overestimated total recoverable aluminum, at the same total suspended solids concentration, total recoverable aluminum extracted by USEPA Method 200.7 (M1) was much higher than the other two digestion methods (M2 and M3). Total recoverable aluminum from different digestion methods indicated that amount of aluminosilicate clay is digested in decreasing order: USEPA 200.7 (M1) > USGS in-bottle (M2) > modified in-bottle (M3). At pH 2.5, positive bias using methods M1, M2 and M3 was 153-287%, 53% and 40% respectively. Positive bias was greatest at pH greater than 4.5. Methods M1, M2 and M3 yielded positive biases of 660-1060%, 120-360% and 200-320% respectively. The results suggest that USEPA method 200.7 (M1) resulted in the greatest bias. Given its application in determining regulatory compliance, this is an important issue requiring further study.

Evolution of water chemistry during Marcellus Shale gas development: A case study in West Virginia.

Hydraulic fracturing (HF) has been used with horizontal drilling to extract gas and natural gas liquids from source rock such as the Marcellus Shale in the Appalachian Basin. Horizontal drilling and HF generates large volumes of waste water known as flowback. While inorganic ion chemistry has been well characterized, and the general increase in concentration through the flowback is widely recognized, the literature contains little information relative to organic compounds and radionuclides. This study examined the chemical evolution of liquid process and waste streams (including makeup water, HF fluids, and flowback) in four Marcellus Shale gas well sites in north central West Virginia. Concentrations of organic and inorganic constituents and radioactive isotopes were measured to determine changes in waste water chemistry during shale gas development. We found that additives used in fracturing fluid may contribute to some of the constituents (e.g., Fe) found in flowback, but they appear to play a minor role. Time sequence samples collected during flowback indicated increasing concentrations of organic, inorganic and radioactive constituents. Nearly all constituents were found in much higher concentrations in flowback water than in injected HF fluids suggesting that the bulk of constituents originate in the Marcellus Shale formation rather than in the formulation of the injected HF fluids. Liquid wastes such as flowback and produced water, are largely recycled for subsequent fracturing operations. These practices limit environmental exposure to flowback.

Investigation of MCHM transport mechanisms and fate: implications for coal beneficiation.

4-Methyl cyclohexane methanol (MCHM) is a flotation reagent often used in fine coal beneficiation and notably involved in the January 9, 2014 Elk River chemical spill in Charleston, WV. This study investigates the mechanisms controlling the transport and fate of MCHM in coal beneficiation plants and surrounding environments. Processes such as volatilization, sorption, and leaching were evaluated through laboratory batch and column experiments. The results indicate volatilization and sorption are important mechanisms which influence the removal of MCHM from water, with sorption being the most significant removal mechanism over short time scales (<1 h). Additionally, leaching experiments show both coal and tailings have high affinity for MCHM, and this reagent does not desorb readily. Overall, the results from these experiments indicate that MCHM is either volatilized or sorbed during coal beneficiation, and it is not likely to transport out of coal beneficiation plant. Thus, use of MCHM in coal beneficiation plant is not likely to pose threat to either surface or groundwater under normal operating conditions.

Complex contaminant mixtures in multistressor Appalachian riverscapes.

Runoff from watersheds altered by mountaintop mining in the Appalachian region (USA) is known to pollute headwater streams, yet regional-scale assessments of water quality have focused on salinization and selenium. The authors conducted a comprehensive survey of inorganic contaminants found in 170 stream segments distributed across a spectrum of historic and contemporary human land use. Principal component analysis identified 3 important dimensions of variation in water chemistry that were significantly correlated with contemporary surface mining (principal component 1: elevated dominant ions, sulfate, alkalinity, and selenium), coal geology and legacy mines (principal component 2: elevated trace metals), and residential development (principal component 3: elevated sodium and chloride). The combination of these 3 dominant sources of pollutants produced a complex stream-to-stream patchwork of contaminant mixtures. Seventy-five percent of headwater streams (catchments < 5 km(2) ) had water chemistries that could be classified as either reference (49%), development only (18%), or mining only (8%). Only 21% of larger streams (catchments > 5 km(2) ) were classified as having reference chemistries, and chemistries indicative of combined mining and development contaminants accounted for 47% of larger streams (compared with 26% of headwater streams). Extreme degradation of larger streams can be attributed to accumulation of contaminants from multiple human land use activities that include contemporary mountaintop mining, underground mining, abandoned mines, and untreated domestic wastewater. Consequently, water quality improvements in this region will require a multicontaminant remediation approach.

Practical measures for reducing the risk of environmental contamination in shale energy production.

Gas recovery from shale formations has been made possible by advances in horizontal drilling and hydraulic fracturing technology. Rapid adoption of these methods has created a surge in natural gas production in the United States and increased public concern about its environmental and human health effects. We surveyed the environmental literature relevant to shale gas development and studied over fifteen well sites and impoundments in West Virginia to evaluate pollution caused by air emissions, light and noise during drilling. Our study also characterized liquid and solid waste streams generated by drilling and hydraulic fracturing and evaluated the integrity of impoundments used to store fluids produced by hydraulic fracturing. While most shale gas wells are completed with little or no environmental contamination, we found that many of the problems associated with shale gas development resulted from inattention to accepted engineering practices such as impoundment construction, improper liner installation and a lack of institutional controls. Recommendations are provided based on the literature and our field studies. They will address not all but a great many of the deficiencies that result in environmental release of contaminants from shale gas development. We also identified areas where new technologies are needed to fully address contaminant releases to air and water.