Impact of past mining activities on water quality in a karst area in the Cévennes region, Southern France.

Sampling and analysis of groundwater and surface water were conducted to assess the potential impacts of abandoned mines on water quality in a karst area in Southern France. The results of multivariate statistical analysis and geochemical mapping revealed that water quality is affected by contaminated drainage from abandoned mine sites. Acid mine drainage with very high concentrations of Fe, Mn, Al, Pb and Zn was identified in a few samples collected from mine openings and near waste dumps. In general, neutral drainage with elevated concentrations of Fe, Mn, Zn, As, Ni and Cd was observed due to buffering by carbonate dissolution. The contamination is spatially limited around abandoned mine sites, suggesting that metal(oid)s are sequestered in secondary phases that form under near-neutral and oxidizing conditions. However, the analysis of seasonal variations in trace metal concentrations showed that the transport of metal contaminants in water is highly variable according to hydrological conditions. During low flow conditions, trace metals are likely to be rapidly sequestered in Fe-oxyhydroxides and carbonate minerals in the karst aquifer and the river sediments, while low or no surface runoff in intermittent rivers limits the transport of contaminants in the environment. On the other hand, significant amounts of metal(loid)s can be transported under high flow conditions, primarily in dissolved form. Dissolved metal(loid) concentrations in groundwater remained elevated despite dilution by uncontaminated water, likely as a result of the increased leaching of mine wastes and the flushing of contaminated waters from mine workings. This work shows that groundwater is the main source of contamination to the environment and highlights the need to better understand the fate of trace metals in karst water systems.

Natural gas of radiolytic origin: An overlooked component of shale gas.

Natural gas is an important fossil energy source that has historically been produced from conventional hydrocarbon reservoirs. It has been interpreted to be of microbial, thermogenic, or, in specific contexts, abiotic origin. Since the beginning of the 21st century, natural gas has been increasingly produced from unconventional hydrocarbon reservoirs including organic-rich shales. Here, we show, based on a careful interpretation of natural gas samples from numerous unconventional hydrocarbon reservoirs and results from recent irradiation experiments, that there is a previously overlooked source of natural gas that is generated by radiolysis of organic matter in shales. We demonstrate that radiolytic gas containing methane, ethane, and propane constitutes a significant end-member that can account for >25% of natural gas mixtures in major shale gas plays worldwide that have high organic matter and uranium contents. The consideration of radiolytic gas in natural gas mixtures provides alternative explanations for so-called carbon isotope reversals and suggests revised interpretations of some natural gas origins. We submit that considering natural gas of radiolytic origin as an additional component in uranium-bearing shale gas formations will lead to a more accurate determination of the origins of natural gas.

Potential Impacts of Shale Gas Development on Inorganic Groundwater Chemistry: Implications for Environmental Baseline Assessment in Shallow Aquifers.

The potential contamination of shallow groundwater with inorganic constituents is a major environmental concern associated with shale gas extraction through hydraulic fracturing. However, the impact of shale gas development on groundwater quality is a highly controversial issue. The only way to reliably assess whether groundwater quality has been impacted by shale gas development is to collect pre-development baseline data against which subsequent changes in groundwater quality can be compared. The objective of this paper is to provide a conceptual and methodological framework for establishing a baseline of inorganic groundwater quality in shale gas areas, which is becoming standard practice as a prerequisite for evaluating shale gas development impacts on shallow aquifers. For this purpose, this paper first reviews the potential sources of inorganic contaminants in shallow groundwater from shale gas areas. Then, it reviews the previous baseline studies of groundwater geochemistry in shale gas areas, showing that a comprehensive baseline assessment includes documenting the natural sources of salinity, potential geogenic contamination, and potential anthropogenic influences from legacy contamination and surface land use activities that are not related to shale gas development. Based on this knowledge, best practices are identified in terms of baseline sampling, selection of inorganic baseline parameters, and definition of threshold levels.

Mobility and speciation of geogenic arsenic in bedrock groundwater from the Canadian Shield in western Quebec, Canada.

High arsenic concentrations occur in groundwater collected from a fractured crystalline bedrock aquifer in western Quebec (Canada). Sampling and analysis of water from 59 private wells reveal that more than half of the bedrock wells exceed the Canadian guideline value of 10µg/l for arsenic, whereas shallow wells in unconsolidated surficial deposits are not affected by the contamination. The weathering of arsenic-bearing sulfides present along the mineralized fault zone is considered to be the primary source of arsenic in groundwater. High-arsenic wells are generally characterized by mildly reducing conditions (Eh<250mV), weak alkaline conditions (pH>7.4), low Ca/Na ratios, elevated dissolved Fe and Mn concentrations and high proportions of As(III). Private bedrock wells are open boreholes that likely receive groundwater from multiple contributing fractures. Hence, it is proposed that dissolved arsenic is mainly derived from the contribution to the well discharge of reducing and alkaline geochemically evolved groundwater that contains arsenic as As(III). Geochemically evolved groundwater provides favorable conditions to release arsenic by reductive dissolution of iron and manganese oxyhydroxides and alkaline desorption from mineral surfaces. Thus, high-arsenic wells would contain a high proportion of geochemically evolved groundwater, while oxidizing low-pH recharge water causes dilution and sequestration of arsenic. In relation with the chemical evolution of groundwater along the flow path, most contaminated wells are located in confined areas whereas most of the wells located in unconfined recharge areas are not contaminated. The occurrence of boreholes with high dissolved arsenic as As(V) and oxidizing conditions is attributed to extensive sulfide oxidation and alkaline desorption. This work shows that the determination of arsenic speciation provides a valuable tool to investigate the behavior of arsenic in bedrock groundwater.