Natural and Anthropogenic Processes Affecting Domestic Groundwater Quality within the Northwestern Appalachian Basin.

Domestic wells serve as the primary drinking-water source for rural residents in the northern Appalachian Basin (NAB), despite a limited understanding of contaminant distributions in groundwater sources. We employ a newly collected dataset of 216 water samples from domestic wells in Ohio and West Virginia and an integrated contaminant-source attribution method to describe water quality in the western NAB and characterize key agents influencing contaminant distributions. Our results reveal arsenic and nitrate concentrations above federal maximum contaminant levels (MCLs) in 6.8 and 1.3% of samples and manganese concentrations above health advisory in 7.3% of samples. Recently recharged groundwaters beneath upland regions appear vulnerable to surface-related impacts, including nitrate pollution from agricultural activities and salinization from road salting and domestic sewage sources. Valley regions serve as terminal discharge points for long-residence-time groundwaters, where mixing with basin brines is possible. Arsenic impairments occurred in alkaline groundwaters with major-ion compositions altered by ion exchange and in low-oxygen metal-rich groundwaters. Mixing with as much as 4-10% of mine discharge-like waters was observed near coal mining operations. Our study provides new insights into key agents of groundwater impairment in an understudied region of the NAB and presents an integrated approach for contaminant-source attribution applicable to other regions of intensive resource extraction.

A Critical Review of State-of-the-Art and Emerging Approaches to Identify Fracking-Derived Gases and Associated Contaminants in Aquifers.

High-volume, hydraulic fracturing (HVHF) is widely applied for natural gas and oil production from shales, coals, or tight sandstone formations in the United States, Canada, and Australia, and is being widely considered by other countries with similar unconventional energy resources. Secure retention of fluids (natural gas, saline formation waters, oil, HVHF fluids) during and after well stimulation is important to prevent unintended environmental contamination, and release of greenhouse gases to the atmosphere. Here, we critically review state-of-the-art techniques and promising new approaches for identifying oil and gas production from unconventional reservoirs to resolve whether they are the source of fugitive methane and associated contaminants into shallow aquifers. We highlight future research needs and propose a phased program, from generic baseline to highly specific analyses, to inform HVHF and unconventional oil and gas production and impact assessment studies. These approaches may also be applied to broader subsurface exploration and development issues (e.g., groundwater resources), or new frontiers of low-carbon energy alternatives (e.g., subsurface H2 storage, nuclear waste isolation, geologic CO2 sequestration).

Inorganic contaminants from diffuse pollution in shallow groundwater of the Campanian Plain (Southern Italy). Implications for geochemical survey.

The Campanian Plain (CP) shallow aquifer (Southern Italy) represents a natural laboratory to validate geochemical methods for differentiating diffuse anthropogenic pollution from natural water-rock interaction processes. The CP is an appropriate study area because of numerous potential anthropogenic pollution vectors including agriculture, animal husbandry, septic/drainage sewage systems, and industry. In order to evaluate the potential for geochemical methods to differentiate various contamination vectors, 538 groundwater wells from the shallow aquifer in Campanian Plain (CP) were sampled. The dataset includes both major and trace elements. Natural water-rock interactions, which primarily depend on local lithology, control the majority of geochemical parameters, including most of the major and trace elements. Using prospective statistical methods in combination with the traditional geochemical techniques, we determined the chemical variables that are enriched by anthropogenic contamination (i.e. NO3, SO4 and U) by using NO3 as the diagnostic variable for detecting polluted groundwater. Synthetic agricultural fertilizers are responsible for the majority of SO4 and U pollution throughout the CP area. Both SO4 and U are present in the groundmass of synthetic fertilizers; the uranium concentration is specifically applicable as a tracer for non-point source agricultural fertilizer contamination. The recognition of non-geological (anthropogenic) inputs of these elements has to be considered in the geochemical investigations of contaminated aquifers.

New tracers identify hydraulic fracturing fluids and accidental releases from oil and gas operations.

Identifying the geochemical fingerprints of fluids that return to the surface after high volume hydraulic fracturing of unconventional oil and gas reservoirs has important applications for assessing hydrocarbon resource recovery, environmental impacts, and wastewater treatment and disposal. Here, we report for the first time, novel diagnostic elemental and isotopic signatures (B/Cl, Li/Cl, δ11B, and δ7Li) useful for characterizing hydraulic fracturing flowback fluids (HFFF) and distinguishing sources of HFFF in the environment. Data from 39 HFFFs and produced water samples show that B/Cl (>0.001), Li/Cl (>0.002), δ11B (25-31‰) and δ7Li (6-10‰) compositions of HFFF from the Marcellus and Fayetteville black shale formations were distinct in most cases from produced waters sampled from conventional oil and gas wells. We posit that boron isotope geochemistry can be used to quantify small fractions (∼0.1%) of HFFF in contaminated fresh water and likely be applied universally to trace HFFF in other basins. The novel environmental application of this diagnostic isotopic tool is validated by examining the composition of effluent discharge from an oil and gas brine treatment facility in Pennsylvania and an accidental spill site in West Virginia. We hypothesize that the boron and lithium are mobilized from exchangeable sites on clay minerals in the shale formations during the hydraulic fracturing process, resulting in the relative enrichment of boron and lithium in HFFF.

Evidence for an extraterrestrial impact 12,900 years ago that contributed to the megafaunal extinctions and the Younger Dryas cooling.

A carbon-rich black layer, dating to approximately 12.9 ka, has been previously identified at approximately 50 Clovis-age sites across North America and appears contemporaneous with the abrupt onset of Younger Dryas (YD) cooling. The in situ bones of extinct Pleistocene megafauna, along with Clovis tool assemblages, occur below this black layer but not within or above it. Causes for the extinctions, YD cooling, and termination of Clovis culture have long been controversial. In this paper, we provide evidence for an extraterrestrial (ET) impact event at approximately equal 12.9 ka, which we hypothesize caused abrupt environmental changes that contributed to YD cooling, major ecological reorganization, broad-scale extinctions, and rapid human behavioral shifts at the end of the Clovis Period. Clovis-age sites in North American are overlain by a thin, discrete layer with varying peak abundances of (i) magnetic grains with iridium, (ii) magnetic microspherules, (iii) charcoal, (iv) soot, (v) carbon spherules, (vi) glass-like carbon containing nanodiamonds, and (vii) fullerenes with ET helium, all of which are evidence for an ET impact and associated biomass burning at approximately 12.9 ka. This layer also extends throughout at least 15 Carolina Bays, which are unique, elliptical depressions, oriented to the northwest across the Atlantic Coastal Plain. We propose that one or more large, low-density ET objects exploded over northern North America, partially destabilizing the Laurentide Ice Sheet and triggering YD cooling. The shock wave, thermal pulse, and event-related environmental effects (e.g., extensive biomass burning and food limitations) contributed to end-Pleistocene megafaunal extinctions and adaptive shifts among PaleoAmericans in North America.