Groundwaters in Northeastern Pennsylvania near intense hydraulic fracturing activities exhibit few organic chemical impacts.

Horizontal drilling with hydraulic fracturing (HDHF) relies on the use of anthropogenic organic chemicals in proximity to residential areas, raising concern for groundwater contamination. Here, we extensively characterized organic contaminants in 94 domestic groundwater sites in Northeastern Pennsylvania after ten years of activity in the region. All analyzed volatile and semi-volatile compounds were below recommended United States Environmental Protection Agency maximum contaminant levels, and integrated concentrations across two volatility ranges, gasoline range organic compounds (GRO) and diesel range organic compounds (DRO), were low (0.13 ± 0.06 to 2.2 ± 0.7 ppb and 5.2-101.6 ppb, respectively). Following dozens of correlation analyses with distance-to-well metrics and inter-chemical indicator correlations, no statistically significant correlations were found except: (1) GRO levels were higher within 2 km of violations and (2) correlation between DRO and a few inorganic species (e.g., Ba and Sr) and methane. The correlation of DRO with inorganic species suggests a potential high salinity source, whereas elevated GRO may result from nearby safety violations. Highest-concentration DRO samples contained bis-2-ethylhexyl phthalate and N,N-dimethyltetradecylamine. Nevertheless, the overall low rate of contamination for the analytes could be explained by a spatially-resolved hydrogeologic model, where estimated transport distances from gas wells over the relevant timeframes were short relative to the distance to the nearest groundwater wells. Together, the observations and modeled results suggest a low probability of systematic groundwater organic contamination in the region.

Assessing Unconventional Oil and Gas Exposure in the Appalachian Basin: Comparison of Exposure Surrogates and Residential Drinking Water Measurements.

Health studies report associations between metrics of residential proximity to unconventional oil and gas (UOG) development and adverse health endpoints. We investigated whether exposure through household groundwater is captured by existing metrics and a newly developed metric incorporating groundwater flow paths. We compared metrics with detection frequencies/concentrations of 64 organic and inorganic UOG-related chemicals/groups in residential groundwater from 255 homes (Pennsylvania n = 94 and Ohio n = 161). Twenty-seven chemicals were detected in ≥20% of water samples at concentrations generally below U.S. Environmental Protection Agency standards. In Pennsylvania, two organic chemicals/groups had reduced odds of detection with increasing distance to the nearest well: 1,2-dichloroethene and benzene (Odds Ratio [OR]: 0.46, 95% confidence interval [CI]: 0.23-0.93) and m- and p-xylene (OR: 0.28, 95% CI: 0.10-0.80); results were consistent across metrics. In Ohio, the odds of detecting toluene increased with increasing distance to the nearest well (OR: 1.48, 95% CI: 1.12-1.95), also consistent across metrics. Correlations between inorganic chemicals and metrics were limited (all |ρ| ≤ 0.28). Limited associations between metrics and chemicals may indicate that UOG-related water contamination occurs rarely/episodically, more complex metrics may be needed to capture drinking water exposure, and/or spatial metrics in health studies may better reflect exposure to other stressors.

Groundwater Methane in Northeastern Pennsylvania Attributable to Thermogenic Sources and Hydrogeomorphologic Migration Pathways.

Conflicting evidence exists as to whether or not unconventional oil and gas (UOG) development has enhanced methane transport into groundwater aquifers over the past 15 years. In this study, recent groundwater samples were collected from 90 domestic wells and 4 springs in Northeastern Pennsylvania located above the Marcellus Shale after more than a decade of UOG development. No statistically significant correlations were observed between the groundwater methane level and various UOG geospatial metrics, including proximity to UOG wells and well violations, as well as the number of UOG wells and violations within particular radii. The δ13C and methane-to-higher chain hydrocarbon signatures suggested that the elevated methane levels were not attributable to UOG development nor could they be explained by using simple biogenic-thermogenic end-member mixing models. Instead, groundwater methane levels were significantly correlated with geochemical water type and topographical location. Comparing a subset of contemporary methane measurements to their co-located pre-drilling records (n = 64 at 49 distinct locations) did not indicate systematic increases in methane concentration but did reveal several cases of elevated concentration (n = 12) across a spectrum of topographies. Multiple lines of evidence suggested that the high-concentration groundwater methane could have originated from shallow thermogenic methane that migrated upward into groundwater aquifers with Appalachian Basin brine.

Late inception of a resiliently oxygenated upper ocean.

Rising oceanic and atmospheric oxygen levels through time have been crucial to enhanced habitability of surface Earth environments. Few redox proxies can track secular variations in dissolved oxygen concentrations around threshold levels for metazoan survival in the upper ocean. We present an extensive compilation of iodine-to-calcium ratios (I/Ca) in marine carbonates. Our record supports a major rise in the partial pressure of oxygen in the atmosphere at ~400 million years (Ma) ago and reveals a step change in the oxygenation of the upper ocean to relatively sustainable near-modern conditions at ~200 Ma ago. An Earth system model demonstrates that a shift in organic matter remineralization to greater depths, which may have been due to increasing size and biomineralization of eukaryotic plankton, likely drove the I/Ca signals at ~200 Ma ago.

Long-Term Climatic and Anthropogenic Impacts on Streamwater Salinity in New York State: INCA Simulations Offer Cautious Optimism.

The long-term application of road salts has led to a rise in surface water chloride (Cl-) concentrations. While models have been used to assess the potential future impacts of continued deicing practices, prior approaches have not incorporated changes in climate that are projected to impact hydrogeology in the 21st century. We use an INtegrated CAtchment (INCA) model to simulate Cl- concentrations in the Tioughnioga River watershed. The model was run over a baseline period (1961-1990) and climate simulations from a range of GCMs run over three 30-year intervals (2010-2039; 2040-2069; 2070-2099). Model projections suggest that Cl- concentrations in the two river branches will continue to rise for several decades, before beginning to decline around 2040-2069, with all GCM scenarios indicating reductions in snowfall and associated salt applications over the 21st century. The delay in stream response is most likely attributed to climate change and continued contribution of Cl- from aquifers. By 2100, surface water Cl- concentrations will decrease to below 1960s values. Catchments dominated by urban lands will experience a decrease in average surface water Cl-, although moderate compared to more rural catchments.

Chloride sources in urban and rural headwater catchments, central New York.

Road salt used as a deicing agent in winter months has become an emerging contaminant to streams and groundwater. In central New York, road salts are applied heavily during winter months. Recognizing potential sources of salinity to a river may reveal processes controlling the salinization of freshwater systems, with implications for future management practices. The Tioughnioga River, located in central New York, is a headwater of the Susquehanna River, which flows into the Chesapeake Bay. Salinity of the Tioughnioga River water has been increasing since the late 1930s. In this study, water samples were collected weekly at the East and West Branches of the Tioughnioga River from 2012 to 2014. We characterize natural and anthropogenic sources of salinity in the Tioughnioga River, using two independent approaches: (1) chloride to bromide ratios (Cl/Br) and (2) linear discriminant analysis. Ratios of Cl/Br suggest that road salt runoff influence is notable in both branches, but is more significant in the West Branch, consistent with a greater area of urban land. Linear discriminant analysis confirms the results of Cl/Br in the West Branch and further indicates presence of Appalachian Basin Brines in the East Branch, although their contribution may be volumetrically small. Longitudinal stream Cl concentration profiles indicate that sources of pollution are particularly concentrated around urban areas. Residence time of Cl in the watershed is estimated to be approximately 20 to 30years using a mixing model, suggesting that stream Cl concentrations likely will continue to rise for several decades.

Oxygen depletion recorded in upper waters of the glacial Southern Ocean.

Oxygen depletion in the upper ocean is commonly associated with poor ventilation and storage of respired carbon, potentially linked to atmospheric CO2 levels. Iodine to calcium ratios (I/Ca) in recent planktonic foraminifera suggest that values less than ∼2.5 µmol mol(-1) indicate the presence of O2-depleted water. Here we apply this proxy to estimate past dissolved oxygen concentrations in the near surface waters of the currently well-oxygenated Southern Ocean, which played a critical role in carbon sequestration during glacial times. A down-core planktonic I/Ca record from south of the Antarctic Polar Front (APF) suggests that minimum O2 concentrations in the upper ocean fell below 70 µmol kg(-1) during the last two glacial periods, indicating persistent glacial O2 depletion at the heart of the carbon engine of the Earth's climate system. These new estimates of past ocean oxygenation variability may assist in resolving mechanisms responsible for the much-debated ice-age atmospheric CO2 decline.