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.

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.

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.

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.