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.

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.

The rapid expansion of unconventional oil and gas development (UD), made possible by horizontal drilling and hydraulic fracturing, has triggered concerns over groundwater contamination and public health risks. To improve our understanding of the risks posed by UD, we develop a physically based, spatially explicit framework for evaluating groundwater well vulnerability to aqueous phase contaminants released from surface spills and leaks at UD well pad locations. The proposed framework utilizes the concept of capture probability and incorporates decision-relevant planning horizons and acceptable risks to support goal-oriented modeling for groundwater protection. We illustrate the approach in northeastern Pennsylvania, where a high intensity of UD activity overlaps with local dependence on domestic groundwater wells. Using two alternative models of the bedrock aquifer and a precautionary paradigm to integrate their results, we found that most domestic wells in the domain had low vulnerability as the extent of their modeled probabilistic capture zones were smaller than distances to the nearest existing UD well pad. We also found that simulated capture probability and vulnerability were most sensitive to the model parameters of matrix hydraulic conductivity, porosity, pumping rate, and the ratio of fracture to matrix conductivity. Our analysis demonstrated the potential inadequacy of current state-mandated setback distances that allow UD within the boundaries of delineated capture zones. The proposed framework, while limited to aqueous phase contamination, emphasizes the need to incorporate information on flow paths and transport timescales into policies aiming to protect groundwater from contamination by UD.

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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 δ 13 C and methane-tohigher 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.