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USGS2025

Triple-oxygen isotopic evidence of prolonged direct bioleaching of pyrite with O2

Sulfate is often touted as containing atmospheric oxygen whose isotopic signature can constrain redox, environmental conditions, and biological activity. Yet, the amount and isotopic fractionation associated with air-O 2 incorporation during sulfate formation is still debated, making its verification difficult. In this study, we identify a distinct, microbially dominated environment with the potential to preserve maximum signals of air-O 2 in sulfate. We report triple-oxygen isotope data for sulfate produced from pyrite oxidation in microbial and abiotic experiments, and from natural dissolved sulfate from the Rio Tinto, Spain, an acid mine drainage site. The oxygen isotope systematics of sulfate in these environments define a unique kinetic isotope effect associated with initial stage pyrite oxidation by Acidithiobacillus ferrooxidans that preserves >80 % oxygen from air-O 2 in sulfate. Unlike experiments, which evolve toward water-oxygen dominated sulfate on short time scales, Rio Tinto, Spain hosts a microbe rich environment with distinct geochemistry that maintains high O 2 -oxygen in sulfate. Therefore, in addition to containing isotopic records from water and air, sulfates can also contain a biosignature that is promising for understanding conditions on Mars and early Earth.

Earth and Planetary Science Letters↗

USGS2024

Remote sensing evapotranspiration in ensemble-based framework to enhance cascade routing and re-infiltration concept in integrated hydrological model applied to support decision making

Integrated hydrological models (IHMs) help characterize the complexity of surface–groundwater interactions. The cascade routing and re-infiltration (CRR) concept, recently applied to a MODFLOW 6 IHM, improved conceptualization and simulation of overland flow processes. The CRR controls the transfer of rejected infiltration and groundwater exfiltration from upslope areas to adjacent downslope areas where that water can be evaporated, re-infiltrated back to subsurface, or discharged to streams as direct runoff. The partitioning between these three components is controlled by uncertain parameters that must be estimated. Thus, by quantifying and reducing those uncertainties, next to uncertainties of the other model parameters (e.g. hydraulic and storage parameters), the reliability of the CRR is improved and the IHM is better suited for decision support modelling, the two key objectives of this work. To this end, the remotely sensed MODIS-ET product was incorporated into the calibration process for complementing traditional hydraulic head and streamflow observations. A total of approximately 150,000 observations guided the calibration of a 13-year MODFLOW 6 IHM simulation of the Sardon catchment (Spain) with daily stress periods. The model input uncertainty was represented by grid-cell-scale parameterization, yielding approximately 500,000 unknown input parameters to be conditioned. The calibration was carried out through an iterative ensemble smoother. Incorporating the MODIS-ET data improved the CRR implementation, and reduced uncertainties associated with other model parameters. Additionally, it significantly reduced the uncertainty associated with net recharge, a critical flux for water management that cannot be directly measured and rather is commonly estimated by IHM simulations.

Sardon catchment↗