Recently, the cyanobacteriumGleomargarita lith-ophorawas shown to be associated with the capability to stronglyaccumulate Ra-226 (radioactive pollutant) and was suggested as anovel bioremediation strategy for the removal of Ra-226. Thebioaccumulation of Ra-226 was suggested to be linked with theability ofG. lithophorato form intracellular amorphous calciumcarbonate mineral inclusions (iACC). However, this claim reliedon indirect evidence, and the fate of (intracellularly) sequestered Ra-226 remains unresolved because of the limited spatial resolutionof conventional analytical instrumentation. Here, using high-resolution nanoscale secondary-ion mass spectrometry (Nano-SIMS), we show that sequestered Ra-226 is primarily associated withiACC and to a lesser degree within polyphosphate inclusions,which are also present inG. lithophora. Moreover, we show thatG.lithophoraaccumulates Ra-226 efficiently in the presence ofcompeting cations such as barium and strontium (frequentlypresent in Ra-bearing effluents). Our results offer fundamentalinsights into the interactions between microorganisms and Ra-226, benefit the future development of efficient Ra-226 bioremediationstrategies, and present a new frontier in the mapping of ultratrace elements in microbial samples using NanoSIMS.

Quantifying the flux of methane from terrestrial environments remains challenging, owing to considerable spatial and temporal variability in emissions. Amongst a myriad of factors, variation in the composition of electron acceptors, including metal (oxyhydr)oxides, may impart controls on methane emission. The purpose of this research is to understand how iron (oxyhydr)oxide minerals with varied physicochemical properties influence microbial methane production and subsequent microbial community development. Incubation experiments, using lake sediment as an inoculum and acetate as a carbon source, were used to understand the influence of one poorly crystalline iron oxide mineral, ferrihydrite, and two well-crystalline minerals, hematite and goethite, on methane production. Iron speciation, headspace methane, and 16S-rRNA sequencing microbial community data were measured over time. Substantial iron reduction only occurred in the presence of ferrihydrite while hematite and goethite had little effect on methane production throughout the incubations. In ferrihydrite experiments the time taken to reach the maximum methane production rate was slower than under other conditions, but methane production, eventually occurred in the presence of ferrihydrite. We suggest that this is due to ferrihydrite transformation into more stable minerals like magnetite and goethite or surface passivation by Fe(II). While all experimental conditions enriched for Methanosarcina, only the presence of ferrihydrite enriched for iron reducing bacteria Geobacter. Additionally, the presence of ferrihydrite continued to influence microbial community development after the onset of methanogenesis, with the dissimilarity between communities growing in ferrihydrite compared to no-Fe-added controls increasing over time. This work improves our understanding of how the presence of different iron oxides influences microbial community composition and methane production in soils and sediments.

Semi-conducting Fe oxide minerals, such as hematite, are well known to influence the fate of contaminants and nutrients in many environmental settings through sorption and release of Fe(II) resulting from microbial or abiotic reduction. Studies of Fe oxide reduction by adsorbed Fe(II) have demonstrated that reduction of Fe(III) at one mineral surface can result in the release of Fe(II) on a different one. This process is termed "Fe(II) catalyzed recrystallization" and is believed to be the result of electron transfer through semi-conducting Fe (hydr)oxides. While it is well understood that Fe(II) plays a central role in redox cycling of elements, the environmental implications of Fe(II) catalyzed recrystallization require further exploration. Here, we demonstrate that hematite links physically separated redox reactions by conducting the electrons involved in those reactions. This is shown using an electrochemical setup where Cr reduction is coupled with a potentiostat or Shewanella putrefaciens, a metal reducing microbe, where electrons donated to hematite produce Fe(II) that ultimately reduces Cr. This work demonstrates that mineral semi-conductivity may provide an additional avenue for redox chemistry to occur in natural soils and sediments, because these minerals can link redox active reactants that could not otherwise react due to physical separation.

The study of in situ microscale biogeochemical processes represents a major challenge in the environmental sciences. The combination of microfluidic devices with X-ray fluorescence microprobe spectroscopy may address this need, but typical materials used in these devices attenuate the X-rays needed to analyze key elements of interest, such as Fe or As. In this work, a method is presented for fabricating an etched silicon microfluidic device that is sealed with a 30 µm thin glass window that is sufficiently transparent for X-ray fluorescence microprobe spectroscopy. The capabilities of these devices for X-ray microprobe spectroscopy are demonstrated using an Fe (hydr)oxide solid that is loaded with As and then infused with sulfide, on beamline 4-BM at NSLS-II, resulting in time-variant Fe precipitation reactions and As sorption. Key results include in situ X-ray fluorescence time-series maps of Fe, As and a Br flow tracer, as well as spot XANES at both the Fe K edge and As K edge. Additionally, multiple energy mapping is used to examine the spatial speciation of As over time. The results of this work clearly demonstrate the capabilities of this novel microfluidic system that can be analyzed using X-ray fluorescence microprobe spectroscopy and can be made to study a wide range of complex microscale geochemical systems.

Semi-conducting Fe oxide minerals, such as hematite, are well known to influence the fate of contaminants and nutrients in many environmental settings and influence microbial growth under suboxic to anoxic conditions through a myriad of different processes. Recent studies of Fe oxide reduction by Fe(II) have demonstrated that reduction of Fe at one surface can result in the release of Fe(II) different one. Termed Fe(II) catalyzed recrystallization, this phenomena is attributed to conduction of additional electrons through the mineral structure from the point of contact to another which occurs because of the minerals’ semi-conductivity. While it is well understood that Fe(II) plays a central role in redox cycling of elements, the environmental implications of Fe(II) catalyzed recrystallization need to be further explored. Here, we provide evidence that the Fe mineral conductivity underpinning Fe(II) catalyzed recrystallization can couple the reduction of Cr, a priority metal contaminant, with an electron source that is cannot directly affect Cr. This is shown for both an abiotic electron source, a potentiostat, as well as the metal reducing bacteria Shewanella Putrefaciens. The implications of this work show that semiconductive minerals may be links in subsurface electrical networks that physically distribute redox chemistry and suggests novel methods for remediating Cr contamination in groundwater.

Produced water generated during unconventional oil and gas extractions contains a complex milieu of natural and anthropogenic potentially toxic chemical constituents including arsenic (As), chromium (Cr), and cadmium (Cd), naturally occurring radioactive materials (NORMs) including U and Ra, and a myriad of organic compounds. The human-ecological health risks and challenges associated with the disposal of produced water may be alleviated by understanding geochemical controls on processes responsible for the solubilization of potentially hazardous natural shale constituents to produced water. Here, we investigated, through a series of batch treatments, the leaching behavior of As, Se, Cu, Fe, Ba, Cr, Cd, and radioactive nuclides U, Ra from shale to produced water. Specifically, the effect of four major controls on element mobility was studied: (1) solution pH, (2) ionic strength of the solution, (3) oxic-anoxic conditions, and (4) an additive used in fracking fluid. The mobilization of metals and metalloids from shale was greatest in treatments containing sodium persulfate, an oxidant and a commonly used additive in fracture fluid. In the high ionic strength treatments, dissolved Ba concentrations increased 5-fold compared to low ionic strength treatments. Overall, anoxic conditions superimposed with low pH resulted in the largest increase of dissolved metals and radionuclides such as Ra. Overall, our results suggest that (1) limiting pore water acidification by injection of alkaline fluid in carbonate-low shale and (2) minimizing strong oxidizing conditions in shale formations may result in cost-effective in situ retention of produced water contaminants.

The hydrochemical composition of most groundwater systems, whether pristine or affected by anthropogenic activities, evolves as a result of complex interactions between flow, solute transport and biogeochemical processes. An in-depth analysis of these processes and their interactions is essential for deciphering what controls groundwater quality. Reactive transport modeling has emerged as an invaluable tool for distilling complex systems into their salient components. Based on experimental data, reactive transport models have been successfully used in the rigorous, process-based quantification of coupled processes at bench and field scales. We illustrate how reactive transport modeling can aid in identifying and quantifying controls over groundwater quality.

226Ra is a naturally occurring radionuclide with a half-life of 1600 years. In contrast, 90Sr is a radionuclide of sole anthropogenic origin, produced by nuclear fission reactions and has a half-life of 29 years; each of these radionuclides poses potential threats to human and ecosystem health. Here, the cyanobacterium Gloeomargarita lithophora, capable of forming intracellular amorphous calcium carbonate inclusions, was investigated for its ability to uptake 226Ra and 90Sr. In BG-11 medium, G. lithophora accumulated 3.9 μg g-1 of 226Ra within 144 h and 47.9 ng g-1 of 90Sr within 1 h, corresponding to ∼99% removal of trace radionuclides. The presence of high-concentration Ca2+ in the background media solution did not inhibit 90Sr and 226Ra uptake by G. lithophora. In contrast, dead biomass of G. lithophora accumulated 0.8 μg g-1 of 226Ra and 8.87 ng g-1 of 90Sr. Moreover, Synechocystis, a nonbiomineralizing cyanobacteria, removed only 14 and 25% of 226Ra and 90Sr, respectively. This suggested that sequestration of 90Sr and 226Ra was not intrinsic to all cyanobacteria but was likely a specific biological trait of G. lithophora related to the formation of intracellular amorphous Ca-carbonates. The unique ability of G. lithophora to uptake 90Sr and 226Ra at high rates makes it an attractive candidate for further studies involving bioremediation of these radionuclides.

Soils, sediments and rock are natural sources of radon (Rn), which poses an ongoing threat to human health. Numerous studies have measured Rn release from bulk earth materials, yet few have examined microscale controls on Rn flux from solids (emanation), which is required to develop a process-based framework for predicting the rate and extent of production. Here, we use a novel closed loop flow-through system to measure Rn emanation from two crushed rock types with disparate physical and geochemical characteristics, shale and granitic pegmatite. We relate the extent of Rn emanation from each sample to microscale characteristics examined using conventional and synchrotron-based techniques, such as Rn parent radionuclide distribution within mineral grains, porosity, and surface area. Our results illustrate that the extent of Rn release from solids is primarily dependent on the position of parent radionuclides within host mineral grains relative to the "recoil range"-the maximum distance a daughter product (such as Rn) may traverse within a solid and into an adjacent pore owing to alpha-recoil-and is less dependent on the bulk parent radionuclide (e.g., radium) activity. We also present a simple model for predicting the emanation coefficient for pure solids based on mineralogical and physical parameters, which is an initial step toward developing a framework for predicting Rn efflux (exhalation) from soils.

The use of low-cost air quality sensors for air pollution research has outpaced our understanding of their capabilities and limitations under real-world conditions, and there is thus a critical need for understanding and optimizing the performance of such sensors in the field. Here we describe the deployment, calibration, and evaluation of electrochemical sensors on the island of Hawai`i, which is an ideal test bed for characterizing such sensors due to its large and variable sulfur dioxide (SO2) levels and lack of other co-pollutants. Nine custom-built SO2 sensors were co-located with two Hawaii Department of Health Air Quality stations over the course of 5 months, enabling comparison of sensor output with regulatory-grade instruments under a range of realistic environmental conditions. Calibration using a nonparametric algorithm (k nearest neighbors) was found to have excellent performance (RMSE < 7 ppb, MAE < 4 ppb, r2 > 0.997) across a wide dynamic range in SO2 (< 1 ppb, > 2 ppm). However, since nonparametric algorithms generally cannot extrapolate to conditions beyond those outside the training set, we introduce a new hybrid linear–nonparametric algorithm, enabling accurate measurements even when pollutant levels are higher than encountered during calibration. We find no significant change in instrument sensitivity toward SO2 after 18 weeks and demonstrate that calibration accuracy remains high when a sensor is calibrated at one location and then moved to another. The performance of electrochemical SO2 sensors is also strong at lower SO2 mixing ratios (< 25 ppb), for which they exhibit an error of less than 2.5 ppb. While some specific results of this study (calibration accuracy, performance of the various algorithms, etc.) may differ for measurements of other pollutant species in other areas (e.g., polluted urban regions), the calibration and validation approaches described here should be widely applicable to a range of pollutants, sensors, and environments.

Radium (Ra) is a radioactive element commonly found within soils, sediments, and natural waters. Elevated Ra activities arising through natural and anthropogenic processes pose a threat to groundwater resources and human health, and Ra isotope ratios are used to decipher groundwater movement, estimate submarine discharge flux, and fingerprint contamination associated with hydraulic fracturing operations. Although adsorption to metal (hydr)oxides and certain clay minerals is well established as a dominant mechanism controlling Ra transport and retention, the extent of Ra sorption to other minerals and under variable environmental conditions (e.g., pH and salinity) is limited. Accordingly, we present results of sorption studies and surface complexation modeling (SCM) of Ra to ferrihydrite, goethite, montmorillonite, and pyrite, for a range of pH values and common background cations. Ra sorption to all substrates is observed under geochemical conditions considered, but varies according to mineral, solution pH and specific competing cations. Literature derived SCMs for Ra sorption were fitted to match either sorption impacts due to pH or different background cations, but were not able to predict the impacts of different geochemical conditions. Despite this, the use of SCMs provided a more mechanistic understanding of Ra sorption as compared to commonly used distribution coefficients.

Models test our understanding of processes and can reach beyond the spatial and temporal scales of measurements. Multi-component Reactive Transport Models (RTMs), initially developed more than three decades ago, have been used extensively to explore the interactions of geothermal, hydrologic, geochemical, and geobiological processes in subsurface systems. Driven by extensive data sets now available from intensive measurement efforts, there is a pressing need to couple RTMs with other community models to explore non-linear interactions among the atmosphere, hydrosphere, biosphere, and geosphere. Here we briefly review the history of RTM development, summarize the current state of RTM approaches, and identify new research directions, opportunities, and infrastructure needs to broaden the use of RTMs. In particular, we envision the expanded use of RTMs in advancing process understanding in the Critical Zone, the veneer of the Earth that extends from the top of vegetation to the bottom of groundwater. We argue that, although parsimonious models are essential at larger scales, process-based models offer tools to explore the highly nonlinear coupling that characterizes natural systems. We present seven testable hypotheses that emphasize the unique capabilities of process-based RTMs for (1) elucidating chemical weathering and its physical and biogeochemical drivers; (2) understanding the interactions among roots, micro-organisms, carbon, water, and minerals in the rhizosphere; (3) assessing the effects of heterogeneity across spatial and temporal scales; and (4) integrating the vast quantity of novel data, including “omics” data (genomics, transcriptomics, proteomics, metabolomics), elemental concentration and speciation data, and isotope data into our understanding of complex earth surface systems. With strong support from data-driven sciences, we are now in an exciting era where integration of RTM framework into other community models will facilitate process understanding across disciplines and across scales.