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At least 433 records · Page 24Linked to original sources

Review: The hydrogeology of critical mineral resources relevant to the energy transition

Attaining the goals of the international treaty on climate change (the Paris Agreement) will greatly increase the demand for the critical minerals required to implement clean-energy technologies. This poses both challenges and opportunities to the hydrogeologic community from several perspectives. Here, important insights that the hydrogeological sciences have to offer for mineral exploration, mineral production, and addressing environmental issues related to mining and mine decommissioning are summarized. This study focuses on copper, cobalt, lithium, and rare earths to represent the broad spectrum of critical minerals and illustrate their relevance by referring to projected demands and production rates. The current understanding of the hydrogeologic processes that form major deposits of these minerals are then summarized. Ore is defined as the naturally occurring material from which minerals of economic value can be extracted, where most ore deposits are the products of complex hydrogeologic couplings between fluid flow, heat transport, solute transport, chemical reactions, and mechanical deformation. Exploration models for the discovery of deeper, hidden deposits are potentially informed by hydrogeologic theory and hydrogeochemical processes. Hydrogeologic understanding and methods are also essential to production and recovery. Longstanding challenges are mine dewatering and (conversely) mine water supply, as well as mineral-extraction practices such as spoil heap leaching and in situ mining. New challenges arise from element extraction from subsurface brines. Finally, the quantity of water use and potential environmental impacts of mining on water quality are at the core of ‘social license’: the approval and acceptance of society to mining activities.

Hydrogeology Journal↗

An ecosystem-scale model of PFAS dynamics in stream-to-riparian food webs

Per- and polyfluoroalkyl substances (PFAS) are widespread contaminants in aquatic ecosystems, where they bioaccumulate and trophically transfer through food webs. We derived an ecosystem-scale model assessing Σ 12 PFAS partitioning, bioaccumulation by larval aquatic insects, bioamplification by adult aquatic insects, and trophic transfer from aquatic insects to riparian spiders using data collected across five streams in a mildly impacted watershed. Partitioning involved the greatest PFAS enrichments (range in posterior median log 10 k d values = 1.5–2.1), with lesser concentration increases from particulates to larval aquatic insects and from larval to adult aquatic insects, and Σ 12 PFAS concentration decreases from adult aquatic insects to spiders. Among the 12 compounds, PFOS had the largest proportional contribution to Σ 12 PFAS concentrations for all sample types, with consistently increasing concentrations from surface water to adult aquatic insects. Σ 12 PFAS concentrations (5.4–51 ppb wet weight), body burdens (0.44–5.2 ng per individual), and bioamplification factors (0.15–4.9) differed considerably among five common aquatic insect taxa. This study presents a robust modeling framework for PFAS trophodynamics and offers insights into the biological controls that contribute to the context dependency of PFAS at the interfaces of aquatic and terrestrial food webs.

Connecticut, Massachusetts↗

Measuring currents in submarine canyons: technological and scientific progress in the past 30 years

The development and application of acoustic and optical technologies and of accurate positioning systems in the past 30 years have opened new frontiers in the submarine canyon research communities. This paper reviews several key advancements in both technology and science in the field of currents in submarine canyons since the1979 publication of Currents in Submarine Canyons and Other Sea Valleys by Francis Shepard and colleagues. Precise placements of high-resolution, high-frequency instruments have not only allowed researchers to collect new data that are essential for advancing and generalizing theories governing the canyon currents, but have also revealed new natural phenomena that challenge the understandings of the theorists and experimenters in their predictions of submarine canyon flow fields. Baroclinic motions at tidal frequencies, found to be intensified both up canyon and toward the canyon floor, dominate the flow field and control the sediment transport processes in submarine canyons. Turbidity currents are found to frequently occur in active submarine canyons such as Monterey Canyon. These turbidity currents have maximum speeds of nearly 200 cm/s, much smaller than the speeds of turbidity currents in geological time, but still very destructive. In addition to traditional Eulerian measurements, Lagrangian flow data are essential in quantifying water and sediment transport in submarine canyons. A concerted experiment with multiple monitoring stations along the canyon axis and on nearby shelves is required to characterize the storm-trigger mechanism for turbidity currents.

Geosphere↗

Experimental dosing of wetlands with coagulants removes mercury from surface water and decreases mercury bioaccumulation in fish

Mercury pollution is widespread globally, and strategies for managing mercury contamination in aquatic environments are necessary. We tested whether coagulation with metal-based salts could remove mercury from wetland surface waters and decrease mercury bioaccumulation in fish. In a complete randomized block design, we constructed nine experimental wetlands in California’s Sacramento–San Joaquin Delta, stocked them with mosquitofish ( Gambusia affinis ), and then continuously applied agricultural drainage water that was either untreated (control), or treated with polyaluminum chloride or ferric sulfate coagulants. Total mercury and methylmercury concentrations in surface waters were decreased by 62% and 63% in polyaluminum chloride treated wetlands and 50% and 76% in ferric sulfate treated wetlands compared to control wetlands. Specifically, following coagulation, mercury was transferred from the filtered fraction of water into the particulate fraction of water which then settled within the wetland. Mosquitofish mercury concentrations were decreased by 35% in ferric sulfate treated wetlands compared to control wetlands. There was no reduction in mosquitofish mercury concentrations within the polyaluminum chloride treated wetlands, which may have been caused by production of bioavailable methylmercury within those wetlands. Coagulation may be an effective management strategy for reducing mercury contamination within wetlands, but further studies should explore potential effects on wetland ecosystems.

California↗

New method for the direct determination of dissolved Fe(III) concentration in acid mine waters

A new method for direct determination of dissolved Fe(III) in acid mine water has been developed. In most present methods, Fe(III) is determined by computing the difference between total dissolved Fe and dissolved Fe(II). For acid mine waters, frequently Fe(II) ≫ Fe(III); thus, accuracy and precision are considerably improved by determining Fe(III) concentration directly. The new method utilizes two selective ligands to stabilize Fe(III) and Fe(II), thereby preventing changes in Fe reduction−oxidation distribution. Complexed Fe(II) is cleanly removed using a silica-based, reversed-phase adsorbent, yielding excellent isolation of the Fe(III) complex. Iron(III) concentration is measured colorimetrically or by graphite furnace atomic absorption spectrometry (GFAAS). The method requires inexpensive commercial reagents and simple procedures that can be used in the field. Calcium(II), Ni(II), Pb(II), Al(III), Zn(II), and Cd(II) cause insignificant colorimetric interferences for most acid mine waters. Waters containing >20 mg of Cu/L could cause a colorimetric interference and should be measured by GFAAS. Cobalt(II) and Cr(III) interfere if their molar ratios to Fe(III) exceed 24 and 5, respectively. Iron(II) interferes when its concentration exceeds the capacity of the complexing ligand (14 mg/L). Because of the GFAAS elemental specificity, only Fe(II) is a potential interferent in the GFAAS technique. The method detection limit is 2 μg/L (40 nM) using GFAAS and 20 μg/L (0.4 μM) by colorimetry.

Environmental Science & Technology↗

Polymeric nanofiber-carbon nanotube composite mats as fast-equilibrium passive samplers for polar organic pollutants

To improve the performance of polymeric electrospun nanofiber mats (ENMs) for equilibrium passive sampling applications in water, we integrated two types of multiwalled carbon nanotubes (CNTs; with and without surface carboxyl groups) into polyacrylonitrile (PAN) and polystyrene (PS) ENMs. For 11 polar and moderately hydrophobic compounds (−0.07 ≤ log K OW ≤ 3.13), 90% of equilibrium uptake was achieved in under 0.8 days ( t 90% values) in nonmixed ENM-CNT systems. Sorption capacity of ENM-CNTs was between 2- and 50-fold greater than pure polymer ENMs, with equilibrium partition coefficients ( K ENM-W values) ranging from 1.4 to 3.1 log units (L/kg) depending on polymer type (hydrophilic PAN or hydrophobic PS), CNT loading (i.e., values increased with weight percent (wt %) of CNTs), and CNT type (i.e., greater uptake with carboxylated CNTs composites). During field deployment at Muddy Creek in North Liberty, Iowa, optimal ENM-CNTs (PAN with 20 wt % carboxylated CNTs) yielded atrazine concentrations in surface water with a 40% difference relative to analysis of a same-day grab sample. We also observed a mean percent difference of 30 (±20)% when comparing ENM-CNT sampler results to grab sample data collected within 1 week of deployment. With their rapid, high capacity uptake and small material footprint, ENM-CNT equilibrium passive samplers represent a promising alternative to complement traditional integrative passive samplers while offering convenience over large volume grab sampling.

Environmental Science & Technology↗

Predicting redox conditions in groundwater at a regional scale

Defining the oxic-suboxic interface is often critical for determining pathways for nitrate transport in groundwater and to streams at the local scale. Defining this interface on a regional scale is complicated by the spatial variability of reaction rates. The probability of oxic groundwater in the Chesapeake Bay watershed was predicted by relating dissolved O 2 concentrations in groundwater samples to indicators of residence time and/or electron donor availability using logistic regression. Variables that describe surficial geology, position in the flow system, and soil drainage were important predictors of oxic water. The probability of encountering oxic groundwater at a 30 m depth and the depth to the bottom of the oxic layer were predicted for the Chesapeake Bay watershed. The influence of depth to the bottom of the oxic layer on stream nitrate concentrations and time lags (i.e., time period between land application of nitrogen and its effect on streams) are illustrated using model simulations for hypothetical basins. Regional maps of the probability of oxic groundwater should prove useful as indicators of groundwater susceptibility and stream susceptibility to contaminant sources derived from groundwater.

Maryland, New York, Pennsylvania, Virginia↗

High-resolution multibeam bathymetry of East and West Flower Gardens and Stetson Banks, Gulf of Mexico

The 1990s have seen rapid advances in seafloor mapping technology. Multibeam sonars are now capable of mapping a wide range of water depths with beams as narrow as 1°, and provide up to a 150° swath. When these multibeam sonars are coupled with an extremely accurate vehicle motion sensor and very precise navigation, they are capable of producing unprecedented images of the seafloor. This technology was used in December 1997 to map the East and West Flower Gardens and Stetson Banks, Gulf of Mexico. The results from this survey provide the most accurate maps of these areas yet produced and reveal features at submeter resolution never mapped in these areas before. The digital data provide a database that should become the fundamental base maps for all subsequent work in this recently established National Marine Sanctuary.

Gulf of Mexico Science↗

Methylmercury bioaccumulation in stream food webs declines with increasing primary production

Opposing hypotheses posit that increasing primary productivity should result in either greater or lesser contaminant accumulation in stream food webs. We conducted an experiment to evaluate primary productivity effects on MeHg accumulation in stream consumers. We varied light for 16 artificial streams creating a productivity gradient (oxygen production =0.048–0.71 mg O 2 L –1 d –1 ) among streams. Two-level food webs were established consisting of phytoplankton/filter feeding clam, periphyton/grazing snail, and leaves/shredding amphipod ( Hyalella azteca ). Phytoplankton and periphyton biomass, along with MeHg removal from the water column, increased significantly with productivity, but MeHg concentrations in these primary producers declined. Methylmercury concentrations in clams and snails also declined with productivity, and consumer concentrations were strongly correlated with MeHg concentrations in primary producers. Heterotroph biomass on leaves, MeHg in leaves, and MeHg in Hyalella were unrelated to stream productivity. Our results support the hypothesis that contaminant bioaccumulation declines with stream primary production via the mechanism of bloom dilution (MeHg burden per cell decreases in algal blooms), extending patterns of contaminant accumulation documented in lakes to lotic systems.

Environmental Science & Technology↗

Human and bovine viruses and bacteria at three Great Lakes beaches: Environmental variable associations and health risk

Waterborne pathogens were measured at three beaches in Lake Michigan, environmental factors for predicting pathogen concentrations were identified, and the risk of swimmer infection and illness was estimated. Waterborne pathogens were detected in 96% of samples collected at three Lake Michigan beaches in summer, 2010. Samples were quantified for 22 pathogens in four microbial categories (human viruses, bovine viruses, protozoa, and pathogenic bacteria). All beaches had detections of human and bovine viruses and pathogenic bacteria indicating influence of multiple contamination sources at these beaches. Occurrence ranged from 40 to 87% for human viruses, 65–87% for pathogenic bacteria, and 13–35% for bovine viruses. Enterovirus, adenovirus A, Salmonella spp. , Campylobacter jejuni , bovine polyomavirus, and bovine rotavirus A were present most frequently. Variables selected in multiple regression models used to explore environmental factors that influence pathogens included wave direction, cloud cover, currents, and water temperature. Quantitative Microbial Risk Assessment was done for C. jejuni , Salmonella spp. , and enteroviruses to estimate risk of infection and illness. Median infection risks for one-time swimming events were approximately 3 × 10 –5 , 7 × 10 –9 , and 3 × 10 –7 for C. jejuni , Salmonella spp., and enteroviruses, respectively. Results highlight the importance of investigating multiple pathogens within multiple categories to avoid underestimating the prevalence and risk of waterborne pathogens.

Wisconsin↗

High frequency data exposes nonlinear seasonal controls on dissolved organic matter in a large watershed

We analyzed a five year, high frequency time series generated by an in situ fluorescent dissolved organic matter (fDOM) sensor installed near the Connecticut River’s mouth, investigating high temporal resolution DOM dynamics in a larger watershed and longer time series than previously addressed. We identified a gradient between large, saturating summer fDOM responses to discharge and linear, subdued responses during colder months. Seasonal response patterns were not consistent with multiple linear regression. Alternatively, we binned measurements across the yearly cycle using environmental indices, such as temperature, and applied moving regression, a novel approach which produced superior fits to calendar day binning. Spatially averaged watershed soil temperature at 10 cm was the best overall index of discharge-fDOM response. DOM fractionation showed fDOM was primarily a surrogate for hydrophobic organic acid (HPOA) concentrations. HPOAs were highly correlated with discharge, but hydrophilics (HPIs) were not. Discharge dependent DOM concentrations driven by the HPOA fraction may be controlled by soil temperature and water table position relative to organic and mineral soil horizons. HPI concentrations were correlated with average watershed soil temperature at 10 cm but were rather stationary throughout the year, further indicating a consistent groundwater source for this nonfluorescent DOM. We present a resolved subseasonal empirical model of DOM concentrations and fluxes, showing that riverine DOM flux and quality depend heavily on seasonal terrestrial carbon dynamics and hydrologic flow paths. High frequency monitoring reveals readily discernible patterns demonstrating that upland biogeochemical signals are maintained even at this large watershed scale.

Environmental Science and Technology↗

Kinetic study on clogging of a geothermal pumping well triggered by mixing-induced biogeochemical reactions

The sustainability of ground-source geothermal systems can be severely impacted by microbially mediated clogging processes. Biofouling of water wells by hydrous ferric oxide is a widespread problem. Although the mechanisms and critical environmental factors associated with clogging development are widely recognized, effects of mixing processes within the wells and time scales for clogging processes are not well characterized. Here we report insights from a joint hydrological, geochemical, and metagenomics characterization of a geothermal doublet in which hydrous ferric oxide and hydrous manganese oxide deposits had formed as a consequence of mixing shallow groundwater containing dissolved oxygen and nitrate with deeper, anoxic groundwater containing dissolved iron (Fe II ) and manganese (Mn II ). Metagenomics identify distinct bacteria consortia in the pumping well oxic and anoxic zones, including autotrophic iron-oxidizing bacteria. Batch mixing experiments and geochemical kinetics modeling of the associated reactions indicate that Fe II and Mn II oxidation are slow compared to the residence time of water in the pumping well; however, adsorption of Fe II and Mn II by accumulated hydrous ferric oxide and hydrous manganese oxide in the well bore and pump riser provides “infinite” time for surface-catalyzed oxidation and a convenient source of energy for iron-oxidizing bacteria, which colonize the surfaces and also catalyze oxidation. Thus, rapid clogging is caused by mixing-induced redox reactions and is exacerbated by microbial activity on accumulated hydrous oxide surfaces.

Orleans↗

Migration through soil of organic solutes in an oil-shale process water

The migration through soil of organic solutes in an oil-shale process water (retort water) was studied by using soil columns and analyzing leachates for various organic constituents. Retort water extracted significant quantities of organic anions leached from ammonium-saturated-soil organic matter, and a distilled-water rinse, which followed retort-water leaching, released additional organic acids from the soil. After being corrected for organic constitutents extracted from soil by retort water, dissolved-organic-carbon fractionation analyses of effluent fractions showed that the order of increasing affinity of six organic compound classes for the soil was as follows: hydrophilic neutrals nearly equal to hydrophilic acids, followed by the sequence of hydrophobic acids, hydrophilic bases, hydrophobic bases, and hydrophobic neutrals. Liquid-chromatographic analysis of the aromatic amines in the hydrophobic- and hydrophilic-base fractions showed that the relative order of the rates of migration through the soil column was the same as the order of migration on a reversed-phase, octadecylsilica liquid-chromatographic column.

Environmental Science & Technology↗

Comparison of the in situ and desorption sediment-water partitioning of polycyclic aromatic hydrocarbons and polychlorinated biphenyls

In situ sediment−porewater partitioning of polycyclic aromatic hydrocarbons (PAHs) measured in three cores from Boston Harbor, MA, has led us to suggest that only a fraction of the total measured sediment PAH concentration is a vailable for e quilibrium p artitioning (AEP fraction). To test this, aqueous PAH concentrations were measured in laboratory desorption experiments using subsamples of the same Boston Harbor sediments. The observed concentrations were consistent with what we predicted from the field-derived AEP values: C aqueous = ( C sediment × AEP)/( f oc × K oc ) where f oc is the fraction organic carbon in the sediment and K oc is the organic carbon normalized sediment−water partition coefficient. Equilibrium partitioning models based on the total measured sediment PAH concentrations overestimated the measured aqueous PAH concentrations by as much as 100 times in some cases. Only a small fraction of the sediment phenanthrene and pyrene concentrations (1−40%) appeared to be available for equilibrium partitioning. Both in situ and laboratory desorption aqueous polychlorinated biphenyl (PCB) concentrations were consistent with equilibrium partitioning models and the assumption that 100% of these compounds was available for equilibrium partitioning. These results are particularly important to efforts to predict the environmental mobility and bioavailability of the PAHs.

Massachusetts↗

Uranium bioaccumulation dynamics in the mayfly Neocloeon triangulifer and application to site-specific prediction

Little is known about the underlying mechanisms governing the bioaccumulation of uranium (U) in aquatic insects. We experimentally parameterized conditional rate constants for aqueous U uptake, dietary U uptake, and U elimination for the aquatic baetid mayfly Neocloeon triangulifer . Results showed that this species accumulates U from both the surrounding water and diet, with waterborne uptake prevailing. Elevated dietary U concentrations decreased feeding rates, presumably by altering food palatability or impairing the mayfly’s digestive processes, or both. Nearly 90% of the accumulated U was eliminated within 24 h after the waterborne exposure ceased, reflecting the desorption of weakly bound U from the insect’s integument. To examine whether the experimentally derived rate constants for N. triangulifer could be generalized to baetid mayflies, mayfly U concentrations were predicted using the water chemistry and U measured in periphyton from springs in Grand Canyon (United States) and were compared to U concentrations in spring-dwelling mayflies. Predicted and observed mayfly U concentrations were in good agreement. Under the modeled site-specific conditions, waterborne U uptake accounted for 52–93% of the bioaccumulated U. U accumulation was limited in these wild populations due to a combination of factors including low concentrations of bioavailable dissolved U species, slow U uptake rates from food, and fast U elimination.

Environmental Science & Technology↗

Environmental fate of roxarsone in poultry litter. I. Degradation of roxarsone during composting

Roxarsone, 3-nitro-4-hydroxyphenylarsonic acid, is an organoarsenic compound that is used extensively in the feed of broiler poultryto control coccidial intestinal parasites, improve feed efficiency, and promote rapid growth. Nearly all the roxarsone in the feed is excreted unchanged in the manure. Poultry litter composed of the manure and bedding material has a high nutrient content and is used routinely as a fertilizer on cropland and pasture. Investigations were conducted to determine the fate of poultrylitter roxarsone in the environment. Experiments indicated that roxarsone was stable in fresh dried litter; the primary arsenic species extracted with water from dried litter was roxarsone. However, when water was added to litter at about 50 wt % and the mixture was allowed to compost at 40 o C, the speciation of arsenic shifted from roxarsone to primarily arsenate in about 30 days. Increasing the amount of water increased the rate of degradation. Experiments also suggested that the degradation process most likely was biotic in nature. The rate of degradation was directly proportional to the incubation temperature; heat sterilization eliminated the degradation. Biotic degradation also was supported by results from enterobacteriaceae growth media that were inoculated with litter slurry to enhance the biotic processes and to reduce the concomitant abiotic effects from the complex litter solution. Samples collected from a variety of litter windrows in Arkansas, Oklahoma, and Maryland also showed that roxarsone originally present had been converted to arsenate.

Environmental Science & Technology↗

Geochemical factors controlling dissolved elemental mercury and methylmercury formation in Alaskan wetlands of varying trophic status

Transformations of aqueous inorganic divalent mercury (Hg(II)i) to volatile dissolved gaseous mercury (Hg(0)(aq)) and toxic methylmercury (MeHg) governs mercury bioavailability and fate in northern ecosystems. This study quantified concentrations of aqueous mercury species (Hg(II)i, Hg(0)(aq), MeHg) and relevant geochemical constituents in pore waters of eight Alaskan wetlands that differ in trophic status (i.e., bog-to-fen gradient) to gain insight on processes controlling dark Hg(II)i reduction and Hg(II)i methylation. Regardless of wetland trophic status, positive correlations were observed between pore water Hg(II)i and dissolved organic carbon (DOC) concentrations. The concentration ratio of Hg(0)(aq) to Hg(II)i exhibited an inverse relationship to Hg(II)i concentration. A ubiquitous pathway for Hg(0)(aq) formation was not identified based on geochemical data, but we surmise that dissolved organic matter (DOM) influences mercury retention in wetland pore waters by complexing Hg(II)i and decreasing the concentration of volatile Hg(0)(aq) relative to Hg(II)i. There was no evidence of Hg(0)(aq) abundance directly limiting mercury methylation. The concentration of MeHg relative to Hg(II)i was greatest in wetlands of intermediate trophic status, and geochemical data suggest mercury methylation pathways vary between wetlands. Our insights on geochemical factors influencing aqueous mercury speciation should be considered in context of the long-term fate of mercury in northern wetlands.

Environmental Science & Technology↗

Cell-Based metabolomics for untargeted screening and prioritization of vertebrate-active stressors in streams across the United States

The U.S. Geological Survey and the U.S. Environmental Protection Agency have assessed contaminants in 38 streams across the U.S., using an extensive suite of target-chemical analysis methods along with a variety of biological effects tools. Here we report zebrafish liver (ZFL) cell-culture based NMR metabolomic analysis of these split stream samples. We used this untargeted approach to evaluate the sites according to overall impact on the ZFL metabolome and found that neither the total number of organics detected at the sites, nor their cumulative concentrations, were good predictors of these impacts. Further, we used partial-least squares regression to compare ZFL endogenous metabolite profiles to values for 455 potential stressors (organics, inorganics, and physical properties) measured in these waters and found that the profiles covaried with at most 280 of the stressors, which were subsequently ranked into quartiles based on the strength of their covariance. While contaminants of emerging concern (CECs) were well represented in the top, most strongly, covarying quartile – suggesting considerable potential for eliciting biological responses at these sites – there was even higher representation of various well-characterized legacy contaminants (e.g., PCBs). These results emphasize the importance of complementing chemical analysis with untargeted bioassays to help focus regulatory efforts on the most significant ecosystem threats.

Environmental Science & Technology↗