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USGS2025

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↗

USGS2008

Volatile selenium flux from the great Salt Lake, Utah

The removal mechanisms that govern Se concentrations in the Great Salt Lake are unknown despite this terminal lake being an avian habitat of hemispheric importance. However, the volatilization flux of Se from the Great Salt Lake has not been previously measured due to challenges of analysis in this hypersaline environment This paper presents results from recent field studies examining the spatial distribution of dissolved volatile Se (areally and with depth) in the south arm (main body) of the Great Salt Lake. The analyses involved collection of dissolved volatile Se in a cryofocusing trap system via sparging with helium. The cryotrapped volatile Se was digested with nitric acid and analyzed by inductively coupled plasma mass spectrometry (ICP-MS). Results show concentrations of dissolved volatile Se that increase with depth in the shallow brine, suggesting that phytoplankton in the open waters and bioherms in shallow sites (<4 m in depth) may be responsible for volatile Se production. Volatile Se flux to the atmosphere was determined using mass transport models corrected to simulate the highly saline environment of the south arm of the Great Salt Lake. The estimated annual flux of volatile Se was 1455 kg/year within a range from 560 to 3780 kg Se/year for the 95% confidence interval and from 970 to 2180 kg Se/year within the 68% confidence interval. ?? 2009 American Chemical Society.

Environmental Science & Technology↗

USGS2002

Characterization of organic contaminants in environmental samples associated with Mount St. Helens 1980 volcanic eruption

Volcanic ash, surface-water, and bottom-material samples obtained in the vicinity of Mount St. Helens after the May 18, 1980, eruption were analyzed for organic contaminants by using capillary gas chromatography-mass spectrometry-computer techniques. Classes of compounds identified include n -alkanes, fatty acids, dicarboxylic acids, aromatic acids and aldehydes, phenols, resin acids, terpenes, and insect juvenile hormones. The most probable source of these compounds is from pyrolysis of plant and soil organic matter during and after the eruption. The toxicity of selected compounds and their environmental significance are discussed.

Washinton↗

USGS1996

Glutathione conjugation and contaminant transformation

The recent identification of a novel sulfonated metabolite of alachlor in groundwater and metolachlor in soil is likely the result of glutathione conjugation. Glutathione conjugation is an important biochemical reaction that leads, in the case of alachlor, to the formation of a rather difficult to detect, water-soluble, and therefore highly mobile, sulfonated metabolite. Research from weed science, toxicology, and biochemistry is discussed to support the hypothesis that glutathione conjugation is a potentially important detoxification pathway carried out by aquatic and terrestrial plants and soil microorganisms. A brief review of the biochemical basis for glutathione conjugation is presented. We recommend that multidisciplinary research focus on the occurrence and expression of glutathione and its attendant enzymes in plants and microorganisms, relationships between electrophilic substrate structure and enzyme activity, and the potential exploitation of plants and microorganisms that are competent in glutathione conjugation for phytoremediation and bioremediation.

Environmental Science & Technology↗

USGS2011

Evaluating remedial alternatives for an acid mine drainage stream: A model post audit

A post audit for a reactive transport model used to evaluate acid mine drainage treatment systems is presented herein. The post audit is based on a paired synoptic approach in which hydrogeochemical data are collected at low (existing conditions) and elevated (following treatment) pH. Data obtained under existing, low-pH conditions are used for calibration, and the resultant model is used to predict metal concentrations observed following treatment. Predictions for Al, As, Fe, H + , and Pb accurately reproduce the observed reduction in dissolved concentrations afforded by the treatment system, and the information provided in regard to standard attainment is also accurate (predictions correctly indicate attainment or nonattainment of water quality standards for 19 of 25 cases). Errors associated with Cd, Cu, and Zn are attributed to misspecification of sorbent mass (precipitated Fe). In addition to these specific results, the post audit provides insight in regard to calibration and sensitivity analysis that is contrary to conventional wisdom. Steps taken during the calibration process to improve simulations of As sorption were ultimately detrimental to the predictive results, for example, and the sensitivity analysis failed to bracket observed metal concentrations.

Colorado↗

USGS2021

The role of hydrates, competing chemical constituents, and surface composition on CLNO2 formation

Atomic chlorine (Cl • ) affects air quality and atmospheric oxidizing capacity. Nitryl chloride (ClNO 2 ) – a common Cl • source–forms when chloride-containing aerosols react with dinitrogen pentoxide (N 2 O 5 ). A recent study showed that saline lakebed (playa) dust is an inland source of particulate chloride (Cl – ) that generates high ClNO 2 . However, the underlying physiochemical factors responsible for observed yields are poorly understood. To elucidate these controlling factors, we utilized single particle and bulk techniques to determine the chemical composition and mineralogy of playa sediment and dust samples from the southwest United States. Single particle analysis shows trace highly hygroscopic magnesium and calcium Cl-containing minerals are present and likely facilitate ClNO 2 formation at low humidity. Single particle and mineralogical analysis detected playa sediment organic matter that hinders N 2 O 5 uptake as well as 10 Å-clay minerals (e.g., Illite) that compete with water and chloride for N 2 O 5 . Finally, we show that the composition of the aerosol surface, rather than the bulk, is critical in ClNO 2 formation. These findings underscore the importance of mixing state, competing reactions, and surface chemistry on N 2 O 5 uptake and ClNO 2 yield for playa dusts and, likely, other aerosol systems. Therefore, consideration of particle surface composition is necessary to improve ClNO 2 and air quality modeling.

Environmental Science Technology↗

USGS2004

Methyl tert-butyl ether occurrence and related factors in public and private wells in southeast New Hampshire

The occurrence of methyl tert -butyl ether (MTBE) in water from public wells in New Hampshire has increased steadily over the past several years. Using a laboratory reporting level of 0.2 μg/L, 40% of samples from public wells and 21% from private wells in southeast New Hampshire have measurable concentrations of MTBE. The rate of occurrence of MTBE varied significantly for public wells by establishment type; for example, 63% of public wells serving residential properties have MTBE concentrations above 0.2 μg/L, whereas lower rates were found for schools (21%). MTBE concentrations correlate strongly with urban factors, such as population density. Surprisingly, MTBE was correlated positively with well depth for public supply wells. Well depth is inversely related to yield in New Hampshire bedrock wells, which may mean that there is less opportunity for dilution of MTBE captured by deep wells. Another possibility is that the source(s) of water to low-yield wells may be dominated by leakage from potentially contaminated shallow groundwater through near-surface fractures or along the well casing. These wells may also have relatively large contributing areas (due to low recharge at the bedrock surface) and therefore have a greater chance of intersecting MTBE sources. This finding is significant because deep bedrock wells are often considered to be less vulnerable to contamination than shallow wells, and in southeast New Hampshire, wells are being drilled deeper in search of increased supply.

New Hampshire↗

USGS2026

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↗

USGS2015

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↗

USGS1999

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↗

USGS2020

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↗

USGS2015

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↗

USGS2015

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↗

USGS2015

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↗

USGS2018

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↗

USGS2019

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↗

USGS2002

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↗

USGS2020

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↗