Geology topics

Charles A. Cravotta

Publications and source records attributed to Charles A. Cravotta.

At least 19 recordsLinked to original sources

USGS2025

Groundwater salinity: Applying the specific conductance and water type proxy

Groundwater is increasingly needed for water supplies but may have limited utility in some locations because of its salinity. Salinity, often expressed as total dissolved solid (TDS), is frequently estimated using specific conductance (SC) measurements. However, the commonly used proxy (0.65 multiplied by SC to indicate TDS, common in many handheld meters) can result in inaccurate TDS estimates. First, the TDS–SC relationship is not linear over the entire concentration range of groundwater. Furthermore, the TDS (and salinity)–SC relationships vary substantially depending on the major-ion composition. Here we develop a proxy method utilizing SC and major-ion water type to estimate TDS and salinity specifically for groundwaters. Compared to most surface waters, groundwater tends to have a wider range of salinity (fresh to highly saline) and higher concentrations of bedrock-derived solutes such as carbonate ions, silica, and many other ions. The dataset used to develop the proxies includes water chemistry data from 149,059 discrete groundwater samples. The groundwater proxies, which employ nonlinear log–log relations, utilize five water types (HCO 3 , Cl, Ca-Mg-SO 4 , Na-K-SO 4 , and mixed waters), are accurate (median percent difference between TDS and salinity determined using the proxy compared to discrete measurements was <±0.8%) over a wide range of SC (up to 200 mS/cm), rapid, cost-effective, and can be measured on-site.

Groundwater↗

USGS2025

Specific conductance and water type as a proxy model for salinity and total dissolved solids measurements in the Upper Colorado River Basin

Salinity levels in streams and tributaries of the Colorado River Basin have been a major concern for the United States and Mexico for over 50 years as the water is used by millions of people for domestic and industrial purposes. Recently, the United States Geological Survey expanded stream monitoring networks including the number of sites where continuous (15-min) specific conductance is measured in the Colorado River Headwaters and Gunnison River Basin located east of the Colorado-Utah state line (hereafter, UCOL). The purpose of this study is to apply a proxy method to determine salinity and total dissolved solids concentrations from specific conductance and major-ion water type that is applicable to monitoring sites in the UCOL. Within the UCOL, carbonate rich waters originate from high-elevation mountain regions in the eastern UCOL, calcium sulfate rich waters are mainly found in the western half of the UCOL including the Gunnison River Basin, and waters of variable composition are found along the lower reaches of the Colorado River and Eagle River. It was found that the chemistry of sites with variable composition changes seasonally and is impacted by both geogenic and anthropogenic processes, potentially including seasonal application of deicing road salt. The specific conductance – water type proxy can be used to reliably (±10 %) predict salinity and total dissolved solids at 66 monitoring sites in the UCOL. The method is rapid, can generate high-resolution measurements, is cost-effective, and greatly expands the utility of specific conductance measurements. Furthermore, the high-resolution estimates provide an accurate approach to determining long-term salinity loads as short-term events are accurately accounted for.

Colorado↗

USGS2024

A multidisciplinary approach that considers occurrence, geochemistry, bioavailability, and toxicity to prioritize critical minerals for environmental research

Critical minerals (or critical elements) are minerals or elements that are essential to global security and development and have supply chains vulnerable to disruption. In general, knowledge of the environmental behavior and health effects of critical elements is needed to support the development of safe and environmentally responsible supplies. This knowledge includes identifying potential consequences of increased critical element production and use, alternative critical element sources such as mine wastes, and adverse effects of critical elements on ecosystem condition and organismal health. Here we identify significant data gaps in the understanding of critical elements in surficial and aquatic environments, and the need, given the large number of commodities (50) identified on the 2022 critical minerals list for the United States, for an approach to prioritize them for study of their environmental fate and effects. We propose a multidisciplinary approach for this prioritization, considering measures of occurrence, geochemistry, bioavailability, and toxicity. We describe relatively easy-to-obtain metrics for each of these topic areas and demonstrate the utility of this integrated prioritization approach using indium and zinc as examples. This approach facilitates prioritizing research with a focus on those critical elements that are most mobile in the environment, bioavailable, toxic, or simply lacking data in these categories.

Environmental Science & Technology↗

USGS2024

Complex hydrology and variability of nitrogen sources in a karst watershed

Streams draining karst areas with rapid groundwater transit times may respond relatively quickly to nitrogen reduction strategies, but the complex hydrologic network of interconnected sinkholes and springs is challenging for determining the placement and effectiveness of management practices. This study aims to inform nitrogen reduction strategies in a representative agricultural karst setting of the Chesapeake Bay watershed (Fishing Creek watershed, Pennsylvania) with known elevated nitrate contamination and a previous documented groundwater residence time of less than a decade. During baseflow conditions, streamflow did not increase with drainage area. Headwaters and the main stem lost substantial flow to sinkholes until eventually discharging along large springs downstream. Seasonal hydrologic conditions shift the flow and nitrogen load spatially among losing and gaining stream sections. A compilation of nitrogen source inputs with the geochemistry and the pattern of enrichment of δ 15 N and δ 18 O suggest that the nitrogen in streams and springs during baseflow represents a mixture of manure, fertilizer, and wastewater sources with low potential for denitrification. The pH and calcite saturation index increased along generalized flow paths from headwaters to springs and indicate shorter groundwater residence times in baseflow during the spring versus summer. Given the substantial investment in management practices, fixed monitoring sites could incorporate synoptic water sampling to properly monitor long-term progress and help inform management actions in karst watersheds. Although karst watersheds have the potential to respond to nitrogen reduction strategies due to shorter groundwater residence times, high nitrogen inputs, effectiveness of conservation practices, and release of legacy nutrients within the karst cavities could confound progress of water quality goals.

Pennsylvania↗

USGS2024

Determination and prediction of micro scale rare earth element geochemical associations in mine drainage treatment wastes

Acid mine drainage (AMD) has been proposed as a novel source of rare earth elements (REE), a group of elements that includes critical metals for clean energy and modern technologies. REE are sequestered in the Fe–Al–Mn-rich precipitates produced during the treatment of AMD. These AMD solids are typically managed as waste but could be a REE source. Here, results from AMD solids characterization and geochemical modeling are presented to determine the minerals/solid phases that are enriched in REE and identify the mechanism(s) of REE attenuation. AMD solids collected from limestone-based AMD treatment systems were subjected to sequential extraction and synchrotron microprobe analyses to characterize the binding nature of the REE. The results of these analyses indicated REEs were mainly associated with Al or Mn phases. Only selected REE (Gd, Dy) were associated with Fe phases, which were less abundant than Al and Mn phases in analyzed samples. The sequential extractions demonstrated that acidic and/or reducing extractions effectively mobilize REE from the AMD solids evaluated. The observed element associations in solids are consistent with geochemical model results that indicate dissolved REE can be effectively attenuated by adsorption on freshly precipitated Fe, Al, and Mn oxides/hydroxides. The model, which simulates dissolution of CaCO 3 and the precipitation of Fe, Al, and Mn oxides with increased pH, accurately predicts the pH dependent accumulation of dissolved REE with Al, Mn, and Fe oxides/hydroxides in the studied AMD treatment systems. The methods and results presented here can be used to identify conditions favorable for accumulation of REE-enriched AMD solids and possible passive or active treatment(s) to extract REE from AMD. This information can be used to design AMD treatment systems for the recovery of REE and is an opportunity to transform the challenges of addressing polluted mine drainage into an environmental and economic asset.

Pennsylvania↗

USGS2024

Legacy sediment as a potential source of orthophosphate: Preliminary conceptual and geochemical models for the Susquehanna River, Chesapeake Bay watershed, USA

Nutrient pollution from agriculture and urban areas plus acid mine drainage (AMD) from legacy coal mines are primary causes of water-quality impairment in the Susquehanna River, which is the predominant source of freshwater and nutrients entering the Chesapeake Bay. Recent increases in the delivery of dissolved orthophosphate (PO 4 ) from the river to the bay may be linked to long-term increases in pH, decreased acidity of precipitation, and decreased acidity, iron, and aluminum loading from widespread AMD. Since the 1950s, baseline pH increased from ~6.5 to ~8 in the West Branch and “North Branch” of the Susquehanna River, which drain bituminous and anthracite coalfields of Pennsylvania. A current baseline pH of ~8 and daily maxima exceeding 9 have been documented along the lower Susquehanna River. In response to improved river quality, bioavailable PO 4 now may be released into solution from legacy sediment that has filled major impoundments in lower reaches of the river. At typical pH (5–8) of natural water, aqueous PO 4 species tend to be adsorbed by hydrous iron, aluminum, and manganese oxides that coat soil and sediment particles; however, PO 4 may be substantially desorbed at pH >8. We created a geochemical model that simulates equilibrium aqueous/solid distributions of PO 4 as pH and other solution characteristics change. Considering current conditions in the lower Susquehanna River, the model demonstrates potential for extensive release of adsorbed PO 4 at pH >8. Empirical data from laboratory experiments corroborate model results. The transfer of PO 4 into the water column may increase algae growth, which removes CO 2 and drives pH to higher values, facilitating additional PO 4 release and exacerbating the potential for harmful algal blooms. Thus, legacy sediment is a currently unquantified source of PO 4 that warrants consideration by resource managers and programs collaborating to reduce phosphorus loads to the bay and similar settings worldwide.

Chesapeake Bay watershed↗

USGS2024

Exploring spatial and temporal symptoms of the freshwater salinization syndrome in a rural to urban watershed

The freshwater salinization syndrome (FSS), a concomitant watershed-scale increase in salinity, alkalinity, and major-cation and trace-metal concentrations, over recent decades, has been described for major rivers draining extensive urban areas, yet few studies have evaluated temporal and spatial FSS variations, or causal factors, at the subwatershed scale in mixed-use landscapes. This study examines the potential influence of land-use practices and wastewater treatment plant (WWTP) effluent on the export of major ions and trace metals from the mixed-use East Branch Brandywine Creek watershed in southeastern Pennsylvania, during the 2019 water year. Separate analysis of baseflow and stormflow subsets revealed similar correlations among land-use characteristics and streamwater chemistry. Positive associations between percent impervious surface cover, which ranged from 1.26 % to 21.9 % for the 13 sites sampled, and concentrations of Ca 2+ , Mg 2+ , Na + , and Cl − are consistent with road-salt driven reverse cation exchange and weathering of the built environment. The relative volume of upstream WWTP was correlated with Cu and Zn, which may be derived in part from corroded water-conveyance infrastructure; chloride to sulfate mass ratios (CSMR) ranged from ~6.3 to ~7.7× the 0.5 threshold indicating serious corrosivity potential. Observed exceedances of U.S. Environmental Protection Agency Na + and Cl − drinking water and aquatic life criteria occurred in winter months. Finally, correlations between percent cultivated cropland and As and Pb concentrations may be explained by the persistence of agricultural pesticides that had been used historically. Study results contribute to the understanding of FSS solute origin, fate, and transport in mixed-use watersheds, particularly those in road salt-affected regions. Study results also emphasize the complexity of trace-metal source attribution and explore the potential for FSS solutes to affect human health, aquatic life, and infrastructure.

Pennsylvania↗

USGS2023

Land development and road salt usage drive long-term changes in major-ion chemistry of streamwater in six exurban and suburban watersheds, southeastern Pennsylvania, 1999-2019

In urbanized areas, the “freshwater salinization syndrome” (FSS), which pertains to long-term increases in concentrations of major ions and metals in fresh surface waters, has been attributed to road salt application. In addition to FSS, the water composition changes as an influx of sodium (Na + ) in recharge may displace calcium (Ca 2+ ), magnesium (Mg 2+ ), potassium (K + ), and trace metals by reverse cation exchange. These changing ion fluxes can result in adverse impacts on groundwater and surface waters used for municipal supplies. Few datasets exist to quantify the FSS on a watershed scale or link its manifestation to potential controlling factors such as changes in urban development, land use/land cover (LULC), or wastewater treatment plant (WWTP) discharges in upstream areas. Here, we use two decades (1999–2019) of monthly streamwater quality data combined with daily streamflow for six exurban and suburban watersheds in southeastern Pennsylvania to examine the relations among Ca 2+ , Mg 2+ , K + , Na + , chloride (Cl − ), sulfate (SO 4 2- ), and alkalinity (HCO 3 − ) concentrations and upstream controlling factors. Flow-normalized annual and baseflow (August ̶ November) concentrations for Ca 2+ , Mg 2+ , Na + , and Cl − increased in all six watersheds over the 20-year study, providing evidence of FSS’s impacts on groundwater that sustains streamflow. Additionally, a redundancy analysis using 2019 flow-normalized values identified the following positive associations between solute concentrations and controlling variables: 1) Cl − , Mg 2+ , and Ca 2+ with impervious surface cover (ISC), 2) Na + and SO 4 2- with ISC and total WWTP discharge volume, and 3) HCO 3 − with agriculture and total WWTP discharge volume. From a human health perspective, 2019 flow-normalized Na + concentrations exceeded the U.S. Environmental Protection Agency’s 20 mg L -1 threshold for individuals restricted to a low sodium diet. Furthermore, indices used to evaluate the corrosivity of source waters to drinking water infrastructure and inform municipal water treatment practices, such as the Chloride to Sulfate Mass Ratio and Larson Ratio, increased between two- and seven-fold over the 20-year time. Collectively, the results elucidate the causal factors of the FSS in suburban and exurban watersheds and its potential impacts on human health and drinking water infrastructure.

Pennsylvania↗

USGS2023

Gross alpha-particle activity and high 226Ra concentrations do not correspond with high 210Po in the Atlantic and Gulf Coastal Plain aquifers of the United States

210 Po, which is of human-health concern based on lifetime ingestion cancer risk, is indirectly regulated in drinking water through the U.S. Environmental Protection Agency’s gross alpha-particle activity (GAPA) maximum contaminant level of 15 pCi/L (picocuries per liter). This regulation requires independent measurement of 226 Ra for samples exceeding the GAPA screening level of 5 pCi/L. There is no such requirement for 210 Po. Co-occurrence of 226 Ra and 210 Po, alpha-emitting 238 U-decay-series progeny, might be helpful in locating high- 210 Po waters but is unverified. Relations among 210 Po, 226 Ra, and GAPA evaluated for samples from 257 public-supply wells from Coastal Plain aquifers showed that concentrations of 226 Ra correlated with GAPA but neither correlated with 210 Po concentrations. The highest concentrations of 226 Ra and 210 Po were found under differing geochemical conditions. The highest 226 Ra occurred in low-pH oxidizing waters and in neutral-pH reducing waters, where geochemical conditions render Fe–Mn-hydroxide sorbents inefficient. 210 Po was highest (10.1 pCi/L) in reducing waters with high pH (>7.5, which results from progressive cation exchange), where 226 Ra was lowest─exchanged to clay minerals. Because 226 Ra and 210 Po did not co-occur, the GAPA screening might not be protective for 210 Po. Independent 210 Po analysis is prudent, especially where groundwater is reducing with high pH and low 226 Ra concentrations.

Environmental Science & Technology Water↗

USGS2023

Salinity and total dissolved solids measurements for natural waters: An overview and a new salinity method based on specific conductance and water type

The total concentration of dissolved constituents in water is routinely quantified by measurements of salinity or total dissolved solids (TDS). However, salinity and TDS are operationally defined by their analytical methods and are not equivalent for most waters. Furthermore, multiple methods are available to determine salinity and TDS, and these methods have inherent differences. TDS is defined as the mass of anhydrous residue remaining in a sample vessel after evaporation and subsequent oven drying at a defined temperature. Salinity is a measure of the mass of dissolved salts in a given mass of solution. In addition, there are approaches that quantify the total solute (TS) concentration, including gases. The purpose of this study is to develop a proxy method using specific conductance and major-ion water type to reliably predict salinity, TDS, and/or TS. Thus, we compared several methods to calculate salinity, TDS, and TS for 6391 surface water samples and conclude the following: TDS measurements are best suited for studies of anhydrous residue (e.g., evaporites); salinity determined by summing the speciated ion concentrations, termed S ∑spec , is the most comprehensive method to represent the concentration of dissolved constituents in natural waters; and TS determinations are useful if dissolved CO 2 and other gases are of interest. Thus, we utilized S ∑spec to compare differences between the various salinity, TDS, and TS methods, and to develop a new proxy method to predict salinity based on specific conductance (SC) and major ion water type, termed S SC_WT . For the surface waters used in this study, the median difference between TDS and S ∑Spec was between −19% and −24%, depending on the method. The median difference between S SC_WT and S ∑Spec was −2.4% for the samples in this study. The S SC_WT approach is cost effective, rapid, and capable of providing reliable real-time salinity determinations at surface water sites where SC data are available and water type is known.

Applied Geochemistry↗

USGS2022

Factors Affecting Groundwater Quality Used for Domestic Supply in Marcellus Shale Region of North-Central and North-East Pennsylvania, USA

Factors affecting groundwater quality used for domestic supply within the Marcellus Shale footprint in north-central and north-east Pennsylvania are identified using a combination of spatial, statistical, and geochemical modeling. Untreated groundwater, sampled during 2011–2017 from 472 domestic wells within the study area, exhibited wide ranges in pH (4.5–9.3), total dissolved solids (TDS, 22–1960 mg/L), sodium (0.3–760 mg/L), chloride (0.3–1020 mg/L), bromide (<0.01–8.6 mg/L), and methane (<0.001–77 mg/L). The wells had depths ranging from 10 to 394 m; 69.5 percent were completed in sandstone bedrock, 19.3 percent in shale, 4.2 percent in siltstone, 4 percent in carbonate, and 3 percent in unconsolidated alluvial or glacial deposits. Groundwater quality in the Delaware River watershed, in the eastern part of the study area where Marcellus gas has not been developed, was similar to that in the Susquehanna, Allegheny, and Genesee River watersheds in the western part of the study area where natural gas production from Marcellus Shale has been ongoing since 2008. Most groundwaters were calcium/bicarbonate type with near-neutral pH; approximately 10 percent were sodium/bicarbonate and 1 percent were sodium/chloride types. Sodium-enriched waters, which were mostly from shale and siltstone aquifers, had the greatest frequency of elevated pH (>8.5) and elevated concentrations of TDS (>250 mg/L), bromide (>0.15 mg/L), methane (>7.0 mg/L), and lithium (>60 μg/L). Geochemical models indicate these characteristics could result from progressive mineral dissolution combined with cation exchange, plus mixing with locally important salinity sources, including as much as 0.7 percent Appalachian Basin brine and/or road-deicing salt. Multivariate correlation models suggest the observed variability in methane concentrations may be attributed to several environmental factors, such as geochemical evolution along groundwater flow paths, redox conditions, and/or mixing with saline groundwater or brine. Most samples having elevated methane were from shale aquifers, which were mainly in the Susquehanna River basin and had the greatest density of gas wells compared to other lithologies . Samples having elevated methane were also observed in the Delaware River watershed and other areas outside gas development. Isotopic compositions of methane for a subset of 39 samples (selected because of elevated methane) and relatively high ratios of methane to ethane in those samples indicated methane could be derived from microbial gas mixed with thermogenic gas that may have undergone degradation and/or fractionation during migration. The methods used in this study could be broadly applicable to understanding major factors affecting groundwater quality, particularly for explaining variations in ionic composition with pH and identifying sources of salinity and associated constituents (e.g. sodium, chloride, bromide, lithium, methane) that may have geogenic or anthropogenic origins.

Pennsylvania↗

USGS2022

Mine drainage precipitates attenuate and conceal wastewater-derived phosphate pollution in stream water

Hydrous ferric-oxide (HFO) coatings on streambed sediments may attenuate dissolved phosphate (PO 4 ) concentrations at acidic to neutral pH conditions, limiting phosphorus (P) transport and availability in aquatic ecosystems. Mesh-covered tiles on which “natural” HFO from abandoned mine drainage (AMD) had precipitated were exposed to treated municipal wastewater (MWW) effluent or a mixture of stream water and effluent. Between 42 and 99% of the dissolved P in effluent was removed from the water to a thin coating (~2 μm) of HFO on the mesh. Geochemical equilibrium model results predicted the removal of 76 to 99% of PO 4 from the water by adsorption to the HFO, depending on the HFO quantity, initial PO 4 concentration, and pH. The measurements and model results indicated the capacity for P removal decreased as the concentration of P associated with the HFO increased. Continuing accumulation of HFO from upstream AMD sources replenish the in-stream capacity for P attenuation below the MWW discharge. This indicates AMD pollution may conceal P inputs and limit the amount of dissolved P transported to downstream ecosystems. However, HFO-rich sediments also represent a potential source of “legacy” P that could confound management practices intended to decrease nutrient and metal loadings.

Pennsylvania↗

USGS2022

Long-term impacts of impervious surface cover change and roadway deicing agent application on chloride concentrations in exurban and suburban watersheds

Roadway deicing agents, including rock salt and brine containing NaCl, have had a profound impact on the water quality and aquatic health of rivers and streams in urbanized areas with temperate climates. Yet, few studies evaluate impacts to watersheds characterized by relatively low impervious surface cover (ISC; < 15 %). Here, we use long-term (1997-2019), monthly streamwater quality data combined with daily streamflow for six exurban and suburban watersheds in southeastern Pennsylvania to examine the relations among chloride (Cl − ) concentrations and ISC. Both flow-normalized Cl − concentrations and ISC increased over time in each of the six watersheds, consistent with changes in watershed management (e.g., ISC, road salt application, etc.). The watersheds that experienced the greatest changes in percent ISC (e.g., agriculture replaced by residential and commercial development) experienced the greatest changes in flow-normalized Cl − concentrations. We also utilized a comprehensive mass-balance model (2011–2018) that indicated Cl − inputs exceeded the outputs for the study watersheds. Road salt applied to state roads, non-state roads, and other impervious surfaces accounted for the majority of Cl − inputs to the six watersheds. Furthermore, increasing Cl − concentrations during baseflow conditions confirm impacts to shallow groundwater. Although flow-normalized Cl − concentrations are below the U.S. Environmental Protection Agency's chronic threshold value for impacts to aquatic organisms, year-round exceedances may result before the end of this century based on current trends. Though reduced Cl − loading to streams may be achieved by limiting the expansion of impervious surfaces in exurban and suburban watersheds, changes in baseflow concentrations are likely to be gradual because of the accumulated Cl − in groundwater.

Pennsylvania↗

USGS2022

Pollutant co-attenuation via in-stream interactions between mine drainage and municipal wastewater

Municipal wastewater (MWW) and mine drainage (MD) are common co-occurring sources of freshwater pollution in mining regions. The physicochemical interactions that occur after mixing MWW and MD in a waterway may improve downstream water quality of an impaired reach by reducing downstream concentrations of nutrients and metals (i.e., “co-attenuation”). A first-order stream (Bradley Run in central Pennsylvania), with coal MD and secondarily treated MWW entering the stream in the same location, was systematically monitored to determine in-stream water-quality dynamics. Monitored constituents included pH, nutrients (i.e., phosphorus and nitrogen), and metals (e.g., iron, aluminum, manganese). Mixing of the MWW, MD, and upstream water decreased concentrations of phosphate, aluminum, and iron by 94%, 91%, and 98%, respectively, relative to conservative mixtures at the 1400-m-downstream site. The pollutant co-attenuation resulted in water quality equivalent to that upstream of the pollutant sources and improved the phosphorus-based trophic status of the stream. Geochemical models indicate the primary mechanisms for P attenuation in the studied stream were precipitation as variscite (AlPO 4 :2H 2 O) or amorphous AlPO 4 plus adsorption to hydrous ferric oxide, despite a much greater abundance of hydrous aluminum oxide. The results presented in this study suggest that in-stream mixing of MD with untreated or secondarily treated MWW may be an important, overlooked factor affecting downstream transport of common pollutants in mining regions. Decreased metals loading and increased pH resulting from natural attenuation and remediation of MD could affect the potential for retention of phosphate by stream sediment and could lead to the release of nutrients from legacy accumulations, highlighting the potential need to address high-nutrient discharges (e.g., improved MWW treatment) in concert with MD remediation.

Pennsylvania↗

USGS2022

Determination and prediction of rare earth element eeochemical associations in acid mine drainage treatment wastes

Acid mine drainage (AMD) has been proposed by various researchers as a novel source of rare earth elements (REE), a group of elements that include critical metals for clean energy and modern technologies. REE tend to be sequestered in the Fe-Al-Mn-rich solids produced during the treatment of AMD. These solids are typically managed as waste, but could be a low-cost, readily available REE source. Here, results from field sampling, solids characterization, and geochemical modeling are presented to identify the mechanism(s) of REE attenuation and determine the minerals/solid phases in AMD solids that are enriched in REE. This study reveals that solids produced from low-pH AMD that was passively treated by limestone contain elevated concentrations of REE with Al, Fe, and/or Mn. AMD solid characterization via sequential extraction demonstrated that Al and Mn oxides were more abundant than Fe oxides and that the REEs are mainly associated with Al/Mn phases. Additionally, sequential extractions demonstrate that for the AMD solids evaluated, acidic and/or reducing extractions are required to mobilize the REE. Finally, the “CausticTitrationREYs.exe” geochemical equilibrium model demonstrated in this study indicates that the observed dissolved REE attenuation can be explained via surface complexation on Fe, Al, and Mn oxides/hydroxides and not by REE compound precipitation. The model accurately predicts the pH dependent removal of dissolved REE and that Al and Mn oxides/hydroxides are largely responsible for dissolved REE removal for the systems evaluated. The modeling results are consistent with the characterization results that show that Al and Mn hydroxides are important hosting phases of REEs in AMD treatment systems. The results presented here can be used to identify conditions favorable for accumulation of REE-enriched AMD solids and possible chemical treatment(s) to mobilize REE. The geochemical model can be applied to active and/or passive AMD treatment systems to predict REE attenuation with Fe, Al, and Mn during treatment and what phases may be enriched in REE. This information can be used to engineer AMD systems to produce specific phases enriched in REE. The recovery of REE from AMD solids is an opportunity to transform the environmental and economical challenge of polluted mine drainage into an asset.

Conference Paper↗

USGS2022

PHREEQ-N-AMDTreat+REYs water-quality modeling tools to evaluate acid mine drainage treatment strategies for recovery of rare-earth elements

The PHREEQ-N-AMDTreat+REYs water-quality modeling tools have the fundamental capability to simulate aqueous chemical reactions and predict the formation of metal-rich solids during the treatment of acid mine drainage (AMD). These new user-friendly, publicly available tools were expanded from the PHREEQ-N-AMDTreat tools to include the precipitation of rare-earth elements plus yttrium (REYs) and the adsorption of REYs onto hydrous Fe, Al, and Mn oxides. The tool set consists of a caustic titration model that indicates equilibrium surface and aqueous speciation of REYs as functions of pH and caustic agent, and a kinetics+adsorption model that simulates progressive changes in pH, major ions, and REYs in water and solids during sequential steps through passive and/or active treatment. Each model has a user interface (UI) that facilitates the input of water-quality data and adjustment to geochemical or treatment system variables; for example, retention time and aeration rate are adjustable parameters in the kinetics model. On-screen graphs display results of changes in metals and associated solute concentrations as functions of pH or retention time; details are summarized in output tables. A goal of such modeling is to identify strategies that could produce a concentrated REYs extract from AMD or mine waste leachate. For example, if REYs could be concentrated after first removing substantial Fe and Al, the final REYs-bearing phase(s) could be more efficiently processed for REYs recovery and, therefore, may represent a more valuable commodity. Preliminary modeling supports the hypothesis that Fe and Al can be removed at pH < 5.5 using conventional sequential oxidation and neutralization treatment processes without removing REYs, and that further increasing pH can promote the adsorption of REYs by hydrous Mn oxides. Alternatively, chemicals such as oxalate or phosphate may be added to precipitate REYs compounds following initial steps to decrease Fe and Al concentrations. The aqueous geochemical model framework is comprehensive and permits evaluation of effects from interactive chemical and physical variables. Field studies that demonstrate REYs attenuation from AMD and corresponding solid-phase formation during specific treatment steps plus laboratory studies of aqueous/solid interactions are helpful to corroborate, refine, and constrain modelin parameters.

Conference Paper↗

USGS2021

Relation between road-salt application and increasing radium concentrations in a low-pH aquifer, southern New Jersey

The Kirkwood–Cohansey aquifer in southern New Jersey is an important source of drinking-water supplies, but the availability of the resource is limited in some areas by high concentrations of radium, a potential carcinogen at elevated concentrations. Radium ( 226 Ra plus 228 Ra) concentrations from a network of 25 drinking-water wells showed a statistically significant increase over a decadal time scale ( p < 0.05), with a median increase of 0.35 picocuries per liter. Increases in Ra are correlated with road-salt application rates, and we hypothesize that the correlation is causal. Geochemical processes associated with road-salt applications that can mobilize Ra into solution include competition by excess sodium for sorption sites and formation of chloride complexes (RaCl + and RaCl 2 ). The largest increases in Ra were in groundwater with low pH (≤5), which is an indirect surrogate for low cation-sorption capacity. Correlations with other potential anthropogenic causes for the increase in Ra were not observed, further suggesting a road-salt effect. Given the significant increase in Ra concentrations in this drinking-water source, the known carcinogenic risks from Ra, the direct link to road-salt application, and the likelihood for continued increases, additional monitoring is necessary in areas with similar hydrogeologic and geochemical settings.

New Jersey↗

USGS2021

Machine-learning predictions of high arsenic and high manganese at drinking water depths of the glacial aquifer system, northern continental United States

Globally, over 200 million people are chronically exposed to arsenic (As) and/or manganese (Mn) from drinking water. We used machine-learning (ML) boosted regression tree (BRT) models to predict high As (>10 μg/L) and Mn (>300 μg/L) in groundwater from the glacial aquifer system (GLAC), which spans 25 states in the northern United States and provides drinking water to 30 million people. Our BRT models’ predictor variables (PVs) included recently developed three-dimensional estimates of a suite of groundwater age metrics, redox condition, and pH. We also demonstrated a successful approach to significantly improve ML prediction sensitivity for imbalanced data sets (small percentage of high values). We present predictions of the probability of high As and high Mn concentrations in groundwater, and uncertainty, at two nonuniform depth surfaces that represent moving median depths of GLAC domestic and public supply wells within the three-dimensional model domain. Predicted high likelihood of anoxic condition (high iron or low dissolved oxygen), predicted pH, relative well depth, several modeled groundwater age metrics, and hydrologic position were all PVs retained in both models; however, PV importance and influence differed between the models. High-As and high-Mn groundwater was predicted with high likelihood over large portions of the central part of the GLAC.

Environmental Science & Technology↗