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 Ca2+, Mg2+, 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.

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 δ15N and δ18O 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.

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 (PO4) 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 PO4 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 PO4 species tend to be adsorbed by hydrous iron, aluminum, and manganese oxides that coat soil and sediment particles; however, PO4 may be substantially desorbed at pH >8. We created a geochemical model that simulates equilibrium aqueous/solid distributions of PO4 as pH and other solution characteristics change. Considering current conditions in the lower Susquehanna River, the model demonstrates potential for extensive release of adsorbed PO4 at pH >8. Empirical data from laboratory experiments corroborate model results. The transfer of PO4 into the water column may increase algae growth, which removes CO2 and drives pH to higher values, facilitating additional PO4 release and exacerbating the potential for harmful algal blooms. Thus, legacy sediment is a currently unquantified source of PO4 that warrants consideration by resource managers and programs collaborating to reduce phosphorus loads to the bay and similar settings worldwide.

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 CaCO3 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.

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.

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 (AlPO4:2H2O) or amorphous AlPO4 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.

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 (PO4) 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 PO4 from the water by adsorption to the HFO, depending on the HFO quantity, initial PO4 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.

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.

Lithium in groundwater used for drinking-water supply in the United States.

Lithium concentrations in untreated groundwater from 1464 public-supply wells and 1676 domestic-supply wells distributed across 33 principal aquifers in the United States were evaluated for spatial variations and possible explanatory factors. Concentrations nationwide ranged from <1 to 396 µg/L (median of 8.1) for public supply wells and <1 to 1700 µg/L (median of 6 µg/L) for domestic supply wells. For context, lithium concentrations were compared to a Health Based Screening Level (HBSL, 10 µg/L) and a drinking-water only threshold (60 µg/L). These thresholds were exceeded in 45% and 9% of samples from public-supply wells and in 37% and 6% from domestic-supply wells, respectively. However, exceedances and median concentrations ranged broadly across geographic regions and principal aquifers. Concentrations were highest in arid regions and older groundwater, particularly in unconsolidated clastic aquifers and sandstones, and lowest in carbonate-rock aquifers, consistent with differences in lithium abundance among major lithologies and rock weathering extent. The median concentration for public-supply wells in the unconsolidated clastic High Plains aquifer (central United States) was 24.6 µg/L; 24% of the wells exceeded the drinking-water only threshold and 86% exceeded the HBSL. Other unconsolidated clastic aquifers in the arid West had exceedance rates comparable to the High Plains aquifer, whereas no public supply wells in the Biscayne aquifer (southern Florida) exceeded either threshold, and the highest concentration in that aquifer was 2.6 µg/L. Multiple lines of evidence indicate natural sources for the lithium concentrations; however, anthropogenic sources may be important in the future because of the rapid increase of lithium battery use and subsequent disposal. Geochemical models demonstrate that extensive evaporation, mineral dissolution, cation exchange, and mixing with geothermal waters or brines may account for the observed lithium and associated constituent concentrations, with the latter two processes as major contributing factors.

Occurrence and Geochemistry of Lead-210 and Polonium-210 Radionuclides in Public-Drinking-Water Supplies from Principal Aquifers of the United States.

On the basis of lifetime cancer risks, lead-210 (210Pb) and polonium-210 (210Po) ≥ 1.0 and 0.7 pCi/L (picocuries per liter), respectively, in drinking-water supplies may pose human-health concerns. 210Pb and 210Po were detected at concentrations greater than these thresholds at 3.7 and 1.5%, respectively, of filtered untreated groundwater samples from 1263 public-supply wells in 19 principal aquifers across the United States. Nationally, 72% of samples with radon-222 (222Rn) concentrations > 4000 pCi/L had 210Pb ≥ 1.0 pCi/L. 210Pb is mobilized by alpha recoil associated with the decay of 222Rn and short-lived progeny. 210Pb concentrations ≥ 1.0 pCi/L occurred most frequently where acidic groundwaters inhibited 210Pb readsorption (felsic-crystalline rocks) and where reducing alkaline conditions favored dissolution of iron-manganese- (Fe-Mn-) oxyhydroxides (which adsorb 210Pb) and formation of lead-carbonate complexes (enhancing lead (Pb) mobility). 210Po concentrations ≥ 0.7 pCi/L occurred almost exclusively in confined Coastal Plain aquifers where old (low percent-modern carbon-14) groundwaters were reducing, with high pH (>7.5) and high sodium/chloride (Na/Cl) ratios resulting from cation exchange. In high-pH environments, aqueous polonium (Po) is poorly sorbed, occurring as dihydrogen polonate (H2PoO3(aq)) or, under strongly reducing conditions, as a hydrogen-polonide anion (HPo-). Fe-Mn- and sulfate-reduction and cation-exchange processes may mobilize polonium from mineral surfaces. Po2+ occurrence in low-to-neutral-pH waters is attenuated by adsorption.

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 (FeII) and manganese (MnII). 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 FeII and MnII oxidation are slow compared to the residence time of water in the pumping well; however, adsorption of FeII and MnII 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.

Emerging investigator series: radium accumulation in carbonate river sediments at oil and gas produced water discharges: implications for beneficial use as disposal management.

In the western U.S., produced water from oil and gas wells discharged to surface water augments downstream supplies used for irrigation and livestock watering. Here we investigate six permitted discharges on three neighboring tributary systems in Wyoming. During 2013-16, we evaluated radium activities of the permitted discharges and the potential for radium accumulation in associated stream sediments. Radium activities of the sediments at the points of discharge ranged from approximately 200-3600 Bq kg-1 with elevated activities above the background of 74 Bq kg-1 over 30 km downstream of one permitted discharge. Sediment as deep as 30 cm near the point of discharge had radium activities elevated above background. X-ray diffraction and targeted sequential extraction of radium in sediments indicate that radium is likely coprecipitated with carbonate and, to a lesser extent, sulfate minerals. PHREEQC modeling predicts radium coprecipitation with aragonite and barite, but over-estimates the latter compared to observations of downstream sediment, where carbonate predominates. Mass-balance calculations indicate over 3 billion Bq of radium activity (226Ra + 228Ra) is discharged each year from five of the discharges, combined, with only 5 percent of the annual load retained in stream sediments within 100 m of the effluent discharges; the remaining 95 percent of the radium is transported farther downstream as sediment-associated and aqueous species.

Inhibition of bacterial oxidation of ferrous iron by lead nitrate in sulfate-rich systems.

Inhibition of bacterial oxidation of ferrous iron (Fe(II)) by Pb(NO(3))(2) was investigated with a mixed culture of Acidithiobacillus ferrooxidans. The culture was incubated at 30 °C in ferrous-sulfate medium amended with 0-24.2 mM Pb(II) added as Pb(NO(3))(2). Anglesite (PbSO(4)) precipitated immediately upon Pb addition and was the only solid phase detected in the abiotic controls. Both anglesite and jarosite (KFe(3)(SO(4))(2)(OH)(6)) were detected in inoculated cultures. Precipitation of anglesite maintained dissolved Pb concentrations at 16.9-17.6 µM regardless of the concentrations of Pb(NO(3))(2) added. Fe(II) oxidation was suppressed by 24.2 mM Pb(NO(3))(2) addition even when anglesite was removed before inoculation. Experiments with 0-48 mM KNO(3) demonstrated that bacterial Fe(II) oxidation decreased as nitrate concentration increased. Therefore, inhibition of Fe(II) oxidation at 24.2 mM Pb(NO(3))(2) addition resulted from nitrate toxicity instead of Pb addition. Geochemical modeling that considered the initial precipitation of anglesite to equilibrium followed by progressive oxidation of Fe(II) and the precipitation of jarosite and an amorphous iron hydroxide phase, without allowing plumbojarosite to precipitate were consistent with the experimental time-series data on Fe(II) oxidation under biotic conditions. Anglesite precipitation in mine tailings and other sulfate-rich systems maintains dissolved Pb concentrations below the toxicity threshold of A. ferrooxidans.

Implications of ground water chemistry and flow patterns for earthquake studies.

Ground water can facilitate earthquake development and respond physically and chemically to tectonism. Thus, an understanding of ground water circulation in seismically active regions is important for earthquake prediction. To investigate the roles of ground water in the development and prediction of earthquakes, geological and hydrogeological monitoring was conducted in a seismogenic area in the Yanhuai Basin, China. This study used isotopic and hydrogeochemical methods to characterize ground water samples from six hot springs and two cold springs. The hydrochemical data and associated geological and geophysical data were used to identify possible relations between ground water circulation and seismically active structural features. The data for delta18O, deltaD, tritium, and 14C indicate ground water from hot springs is of meteoric origin with subsurface residence times of 50 to 30,320 years. The reservoir temperature and circulation depths of the hot ground water are 57 degrees C to 160 degrees C and 1600 to 5000 m, respectively, as estimated by quartz and chalcedony geothermometers and the geothermal gradient. Various possible origins of noble gases dissolved in the ground water also were evaluated, indicating mantle and deep crust sources consistent with tectonically active segments. A hard intercalated stratum, where small to moderate earthquakes frequently originate, is present between a deep (10 to 20 km), high-electrical conductivity layer and the zone of active ground water circulation. The ground water anomalies are closely related to the structural peculiarity of each monitoring point. These results could have implications for ground water and seismic studies in other seismogenic areas.

Size and performance of anoxic limestone drains to neutralize acidic mine drainage.

Acidic mine drainage (AMD) can be neutralized effectively in underground, anoxic limestone drains (ALDs). Owing to reaction between the AMD and limestone (CaCO3), the pH and concentrations of alkalinity and calcium increase asymptotically with detention time in the ALD, while concentrations of sulfate, ferrous iron, and manganese typically are unaffected. This paper introduces a method to predict the alkalinity produced within an ALD and to estimate the mass of limestone required for its construction on the basis of data from short-term, closed-container (cubitainer) tests. The cubitainer tests, which used an initial mass of 4 kg crushed limestone completely inundated with 2.8 L AMD, were conducted for 11 to 16 d and provided estimates for the initial and maximum alkalinities and corresponding rates of alkalinity production and limestone dissolution. Long-term (5-11 yr) data for alkalinity and CaCO3 flux at the Howe Bridge, Morrison, and Buck Mountain ALDs in Pennsylvania, USA, indicate that rates of alkalinity production and limestone dissolution under field conditions were comparable with those in cubitainers filled with limestone and AMD from each site. The alkalinity of effluent and intermediate samples along the flow path through the ALDs and long-term trends in the residual mass of limestone and the effluent alkalinity were estimated as a function of the computed detention time within the ALD and second-order dissolution rate models for cubitainer tests. Thus, cubitainer tests can be a useful tool for designing ALDs and predicting their performance.