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In situ spectroscopic and solution analyses of the reductive dissolution of Mn02 by Fe(II)

The reductive dissolution of MnO 2 by Fe(II) under conditions simulating acid mine drainage (pH 3, 100 mM SO 4 2 - ) was investigated by utilizing a flow-through reaction cell and synchrotron X-ray absorption spectroscopy. This configuration allows collection of in situ, real-time X-ray absorption near-edge structure (XANES) spectra and bulk solution samples. Analysis of the solution chemistry suggests that the reaction mechanism changed (decreased reaction rate) as MnO 2 was reduced and Fe(III) precipitated, primarily as ferrihydrite. Simultaneously, we observed an additional phase, with the local structure of jacobsite (MnFe 2 O 4 ), in the Mn XANES spectra of reactants and products. The X-ray absorbance of this intermediate phase increased during the experiment, implying an increase in concentration. The presence of this phase, which probably formed as a surface coating, helps to explain the reduced rate of dissolution of manganese(IV) oxide. In natural environments affected by acid mine drainage, the formation of complex intermediate solid phases on mineral surfaces undergoing reductive dissolution may likewise influence the rate of release of metals to solution.

Environmental Science & Technology↗

Soil property control of biogeochemical processes beneath two subtropical stormwater infiltration basins

Substantially different biogeochemical processes affecting nitrogen fate and transport were observed beneath two stormwater infiltration basins in north-central Florida. Differences are related to soil textural properties that deeply link hydroclimatic conditions with soil moisture variations in a humid, subtropical climate. During 2008, shallow groundwater beneath the basin with predominantly clayey soils (median, 41% silt+clay) exhibited decreases in dissolved oxygen from 3.8 to 0.1 mg L -1 and decreases in nitrate nitrogen (NO 3 - &ndash;N) from 2.7 mg L -1 to <0.016 mg L -1 , followed by manganese and iron reduction, sulfate reduction, and methanogenesis. In contrast, beneath the basin with predominantly sandy soils (median, 2% silt+clay), aerobic conditions persisted from 2007 through 2009 (dissolved oxygen, 5.0&ndash;7.8 mg L -1 ), resulting in NO 3 - &ndash;N of 1.3 to 3.3 mg L -1 in shallow groundwater. Enrichment of d15N and d18O of NO 3 - combined with water chemistry data indicates denitrification beneath the clayey basin and relatively conservative NO 3 - transport beneath the sandy basin. Soil-extractable NO 3 - &ndash;N was significantly lower and the copper-containing nitrite reductase gene density was significantly higher beneath the clayey basin. Differences in moisture retention capacity between fine- and coarse-textured soils resulted in median volumetric gas-phase contents of 0.04 beneath the clayey basin and 0.19 beneath the sandy basin, inhibiting surface/subsurface oxygen exchange beneath the clayey basin. Results can inform development of soil amendments to maintain elevated moisture content in shallow soils of stormwater infiltration basins, which can be incorporated in improved best management practices to mitigate NO 3 - impacts.

Florida↗

Hydrology of Area 7, Eastern Coal Province, Ohio

The U.S. Geological Survey established 24 study areas in Eastern Appalachian Coal Province to appraise the hydrology and water resources from Alabama to Pennsylvania. Chemical, physical, biological, and streamflow data were collected from 138 synoptic sites in Area 7, eastern Ohio. The data are evaluated and presented in this report. Area 7 lies within the drainage basins of Muskingum Rivers and Duck and Willis Creeks in eastern Ohio. Walhounding, Tuscarawas, and Little Muskingum, and Muskingum Rivers and Wills and Duck Creeks are the major streams draining the study area. In Ohio, surface and subsurface coal mining has altered the environment. In areas where land has been reclaimed, the environmental stress expected to be temporary. Hydrologic problems related to coal mining are erosion and sedimentation which degrade water-quality. Based on available sediment data, suspended sediment concentration were highest in abandoned mine areas, followed by currently mined and reclaimed areas, and lowest in unmined areas. Low pH, high specific conductance, high concentrations of iron, sulfate and manganese, increased sediment yields, discoloration of streambeds, limited aquatic vegetation and animal life typify streams draining areas with abandoned mines. In abandoned mine areas, the specific conductance of water ranged from 800 to 2,300 micromhos; pH ranged from 2.8 to 5.8; dissolved-iron concentrations ranged from 1,000 to 85,000 micrograms per liter; dissolved-sulfate concentrations ranged from 14 to 1,200 milligrams per liter and dissolved-manganese concentration commonly exceeded 2,000 micrograms per liter. Red and yellow coloration on the streambeds were precipitates from the hydrolysis of iron, manganese, and sulfate minerals carried into the stream channel by increased sediment erosion from abandoned coal mines. Trace metal concentrations (arsenic, cadmium, chromium, cobalt, copper, lead, mercury, selenium, and zinc) were generally low. Degradation of fish habitat is illustrated by conceptual model of the aquatic biology related to water chemistry.

Open-File Report↗

Relationships between microbial communities and environmental parameters at sites impacted by mining of volcanogenic massive sulfide deposits, Prince William Sound, Alaska

The relations among geochemical parameters and sediment microbial communities were examined at three shoreline sites in the Prince William Sound, Alaska, which display varying degrees of impact by acid-rock drainage (ARD) associated with historic mining of volcanogenic massive sulfide deposits. Microbial communities were examined using total fatty acid methyl esters (FAMEs), a class of compounds derived from lipids produced by eukaryotes and prokaryotes (bacteria and Archaea); standard extraction techniques detect FAMEs from both living (viable) and dead (non-viable) biomass, but do not detect Archaeal FAMEs. Biomass and diversity (as estimated by FAMEs) varied strongly as a function of position in the tidal zone, not by study site; subtidal muds, Fe oxyhydroxide undergoing biogenic reductive dissolution, and peat-rich intertidal sediment had the highest values. These estimates were lowest in acid-generating, intertidal zone sediment; if valid, the estimates suggest that only one or two bacterial species predominate in these communities, and/or that Archeal species are important members of the microbial community in this sediment. All samples were dominated by bacterial FAMEs (median value >90%). Samples with the highest absolute abundance of eukaryotic FAMEs were biogenic Fe oxyhydroxides from shallow freshwater pools (fungi) and subtidal muds (diatoms). Eukaryotic FAMEs were practically absent from low-pH, sulfide-rich intertidal zone sediments. The relative abundance of general microbial functional groups such as aerobes/anaerobes and gram(+)/gram(-) was not estimated due to severe inconsistency among the results obtained using several metrics reported in the literature. Principal component analyses (PCAs) were performed to investigate the relationship among samples as separate functions of water, sediment, and FAMEs data. PCAs based on water chemistry and FAMEs data resulted in similar relations among samples, whereas the PCA based on sediment chemistry produced a very different sample arrangement. Specifically, the sediment parameter PCA grouped samples with high bulk trace metal concentration regardless of whether the metals were incorporated into secondary precipitates or primary sulfides. The water chemistry PCA and FAMEs PCA appear to be less prone to this type of artifact. Signature lipids in sulfide-rich sediments could indicate the presence of acid-tolerant and/or acidophilic members of the genus Thiobacillus or they could indicate the presence of SO4-reducing bacteria. The microbial community documented in subtidal and offshore sediments is rich in SRB and/or facultative anaerobes of the Cytophaga-Flavobacterium group; both could reasonably be expected in PWS coastal environments. The results of this study provide evidence for substantial feedback between local (meter to centimeter-scale) geochemical variations, and sediment microbial community composition, and show that microbial community signatures in the intertidal zone are significantly altered at sites where ARD drainage is present relative to sites where it is not, even if the sediment geochemistry indicates net accumulation of ARD-generated trace metals in the intertidal zone. ?? 2007 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗

Baseline and premining geochemical characterization of mined sites

A rational goal for environmental restoration of new, active, or inactive mine sites would be ‘natural background’ or the environmental conditions that existed before any mining activities or other related anthropogenic activities. In a strictly technical sense, there is no such thing as natural background (or entirely non-anthropogenic) existing today because there is no part of the planet earth that has not had at least some chemical disturbance from anthropogenic activities. Hence, the terms ‘baseline’ and ‘pre-mining’ are preferred to describe these conditions. Baseline conditions are those that existed at the time of the characterization which could be pre-mining, during mining, or post-mining. Protocols for geochemically characterizing pre-mining conditions are not well-documented for sites already mined but there are two approaches that seem most direct and least ambiguous. One is characterization of analog sites along with judicious application of geochemical modeling. The other is reactive-transport modeling (based on careful synoptic sampling with tracer-injection) and subtracting inputs from known mining and mineral processing. Several examples of acidic drainage are described from around the world documenting the range of water compositions produced from pyrite oxidation in the absence of mining. These analog sites provide insight to the processes forming mineralized waters in areas untouched by mining. Natural analog water-chemistry data is compared with the higher metal concentrations, metal fluxes, and weathering rates found in mined areas in the few places where comparisons are possible. The differences are generally 1–3 orders of magnitude higher for acid mine drainage.

Applied Geochemistry↗

Trace analysis of antidepressant pharmaceuticals and their select degradates in aquatic matrixes by LC/ESI/MS/MS

Treated wastewater effluent is a potential environmental point source for antidepressant pharmaceuticals. A quantitative method was developed for the determination of trace levels of antidepressants in environmental aquatic matrixes using solid-phase extraction coupled with liquid chromatography-electrospray ionization tandem mass spectrometry. Recoveries of parent antidepressants from matrix spiking experiments for the individual antidepressants ranged from 72 to 118% at low concentrations (0.5 ng/L) and 70 to 118% at high concentrations (100 ng/L) for the solid-phase extraction method. Method detection limits for the individual antidepressant compounds ranged from 0.19 to 0.45 ng/L. The method was applied to wastewater effluent and samples collected from a wastewater-dominated stream. Venlafaxine was the predominant antidepressant observed in wastewater and river water samples. Individual antidepressant concentrations found in the wastewater effluent ranged from 3 (duloxetine) to 2190 ng/L (venlafaxine), whereas individual concentrations in the waste-dominated stream ranged from 0.72 (norfluoxetine) to 1310 ng/L (venlafaxine).

Analytical Chemistry↗

Toxicity and hazard of vanadium to mallard ducks (Anas platyrhynchos) and Canada geese (Branta canadensis)

A recent Canada goose ( Branta canadensis ) die-off at a petroleum refinery fly ash pond in Delaware was attributed to vanadium (V) toxicity. Because of the paucity of V toxicity data for wild birds, a series of studies was undertaken using the forms of V believed to have resulted in this incident. In 7-d single oral dose trials with mallard drakes ( Anas platyrhynchos ), the estimated median lethal dose (LD50) for vanadium pentoxide was 113 mg/kg body weight, while the LD50 for sodium metavanadate was 75.5 mg/kg. Sodium metavanadate was found to be even more potent (LD50 = 37.2 mg/kg) in male Canada geese. The most distinctive histopathological lesion of both forms of V was lympho-granulocytic enteritis with hemorrhage into the intestinal lumen. Vanadium accumulation in liver and kidney was proportional to the administered dose, and predictive analyses based on these data suggest that V concentrations of 10 μg/g dry weight (dw) in liver and 25 μg/g dw in kidney are associated with mortality (>90% confidence that exposure is >LD50) in mallards acutely exposed to sodium metavanadate. Chronic exposure to increasing dietary concentrations of sodium metavanadate (38.5 to 2651 ppm) over 67 d resulted in V accumulation in liver and kidney (25.2 and 13.6 μg/g dw, respectively), mild intestinal hemorrhage, blood chemistry changes, and evidence of hepatic oxidative stress in mallards, although some of these responses may have been confounded by food avoidance and weight loss. Dietary exposure of mallards to 250 ppm sodium metavanadate for 4 wk resulted in modest accumulation of V in liver and kidney (<5 μg/g dw) and mild intestinal hemorrhage. Based on these data and other observations, it is unlikely that chronic low-level dietary exposure to V poses a direct lethal hazard to wildlife. However, point sources, such as the V-laden fly ash pond encountered by geese at the petroleum refinery in Delaware, may pose a significant hazard to water birds.

Journal of Toxicology and Environmental Health, Pa↗

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↗

Weathering of sulfidic shale and copper mine waste: Secondary minerals and metal cycling in Great Smoky Mountains National Park, Tennessee, and North Carolina, USA

Metal cycling via physical and chemical weathering of discrete sources (copper mines) and regional (non-point) sources (sulfide-rich shale) is evaluated by examining the mineralogy and chemistry of weathering products in Great Smoky Mountains National Park, Tennessee, and North Carolina, USA. The elements in copper mine waste, secondary minerals, stream sediments, and waters that are most likely to have negative impacts on aquatic ecosystems are aluminum, copper, zinc, and arsenic because these elements locally exceed toxicity guidelines for surface waters or for stream sediments. Acid-mine drainage has not developed in streams draining inactive copper mines. Acid-rock drainage and chemical weathering processes that accompany debris flows or human disturbances of sulfidic rocks are comparable to processes that develop acid-mine drainage elsewhere. Despite the high rainfall in the mountain range, sheltered areas and intermittent dry spells provide local venues for development of secondary weathering products that can impact aquatic ecosystems.

Environmental Geology↗

Geochemical and isotopic variations in shallow groundwater in areas of the Fayetteville Shale development, north-central Arkansas

Exploration of unconventional natural gas reservoirs such as impermeable shale basins through the use of horizontal drilling and hydraulic fracturing has changed the energy landscape in the USA providing a vast new energy source. The accelerated production of natural gas has triggered a debate concerning the safety and possible environmental impacts of these operations. This study investigates one of the critical aspects of the environmental effects; the possible degradation of water quality in shallow aquifers overlying producing shale formations. The geochemistry of domestic groundwater wells was investigated in aquifers overlying the Fayetteville Shale in north-central Arkansas, where approximately 4000 wells have been drilled since 2004 to extract unconventional natural gas. Monitoring was performed on 127 drinking water wells and the geochemistry of major ions, trace metals, CH 4 gas content and its C isotopes (&delta; 13 C CH4 ), and select isotope tracers (&delta; 11 B, 87 Sr/ 86 Sr, &delta; 2 H, &delta; 18 O, &delta; 13 C DIC ) compared to the composition of flowback-water samples directly from Fayetteville Shale gas wells. Dissolved CH 4 was detected in 63% of the drinking-water wells (32 of 51 samples), but only six wells exceeded concentrations of 0.5 mg CH 4 /L. The &delta; 13 C CH4 of dissolved CH 4 ranged from &minus;42.3&permil; to &minus;74.7&permil;, with the most negative values characteristic of a biogenic source also associated with the highest observed CH 4 concentrations, with a possible minor contribution of trace amounts of thermogenic CH 4 . The majority of these values are distinct from the reported thermogenic composition of the Fayetteville Shale gas (&delta; 13 C CH4 = &minus;35.4&permil; to &minus;41.9&permil;). Based on major element chemistry, four shallow groundwater types were identified: (1) low (<100 mg/L) total dissolved solids (TDS), (2) TDS > 100 mg/L and Ca&ndash;HCO 3 dominated, (3) TDS > 100 mg/L and Na&ndash;HCO 3 dominated, and (4) slightly saline groundwater with TDS > 100 mg/L and Cl > 20 mg/L with elevated Br/Cl ratios (>0.001). The Sr ( 87 Sr/ 86 Sr = 0.7097&ndash;0.7166), C (&delta; 13 C DIC = &minus;21.3&permil; to &minus;4.7&permil;), and B (&delta; 11 B = 3.9&ndash;32.9&permil;) isotopes clearly reflect water&ndash;rock interactions within the aquifer rocks, while the stable O and H isotopic composition mimics the local meteoric water composition. Overall, there was a geochemical gradient from low-mineralized recharge water to more evolved Ca&ndash;HCO 3 , and higher-mineralized Na&ndash;HCO 3 composition generated by a combination of carbonate dissolution, silicate weathering, and reverse base-exchange reactions. The chemical and isotopic compositions of the bulk shallow groundwater samples were distinct from the Na&ndash;Cl type Fayetteville flowback/produced waters (TDS &sim;10,000&ndash;20,000 mg/L). Yet, the high Br/Cl variations in a small subset of saline shallow groundwater suggest that they were derived from dilution of saline water similar to the brine in the Fayetteville Shale. Nonetheless, no spatial relationship was found between CH 4 and salinity occurrences in shallow drinking water wells with proximity to shale-gas drilling sites. The integration of multiple geochemical and isotopic proxies shows no direct evidence of contamination in shallow drinking-water aquifers associated with natural gas extraction from the Fayetteville Shale.

Applied Geochemistry↗

Using geochemistry to identify the source of groundwater to Montezuma Well, a natural spring in Central Arizona, USA: Part 2

Montezuma Well is a unique natural spring located in a sinkhole surrounded by travertine. Montezuma Well is managed by the National Park Service, and groundwater development in the area is a potential threat to the water source for Montezuma Well. This research was undertaken to better understand the sources of groundwater to Montezuma Well. Strontium isotopes ( 87 Sr/ 86 Sr) indicate that groundwater in the recharge area has flowed through surficial basalts with subsequent contact with the underlying Permian aged sandstones and the deeper, karstic, Mississippian Redwall Limestone. The distinctive geochemistry in Montezuma Well and nearby Soda Springs (higher concentrations of alkalinity, As, B, Cl, and Li) is coincident with added carbon dioxide and mantle-sourced He. The geochemistry and isotopic data from Montezuma Well and Soda Springs allow for the separation of groundwater samples into four categories: (1) upgradient, (2) deep groundwater with carbon dioxide, (3) shallow Verde Formation, and (4) mixing zone. δ 18 O and δD values, along with noble gas recharge elevation data, indicate that the higher elevation areas to the north and east of Montezuma Well are the groundwater recharge zones for Montezuma Well and most of the groundwater in this portion of the Verde Valley. Adjusted groundwater age dating using likely 14 C and δ 13 C sources indicate an age for Montezuma Well and Soda Springs groundwaters at 5,400–13,300 years, while shallow groundwater in the Verde Formation appears to be older (18,900). Based on water chemistry and isotopic evidence, groundwater flow to Montezuma Well is consistent with a hydrogeologic framework that indicates groundwater flow by (1) recharge in higher elevation basalts to the north and east of Montezuma Well, (2) movement through the upgradient Permian and Mississippian units, especially the Redwall Limestone, and (3) contact with a basalt dike/fracture system that provides a mechanism for groundwater to flow to the surface. While the exact nature of the groundwater flow connections is still uncertain, the available data indicate that flow to Montezuma Well may be more susceptible to future groundwater development in the Redwall Limestone than from any other geologic unit. Overall, the shallow groundwater in the surrounding Verde Formation appears to be largely disconnected from deeper groundwater flowing to Montezuma Well.

Arizona↗

Widespread chemical dilution of streams continues as long-term effects of acidic deposition slowly reverse

Studies of recovery from acidic deposition have focused on reversal of acidification and its associated effects, but as recovery proceeds slowly, chemical dilution of surface waters is emerging as a key factor in the recovery process that has significant chemical and biological implications. This investigation uses long-term chemical records from 130 streams in the Adirondack region of New York, USA, to evaluate the role of ongoing decreases in conductance, an index of dilution, in the recovery of these streams. Stream chemistry data spanning up to 40 years (1980s–2022) showed that acid-neutralizing capacity has increased in 92% of randomly selected streams, but that harmful levels of acidification still occur in 37% of these streams. Conductance and Ca 2+ concentrations decreased in 79% of streams, and SO 4 2− concentrations in streams continued to show strong decreases but remained several times higher than concentrations in precipitation. These changes were ongoing through 2022 even though acidic deposition levels were approaching those estimated for pre-industrialization. Further dilution is continuing through ongoing decreases in stream SO 4 2− . Nevertheless, Ca 2+ continued to be leached from soils by SO 4 2− , organic acids and NO 3 − , limiting the replenishment of available soil Ca 2+ , a prerequisite to stem further dilution of stream water.

Environmental Pollution↗

Sediment studies in the Assabet River, central Massachusetts, 2003

From its headwaters in Westborough, Massachusetts, to its confluence with the Sudbury River, the 53-kilometer-long Assabet River passes through a series of small towns and mixed land-use areas. Along the way, wastewater-treatment plants release nutrient-rich effluents that contribute to the eutrophic state of this waterway. This condition is most obvious where the river is impounded by a series of dams that have sequestered large amounts of sediment and support rooted and floating macrophytes and epiphytic algae. The water in parts of these impoundments may also have low concentrations of dissolved oxygen, another symptom of eutrophication. All of the impoundments had relatively shallow maximum water depths, which ranged from approximately 2.4 to 3.4 meters, and all had extensive shallow areas. Sediment volumes estimated for the six impoundments ranged from approximately 380 cubic meters in the Aluminum City impoundment to 580,000 cubic meters in the Ben Smith impoundment. The other impoundments had sediment volumes of 120,000 cubic meters (Powdermill), 67,000 cubic meters (Gleasondale), 55,000 cubic meters (Hudson), and 42,000 cubic meters (Allen Street). The principal objective of this study was the determination of sediment volume, extent, and chemistry, in particular, the characterization of toxic inorganic and organic chemicals in the sediments. To determine the bulk-sediment chemical-constituent concentrations, more than one hundred sediment cores were collected in pairs from the six impoundments. One core from each pair was sampled for inorganic constituents and the other for organic constituents. Most of the cores analyzed for inorganics were sectioned to provide information on the vertical distribution of analytes; a subset of the cores analyzed for organics was also sectioned. Approximately 200 samples were analyzed for inorganic constituents and 100 for organics; more than 10 percent were quality-control replicate or blank samples. Maximum bulk-sediment phosphorus concentrations in surface samples from the impoundments increased along a downstream gradient, with the exception of samples from the last impoundment, where the concentrations decreased. In addition, the highest phosphorus concentrations were generally in the surface samples; this finding may prove helpful if surface dredging is selected as a means to control phosphorus release from sediments. There is no known relation, however, between bulk-sediment concentration of phosphorus and the concentrations of phosphorus available to biota. Potentially toxic metals, including arsenic, cadmium, chromium, copper, nickel, lead, and zinc were frequently measured at concentrations that exceeded U.S. Environmental Protection Agency sediment-quality guidelines for the protection of aquatic life and that occasionally exceeded Massachusetts Department of Environmental Protection guidelines governing landfill disposal (reuse). Due to the effects of matrix interference and sample dilution on laboratory analyses, neither pesticides nor volatile organic compounds were detected at any sites. However, samples collected in other studies from nearby streams indicated the possibility that pesticides might have been detected in the impoundments if not for these analytical problems. Although polychlorinated biphenyl concentrations, as individual Aroclors, generally exceeded published U.S. Environmental Protection Agency guideline concentrations for potential effects on aquatic life, the U.S. Environmental Protection Agency guideline concentrations for human contact or the Massachusetts guidelines for landfill reuse were rarely exceeded. Concentrations of polycyclic aromatic hydrocarbons, both individually and total, frequently were greater than guideline concentrations. Concentrations of total extractable petroleum hydrocarbons did not exceed Massachusetts guideline concentrations in any samples. When the sediment analytes from surface samples are considered togethe

Scientific Investigations Report↗

Effect of calcium carbonate saturation of seawater on coral calcification

The carbonate chemistry of seawater is usually not considered to be an important factor influencing calcium-carbonate-precipitation by corals because surface seawater is supersaturated with respect to aragonite. Recent reports, however, suggest that it could play a major role in the evolution and biogeography of recent corals. We investigated the calcification rates of five colonies of the zooxanthellate coral Stylophora pistillata in synthetic seawater using the alkalinity anomaly technique. Changes in aragonite saturation from 98% to 585% were obtained by manipulating the calcium concentration. The results show a nonlinear increase in calcification rate as a function of aragonite saturation level. Calcification increases nearly 3-fold when aragonite saturation increases from 98% to 390%, i.e., close to the typical present saturation state of tropical seawater. There is no further increase of calcification at saturation values above this threshold. Preliminary data suggest that another coral species, Acropora sp., displays a similar behaviour. These experimental results suggest: (l) that the rate of calcification does not change significantly within the range of saturation levels corresponding to the last glacial-interglacial cycle, and (2) that it may decrease significantly in the future as a result of the decrease in the saturation level due to anthropogenic release of CO2 into the atmosphere. Experimental studies that control environmental conditions and seawater composition provide unique opportunities to unravel the response of corals to global environmental changes.

Global and Planetary Change↗

Ground-water quality data in the Owens and Indian Wells Valleys study unit, 2006: Results from the California GAMA Program

Ground-water quality in the approximately 1,630 square-mile Owens and Indian Wells Valleys study unit (OWENS) was investigated in September-December 2006 as part of the Priority Basin Project of Groundwater Ambient Monitoring and Assessment (GAMA) Program. The GAMA Priority Basin Project was developed in response to the Groundwater Quality Monitoring Act of 2001 and is being conducted by the U.S. Geological Survey (USGS) in collaboration with the California State Water Resources Control Board (SWRCB). The Owens and Indian Wells Valleys study was designed to provide a spatially unbiased assessment of raw ground-water quality within OWENS study unit, as well as a statistically consistent basis for comparing water quality throughout California. Samples were collected from 74 wells in Inyo, Kern, Mono, and San Bernardino Counties. Fifty-three of the wells were selected using a spatially distributed, randomized grid-based method to provide statistical representation of the study area (grid wells), and 21 wells were selected to evaluate changes in water chemistry in areas of interest (understanding wells). The ground-water samples were analyzed for a large number of synthetic organic constituents [volatile organic compounds (VOCs), pesticides and pesticide degradates, pharmaceutical compounds, and potential wastewater- indicator compounds], constituents of special interest [perchlorate, N-nitrosodimethylamine (NDMA), and 1,2,3- trichloropropane (1,2,3-TCP)], naturally occurring inorganic constituents [nutrients, major and minor ions, and trace elements], radioactive constituents, and microbial indicators. Naturally occurring isotopes [tritium, and carbon-14, and stable isotopes of hydrogen and oxygen in water], and dissolved noble gases also were measured to help identify the source and age of the sampled ground water. This study evaluated the quality of raw ground water in the aquifer in the OWENS study unit and did not attempt to evaluate the quality of treated water delivered to consumers. Water supplied to consumers typically is treated after withdrawal from the ground, disinfected, and blended with other waters to maintain acceptable water quality. Regulatory thresholds apply to treated water that is served to the consumer, not to raw ground water. However, to provide some context for the results, concentrations of constituents measured in the raw ground water were compared with regulatory and non-regulatory health-based thresholds established by the U.S. Environmental Protection Agency (USEPA) and California Department of Public Health (CDPH) and non-regulatory thresholds established for aesthetic concerns (secondary maximum contamination levels, SMCL-CA) by CDPH. VOCs and pesticides were detected in samples from less than one-third of the grid wells; all detections were below health-based thresholds, and most were less than one-one hundredth of threshold values. All detections of perchlorate and nutrients in samples from OWENS were below health-based thresholds. Most detections of trace elements in ground-water samples from OWENS wells were below health-based thresholds. In samples from the 53 grid wells, three constituents were detected at concentrations above USEPA maximum contaminant levels: arsenic in 5 samples, uranium in 4 samples, and fluoride in 1 sample. Two constituents were detected at concentrations above CDPH notification levels (boron in 9 samples and vanadium in 1 sample), and two were above USEPA lifetime health advisory levels (molybdenum in 3 samples and strontium in 1 sample). Most of the samples from OWENS wells had concentrations of major elements, TDS, and trace elements below the non-enforceable standards set for aesthetic concerns. Samples from nine grid wells had concentrations of manganese, iron, or TDS above the SMCL-CAs.

California↗

Acid neutralizing capacity and leachate results for igneous rocks, with associated carbon contents of derived soils, Animas River AML site, Silverton, Colorado

Mine planning efforts have historically overlooked the possible acid neutralizing capacity (ANC) that local igneous rocks can provide to help neutralize acidmine drainage. As a result, limestone has been traditionally hauled to mine sites for use in neutralizing acid drainage. Local igneous rocks, when used as part of mine life-cycle planning and acid mitigation strategy, may reduce the need to transport limestone to mine sites because these rocks can contain acid neutralizing minerals. Igneous hydrothermal events often introduce moderately altered mineral assemblages peripheral to more intensely altered rocks that host metal-bearing veins and ore bodies. These less altered rocks can contain ANC minerals (calcite-chlorite-epidote) and are referred to as a propylitic assemblage. In addition, the carbon contents of soils in areas of new mining or those areas undergoing restoration have been historically unknown. Soil organic carbon is an important constituent to characterize as a soil recovery benchmark that can be referred to during mine cycle planning and restoration. <br/> This study addresses the mineralogy, ANC, and leachate chemistry of propylitic volcanic rocks that host polymetallic mineralization in the Animas River watershed near the historical Silverton, Colorado, mining area. Acid titration tests on volcanic rocks containing calcite (2 &ndash; 20 wt %) and chlorite (6 &ndash; 25 wt %), have ANC ranging from 4 &ndash; 146 kg/ton CaCO<sub>3</sub> equivalence. Results from a 6-month duration, kinetic reaction vessel test containing layered pyritic mine waste and underlying ANC volcanic rock (saturated with deionized water) indicate that acid generating mine waste (pH 2.4) has not overwhelmed the ANC of propylitic volcanic rocks (pH 5.8). Sequential leachate laboratory experiments evaluated the concentration of metals liberated during leaching. Leachate concentrations of Cu-Zn-As-Pb for ANC volcanic rock are one-to-three orders of magnitude lower when compared to leached solution from mine waste used in the kinetic reaction vessel test. This finding suggests that mine waste and not ANC rock may generate the majority of leachable metals in a field scenario. <br/> The organic carbon content of naturally reclaimed soils derived from weathering of propylitically-altered andesite was determined in catchments where ANC studies were initiated. Soils were found to have total carbon concentrations (TOC) that exceed global average soil TOC abundances by as much as 1.5 &ndash; 5 times. These data support an environmental management system involving use of ANC rocks as part of life-cycle mine planning to reduce post-mine closure acid mitigation measures. Carbon contents of undisturbed soils in mined catchments can possibly be used to validate post-reclamation success and help quantify carbon sequestration for CO<sub>2</sub> emission offset trading as carbon markets mature.

Colorado↗

Application of electromagnetic techniques in survey of contaminated groundwater at an abandoned mine complex in southwestern Indiana, U.S.A.

In part of a large abandoned mining complex, electromagnetic geophysical surveys were used along with data derived from cores and monitoring wells to infer sources of contamination and subsurface hydrologic connections between acidic refuse deposits and adjacent undisturbed geologic materials. Electrical resistivity increases sharply along the boundary of an elevated deposit of pyritic coarse refuse, which is highly contaminated and electrically conductive, indicating poor subsurface hydrologic connections with surrounding deposits of fine refuse and undisturbed glacial material. Groundwater chemistry, as reflected in values of specific conductance, also differs markedly across the deposit's boundary, indicating that a widespread contaminant plume has not developed around the coarse refuse in more than 40 yr since the deposit was created. Most acidic drainage from the coarse refuse is by surface runoff and is concentrated around stream channels. Although most of the contaminated groundwater within the study area is concentrated within the surficial refuse deposits, transects of apparent resistivity and phase angle indicate the existence of an anomalous conductive layer at depth (>4 m) in thick alluvial sediments along the northern boundary of the mining complex. Based on knowledge of local geology, the anomaly is interpreted to represent a subsurface connection between the alluvium and a flooded abandoned underground mine. ?? 1991 Springer-Verlag New York Inc.

Environmental Geology and Water Sciences↗

Chloride concentrations, loads, and yields in four watersheds along Interstate 95, southeastern Connecticut, 2008-11: factors that affect peak chloride concentrations during winter storms

Chloride (Cl - ) concentrations and loads and other water chemistry characteristics were assessed to evaluate potential effects of road-deicer applications on streamwater quality in four watersheds along Interstate 95 (I&ndash;95) in southeastern Connecticut from November 1, 2008, through September 30, 2011. Streamflow and water quality were studied in the Four Mile River, Oil Mill Brook, Stony Brook, and Jordan Brook watersheds, where developed land ranged from 9 to 32 percent. Water-quality samples were collected and specific conductance was measured continuously at paired water-quality monitoring sites, upstream and downstream from I&ndash;95. Specific conductance values were related to Cl - concentrations to assist in determining the effects of road-deicing operations on the levels of Cl - in the streams. Streamflow and water-quality data were compared with weather data and with the timing, amount, and composition of deicers applied to State highways. Grab samples were collected during winter stormwater-runoff events, such as winter storms or periods of rain or warm temperatures in which melting takes place. Grab samples were also collected periodically during the spring and summer and during base-flow conditions. The estimated Cl - concentrations at the eight water-quality monitoring sites during winter storms peaked as high as 270 milligrams per liter (mg/L) and were well below the U.S. Environmental Protection Agency (EPA) recommended acute chloride toxicity criterion of 860 mg/L and the chronic 4-day average toxicity criterion of 230 mg/L. Cl - concentrations in streams, particularly at sites downstream from I&ndash;95, peaked during increased streamflow in the winter and early spring as a result of deicers applied to roads and washed off by stormwater or meltwater. Cl - concentrations during most of the nonwinter seasons decreased during increases in streamflow because storm runoff was more dilute than base flow. However, peaks in specific conductance and estimated chloride concentrations at streams in more urbanized watersheds corresponded to peaks in streamflow well after winter snow or ice events; these delayed peaks in Cl - concentration likely resulted from deicer residue that remained in melting snow piles and on roadsides and (or) that were flushed from soils and shallow groundwater, then discharged downstream. Estimated peak Cl - concentrations varied with the type of winter storm event and were highest during or after winter storms of frozen precipitation and rain, in which the rain or meltwater effectively washed off the deicers. Estimated peak Cl - concentrations correlated positively with the duration of deicer application but generally not with streamflow. Estimated peak Cl - concentrations during the winter season were highest during low streamflow at most sites. Chloride concentrations varied considerably in shallow groundwater as a result of land-use differences. Cl - concentrations were very high (as high as 800 mg/L) in shallow groundwater downstream from I&ndash;95 at the Four Mile River site. Chloride/bromide mass concentration ratios and the proximity of a former landfill and sewage lagoon upstream indicate a likely source of Cl - is landfill leachate and possibly sewage leachate. Cl - loads in streams generally were highest in the winter and early spring. The estimated daily Cl - yield for the four monitoring sites downstream from I&ndash;95 ranged from 0.0004 ton per day per square mile for one of the least developed watersheds to 0.052 ton per day per square mile for the watershed with the highest percentage of urban development and impervious area. The estimated median contribution of Cl - load from atmospheric deposition was small and ranged from 0.07 percent of Cl - load at the Jordan Brook watershed to 0.57 percent at the Oil Mill Brook watershed. The Cl - loads in streams (outputs) were compared with Cl - load inputs, which include atmospheric deposition and deicer applications; Cl - load inputs were slightly larger than the Cl - load outputs at most of the sites during most years but do not account for the Cl - load in groundwater leaving the watersheds. A multiple linear regression model was developed to describe the variability of the natural log of peak specific conductance, as well as estimated Cl - concentrations. Five significant variables best explained the variability in the natural log of the peak specific conductance after deicing events: (1) snow on ground before deicing event; (2) winter precipitation with rain; (3) specific conductance in base flow; (4) State-operated road lane miles divided by watershed area; and (5) amount of Cl - from deicers applied to State-operated roads per lane mile. In this report, winter precipitation is defined as any type of precipitation, including frozen precipitation and rain, that occurs during the active deicing season, typically November through March. Frozen precipitation is defined here as snow, sleet, freezing rain, or any winter precipitation except rain. The addition of a lane mile in both directions on I&ndash;95 would result in an estimate of approximately 2 to 11 percent increase in Cl - input from deicers applied to I&ndash;95 and other roads maintained by Connecticut Department of Transportation. The largest estimated increase in Cl - load was in the watersheds with the greatest number miles of I&ndash;95 corridor relative to the total lane miles maintained by Connecticut Department of Transportation. On the basis of these estimates and the estimated peak Cl - concentrations during the study period, it is unlikely that the increased use of deicers on the additional lanes would lead to Cl - concentrations that exceed the aquatic habitat criteria.

Connecticut↗