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Ra and Rn isotopes as natural tracers of submarine groundwater discharge in Tampa Bay, Florida

A suite of naturally occurring radionuclides in the U/Th decay series ( 222 Rn, 223,224,226,228 Ra) were studied during wet and dry conditions in Tampa Bay, Florida, to evaluate their utility as groundwater discharge tracers, both within the bay proper and within the Alafia River/estuary — a prominent free-flowing river that empties into the bay. In Tampa Bay, almost 30% of the combined riverine inputs still remain ungauged. Consequently, groundwater/surface water (hyporheic) exchange in the discharging coastal rivers, as well as submarine groundwater discharge (SGD) within the bay, are still unresolved components of this system's water and material budgets. Based on known inputs and sinks, there exists an excess of 226 Ra in the water column of Tampa Bay, which can be evaluated in terms of a submarine groundwater contribution to the bay proper. Submarine groundwater discharge rates calculated using a mass balance of excess 226 Ra ranged from 2.2 to 14.5 L m − 2 day − 1 , depending on whether the estuarine residence time was calculated using 224 Ra/xs 228 Ra isotope ratios, or whether a long term, averaged model-derived estuarine residence time was used. When extrapolated to the total shoreline length of the bay, such SGD rates ranged from 1.6 to 10.3 m 3 m − 1 day − 1 . Activities of 222 Rn were also elevated in surface water and shallow groundwater of the bay, as well as in the Alafia River estuary, where upstream activities as high as 250 dpm L − 1 indicate enhanced groundwater/surface water exchange, facilitated by an active spring vent. From average nutrient concentrations of 39 shallow, brackish, groundwater samples, rates of nutrient loading into Tampa Bay by SGD rates were estimated, and these ranged from 0.2 to 1.4 × 10 5 mol day − 1 (PO 4 3− ), 0.9–6.2 × 10 5 mol day − 1 (SiO 4 − ), 0.7–5.0 × 10 5 mol day − 1 (dissolved organic nitrogen, DON), and 0.2–1.4 × 10 6 mol day − 1 (total dissolved nitrogen, TDN). Such nutrient loading estimates, when compared to average river discharge estimates (e.g., TDN = 6.9 × 10 5 mol day − 1 ), suggest that SGD-derived nutrient fluxes to Tampa Bay are indeed important components to the overall nutrient economy of these coastal waters.

Florida↗

Determination of uranium in natural waters

The fluorophotometric determination of uranium was studied to develop a procedure applicable to the routine analysis of waters. Three grams of the high carbonate flux are used in a dilution procedure with spiking. Because of the comparatively high reflectivity of this large disk and the low uranium concentration, a correction for nonquenched light is required. A formula is developed to compensate for the effect, an electrical fusion device is described, and the problem of fixing uranium in waters is discussed.

Analytical Chemistry↗

Environmental tracers of groundwater source, age, and geochemical evolution

Hexavalent chromium, Cr(VI), was discharged in cooling wastewater to unlined surface ponds from 1952 to 1964 and reached the underlying unconsolidated aquifer at the Pacific Gas and Electric Company (PG&E) Hinkley compressor station in the Mojave Desert, 80 miles northeast of Los Angeles, California. A suite of environmental tracers was analyzed in water samples collected from more than 100 wells to characterize the source, age, and geochemical evolution of groundwater within and near the Cr(VI) plume in Hinkley and Water Valleys. This information was used to help determine the extent of Cr(VI) associated with releases from the Hinkley compressor station and to identify Cr(VI) associated with natural sources. The source of water in most wells, indicated by stable oxygen and hydrogen isotope values for water, delta oxygen-18 and delta deuterium, was recharge by infiltration of intermittent surface flows in the Mojave River. With the exception of small flows in 1958, the Mojave River was largely dry between 1952 and 1969. This dry period spans the period of Cr(VI) releases from the Hinkley compressor station; 1952–69 also spans the period of high tritium levels in precipitation resulting from the atmospheric testing of nuclear weapons and, as a consequence, tritium concentrations in groundwater in Hinkley Valley were comparatively low. Groundwater ages (time since recharge) increased downgradient from the Mojave River and with depth. Tritium, measured by helium ingrowth with a study reporting level of 0.05 tritium unit, was detected in water from 51 percent of wells, with detectable tritium as far as 7 miles downgradient from the Mojave River. Tritium concentrations were higher, and tritium/helium-3 groundwater ages younger, in water from wells near the Mojave River and in water from shallower wells downgradient. Agricultural pumping has decreased groundwater levels as much as 60 feet since 1952. As a result of this pumping, some groundwater containing tritium, and presumably anthropogenic Cr(VI), has been removed from the aquifer. The distribution of wells having carbon-14 activities near or greater than 100-percent modern carbon, consistent with post-1952 recharge water, was similar to the distribution of wells containing detectable tritium. Carbon-14 activities as low as 8.9-percent modern carbon, with carbon-14 ages (unadjusted for reactions with aquifer materials) of almost 20,000 years before present (ybp), were sampled in water from some deep wells. Hexavalent chromium concentrations in older groundwater were as high as 11 micrograms per liter but did not exceed 3.6 micrograms per liter in older water from wells completed in “Mojave-type” deposits (composed of felsic Mojave River stream and near-shore lake deposits sourced from the Mojave River); this value may represent an upper limit on Cr(VI) concentrations in groundwater within Mojave-type deposits that likely approximates background Cr(VI) concentrations in the study area. Chlorofluorocarbons were released to the atmosphere and hydrologic cycle as a result of industrial activity beginning in the 1930s. Chlorofluorocarbon data were not generally suitable for groundwater-age dating in Hinkley and Water Valley because of nonatmospheric contributions from local sources. Strontium-87/86 isotope ratios and stable chromium isotopes, delta chromium-53, provide information on the geochemical evolution of groundwater in the aquifer. Highly radiogenic strontium-87/86 ratios greater than 0.71000 were present in water from wells completed in coarse-textured Mojave-type deposits having low chromium concentrations but were not diagnostic of these materials. Nonradiogenic strontium-87/86 ratios less than 0.70950 were diagnostic of weathered materials in the northern subarea of Hinkley and in Water Valley that were eroded from Miocene (23–5 million ybp) deposits east of the study area. Values for delta chromium-53 ranged from near 0 to 2.8 parts per thousand (‰) difference. The extent of reductive fractionation, mixing with native groundwater, and longitudinal dispersion within the October–December 2015 (Q4 2015) regulatory Cr(VI) plume can be estimated on the basis of the delta chromium-53 isotope composition of groundwater within the plume. Reduction of Cr(VI) to trivalent chromium, Cr(III), can occur in the presence of natural reductants in oxic groundwater. Although not diagnostic of anthropogenic chromium at the concentrations of interest near the Q4 2015 regulatory Cr(VI) plume margin, delta chromium-53 data indicate anthropogenic Cr(VI) within the plume is not conservative and has reacted with aquifer materials; these reactions have removed some anthropogenic Cr(VI) from groundwater. Environmental tracers, and the distribution of modern (post-1952) and premodern (pre-1952) groundwater, inform understanding of the extent of anthropogenic and naturally occurring Cr(VI) near the Q4 2015 regulatory Cr(VI) plume and the understanding of geochemical processes occurring in and near the margins of the Cr(VI) plume. The oxygen and hydrogen isotope compositions of water, tritium/helium-3 groundwater-age data, and carbon-14 data were used with mineralogy and chemistry data as part of a summative-scale analysis to determine the Cr(VI) plume extent later in this professional paper (chapter G).

California↗

Treatability study to evaluate bioremediation of trichloroethene at Site K, former Twin Cities Army Ammunition Plant, Arden Hills, Minnesota, 2020–22

Executive Summary Chlorinated solvents, including trichloroethene (TCE) and other chlorinated volatile organic compounds (cVOCs), are widespread contaminants that can be treated by bioremediation approaches that enhance anaerobic reductive dechlorination. Reductive dechlorination can be enhanced either through the addition of an electron donor (biostimulation) or the addition of a known dechlorinating culture (bioaugmentation) along with an electron donor. Although bioremediation has been applied at many TCE-contaminated groundwater sites, application in source zones at sites where residual dense nonaqueous phase liquid (DNAPL) is present is more limited. In this study, laboratory and field treatability tests were completed to evaluate the potential application of anaerobic bioremediation for a shallow groundwater plume containing TCE in a perched alluvial aquifer at Site K, former Twin Cities Army Ammunition Plant, Arden Hills, Minnesota, which was on the National Priorities List as the New Brighton/Arden Hills Superfund site until 2019. In addition to the presence of residual DNAPL at the site, temporal variability in groundwater flow directions and input of oxygenated recharge were possible complicating factors for the application of enhanced anaerobic biodegradation in the shallow plume. The Site K plume extends beneath the footprint of Building 103, which was demolished in 2006, and soil excavations to a maximum depth of 6 feet (ft) below ground surface in 2014 were known to leave some deeper contaminated soil in place in the TCE source area. Groundwater treatment at the site, formalized as part of the 1997 Record of Decision, has been in operation since 1986 and consists of an extraction trench at the downgradient edge of the plume to collect groundwater, which is then pumped to an on-site air stripper. Groundwater concentrations in the plume have been relatively stable since treatment began, indicating a continued source of TCE in the aquifer. The desire for a destructive remedy that would enhance the removal of cVOCs in the aquifer at Site K and shorten the remediation timeframe led the U.S. Army to request that the U.S. Geological Survey conduct a groundwater treatability study to assess bioremediation. This report describes the U.S. Geological Survey bioremediation treatability study conducted during 2020–22, including pre-design site characterization to assist in formulating the bioremediation approach, laboratory experiments to support the design of the field pilot test, and implementation and 1-year performance monitoring results for the pilot test. Pre-design site characterization included the collection of soil cores for cVOC analysis and lithologic descriptions and the re-installment of three wells to obtain hydrologic measurements and initial groundwater chemistry. Relatively flat head gradients were measured at the site, and substantial decreases in water-level elevations occurred from spring to summer (May–July 2021). Continuous water-level monitoring indicated a rapid response to precipitation. Groundwater flow velocities were consistently less than 0.5 foot per day, and the pilot bioremediation test was therefore designed with short lateral distances (about 5 ft) between injection and individual monitoring points. Soil analyses confirmed that high volatile organic compound contamination was left in place in the source area. The highest concentrations were near or in clay at the base of the perched aquifer. Concentrations of cVOCs measured in the replaced wells were consistent with historical data and had a maximum TCE concentration of 57,700 micrograms per liter (μg/L), indicative of nearby residual DNAPL based on the general rule of observed concentrations exceeding 1 percent of solubility. The primary TCE daughter product detected was 1,2-cis-dichloroethene (cisDCE), which indicated limited reductive dechlorination in the plume. Groundwater in both the source and downgradient areas was relatively reducing during the pre-design characterization, particularly in the source area where methane concentrations greater than 400 μg/L were measured. Initial laboratory tests conducted using native aquifer microorganisms from the three replacement wells showed that anaerobic TCE biodegradation rates were low when biostimulated with the addition of sodium lactate as an electron donor, also known as a carbon donor, and resulted in the production of only cisDCE. Addition of a known dechlorinating culture, WBC-2, however, resulted in rapid biodegradation and production of ethene, verifying complete reductive dechlorination of TCE. Microcosms constructed with aquifer soil collected from the site were used to evaluate other electron donors besides lactate to support reductive dechlorination by WBC-2, including corn syrup as an alternative fast-release compound and whey, soy-based vegetable oil, and 3-D Microemulsion (Regenesis, San Clemente, California) as slow-release compounds. First-order rate constants for total organic chlorine removal in these WBC-2 amended microcosms were greatest with either lactate or vegetable oil as the donor, ranging between 0.061 and 0.047 per day or corresponding half-lives of 11–15 days. Testing of commercial products in other WBC-2-bioaugmented microcosms led to selection for the field pilot test of an emulsified vegetable oil product that also contained some sodium lactate as a fast-release donor. Delaying the addition of WBC-2 relative to the donor in the microcosms resulted in the most rapid overall biodegradation rates. The selected design for the pilot test utilized three separate test plots, each about 30-ft wide and 60-ft long: plots GS1 and GS2 in the source area of the plume and plot GS3 in the downgradient area of the plume near the excavation trench. Each test plot had one injection well, one monitoring well upgradient from the injection point, and 12 surrounding monitoring wells in a grid to capture variable groundwater flow directions. Donor injections, which included a bromide tracer, were completed in October 2021, immediately following baseline sampling, and the WBC-2 culture was injected about 40 days later, between November 30 and December 2, 2021. Performance monitoring conducted until December 2022 included hydrologic measurements and analyses of cVOCs, redox-sensitive constituents, dissolved organic carbon, bromide, volatile fatty acids, compound-specific carbon isotopes, and microbial communities. The biogeochemical data collected during the pilot tests in the three treatment plots showed that enhanced, complete reductive dechlorination of cVOCs in the groundwater was achieved in the GS1 and GS3 plots. In contrast, evidence of distribution of the injected amendments and subsequent biodegradation was limited in GS2, which was in an area of more heterogeneous soil lithology and low water table elevations. The molar composition of volatile organic compounds in the GS1 and GS3 plots was dominated by ethene in wells that were reached by the injected amendments by the end of the monitoring period. In the GS1 and GS3 plots, similar patterns were observed of cVOC concentrations decreasing to near detection levels, or below, at some wells sampled in July and October 2022, whereas ethene became dominant and indicated sustained complete reductive dechlorination. Baseline cVOC concentrations were more than a factor of 10 higher in the groundwater in the GS1 plot than in GS3, but no apparent inhibition of complete dechlorination occurred. As expected from the initial pre-design site data and the laboratory experiments, enhanced dissolution of residual DNAPL coupled to biodegradation was evident in the GS1 plot, where a marked increase in dichloroethene (DCE) above the initial baseline and upgradient TCE and DCE concentrations occurred. DCE concentrations subsequently declined where DNAPL dissolution was evident, concurrent with production of vinyl chloride and then predominantly ethene. Thus, overall biodegradation rates outpaced the DNAPL dissolution and desorption and DCE production in the source area. This success in complete degradation to predominantly ethene was achieved even in areas where the DCE concentrations reached a maximum of about 30,000 μg/L. Compound specific isotope analysis of carbon in TCE, cisDCE, trans-1,2-dichloroethene, and vinyl chloride was conducted to provide another line of evidence of the occurrence and extent of anaerobic biodegradation. Along a flow path in each plot that was affected by the injected amendments, carbon isotopes in the TCE and daughter cVOCs in the groundwater became isotopically heavier, indicating biodegradation. Enhanced biodegradation rates calculated from the field tests in GS1 and GS3 showed half-lives of 36.9–75.3 days for DCE degradation and 9.48–38.5 days for ethene production. Notably, these ethene production rates calculated from the field tests are consistent with the results of WBC-2-bioaugmented microcosms amended with either lactate or vegetable oil, which had half-lives for total organic chlorine removal that ranged from 11 to 15 days. These rates indicated rapid enhanced biodegradation, which is promising for application of a full-scale bioremediation remedy. Ultimately, however, the mass of residual or sorbed TCE in the aquifer that remains accessible for dissolution and biodegradation would likely control the time required for a full-scale bioremediation effort to achieve performance goals for TCE and cisDCE specified in the Record of Decision for Site K. The field pilot tests showed that the relatively low hydraulic head gradients and temporal changes in groundwater flow directions in the shallow aquifer would add complexity to a full-scale bioremediation effort. The radius of influence (ROI) at GS1 and GS3 (16.3 ft and 12.7 ft, respectively) were close to the design ROI of 15 ft. The estimated ROI at GS2 was about four times the design ROI, but may be less reliable at this location owing to groundwater flow direction. In addition, the low temperatures following WBC-2 injection in late November to early December 2021, in combination with the low hydraulic head gradients, were probably major factors in the delay observed before the onset of enhanced biodegradation following injection of the culture. Additional test injections could be beneficial to optimize the timing of donor and culture injections with the variable temperatures and hydraulic head in the shallow aquifer.

Minnesota↗

Aquatic fulvic acids in microbially based ecosystems: results from two desert lakes in Antarctica

These lakes receive very limited input of organic material from the surrounding barren desert, but they sustain algal and bacterial populations under permanent ice cover. One lake has an extensive anoxic zone and high salinities; the other is oxic and has low salinities. Despite these differences, fulvic acids from both lakes had similar elemental compositions, carbon distributions, and amino acid contents, indicating that the chemistry of microbially derived fulvic acvids is not strongly influenced by chemical conditions in the water column. Compared to fulvic acids from other natural waters, these fulvic acids have low C:N atomic ratios (19-25) and low contents of aromatic carbons (5-7% of total carbon atoms); they are most similar to marine fulvic acids. -from Authors

Limnology and Oceanography↗

Ambient quality of ground water in the vicinity of Naval Submarine Base Bangor, Kitsap County, Washington, 1995

A study of the ambient ground-water quality in the vicinity of Naval Submarine Base (SUBASE) Bangor was conducted to provide the U.S. Navy with background levels of selected constituents. The Navy needs this information to plan and manage cleanup activities on the base. During March and April 1995, 136 water-supply wells were sampled for common ions, trace elements, and organic compounds; not all wells were sampled for all constituents. Man-made organic compounds were detected in only two of fifty wells, and the sources of these organic compounds were attributed to activities in the immediate vicinities of these off-base wells. Drinking water standards for trichloroethylene, iron, and manganese were exceeded in one of these wells, which was probably contaminated by an old local (off-base) dump. Ground water from wells open to the following hydrogeologic units (in order from shallow to deep) was investigated: the Vashon till confining unit (Qvt, three wells); the Vashon aquifer (Qva, 54 wells); the Upper confining unit (QC1, 16 wells); the Permeable interbeds within QC1 (QC1pi, 34 wells); and the Sea-level aquifer (QA1, 29 wells).The 50th and 90th percentile ambient background levels of 35 inorganic constituents were determined for each hydrogeologic unit. At least ten measurements were required for a constituent in each hydrogeologic unit for determination of ambient background levels, and data for three wells determined to be affected by localized activities were excluded from these analyses. The only drinking water standards exceeded by ambient background levels were secondary maximum contaminant levels for iron (300 micrograms per liter), in QC1 and QC1pi, and manganese (50 micrograms per liter), in all of the units. The 90th percentile values for arsenic in QC1pi, QA1, and for the entire study area are above 5 micrograms per liter, the Model Toxics Control Act Method A value for protecting drinking water, but well below the maximum contaminant level of 50 micrograms per liter for arsenic. The manganese standard was exceeded in 38 wells and the standard for iron was exceeded in 12 wells. Most of these wells were in QC1 or QC1pi and had dissolved oxygen concentrations of less than 1 milligram per liter and dissolved organic carbon concentrations greater than 1 milligram per liter. The dissolved oxygen concentration is generally lower in the deeper units, while pH increases; the recommended pH range of 6.5-8.5 standard units was exceeded in 9 wells. The common-ion chemistry was similar for all of the units.

Washington↗

Evaluation of stream chemistry trends in US Geological Survey reference watersheds, 1970-2010

The Hydrologic Benchmark Network (HBN) is a long-term monitoring program established by the US Geological Survey in the 1960s to track changes in the streamflow and stream chemistry in undeveloped watersheds across the USA. Trends in stream chemistry were tested at 15 HBN stations over two periods (1970–2010 and 1990–2010) using the parametric Load Estimator (LOADEST) model and the nonparametric seasonal Kendall test. Trends in annual streamflow and precipitation chemistry also were tested to help identify likely drivers of changes in stream chemistry. At stations in the northeastern USA, there were significant declines in stream sulfate, which were consistent with declines in sulfate deposition resulting from the reductions in SO 2 emissions mandated under the Clean Air Act Amendments. Sulfate declines in stream water were smaller than declines in deposition suggesting sulfate may be accumulating in watershed soils and thereby delaying the stream response to improvements in deposition. Trends in stream chemistry at stations in other part of the country generally were attributed to climate variability or land disturbance. Despite declines in sulfate deposition, increasing stream sulfate was observed at several stations and appeared to be linked to periods of drought or declining streamflow. Falling water tables might have enhanced oxidation of organic matter in wetlands or pyrite in mineralized bedrock thereby increasing sulfate export in surface water. Increasing sulfate and nitrate at a station in the western USA were attributed to release of soluble salts and nutrients from soils following a large wildfire in the watershed.

Environmental Monitoring and Assessment↗

Use of dissolved oxygen monitoring to evaluate phosphorus loading in Connecticut streams, 2015–18

The Connecticut Department of Energy and Environmental Protection (CT DEEP) has developed an interim phosphorus reduction strategy to establish water-quality-based phosphorus limits in nontidal freshwaters for industrial and municipal water pollution control facilities. A recommendation in the strategy included the addition of diurnal dissolved oxygen (DO) sampling to the sampling of diatom communities collected by CT DEEP. The chemistry data coupled with biological data will help to examine the effects of phosphorus loading in streams. The U.S. Geological Survey (USGS), in cooperation with the CT DEEP and New England Interstate Water Pollution Control Commission, implemented a summer DO monitoring program from 2015 to 2018 to examine the effects of phosphorus loading in streams. Continuous DO data were collected at 18 sites in streams with varying concentrations of phosphorus throughout the State of Connecticut. Discrete water-quality nutrient data were collected by the USGS at 11 of the 18 sites. All continuous and discrete data collected from June to September for the 4 years were examined for all sites. This report documents a pattern of diurnal DO for monitoring sites across 4 years and presents estimated daily gross primary productivity (GPP), ecosystem respiration (ER), and a standardized rate coefficient for gas exchange for selected streams. Relations of phosphorus concentrations to the diurnal DO response and stream metabolism are described. Interannual variability in average annual total phosphorus (TP) concentrations and maximum daily DO concentrations were evaluated among sites in years of the study. Streams identified as impaired by CT DEEP such as Naugatuck River at Beacon Falls (USGS station 01208500), Still River at Route 7 at Brookfield Center (USGS station 01201487), and Quinnipiac River at Wallingford (USGS station 01196500) had higher TP concentrations (greater than 0.10 milligram per liter [mg/L]) throughout the study. Reference streams considered unimpaired had lower concentrations of TP (less than 0.10 mg/L). The range in daily DO concentrations remained less than 4 mg/L for most of the sites during the study except for Naugatuck River at Beacon Falls and Still River at Route 7 at Brookfield Center. Daily GPP and ER were summarized for 11 sites using the maximum likelihood estimation model of the streamMetabolizer package in the R statistical program. The models indicated that most sites had an estimated negative net primary productivity, based on the daily estimates of GPP and ER, which indicates the systems are heterotrophic and dominated by respiration. The high variation of GPP and ER reported for several sites can be affected by many physical, chemical, and biological factors, including the abundance and community composition of phytoplankton, periphyton, and macrophyte algae present. The variability in mean GPP was similar to the variability in maximum DO concentrations when plotted against annual average TP concentrations for the maximum likelihood estimation model in streamMetabolizer. The concept that phosphorus loading can affect the stream metabolism requires more detailed knowledge of stream geomorphic variables (canopy cover, stream velocity, water depth) and algal communities to help improve the scientific basis for managing phosphorus loading.

Connecticut↗

Development of high surface area organosilicate nanoparticulate thin films for use in sensing hydrophobic compounds in sediment and water

The scope of this study was to apply advances in materials science, specifically the use of organosilicate nanoparticles as a high surface area platform for passive sampling of chemicals or pre-concentration for active sensing in multiple-phase complex environmental media. We have developed a novel nanoporous organosilicate (NPO) film as an extraction phase and proof of concept for application in adsorbing hydrophobic compounds in water and sediment. We characterized the NPO film properties and provided optimization for synthesis and coatings in order to apply the technology in environmental media. NPO films in this study had a very high surface area, up to 1325 m 2 /g due to the high level of mesoporosity in the film. The potential application of the NPO film as a sorbent phase for sensors or passive samplers was evaluated using a model hydrophobic chemical, polychlorinated biphenyls (PCB), in water and sediment. Sorption of PCB to this porous high surface area nanoparticle platform was highly correlated with the bioavailable fraction of PCB measured using whole sediment chemistry, porewater chemistry determined by solid-phase microextraction fiber methods, and the Lumbriculus variegatus bioaccumulation bioassay. The surface-modified NPO films in this study were found to highly sorb chemicals with a log octanol-water partition coefficient (K ow ) greater than four; however, surface modification of these particles would be required for application to other chemicals.

Biosensors↗

Bottom-sediment chemistry in Devil's Lake, northeast North Dakota

Devils Lake is a 200 km 2 terminal lake that contains sodium sulfate type water. Dissolved solids concentrations range from about 3,500 mg/L to 10,000 mg/L depending on location To investigate geochemical processes in the bottom sediments of Devils Lake, sediment cores were collected at two sites in the western half of the lake during a period of bottom water oxygen depletion. The upper 10 cm of the sediments consist of about 60 weight percent silicates (quartz, feldspar, and clays) 35 weight percent carbonates and 5 weight percent organic material. At depths between 1 and 3 cm in the sediments bacterial sulfate reduction and associated degradation of organic material cause minima in sulfate concentrations and δ 13 C values of dissolved inorganic carbon and maxima in alkalinity, ammonia, phosphate, and sulfide concentrations and δ 34 S values of dissolved sulfate. Downward increases of sodium, magnesium, potassium, and calcium concentrations result from upward diffusion of ions from saline pore water and dissolving sulfate minerals below 30 cm depth in the sediments. High magnesium calcite 8 mole percent MgCO 3 is the most abundant carbonate at the sediment surface. With increasing depth abundances of high magnesium carbonate decrease and abundances of low magnesium calcite aragonite and dolomite increase. Carbon isotope compositions of bulk carbonates range from δ 13 C = -0.7 to +0.5%. These values are close to equilibrium with dissolved inorganic carbon in lake water ( δ 13 C = -2%) but far from equilibrium with dissolved inorganic carbon in pore water ( δ 13 C = -16.3- -10/0%). Disequilibrium between pore water and carbonates suggests that the carbonates did not recrystallize substantially in the presence of pore water. Therefore the change of carbonate mineral proportions with depth in the sediments is due mainly to temporal changes in the proportions of endogenic, detrital, and biologic carbonates that were deposited on the lake bottom rather than postdepositional carbonate diagenesis.

North Dakota↗

Chemical contaminants in water and sediment near fish nesting sites in the Potomac River basin: determining potential exposures to smallmouth bass (Micropterus dolomieu)

The Potomac River basin is an area where a high prevalence of abnormalities such as testicular oocytes (TO), skin lesions, and mortality has been observed in smallmouth bass (SMB, Micropterus dolomieu). Previous research documented a variety of chemicals in regional streams, implicating chemical exposure as one plausible explanation for these biological effects. Six stream sites in the Potomac basin (and one out-of-basin reference site) were sampled to provide an assessment of chemicals in these streams. Potential early life-stage exposure to chemicals detected was assessed by collecting samples in and around SMB nesting areas. Target chemicals included those known to be associated with important agricultural and municipal wastewater sources in the Potomac basin. The prevalence and severity of TO in SMB were also measured to determine potential relations between chemistry and biological effects. A total of 39 chemicals were detected at least once in the discrete-water samples, with atrazine, caffeine, deethylatrazine, simazine, and iso-chlorotetracycline being most frequently detected. Of the most frequently detected chemicals, only caffeine was detected in water from the reference site. No biogenic hormones/sterols were detected in the discrete-water samples. In contrast, 100 chemicals (including six biogenic hormones/sterols) were found in a least one passive-water sample, with 25 being detected at all such samples. In addition, 46 chemicals (including seven biogenic hormones/sterols) were found in the bed-sediment samples, with caffeine, cholesterol, indole, para-cresol, and sitosterol detected in all such samples. The number of herbicides detected in discrete-water samples per site had a significant positive relation to TO rank (a nonparametric indicator of TO), with significant positive relations between TO rank and atrazine concentrations in discrete-water samples and to total hormone/sterol concentration in bed-sediment samples. Such significant correlations do not necessarily imply causation, as these chemical compositions and concentrations likely do not adequately reflect total SMB exposure history, particularly during critical life stages.

Potomac River Basin↗

Long-term changes in soil and stream chemistry across an acid deposition gradient in the northeastern United States

D eclines in acidic deposition across Europe and North America have led to decreases in surface water acidity and signs of chemical recovery of soils from acidification. To better understand the link between recovery of soils and surface waters, chemical trends in precipitation, soils, and streamwater were investigated in three watersheds representing a depositional gradient from high to low across the northeastern United States. Significant declines in concentrations of H + (ranging from −1.2 to −2.74 microequivalents [μeq] L −1 yr −1 ), NO 3 − (ranging from −0.6 to −0.84 μeq L −1 yr −1 ), and SO 4 2− (ranging from −0.95 to −2.13 μeq L −1 yr −1 ) were detected in precipitation in the three watersheds during the period 1999 to 2013. Soil chemistry in the A horizon of the watershed with the greatest decrease in deposition showed significant decreases in exchangeable Al and increases in exchangeable bases. Soil chemistry did not significantly improve during the study in the other watersheds, and base saturation in the Oa and upper B horizons significantly declined in the watershed with the smallest decrease in deposition. Streamwater SO 4 2− concentrations significantly declined in all three streams (ranging from −2.01 to −2.87 μeq L −1 yr −1 ) and acid neutralizing capacity increased (ranging from 1.38 to 1.60 μeq L −1 yr −1 ) in the two streams with the greatest decreases in deposition. Recovery of soils has likely been limited by decades of acid deposition that have leached base cations from soils with base-poor parent material.

Journal of Environmental Quality↗

Dissolved organic carbon in Alaskan boreal forest: Sources, chemical characteristics, and biodegradability

The fate of terrestrially-derived dissolved organic carbon (DOC) is important to carbon (C) cycling in both terrestrial and aquatic environments, and recent evidence suggests that climate warming is influencing DOC dynamics in northern ecosystems. To understand what determines the fate of terrestrial DOC, it is essential to quantify the chemical nature and potential biodegradability of this DOC. We examined DOC chemical characteristics and biodegradability collected from soil pore waters and dominant vegetation species in four boreal black spruce forest sites in Alaska spanning a range of hydrologic regimes and permafrost extents (Well Drained, Moderately Well Drained, Poorly Drained, and Thermokarst Wetlands). DOC chemistry was characterized using fractionation, UV-Vis absorbance, and fluorescence measurements. Potential biodegradability was assessed by incubating the samples and measuring CO2 production over 1 month. Soil pore water DOC from all sites was dominated by hydrophobic acids and was highly aromatic, whereas the chemical composition of vegetation leachate DOC varied significantly with species. There was no seasonal variability in soil pore water DOC chemical characteristics or biodegradability; however, DOC collected from the Poorly Drained site was significantly less biodegradable than DOC from the other three sites (6% loss vs. 13-15% loss). The biodegradability of vegetation-derived DOC ranged from 10 to 90% loss, and was strongly correlated with hydrophilic DOC content. Vegetation such as Sphagnum moss and feathermosses yielded DOC that was quickly metabolized and respired. In contrast, the DOC leached from vegetation such as black spruce was moderately recalcitrant. Changes in DOC chemical characteristics that occurred during microbial metabolism of DOC were quantified using fractionation and fluorescence. The chemical characteristics and biodegradability of DOC in soil pore waters were most similar to the moderately recalcitrant vegetation leachates, and to the microbially altered DOC from all vegetation leachates.

Alaska↗

A primer on trace metal-sediment chemistry

In most aquatic systems, concentrations of trace metals in suspended sediment and the top few centimeters of bottom sediment are far greater than concentrations of trace metals dissolved in the water column. Consequently, the distribution, transport, and availability of these constituents can not be intelligently evaluated, nor can their environmental impact be determined or predicted solely through the sampling and analysis of dissolved phases. This Primer is designed to acquaint the reader with the basic principles that govern the concentration and distribution of trace metals associated with bottom and suspended sediments. The sampling and analysis of suspended and bottom sediments are very important for monitoring studies, not only because trace metal concentrations associated with them are orders of magnitude higher than in the dissolved phase, but also because of several other factors. Riverine transport of trace metals is dominated by sediment. In addition, bottom sediments serve as a source for suspended sediment and can provide a historical record of chemical conditions. This record will help establish area baseline metal levels against which existing conditions can be compared. Many physical and chemical factors affect a sediment's capacity to collect and concentrate trace metals. The physical factors include grain size, surface area, surface charge, cation exchange capacity, composition, and so forth. Increases in metal concentrations are strongly correlated with decreasing grain size and increasing surface area, surface charge, cation exchange capacity, and increasing concentrations of iron and manganese oxides, organic matter, and clay minerals. Chemical factors are equally important, especially for differentiating between samples having similar bulk chemistries and for inferring or predicting environmental availability. Chemical factors entail phase associations (with such sedimentary components as interstitial water, sulfides, carbonates, and organic matter) and ways in which the metals are entrained by the sediments (such as adsorption, complexation, and within mineral lattices).

Water Supply Paper↗

Global occurrence of tellurium-rich ferromanganese crusts and a model for the enrichment of tellurium

Hydrogenetic ferromanganese oxyhydroxide crusts (Fe-Mn crusts) precipitate out of cold ambient ocean water onto hard-rock surfaces (seamounts, plateaus, ridges) at water depths of about 400 to 4000 m throughout the ocean basins. The slow-growing (mm/Ma) Fe-Mn crusts concentrate most elements above their mean concentration in the Earth’s crust. Tellurium is enriched more than any other element (up to about 50,000 times) relative to its Earth’s crustal mean of about 1 ppb, compared with 250 times for the next most enriched element. We analyzed the Te contents for a suite of 105 bulk hydrogenetic crusts and 140 individual crust layers from the global ocean. For comparison, we analyzed 10 hydrothermal stratabound Mn-oxide samples collected from a variety of tectonic environments in the Pacific. In the Fe-Mn crust samples, Te varies from 3 to 205 ppm, with mean contents for Pacific and Atlantic samples of about 50 ppm and a mean of 39 ppm for Indian crust samples. Hydrothermal Mn samples have Te contents that range from 0.06 to 1 ppm. Continental margin Fe-Mn crusts have lower Te contents than open-ocean crusts, which is the result of dilution by detrital phases and differences in growth rates of the hydrogenetic phases. Correlation coefficient matrices show that for hydrothermal deposits, Te has positive correlations with elements characteristic of detrital minerals. In contrast, Te in open-ocean Fe-Mn crusts usually correlates with elements characteristic of the MnO 2 , carbonate fluorapatite, and residual biogenic phases. In continental margin crusts, Te also correlates with FeOOH associated elements. In addition, Te is negatively correlated with water depth of occurrence and positively correlated with crust thickness. Q-mode factor analyses support these relationships. However, sequential leaching results show that most of the Te is associated with FeOOH in Fe-Mn crusts and ≤10% is leached with the MnO 2 . Thermodynamic calculations indicate that Te occurs predominantly as H 5 TeO 6 − in ocean water. The speciation of Te in ocean water and charge balance considerations indicate that Te should be scavenged by FeOOH, which is in agreement with our leaching results. The thermodynamically more stable Te(IV) is less abundant by factors of 2 to 3.5 than Te(VI) in ocean water. This can be explained by preferential (not exclusive) scavenging of Te(IV) by FeOOH at the Fe-Mn crust surface and by Fe-Mn colloids in the water column. We propose a model in which the extreme enrichment of Te in Fe-Mn crusts is likely the result of an oxidation reaction on the surface of FeOOH. A similar oxidation process has been confirmed for Co, Ce, and Tl at the surface of MnO 2 in crusts, but has not been suggested previously to occur in association with FeOOH in Fe-Mn crusts. Mass-balance considerations indicate that ocean floor Fe-Mn deposits are the major sink for Te in the oceans. The concentration and redox chemistry of Te in the global ocean are likely controlled by scavenging on Fe-Mn colloids in the water column and Fe-Mn deposits on the ocean floor, as is also the case for Ce.

Geochimica et Cosmochimica Acta↗