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Mercury cycling in stream ecosystems. 3. Trophic dynamics and methylmercury bioaccumulation

Trophic dynamics (community composition and feeding relationships) have been identified as important drivers of methylmercury (MeHg) bioaccumulation in lakes, reservoirs, and marine ecosystems. The relative importance of trophic dynamics and geochemical controls on MeHg bioaccumulation in streams, however, remains poorly characterized. MeHg bioaccumulation was evaluated in eight stream ecosystems across the United States (Oregon, Wisconsin, and Florida) spanning large ranges in climate, landscape characteristics, atmospheric Hg deposition, and stream chemistry. Across all geographic regions and all streams, concentrations of total Hg (THg) in top predator fish and forage fish, and MeHg in invertebrates, were strongly positively correlated to concentrations of filtered THg (FTHg), filtered MeHg (FMeHg), and dissolved organic carbon (DOC); to DOC complexity (as measured by specific ultraviolet absorbance); and to percent wetland in the stream basins. Correlations were strongest for nonurban streams. Although regressions of log[Hg] versus δ 15 N indicate that Hg in biota increased significantly with increasing trophic position within seven of eight individual streams, Hg concentrations in top predator fish (including cutthroat, rainbow, and brown trout; green sunfish; and largemouth bass) were not strongly influenced by differences in relative trophic position. Slopes of log[Hg] versus δ 15 N, an indicator of the efficiency of trophic enrichment, ranged from 0.14 to 0.27 for all streams. These data suggest that, across the large ranges in FTHg (0.14−14.2 ng L −1 ), FMeHg (0.023−1.03 ng L −1 ), and DOC (0.50−61.0 mg L −1 ) found in this study, Hg contamination in top predator fish in streams likely is dominated by the amount of MeHg available for uptake at the base of the food web rather than by differences in the trophic position of top predator fish.

Environmental Science & Technology↗

Hydrogeologic characterization, groundwater chemistry, and vulnerability assessment, Ute Mountain Ute Reservation, Colorado and Utah

The U.S. Geological Survey, in cooperation with the Ute Mountain Ute Tribe (UMUT), initiated a study in 2016 to increase understanding of the hydrogeology and chemistry of groundwater within select areas of the Ute Mountain Ute Reservation (UMUR) in Colorado and Utah, identify vulnerabilities to the system and other natural resources, and outline information needs to aid in the understanding and protection of groundwater resources. The results presented for this study can be used to support the UMUT’s goal of protecting their vital groundwater resources on the UMUR. Hydrogeologic conditions were characterized for the surficial aquifer contained in Quaternary-age unconsolidated surficial deposits and the Dakota aquifer contained in the Cretaceous-age Dakota Sandstone. In the surficial aquifer, median depth to water ranges from about 5.4 to 17.2 feet below land surface in the Farm and Ranch Enterprise area and 11 to 34 feet below land surface in the Towaoc area, and the water table slopes generally southwest or south. A map of depth to the top of the Dakota Sandstone was constructed from existing well data. Depths range from zero in outcrop areas to more than 3,000 feet below land surface on mesas in the southeastern part of the UMUR. Groundwater-chemistry data were collected by the UMUT from 13 springs and 31 wells from 1996 through 2017. Specific conductance was much lower for samples from springs than from wells; median values were 512 and 6,024 microsiemens per centimeter at 25 degrees Celsius, respectively. Spring samples were well oxygenated. A few well samples were anoxic (dissolved oxygen concentrations less than 0.5 milligrams per liter [mg/L]), indicating reducing conditions in the aquifer. About 75 percent of spring samples had fresh water (total dissolved solids concentrations less than 1,000 mg/L), and about 85 percent of well samples had brackish or highly saline water (total dissolved solids concentrations greater than 1,000 mg/L). Water type for springs on the Ute Mountains was calcium bicarbonate. Lower-altitude springs had a calcium-sulfate water type. Most well samples had sodium as the dominant cation, and sulfate, bicarbonate, and chloride as the dominant anions. Fluoride concentrations in about 45 percent of well samples were greater than an agricultural-use standard of 2 mg/L. Nitrate plus nitrite concentrations in most spring and well samples were less than about 1.6 mg/L per liter. Concentrations in samples from wells in the irrigated agricultural area were elevated; the maximum concentration was 78.5 mg/L. About one-half of the trace-element samples had concentrations that were less than laboratory reporting limits. Only aluminum, arsenic, and selenium in spring samples, and boron and selenium in well samples, were detected at concentrations greater than surface-water standards or water-quality standards for agricultural use of groundwater. Only three organic compounds, the pesticides alachlor and atrazine and the volatile organic compound di(2-ethylhexyl) phthalate, were detected in well samples. The Escherichia coli bacteria was detected in 47 and 23 percent of samples from wells and springs, respectively. The E. coli detections included samples from three culturally significant springs, which did not meet the UMUT cultural-use standard of total absence of E. coli. Tritium and carbon-14 were the primary environmental tracers used for interpreting groundwater ages for Lopez 2 Spring and five wells (AP–1, 5000 Block, Cottonwood Spring, Goodknight, and SE Toe). Water from the AP–1 well contained a mixture of pre- and post-1950s recharge. Tritium and carbon-14 recharge ages for Lopez 2 Spring (post-1950s in age), Goodknight and SE Toe wells (pre-1950s in age), and Cottonwood Spring well (primarily pre-1950s in age) are supported by helium-4 data. The helium-4 data for the 5000 Block well are inconsistent with the tritium and carbon-14 age of pre-1950s recharge because of interference caused by high methane concentrations in the water. Springs and surficial deposits are more vulnerable to contamination from anthropogenic chemicals than deeper bedrock wells. Bedrock aquifers are vulnerable in areas where the geologic formations containing the aquifers are exposed at the land surface. Groundwater in deep bedrock aquifers is likely thousands of years old and is not currently affected by present-day land uses. Both shallow and deep groundwater are vulnerable to naturally occurring salts and minerals, such as of total dissolved solids, major ions, nitrate, and trace elements. Effects of a changing climate on water resources and other ecological characteristics of the UMUR could include changes in evapotranspiration, a decrease in snowpack, decreased aquifer recharge and flow of springs, a decrease in soil moisture, and increased occurrence of wildfires and forest mortality. Of particular interest for the UMUT are possible effects of a changing climate on medicinal and culturally important plants and springs Several information needs were identified during this study that would aid in the understanding and protection of groundwater resources on the UMUR. These include well-completion information for bedrock wells, the collection of environmental tracer data at additional wells, the addition of methane and hydrocarbon analysis to well sampling plans, and the resampling of springs and wells that were last sampled in 2002 or earlier.

Colorado↗

Soil aggregates as a source of dissolved organic carbon to streams: An experimental study on the effect of solution chemistry on water extractable carbon

Over the past two decades, headwater streams of the northern hemisphere have shown increased amounts of dissolved organic carbon (DOC), coinciding with decreased acid deposition. The exact nature of the mechanistic link between precipitation composition and stream water DOC is still widely debated in the literature. We hypothesize that soil aggregates are the main source of stream water DOC and that DOC release is greater in organic rich, riparian soils vs. hillslope soils. To test these hypotheses, we collected soils from two main landscape positions (hillslope and riparian zones) from the acid-impacted Sleepers River Research Watershed in northeastern Vermont. We performed aqueous soil extracts with solutions of different ionic strength (IS) and composition to simulate changes in soil solution. We monitored dynamic changes in soil particle size, aggregate architecture and composition, leachate DOC concentrations, dissolved organic matter (DOM) characteristics by fluorescence spectroscopy and trends in bioavailability. In low IS solutions, extractable DOC concentrations were significantly higher, particle size (by laser diffraction) was significantly smaller and organic material was separated from mineral particles in scanning electron microscope observations. Furthermore, higher DOC concentrations were found in Na + compared to Ca 2+ solutions of the same IS. These effects are attributed to aggregate dispersion due to expanding diffuse double layers in decreased IS solutions and to decreased bridging by divalent cations. Landscape position impacted quality but not quantity of released DOC. Overall, these results indicate that soil aggregates might be one important link between Critical Zone inputs (i.e., precipitation) and exports in streams.

Vermont↗

Hydrogeology, water quality, and stormwater-sediment chemistry of the Grande Wash area, Fort McDowell Indian Reservation, Maricopa County, Arizona

Grande Wash is a tributary of the Verde River and drains an area of 13 square miles within the McDowell Mountains and the Town of Fountain Hills in Central Arizona. The wash enters the Fort McDowell Indian Reservation at the eastern boundary of Fountain Hills and is incised in coarse-grained alluvium that is contiguous with the alluvial aquifer along the Verde River. The aquifer is used by the Fort McDowell Indian Community and the City of Phoenix for municipal water supplies. Episodic flows in Grande Wash, in response to storms, carry potentially hazardous runoff from Fountain Hills onto the reservation. Additional potential hazards to ground water include contamination from a wastewater-treatment plant located less than 1 mile upstream from the reservation boundary, and from a landfill and a cement-processing plant immediately adjacent to the main channel of the wash. Coarse-grained deposits in Grande Wash also include recent stream-channel deposits, soil backfill, landfill material, and the upper coarse-grained layer of basin-fill sediments. Surface-geophysical surveys and drilling indicated that the coarse-grained deposits are less than 60-feet thick along the wash and in adjacent areas within the reservation, and are underlain by a thick clay and silt unit, the base of which is below the bottom of the deepest monitor well (317 feet below land surface). The coarse-grained deposits form the alluvial aquifer beneath Grande Wash. Ground water in the alluvial aquifer beneath the wash is shallow and mounded above a less permeable clay and silt unit. Depth to water in the aquifer ranges from 1 to 22 feet below land surface. Saturation of the coarse-grained deposits does not extend laterally for more than about 1,000 feet from the main channel of Grande Wash; the extent varies in response to recharge amounts. Flux of ground water through the alluvial aquifer beneath the wash is toward the Verde River and is estimated to be about 8,000 cubic feet per day (about 0.2 acre-feet per day). The flow rate is four orders of magnitude less than the flow rate in the Verde River. Vertical flux of ground water through the underlying clay and silt unit is estimated to be 7,000 cubic feet per day (0.17 acre-feet per day). The volume of ground water in storage in the alluvial aquifer beneath Grande Wash is estimated to be about 5.6 million cubic feet (129 acre-feet). Concentrations of dissolved inorganic constituents in ground water and surface water are high relative to concentrations found in the regional aquifer in surrounding areas and are indicative of salts that can be expected to be mobilized by runoff in the drainage area. Concentrations of nitrate, chloride, and sulfate are near U.S. Environmental Protection Agency Primary or Secondary Drinking-Water Regulations. Concentrations of arsenic, antimony, and strontium are below drinking-water standards but can be attributed to geologic deposits in and near the study area. Low concentrations of anthropogenic compounds, including chloroform and dichlorobromomethane, were detected. These compounds are disinfection by-products of chlorinated water. Eight pesticide compounds were detected in the surface water, and two pesticide compounds were detected in the ground water. Pesticide concentrations were below U.S. Environmental Protection Agency Maximum Contaminant Levels. Several other organic anthropogenic compounds that probably originated from commercial activities in the area were detected but at concentrations below laboratory calibration standards. Concentrations of trace metals in the stormwater sediment collected from the sediment retention basin in the lowest part of the wash were low and several were below the laboratory’s detection limits. Concentrations of most organic compounds in the stormwater sediment were below detection limits. Organic compounds present at concentrations above detection limits were p-cresol and two phthalate esters—bis (2-ethylhexyl) phthalate and dibutyl phthalate. P-cresol is used in pesticides or in disinfectants and deodorizers, and phthalate esters are commonly used in plastics, hydraulic fluid, and electric capacitors.

Arizona↗

Aquifer geochemistry at potential aquifer storage and recovery sites in coastal plain aquifers in the New York city area, USA

The effects of injecting oxic water from the New York city (NYC) drinking-water supply and distribution system into a nearby anoxic coastal plain aquifer for later recovery during periods of water shortage (aquifer storage and recovery, or ASR) were simulated by a 3-dimensional, reactive-solute transport model. The Cretaceous aquifer system in the NYC area of New York and New Jersey, USA contains pyrite, goethite, locally occurring siderite, lignite, and locally varying amounts of dissolved Fe and salinity. Sediment from cores drilled on Staten Island and western Long Island had high extractable concentrations of Fe, Mn, and acid volatile sulfides (AVS) plus chromium-reducible sulfides (CRS) and low concentrations of As, Pb, Cd, Cr, Cu and U. Similarly, water samples from the Lloyd aquifer (Cretaceous) in western Long Island generally contained high concentrations of Fe and Mn and low concentrations of other trace elements such as As, Pb, Cd, Cr, Cu and U, all of which were below US Environmental Protection Agency (USEPA) and NY maximum contaminant levels (MCLs). In such aquifer settings, ASR operations can be complicated by the oxidative dissolution of pyrite, low pH, and high concentrations of dissolved Fe in extracted water.The simulated injection of buffered, oxic city water into a hypothetical ASR well increased the hydraulic head at the well, displaced the ambient groundwater, and formed a spheroid of injected water with lower concentrations of Fe, Mn and major ions in water surrounding the ASR well, than in ambient water. Both the dissolved O2 concentrations and the pH of water near the well generally increased in magnitude during the simulated 5-a injection phase. The resultant oxidation of Fe2+ and attendant precipitation of goethite during injection provided a substrate for sorption of dissolved Fe during the 8-a extraction phase. The baseline scenario with a low (0.001M) concentration of pyrite in aquifer sediments, indicated that nearly 190% more water with acceptably low concentrations of dissolved Fe could be extracted than was injected. Scenarios with larger amounts of pyrite in aquifer sediments generally resulted in less goethite precipitation, increased acidity, and increased concentrations of dissolved Fe in extracted water. In these pyritic scenarios, the lower amounts of goethite precipitated and the lower pH during the extraction phase resulted in decreased sorption of Fe2+ and a decreased amount of extractable water with acceptably low concentrations of dissolved Fe (5.4??10-6M). A linear decrease in recovery efficiency with respect to dissolved Fe concentrations is caused by pyrite dissolution and the associated depletion of dissolved O2 (DO) and increase in acidity. Simulations with more than 0.0037M of pyrite, which is the maximum amount dissolved in the baseline scenario, had just over a 50% recovery efficiency. The precipitation of ferric hydroxide minerals (goethite) at the well screen, and a possible associated decrease in specific capacity of the ASR well, was not apparent during the extraction phase of ASR simulations, but the model does not incorporate the microbial effects and biofouling associated with ferric hydroxide precipitation.The host groundwater chemistry in calcite-poor Cretaceous aquifers of the NYC area consists of low alkalinity and moderate to low pH. The dissolution of goethite in scenarios with unbuffered injectate indicates that corrosion of the well could occur if the injectate is not buffered. Simulations with buffered injectate resulted in greater precipitation of goethite, and lower concentrations of dissolved Fe, in the extracted water. Dissolved Fe concentrations in extracted water were highest in simulations of aquifers (1) in which pyrite and siderite in the aquifer were in equilibrium, and (2) in coastal areas affected by saltwater intrusion, where high dissolved-cation concentrations provide a greater exchange of Fe2+ (FeX2). Results indicate that ASR in pyrite-beari

Applied Geochemistry↗

Metal reactivity in laboratory burned wood from a watershed affected by wildfires

We investigated interfacial processes affecting metal mobility by wood ash under laboratory-controlled conditions using aqueous chemistry, microscopy, and spectroscopy. The Valles Caldera National Preserve in New Mexico experiences catastrophic wildfires of devastating effects. Wood samples of Ponderosa Pine, Colorado Blue Spruce, and Quaking Aspen collected from this site were exposed to temperatures of 60, 350, and 550 °C. The 350 °C Pine ash had the highest content of Cu (4997 ± 262 mg kg –1 ), Cr (543 ± 124 mg kg –1 ), and labile dissolved organic carbon (DOC, 11.3 ± 0.28 mg L –1 ). Sorption experiments were conducted by reacting 350 °C Pine, Spruce, and Aspen ashes separately with 10 μM Cu(II) and Cr(VI) solutions. Up to a 94% decrease in Cu(II) concentration was observed in solution while Cr(VI) concentration showed a limited decrease (up to 13%) after 180 min of reaction. X-ray photoelectron spectroscopy (XPS) analyses detected increased association of Cu(II) on the near surface region of the reacted 350 °C Pine ash from the sorption experiments compared to the unreacted ash. The results suggest that dissolution and sorption processes should be considered to better understand the potential effects of metals transported by wood ash on water quality that have important implications for postfire recovery and response strategies.

Environmental Science & Technology↗

Humic acid facilitates the transport of ARS-labeled hydroxyapatite nanoparticles in iron oxyhydroxide-coated sand

Hydroxyapatite nanoparticles (nHAP) have been widely used to remediate soil and wastewater contaminated with metals and radionuclides. However, our understanding of nHAP transport and fate is limited in natural environments that exhibit significant variability in solid and solution chemistry. The transport and retention kinetics of Alizarin red S (ARS)-labeled nHAP were investigated in water-saturated packed columns that encompassed a range of humic acid concentrations (HA, 0–10 mg L –1 ), fractional surface coverage of iron oxyhydroxide coatings on sand grains (λ, 0–0.75), and pH (6.0–10.5). HA was found to have a marked effect on the electrokinetic properties of ARS-nHAP, and on the transport and retention of ARS-nHAP in granular media. The transport of ARS-nHAP was found to increase with increasing HA concentration because of enhanced colloidal stability and the reduced aggregate size. When HA = 10 mg L –1 , greater ARS-nHAP attachment occurred with increasing λ because of increased electrostatic attraction between negatively charged nanoparticles and positively charged iron oxyhydroxides, although alkaline conditions (pH 8.0 and 10.5) reversed the surface charge of the iron oxyhydroxides and therefore decreased deposition. The retention profiles of ARS-nHAP exhibited a hyperexponential shape for all test conditions, suggesting some unfavorable attachment conditions. Retarded breakthrough curves occurred in sands with iron oxyhydroxide coatings because of time-dependent occupation of favorable deposition sites. Consideration of the above effects is necessary to improve remediation efficiency of nHAP for metals and actinides in soils and subsurface environments.

Environmental Science & Technology↗

Effect of river sediment on phosphorus chemistry of similarly aged natural and created wetlands in the Atchafalaya Delta, Louisiana, USA

The goal of wetland creation is to produce an artificial wetland that functions as a natural wetland. Studies comparing created wetlands to similarly aged natural wetlands provide important information about creation techniques and their improvement so as to attain that goal. We hypothesized that differences in sediment phosphorus accretion, deposition, and chemistry between created and natural wetlands in the Atchafalaya Delta, Louisiana, USA were a function of creation technique and natural river processes. Sediment deposition was determined with feldspar marker horizons located in created and natural wetlands belonging to three age classes (<3, 5-10, and 15-20 yr old). Phosphorus fractions were measured in these deposited sediments and in suspended and bedload sediment from the Atchafalaya River. Bedload sediment had significantly lower iron- and aluminum-bound, reductant-soluble, and total phosphorus than suspended sediment due to its high sand percentage. This result indicates that wetlands artificially created in the Atchafalaya Delta using bedload sediment will initially differ from natural wetlands of the same age. Even so, similarities between the mudflat stratum of the <1- to 3-yr-old created wetland and the mudflat stratum of the 15- to 20-yr-old natural wetland support the contention that created wetlands in the Atchafalaya Delta can develop natural characteristics through the deposition of river suspended sediment. Differences between three created wetland strata, the 15- to 20-yr-old willow stratum and the < 1- to 3-yr-old willow and mixed marsh strata, and their natural counterparts were linked to design elements of the created wetlands that prevented the direct deposition of the river's suspended sediment. ?? ASA, CSSA, SSSA.

Journal of Environmental Quality↗

Sources and magnitude of bias associated with determination of polychlorinated biphenyls in environmental samples

Recently compiled data on the composition of commercial Aroclor mixtures and ECD (electron capture detector) response factors for all 209 PCB congeners are used to develop estimates of the bias associated with determination of polychlorinated blphenyis. During quantitation of multlcomponent peaks by congener-specific procedures error is introduced because of variable ECD response to isomeric PCBs. Under worst case conditions, the magnitude of this bias can range from less than 2% to as much as 600%. Multicomponent peaks containing the more highly and the lower chlorinated congeners experience the most bias. For this reason, quantitation of Σ PCB in Aroclor mixtures dominated by these species (e.g. 1016) are potentially subject to the greatest error. Comparison of response factor data for ECDs from two laboratories shows that the sign and magnitude of calibration bias for a given multicomponent peak is variable and depends, in part, on the response characteristics of individual detectors. By using the most abundant congener (of each multicomponent peak) for purposes of calibration, one can reduce the maximum bias to less than 55%. Moreover, due to cancellation of errors, the bias resulting from summation of all peak concentrations (i.e. Σ PCB) becomes vanishingly small (<1.2%). In contrast, bias associated with determination of Σ PCB as Aroclor equivalents by the traditional Aroclor method is potentially large (>200%) and highly variable in sign and magnitude. In this case, bias originates not only from the incomplete chromatographic resolution of PCB congeners but also the overlapping patterns of the Aroclor mixtures. Together these results illustrate the advantages of the congener-specific method of PCB quantitation over the traditional Aroclor Method and the extreme difficulty of estimating bias incurred by the latter procedure on a post hoc basis.

Analytical Chemistry↗

Multi-decadal increases in dissolved organic carbon and alkalinity flux from the Mackenzie drainage basin to the Arctic Ocean

Riverine exports of organic and inorganic carbon (OC, IC) to oceans are intricately linked to processes occurring on land. Across high latitudes, thawing permafrost, alteration of hydrologic flow paths, and changes in vegetation may all affect this flux, with subsequent implications for regional and global carbon (C) budgets. Using a unique, multi-decadal dataset of continuous discharge coupled with water chemistry measurements for the Mackenzie River, we show major increases in dissolved OC (DOC) and IC (as alkalinity) fluxes since the early 1970s, for a watershed that covers 1.8 M km 2 of northwestern Canada, and provides substantial inputs of freshwater and biogeochemical constituents to the Arctic Ocean. Over a 39-year period of record, DOC flux at the Mackenzie mouth increased by 39.3% (44.5 ± 22.6 Gmol), while alkalinity flux increased by 12.5% (61.5 ± 60.1 Gmol). Isotopic analyses and substantial increases in sulfate flux indicate that increases in alkalinity are driven by accelerating sulfide oxidation, a process that liberates IC from rock and soils in the absence of CO 2 consumption. Seasonal and sub-catchment trends suggest that permafrost thaw plays an important role in the observed increases in DOC and alkalinity: sub-catchment increases for all constituents are confined to northern, permafrost-affected regions, while observed increases in autumn to winter are consistent with documented landscape-scale changes that have resulted from changing thaw dynamics. This increase in DOC and sulfide-derived alkalinity represents a substantial intensification of land-to-ocean C mobilization, at a level that is significant within the regional C budget. The change we observe, for example, is similar to current and projected future rates of CO 2 consumption by weathering in the Mackenzie basin.

Environmental Research Letters↗

Evaluation of a rapid, quantitative real-time PCR method for enumeration of pathogenic Candida cells in water

Quantitative PCR (QPCR) technology, incorporating fluorigenic 5&prime; nuclease (TaqMan) chemistry, was utilized for the specific detection and quantification of six pathogenic species of Candida ( C. albicans , C. tropicalis , C. krusei , C. parapsilosis , C. glabrata and C. lusitaniae ) in water. Known numbers of target cells were added to distilled and tap water samples, filtered, and disrupted directly on the membranes for recovery of DNA for QPCR analysis. The assay's sensitivities were between one and three cells per filter. The accuracy of the cell estimates was between 50 and 200% of their true value (95% confidence level). In similar tests with surface water samples, the presence of PCR inhibitory compounds necessitated further purification and/or dilution of the DNA extracts, with resultant reductions in sensitivity but generally not in quantitative accuracy. Analyses of a series of freshwater samples collected from a recreational beach showed positive correlations between the QPCR results and colony counts of the corresponding target species. Positive correlations were also seen between the cell quantities of the target Candida species detected in these analyses and colony counts of Enterococcus organisms. With a combined sample processing and analysis time of less than 4 h, this method shows great promise as a tool for rapidly assessing potential exposures to waterborne pathogenic Candida species from drinking and recreational waters and may have applications in the detection of fecal pollution.

Applied and Environmental Microbiology↗

Aquatic dissipation of triclopyr in Lake Seminole, Georgia

A field study was conducted to evaluate the environmental dissipation of triclopyr herbicide under aquatic-use conditions. Three 4-h plots in Lake Seminole, Georgia, were selected for use: one control, one aerial plot, and one subsurface plot; both applications were at the maximum aquatic-use rate of 2.5 mg/L. Water, sediment, plants, fish, clams, and crayfish were all analyzed for residues, and water temperature, oxygen levels, pH, and conductivity were monitored. The half-life for aqueous-phase triclopyr ranged from 0.5 to 3.6 days, and the dissipation in surface and bottom waters was equivalent. The intermediate decay product of triclopyr, 3,5,6-trichloro-2-pyridinol (TCP), had an observed aquatic half-life of less than 1 day. No accumulation of triclopyr or TCP on sediment was observed. The half-life of triclopyr metabolized by aquatic plants averaged 4 days. Fish species did not exhibit any bioconcentration of triclopyr or TCP, with only trace amounts of either compound found in fish tissue. Both clams and crayfish contained detectable residues of triclopyr. The elimination of triclopyr from clam tissue was more rapid, with an observed half-life of 1.5 days, vs 12 days for crayfish; retention of triclopyr in the crayfish carcass (carapace, chelopeds, and gills) may have been an important mechanism. There was no detectable decline in water quality in either treatment plot. ?? 1993 American Chemical Society.

Journal of Agricultural and Food Chemistry↗

Assessment of methods for soil monitoring in the Adirondack region of New York

Repeated sampling to detect changes in forest soils was rarely used before 1990, but the value of soil monitoring in understanding environmental change is becoming well established. The growing number of resampling studies has shown that sampling designs and procedures must be adapted to the objectives of the monitoring program and the soils being monitored. In the Adirondack region, current priorities include the response of soils to large increases, and more recently, large decreases in acidic deposition, and changes driven by trending climate such as altered pools of soil organic carbon, as well as other unforeseen factors that will occur in the future. To improve methods and assess the feasibility of long-term soil monitoring in the Adirondack region, the United States Geological Survey (USGS) conducted a pilot project to evaluate a new sampling method for characterizing soils on a watershed basis. Results obtained with this new approach, referred to as the ADK sampling method, was compared to methods used in previous sampling conducted in 2004 as part of the Western Adirondack Stream Survey (WASS), and also to previous high-replication pit sampling in the North and South Tributary watersheds of Buck Creek (North Buck and South Buck). The number of sampling locations and spatial distribution of sampling points within watersheds differed among the methods, although pit excavation was used to obtain samples in all cases. In addition, this investigation evaluated the use of small diameter corers as a means to measure forest floor mass with greater accuracy and precision than commonly used methods such as pit excavation. Sufficient statistical power to detect ecologically relevant changes in upper profile horizons (Oe, Oa and upper 10 cm of the B) were achieved with the ADK sampling method that utilized 18 pit excavations per watershed. The sampling locations were organized within each watershed into three study areas (six sampling locations per study area) that represented the primary types of landscape within the watershed. Sampling at 18 locations per watershed was found to be nearly as effective at detecting changes as sampling at 28 locations per watershed. Numerous significant changes (P < 0.10) were detected with both 18 and 28 sampling locations at sampling intervals of 12 to 16 years. The relationship between soil data obtained with the ADK method and stream chemistry at the base of the watershed suggested that this approach adequately characterized soil variability within the watershed for the purpose of studying soil-stream linkages. Significant changes in upper B horizon calcium (P < 0.10) and Oa horizon aluminum (P < 0.01) were detected when the data from the four WASS watersheds were combined with the two Buck Creek watersheds, which suggested that there would be value in resampling other WASS watersheds previously sampled in 2004 to support a regional assessment. Study results support small diameter cores as a useful method to monitor changes in the organic matter mass of the forest floor. This method showed high reproducibility in repeated sampling tests and lower spatial variability in sample data than traditional approaches when compared on a watershed basis. Soil coring is also faster and requires less equipment than pit excavation methods, which makes it more conducive to sampling over large areas. However, organic matter mass of the forest floor determined by coring was consistently less than the values obtained by the ADK sampling method that used pit sampling and vertical horizon measurements, and also literature values of a previous Adirondack study that utilized pit sampling in which the entire horizon was collected over a measured area. However, a high correlation (R2 = 0.87) occurred between organic matter content (expressed as Mg ha-1) determined by coring and the ADK sampling method. Differing methods with regard to where sample could be collected, and how organic matter was collected for chemical analysis were the likely reasons for differences in quantification of forest floor organic mass. Collection of forest floor cores in conjunction with the ADK method is recommended to provide improved sensitivity in detecting changes in the forest floor in proximity of where full analyses of the soil profile are being done. This duel sampling approach represents an optimized method for measuring and understanding how Adirondack soils will change in the future.

New York↗

Phosphorus amendment reduces hematological effects of lead in mallards ingesting contaminated sediments

Lead poisoning of waterfowl has been reported for decades in the Coeur d?Alene River Basin (CDARB) in Idaho as a result of the ingestion of lead-contaminated sediments. This study was conducted to determine whether the addition of phosphoric acid to sediments would reduce the bioavailability and toxicity of lead to mallards (Anas platyrhynchos) as related to adverse hematological effects and altered plasma chemistries. Mallards received diets containing 12% clean sediment (controls) or 12% sediment from three different CDARB sites containing 4520, 5390, or 6990 :g/g lead (dw) with or without phosphoric acid amendment. Blood lead concentrations were significantly higher in all CDARB treatment groups and ranged from geometric mean values of 5.0 ug/g for the first two sites to 6.2 ug/g for the third site. With amendments, all blood lead concentrations became 41% to 64% lower. Red blood cell ALAD activity was depressed by 90% or more with lead-contaminated sediment from all sites and did not differ with amended diets. Free erythrocyte protoporphyrin (FEP) concentrations were elevated by contaminated sediment from all sites. Amendment decreased the elevations in FEP by as much as 80%. Hematocrit values and hemoglobin concentrations were lower for all lead site sediments by as much as 30% for site 3. Plasma enzyme activities for ALT, CK, and LDH-L were elevated by as much as 2.2-fold, and plasma creatinine concentration was 1.7-fold higher for site 3 sediment. Amendments restored hematocrit, hemoglobin, and plasma enzyme activities so that they did not differ from controls. Although amendments of phosphorus substantially reduced the bioavailability of lead and alleviated many of the adverse hematological effects, lead concentrations in the blood of mallards fed the amended sediments were still above those believed to be harmful to waterfowl under the present conditions.

Archives of Environmental Contamination and Toxico↗

Herbicides and their transformation products in source-water aquifers tapped by public-supply wells in Illinois, 2001-02

During 2001-02, ground-water samples were collected from 117 public-supply wells distributed throughout Illinois to evaluate the occurrence of herbicides and their transformation products in the State?s source-water aquifers. Wells were selected using a stratified-random method to ensure representation of the major types of source-water aquifers in the State. Samples were analyzed for 18 herbicides and 18 transformation products, including 3 triazine and 14 chloroacetanilide products. Herbicide compounds (field-applied parent herbicides and their transformation products) were detected in 34 percent of samples. A subset of samples was collected unfiltered to determine if analytical results for herbicides in unfiltered samples are similar to those in paired filtered samples and, thus, can be considered equally representative of herbicide concentrations in ground water supplied to the public. The study by the U.S. Geological Survey was done in cooperation with the Illinois Environmental Protection Agency. Parent herbicides were detected in only 4 percent of all samples. The six most frequently detected herbicide compounds (from 5 to 28 percent of samples) were chloroacetanilide transformation products. The frequent occurrence of transformation products and their higher concentrations relative to those of most parent herbicides confirm the importance of obtaining information on transformation products to understand the mobility and fate of herbicides in ground-water systems. No sample concentrations determined during this study exceeded current (2003) Federal or State drinking-water standards; however, standards are established for only seven parent herbicides. Factors related to the occurrence of herbicide compounds in the State?s source-water aquifers include unconsolidated and unconfined conditions, various hydrogeologic characteristics and well-construction aspects at shallow depths, and proximity to streams. Generally, the closer an aquifer (or well location) is to a recharge area and (or) the stronger the hydraulic connection between an aquifer and a recharge area, the younger the ground water and the more vulnerable the aquifer will be to contamination by herbicide compounds. The weak relation between current (2001) statewide application rates of herbicides and current (2001-02) occurrence of herbicide compounds in source-water aquifers indicates that additional factors must be considered when relating herbicide-application rates to occurrence. These factors include historical application rates and the mobility and persistence of the various herbicide compounds in ground-water systems. Frequency of detection and concentrations of herbicides compounds in the State?s source-water aquifers are indicated to be highest during the spring, when crops are planted and herbicides primarily are applied. Excess nitrate (concentrations of nitrate, as nitrogen, higher than 3 milligrams per liter) in ground water strongly indicates the co-occurrence of herbicide compounds. However, nitrate concentrations are not a reliable indicator of herbicide-compound concentrations. The inverse relation found between current use of land for corn and soybean production and current occurrence of herbicide compounds in underlying aquifers indicates that various factors, along with current agricultural land use, contribute to herbicide occurrence. These factors include, among others, land-use history, ground-water age, ground-water-flow patterns, geology, soil microbiology, and chemistry and persistence of the herbicide compounds. Detection of agriculture-specific herbicide compounds in 71 percent of samples from urban areas with no current or recent agricultural land use near the sampled wells indicates that recharge to certain high-capacity supply wells may originate at considerable distances (up to about 10 miles) from the wells. Essentially no difference was found between the analytical results for herbicides in paired unfiltered and filtered samples,

Water-Resources Investigations Report↗

Groundwater chemistry and occurrence of arsenic in the Meghna floodplain aquifer, southeastern Bangladesh

Dissolved major ions and important heavy metals including total arsenic and iron were measured in groundwater from shallow (25-33 m) and deep (191-318 m) tube-wells in southeastern Bangladesh. These analyses are intended to help describe geochemical processes active in the aquifers and the source and release mechanism of arsenic in sediments for the Meghna Floodplain aquifer. The elevated Cl- and higher proportions of Na+ relative to Ca2+, Mg2+, and K+ in groundwater suggest the influence by a source of Na+ and Cl-. Use of chemical fertilizers may cause higher concentrations of NH 4+ and PO 43- in shallow well samples. In general, most ions are positively correlated with Cl-, with Na+ showing an especially strong correlation with Cl-, indicating that these ions are derived from the same source of saline waters. The relationship between Cl-/HCO 3- ratios and Cl- also shows mixing of fresh groundwater and seawater. Concentrations of dissolved HCO 3- reflect the degree of water-rock interaction in groundwater systems and integrated microbial degradation of organic matter. Mn and Fe-oxyhydroxides are prominent in the clayey subsurface sediment and well known to be strong adsorbents of heavy metals including arsenic. All five shallow well samples had high arsenic concentration that exceeded WHO recommended limit for drinking water. Very low concentrations of SO 42- and NO 3- and high concentrations of dissolved Fe and PO 43- and NH 4+ ions support the reducing condition of subsurface aquifer. Arsenic concentrations demonstrate negative co-relation with the concentrations of SO 42- and NO 3- but correlate weakly with Mo, Fe concentrations and positively with those of P, PO 43- and NH 4+ ions. ?? 2007 Springer-Verlag.

Environmental Geology↗

Toxicity of sediment cores collected from the Ashtabula River in northeastern Ohio, USA, to the amphipod Hyalella azteca

This study was conducted to support a Natural Resource Damage Assessment and Restoration project associated with the Ashtabula River in Ohio. The objective of the study was to evaluate the chemistry and toxicity of 50 sediment samples obtained from five cores collected from the Ashtabula River (10 samples/core, with each 10-cm-diameter core collected to a total depth of about 150 cm). Effects of chemicals of potential concern (COPCs) measured in the sediment samples were evaluated by measuring whole-sediment chemistry and whole-sediment toxicity in the sediment samples (including polycyclic aromatic hydrocarbons [PAHs], polychlorinated biphenyls [PCBs], organochlorine pesticides, and metals). Effects on the amphipod Hyalella azteca at the end of a 28-day sediment toxicity test were determined by comparing survival or length of amphipods in individual sediment samples in the cores to the range of responses of amphipods exposed to selected reference sediments that were also collected from the cores. Mean survival or length of amphipods was below the lower limit of the reference envelope in 56% of the sediment samples. Concentrations of total PCBs alone in some samples or concentrations of total PAHs alone in other samples were likely high enough to have caused the reduced survival or length of amphipods (i.e., concentrations of PAHs or PCBs exceeded mechanistically based and empirically based sediment quality guidelines). While elevated concentrations of ammonia in pore water may have contributed to the reduced length of amphipods, it is unlikely that the reduced length was caused solely by elevated ammonia (i.e., concentrations of ammonia were not significantly correlated with the concentrations of PCBs or PAHs and concentrations of ammonia were elevated both in the reference sediments and in the test sediments). Results of this study show that PAHs, PCBs, and ammonia are the primary COPCs that are likely causing or substantially contributing to the toxicity to sediment-dwelling organisms. ?? 2009 US Government.

Archives of Environmental Contamination and Toxico↗

Using heat to characterize streambed water flux variability in four stream reaches

Estimates of streambed water flux are needed for the interpretation of streambed chemistry and reactions. Continuous temperature and head monitoring in stream reaches within four agricultural watersheds (Leary Weber Ditch, IN; Maple Creek, NE; DR2 Drain, WA; and Merced River, CA) allowed heat to be used as a tracer to study the temporal and spatial variability of fluxes through the streambed. Synoptic methods (seepage meter and differential discharge measurements) were compared with estimates obtained by using heat as a tracer. Water flux was estimated by modeling one-dimensional vertical flow of water and heat using the model VS2DH. Flux was influenced by physical heterogeneity of the stream channel and temporal variability in stream and ground-water levels. During most of the study period (April–December 2004), flux was upward through the streambeds. At the IN, NE, and CA sites, high-stage events resulted in rapid reversal of flow direction inducing short-term surface-water flow into the streambed. During late summer at the IN site, regional ground-water levels dropped, leading to surface-water loss to ground water that resulted in drying of the ditch. Synoptic measurements of flux generally supported the model flux estimates. Water flow through the streambed was roughly an order of magnitude larger in the humid basins (IN and NE) than in the arid basins (WA and CA). Downward flux, in response to sudden high streamflows, and seasonal variability in flux was most pronounced in the humid basins and in high conductivity zones in the streambed.

Journal of Environmental Quality↗