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Effects of dietary cadmium on mallard ducklings

Mallard (Anas platyrhynchos) ducklings were fed cadmium in the diet at 0, 5, 10, or 20 ppm from 1 day of age until 12 weeks of age. At 4-week intervals six males and six females from each dietary group were randomly selected, bled by jugular venipuncture, and necropsied. Significant decreases in packed cell volume (PCV) and hemoglobin (Hb) concentration and a significant increase in serum glutamic pyruvic transaminase (GPT) were found at 8 weeks of age in ducklings fed 20 ppm cadmium. Mild to severe kidney lesions were evident in ducklings fed 20 ppm cadmium for 12 weeks. No other blood chemistry measurement, hematological parameter, or tissue histopathological measurement indicated a reaction to cadmium ingestion. Body weight, liver weight, and the ratio of the femur weight to length were not affected by dietary cadmium. Femur cadmium concentration In all ducklings 12 weeks of age declined from the values detected at 4 and 8 weeks of age. Liver cadmium concentrations were significantly higher in relation to the increased dietary levels and in relation to the length of time the ducklings were fed the cadmium diets. At 12 weeks of age the cadmium concentration in liver tissue was twice that in the diet.

Environmental Research↗

Fluorine

Fluorine compounds are essential in numerous chemical and manufacturing processes. Fluorspar is the commercial name for fluorite (isometric CaF 2 ), which is the only fluorine mineral that is mined on a large scale. Fluorspar is used directly as a fluxing material and as an additive in different manufacturing processes. It is the source of fluorine in the production of hydrogen fluoride or hydrofluoric acid, which is used as the feedstock for numerous organic and inorganic chemical compounds. The United States was the world’s leading producer of fluorspar until the mid-1950s. In the mid-1970s, the U.S. fluorspar mining industry began to decline because of foreign competition. By 1982, there was essentially only a single U.S. producer left, and that company ceased mining in 1996. Consumption of fluorspar in the United States peaked in the early 1970s, which was also the peak period of U.S. steel production. Since then, U.S. fluorspar consumption has decreased substantially; the United States has nonetheless increased its imports of downstream fluorine compounds, such as, in order of tonnage imported, hydrofluoric acid, aluminum fluoride, and cryolite. This combination of no U.S. production (until recently) and high levels of consumption has made the United States the world’s leading fluorspar-importing country, in all its various forms. The number of fluorspar-exporting countries has decreased substantially in recent decades, and, as a result, the United States has become dependent on just a few countries to supply its needs. In 2013, the United States imported the majority of its fluorspar from three countries, which were, in descending order of the amount imported, Mexico, China, and South Africa. Geologically, in igneous systems, fluorine is one of a number of elements that are “incompatible.” These incompatible elements become concentrated in the residual magma while the common silicates crystallize upon magma ascent and cooling, leading to relatively high fluorine concentrations in the more evolved or differentiated igneous rocks and in hydrothermal deposits associated with those evolved igneous rocks. In sedimentary rocks, fluorine’s highest concentrations are found in phosphorites because fluorine substitutes for hydroxyl ions in apatite, which leads to fluorine concentrations of, typically, from 2 to 4 weight percent in phosphorites. Because of the presence of fluorine, phosphate fertilizer manufacturers can produce a fluorosilicic acid byproduct. Most deposits mined for fluorine are hydrothermal, however, and consist of fluorine minerals that precipitated from hot water. Magmatic brines and brines from deep within sedimentary basins that have high concentrations of dissolved fluoride are the mineralizing fluids for various types of hydrothermal fluorspar deposits. Relatively dilute hydrothermal fluids that formed in some volcanic rocks can also transport sufficient fluoride to form a high-grade fluorspar deposit. Fluorite has low solubility in a common range of hydrothermal temperatures, particularly from about 160 degrees Celsius (°C) down to 60 °C. The increasing fluorite solubility below 60 °C partly explains why some water with exceptionally high levels of dissolved fluorine are found even at ambient temperatures in evaporitic lake basins in some East African Rift valleys in Kenya and Tanzania. The geologic conditions that led to the high concentrations there are known to exist in a number of other places in the world as well, including, perhaps, places in the Basin and Range province of the United States. Eight minerals or mineral groups have sufficient fluorine in their structures to be considered as possible ores of the element; they are bastnaesite (also spelled bastnäsite; and other fluorocarbonates), cryolite, sellaite, villiaumite, fluorite, fluorapatite (in phosphorites), various phyllosilicates, and topaz. Fluorite is currently the only mineral that is mined for fluorine, and nomineral except fluorite is likely to become a source of commercially produced fluorine as a primary product as long as supplies from relatively thick and high-grade fluorite deposits continue to be available. At least seven classes (which include one subclass) of hydrothermal fluorite deposits are recognized; they are classified according to their tectonic and (or) magmatic settings, as follows: (1) carbonatite-related fluorspar deposits; (2) alkaline-intrusion-related fluorspar deposits; (3) alkaline-volcanic-related epithermal fluorspar deposits; (4) Mississippi Valley-type fluorspar deposits (and a subclass of salt-related carbonate-hosted fluorspar deposits); (5) fluorspar deposits related to strongly differentiated granites; (6) subalkaline-volcanic-related epithermal fluospar deposits; and (7) fluorspar deposits that appear to be conformable within tuffaceous limy lacustrine sediments. An eighth class (not hydrothermal) is that of fluorspar deposits concentrated in soils and weathered zones; that is, residual fluorspar deposits. Generally, fluorspar deposits related to strongly differentiated granites have larger tonnages and lower grades than carbonatite-related fluorspar deposits, which, in turn, have larger tonnages and lower grades than fluorspar vein deposits from various other classes. The United States has a few identified resources of fluorspar, most notably the Klondike II property in the Illinois- Kentucky fluorspar district located about 8 kilometers southwest of Salem, Kentucky, which has a large vein that contains at least 1.6 million metric tons at a grade of 60 percent CaF 2 (Feytis, 2009). Additional fluorspar resources of lower grade but larger tonnage have been identified at Hicks Dome in the Illinois-Kentucky fluorspar district and at Lost River near the western tip of the Seward Peninsula in Alaska, along with a couple of dozen smaller, higher grade resources. Internationally, new mines that either opened before the beginning of 2013 or were scheduled to open soon after that time include the Nui Phao tungsten-fluorspar-bismuth-copper-gold deposit in northern Vietnam; the St. Lawrence project in Newfoundland, Canada, which is located in a well-known fluorspar district; the Bamianshan deposit, which is related to a strongly differentiated granite in northwestern Zhejiang Province, China, near some of that Province’s large, subalkaline-volcanic-related epithermal veins; and the Nokeng project in South Africa, which is also related to a strongly differentiated granite. Other deposits in northwestern Australia, Nevada (United States), Norway, South Africa, and Sweden have been identified and could be put into production within just a few years. Among undiscovered resources, an interesting possibility might be to produce a fluorine product from evaporitic, high-fluorine, high-pH sodium-carbonate brines like Lake Magadi (Kenya) and Lake Natron (Tanzania) in Africa’s Eastern Rift Valley. In addition, apparently conformable fluorspar deposits in tuffaceous limy lacustrine sediments, such as those in Italy, are likely to occur in similar young alkalic volcanic settings elsewhere in the world. Modern geophysical and geochemical exploration techniques have typically not been brought to bear in exploration for new fluorspar deposits, although such techniques are likely to be used in future exploration. The tendency for fluorine to dissolve in significant concentrations in water at low temperature allows both surface water and groundwater to be used as sampling media in geochemical exploration. Evolved granite-related fluorspar deposits may be particularly susceptible to geophysical exploration methods because crystalline rocks that form a basement to sedimentary sections can be approximately defined with gravity and magnetic methods, and magnetite-bearing skarns can be directly detected with magnetic surveys. Environmental considerations of fluorine mining focus especially on drinking water, where high fluorine concentrations can lead to tooth decay; dental and skeletal fluorosis; and bone and cartilage conditions, including genu valgum, which is the crippling bone deformity more commonly known as knock knee. Trace amounts of other elements in fluorspar ores are a concern at some deposits; for example, high beryllium concentrations in alkaline-volcanic-related epithermal deposits or high cadmium concentrations associated with Mississippi Valley-type and salt-related carbonate-hosted fluorspar deposits. Future research might include testing whether fluorine can be extracted economically from high-pH, sodium-carbonate brines and exploring for new occurrences of apparently conformable fluorspar deposits in tuffaceous limy lacustrine sediments outside of the Latium Region of Italy. Other promising new areas of research could be studies of fluorspar deposit fluid inclusion compositions by quadrupole mass spectrometry, by noble gas mass spectrometry on irradiated fluid inclusions, or by chlorine isotopes, while also measuring the chemistry of the same fluid inclusions either by bulk crush-and-leach methods or by laser ablation-inductively coupled plasma mass spectrometry. Advanced studies of fluid inclusion chemistry could be applied beneficially to some of the enigmatic large epithermal fluorspar veins at various places in the world, where they might determine those deposits’ possible relationships to igneous intrusions, or to dissolved salt, or to heated meteoric water in volcanic sections, or perhaps to all three. This knowledge could help focus new exploration.

Professional Paper↗

Principal aquifers can contribute radium to sources of drinking water under certain geochemical conditions

What are the most important factors affecting dissolved radium concentrations in principal aquifers used for drinking water in the United States? Study results reveal where radium was detected and how rock type and chemical processes control radium occurrence. Knowledge of the geochemical conditions may help water-resource managers anticipate where radium may be elevated in groundwater and minimize exposure to radium, which contributes to cancer risk. Summary of Major Findings: * Concentrations of radium in principal aquifers used for drinking water throughout the United States generally were below 5 picocuries per liter (pCi/L), the U.S. Environmental Protection Agency (USEPA) maximum contaminant level (MCL) for combined radium - radium-226 (Ra-226) plus radium-228 (Ra-228) - in public water supplies. About 3 percent of sampled wells had combined radium concentrations greater than the MCL. * Elevated concentrations of combined radium were more common in groundwater in the eastern and central United States than in other regions of the Nation. About 98 percent of the wells that contained combined radium at concentrations greater than the MCL were east of the High Plains. * The highest concentrations of combined radium were in the Mid-Continent and Ozark Plateau Cambro-Ordovician aquifer system and the Northern Atlantic Coastal Plain aquifer system. More than 20 percent of sampled wells in these aquifers had combined radium concentrations that were greater than or equal to the MCL. * Concentrations of Ra-226 correlated with those of Ra-228. Radium-226 and Ra-228 occur most frequently together in unconsolidated sand aquifers, and their presence is strongly linked to groundwater chemistry. * Three common geochemical factors are associated with the highest radium concentrations in groundwater: (1) oxygen-poor water, (2) acidic conditions (low pH), and (3) high concentrations of dissolved solids.

Fact Sheet↗

The response of soil and stream chemistry to decreases in acid deposition in the Catskill Mountains, New York, USA

The Catskill Mountains have been adversely impacted by decades of acid deposition, however, since the early 1990s, levels have decreased sharply as a result of decreases in emissions of sulfur dioxide and nitrogen oxides. This study examines trends in acid deposition, stream-water chemistry, and soil chemistry in the southeastern Catskill Mountains. We measured significant reductions in acid deposition and improvement in stream-water quality in 5 streams included in this study from 1992 to 2014. The largest, most significant trends were for sulfate (SO 4 2− ) concentrations (mean trend of −2.5 μeq L −1 yr −1 ); hydrogen ion (H + ) and inorganic monomeric aluminum (Al im ) also decreased significantly (mean trends of −0.3 μeq L −1 yr −1 for H + and −0.1 μeq L −1 yr −1 for Al im for the 3 most acidic sites). Acid neutralizing capacity (ANC) increased by a mean of 0.65 μeq L −1 yr −1 for all 5 sites, which was 4 fold less than the decrease in SO 4 2− concentrations. These upward trends in ANC were limited by coincident decreases in base cations (−1.3 μeq L −1 yr −1 for calcium + magnesium). No significant trends were detected in stream-water nitrate (NO 3 − ) concentrations despite significant decreasing trends in NO 3 − wet deposition. We measured no recovery in soil chemistry which we attributed to an initially low soil buffering capacity that has been further depleted by decades of acid deposition. Tightly coupled decreasing trends in stream-water silicon (Si) (−0.2 μeq L −1 yr −1 ) and base cations suggest a decrease in the soil mineral weathering rate. We hypothesize that a decrease in the ionic strength of soil water and shallow groundwater may be the principal driver of this apparent decrease in the weathering rate. A decreasing weathering rate would help to explain the slow recovery of stream pH and ANC as well as that of soil base cations.

New York↗

Mercury cycling in stream ecosystems. 1. Water column chemistry and transport

We studied total mercury (THg) and methylmercury (MeHg) in eight streams, located in Oregon, Wisconsin, and Florida, that span large ranges in climate, landscape characteristics, atmospheric Hg deposition, and water chemistry. While atmospheric deposition was the source of Hg at each site, basin characteristics appeared to mediate this source by providing controls on methylation and fluvial THg and MeHg transport. Instantaneous concentrations of filtered total mercury (FTHg) and filtered methylmercury (FMeHg) exhibited strong positive correlations with both dissolved organic carbon (DOC) concentrations and streamflow for most streams, whereas mean FTHg and FMeHg concentrations were correlated with wetland density of the basins. For all streams combined, whole water concentrations (sum of filtered and particulate forms) of THg and MeHg correlated strongly with DOC and suspended sediment concentrations in the water column.

Environmental Science & Technology↗

Environmental geochemistry of a Kuroko-type massive sulfide deposit at the abandoned Valzinco mine, Virginia, USA

The abandoned Valzinco mine, which worked a steeply dipping Kuroko-type massive sulfide deposit in the Virginia Au-pyrite belt, contributed significant metal-laden acid-mine drainage to the Knight's Branch watershed. The host rocks were dominated by metamorphosed felsic volcanic rocks, which offered limited acid-neutralizing potential. The ores were dominated by pyrite, sphalerite, galena, and chalcopyrite, which represented significant acid-generating potential. Acid-base accounting and leaching studies of flotation tailings - the dominant mine waste at the site - indicated that they were acid generating and therefore, should have liberated significant quantities of metals to solution. Field studies of mine drainage from the site confirmed that mine drainage and the impacted stream waters had pH values from 1.1 to 6.4 and exceeded aquatic ecosystem toxicity limits for Fe, Al, Cd, Cu, Pb and Zn. Stable isotope studies of water, dissolved SO42 -, and primary and secondary sulfate and sulfide minerals indicated that two distinct sulfide oxidation pathways were operative at the site: one dominated by Fe(III) as the oxidant, and another by molecular O2 as the oxidant. Reaction-path modeling suggested that geochemical interactions between tailings and waters approached a steady state within about a year. Both leaching studies and geochemical reaction-path modeling provided reasonable predictions of the mine-drainage chemistry.

Applied Geochemistry↗

Utica shale play oil and gas brines: Geochemistry and factors influencing wastewater management

The Utica and Marcellus Shale Plays in the Appalachian Basin are the fourth and first largest natural gas producing plays in the United States, respectively. Hydrocarbon production generates large volumes of brine (“produced water”) that must be disposed of, treated, or reused. Though Marcellus brines have been studied extensively, there are few studies from the Utica Shale Play. This study presents new brine chemical analyses from 16 Utica Shale Play wells in Ohio and Pennsylvania. Results from Na–Cl–Br systematics and stable and radiogenic isotopes suggest that the Utica Shale Play brines are likely residual pore water concentrated beyond halite saturation during the formation of the Ordovician Beekmantown evaporative sequence. The narrow range of chemistry for the Utica Shale Play produced waters (e.g., total dissolved solids = 214–283 g/L) over both time and space implies a consistent composition for disposal and reuse planning. The amount of salt produced annually from the Utica Shale Play is equivalent to 3.4% of the annual U.S. halite production. Utica Shale Play brines have radium activities 580 times the EPA maximum contaminant level and are supersaturated with respect to barite, indicating the potential for surface and aqueous radium hazards if not properly disposed of.

Kentucky, Maryland, New York, Ohio, Pennsylvania, ↗

Design and methods of the Pacific Northwest Stream Quality Assessment (PNSQA), 2015

In 2015, the U.S. Geological Survey (USGS) National Water-Quality Assessment (NAWQA) project conducted the Pacific Northwest Stream Quality Assessment (PNSQA) to investigate stream quality across the western part of the Pacific Northwest. The goal of the PNSQA was to assess the health of streams in the region by characterizing multiple water-quality factors that are stressors to in-stream aquatic life and by evaluating the relation between these stressors and the condition of biological communities. The effects of urbanization and agriculture on stream quality for the Puget Lowland and Willamette Valley Level III Ecoregions were the focus of this regional study. Findings will help inform the public and policymakers about human and environmental factors that are the most critical in affecting stream quality and, thus, provide insights into possible strategies to protect or improve the health of streams in the region. Land-use data were used in the study to identify and select sites within the region that ranged in levels of urban and agricultural development. A total of 88 sites were selected across the region—69 were on streams that explicitly spanned a range of urban land use in their watersheds, 8 were on streams in agricultural watersheds, and 11 were reference sites with little or no development in their watersheds. Depending on the type of land use, sites were sampled for contaminants, nutrients, and sediment for either a 4- or 10-week period during April, May, and June 2015. This water-quality “index period” was immediately followed with an ecological survey of all sites that included stream habitat, benthic algae, benthic macroinvertebrates, and fish. Additionally, streambed sediment was collected during the ecological survey for analysis of sediment chemistry and toxicity testing. This report provides a detailed description of the specific study components and methods of the PNSQA, including (1) surveys of stream habitat and aquatic biota, (2) discrete water sampling, (3) deployment of passive polar organic chemical integrative samplers for pesticides and pharmaceuticals, and (4) sampling of streambed sediment. At selected study sites, toxicity testing of streambed sediment, continuous water-quality monitoring, and daily pesticide sampling also were conducted and are described.

Oregon, Washington↗

Water quality and environmental isotopic analyses of ground-water samples collected from the Wasatch and Fort Union Formations in areas of coalbed methane development — Implications to recharge and ground-water flow, eastern Powder River Basin, Wyoming

Chemical analyses of ground-water samples were evaluated as part of an investigation of lower Tertiary aquifers in the eastern Powder River Basin where coalbed methane is being developed. Ground-water samples were collected from two springs discharging from clinker, eight monitoring wells completed in the Wasatch aquifer, and 13 monitoring or coalbed methane production wells completed in coalbed aquifers. The ground-water samples were analyzed for major ions and environmental isotopes (tritium and stable isotopes of hydrogen and oxygen) to characterize the composition of waters in these aquifers, to relate these characteristics to geochemical processes, and to evaluate recharge and ground-water flow within and between these aquifers. This investigation was conducted in cooperation with the Wyoming State Engineer's Office and the Bureau of Land Management. Water quality in the different aquifers was characterized by major-ion composition. Samples collected from the two springs were classified as calcium-sulfate-type and calcium-bicarbonate-type waters. All ground-water samples from the coalbed aquifers were sodium-bicarbonate-type waters as were five of eight samples collected from the overlying Wasatch aquifer. Potential areal patterns in ionic composition were examined. Ground-water samples collected during this and another investigation suggest that dissolved-solids concentrations in the coalbed aquifers may be lower south of the Belle Fourche River (generally less than 600 milligrams per liter). As ground water in coalbed aquifers flows to the north and northwest away from an inferred source of recharge (clinker in the study area), dissolved-solids concentrations appear to increase. Variation in ionic composition in the vertical dimension was examined qualitatively and statistically within and between aquifers. A relationship between ionic composition and well depth was noted and corroborates similar observations by earlier investigators in the Powder River Basin in both Wyoming and Montana. This relationship results in two different water-quality zones with different characteristics - a shallow zone, comprising the upper part of the Wasatch aquifer, characterized by mixed cation composition and either sulfate or bicarbonate as the dominant anion; and a deeper zone, comprising the lower (deeper) part of the Wasatch aquifer and the underlying coalbed aquifers, characterized by sodium-bicarbonate-type waters. The zonation appears to be related to geochemical processes described by earlier investigators such as dissolution and precipitation of minerals, ion exchange, sulfate reduction, and mixing of waters. Qualitative and statistically significant differences were observed in sulfate concentrations between the coalbed aquifers and the overlying Wasatch aquifer. Ionic composition suggests that bacterially mediated redox processes such as sulfate reduction were probably the dominant geochemical processes in the anaerobic coalbed aquifers. Tritium was used to qualitatively estimate the time of ground-water recharge. Tritium concentrations in both springs suggests that both were recharged after 1952 and contain modern water. Tritium was not detected at concentrations suggestive of modern water in any ground-water samples collected from the coalbed aquifers or in six of eight ground-water samples collected from the overlying Wasatch aquifer. Tritium concentrations in the remaining two wells from the Wasatch aquifer suggest a mixture between submodern (recharged before 1952) and modern water, although the low concentrations suggest that ground water in these two wells have very little modern water. The relative absence of modern water in all aquifers in the study area suggests that recharge processes to these aquifers are probably very slow. Paired d 2 H (deuterium/hydrogen isotopic ratio) and d 18 O (oxygen-18/oxygen-16 isotopic ratio) values for samples collected from the springs and all aquifers are close to the Global Meteoric Water Line, a meteoric water line for North American continental precipitation, and an estimated local meteoric water line, suggesting the water in the aquifers is of meteoric origin. The d 2 H and d 18 O values suggest that the waters were recharged in a colder climate or temperature, mid-latitudes, and mid-continent. In general, the samples do not form separate groups based on aquifer origin; this suggests either intermixing of the waters in the aquifers or that the different aquifers are subject to similar recharge and/or evolutional paths for the water. However, examination of the differences in the values of d 2 H and d 18 O, in combination with major-ion chemistry at three monitoring-well clusters, suggest that changes in the values with depth may represent different timing or sources of recharge to the different aquifers. The areal distribution of d 2 H was examined and an apparent break in the d 2 H along a northwest to southeast trend was observed. In the coalbed aquifers, all but one ground-water sample (collected from the Big George coal bed), show a pattern where the d 2 H values become more negative towards the center of the Powder River Basin and values greater (less negative) than an arbitrary reference value of -140 ‰ (per mil or parts per thousand) were observed near the outcrop area of the Wyodak-Anderson coal zone. In the overlying Wasatch aquifer, the d 2 H values became less negative towards the center of the basin. The values more negative than -140 ‰ are near the outcrop area and the values that are less negative than -140 ‰ are closer to the basin center. It is unclear if this pattern is a result of sample size, different recharge mechanisms, geochemical processes, or if the processes producing these differences are independent or unrecognized. Results of water-quality sampling were compared with selected regulatory and non-regulatory standards as well as commonly-used guidelines for proposed water uses. Dissolved solids was the measure that most frequently exceeded U.S. Environmental Protection Agency public water-supply standards and State of Wyoming domestic-use standards in ground-water samples collected from the Wasatch aquifer and coalbed aquifers. The State of Wyoming agricultural standards (irrigation) for sulfate and dissolved solids were exceeded in some samples collected from the Wasatch aquifer and coalbed aquifers. The State of Wyoming livestock standard for pH was exceeded in some samples collected from the Wasatch aquifer. Water from the Wasatch aquifer ranged from soft to very hard, and water from the coalbed aquifers ranged from moderately hard to very hard. Samples collected from wells completed in both the Wasatch aquifer and coalbed aquifers plotted in a wide range of both sodium- and salinity-hazard classes, but most samples clustered in or near the combined medium-sodium-hazard—high-salinity-hazard classes.

Wyoming↗

Analytical Results for Agricultural Soils Samples from a Monitoring Program Near Deer Trail, Colorado (USA)

Since late 1993, Metro Wastewater Reclamation District of Denver (Metro District, MWRD), a large wastewater treatment plant in Denver, Colorado, has applied Grade I, Class B biosolids to about 52,000 acres of nonirrigated farmland and rangeland near Deer Trail, Colorado, USA. In cooperation with the Metro District in 1993, the U.S. Geological Survey (USGS) began monitoring groundwater at part of this site. In 1999, the USGS began a more comprehensive monitoring study of the entire site to address stakeholder concerns about the potential chemical effects of biosolids applications to water, soil, and vegetation. This more comprehensive monitoring program has recently been extended through 2010. Monitoring components of the more comprehensive study include biosolids collected at the wastewater treatment plant, soil, crops, dust, alluvial and bedrock groundwater, and stream bed sediment. Soils for this study were defined as the plow zone of the dry land agricultural fields - the top twelve inches of the soil column. This report presents analytical results for the soil samples collected at the Metro District farm land near Deer Trail, Colorado, during three separate sampling events during 1999, 2000, and 2002. Soil samples taken in 1999 were to be a representation of the original baseline of the agricultural soils prior to any biosolids application. The soil samples taken in 2000 represent the soils after one application of biosolids to the middle field at each site and those taken in 2002 represent the soils after two applications. There have been no biosolids applied to any of the four control fields. The next soil sampling is scheduled for the spring of 2010. Priority parameters for biosolids identified by the stakeholders and also regulated by Colorado when used as an agricultural soil amendment include the total concentrations of nine trace elements (arsenic, cadmium, copper, lead, mercury, molybdenum, nickel, selenium, and zinc), plutonium isotopes, and gross alpha and beta activity (Colorado Department of Public Health and Environment, Hazardous Materials and Waste Management Division, 1997; Colorado Department of Public Health and Environment,1998; U.S. Environmental Protection Agency, 1993). Since these were the identified priority parameters for the biosolids, the soils have the same set of priority parameters. Although the composite soils' priority analytes have been reported earlier to Metro District, the remaining elemental datasets for both the composite soils samples and selected fields' individual subsamples' data are presented here for the first time. More information about the other monitoring components is presented elsewhere in the literature (http://co.water.usgs.gov/projects/CO406/CO406.html). In general, the objective of each component of the study was to determine whether concentrations of priority parameters (1) were higher than regulatory limits, (2) were increasing with time, and(or) (3) were significantly higher in biosolids-applied areas than in a similar farmed area where biosolids were not applied. The method chosen for sampling the soils proved to be an efficient and reliable representation of the average composition of each field. This was shown by analyzing individual subsamples, averaging the resulting values, and then comparing the values to the composited samples' values. The soil chemistry shows distinct differences between the two sites, most likely due to the different underlying parent material. Biosolids data were used to compile an inorganic-chemical biosolids signature that can be contrasted with the geochemical signature of the agricultural soils for this site. The biosolids signature and an understanding of the geology and hydrology of the site can be used to separate biosolids effects from natural geochemical effects. Elements of particular interest for a biosolids signature after application in the soils include bismuth, copper, silver, mercury, and phosphorus. This signat

Open-File Report↗

Design and methods of the Midwest Stream Quality Assessment (MSQA), 2013

During 2013, the U.S. Geological Survey (USGS) National Water-Quality Assessment Project (NAWQA), in collaboration with the USGS Columbia Environmental Research Center, the U.S. Environmental Protection Agency (EPA) National Rivers and Streams Assessment (NRSA), and the EPA Office of Pesticide Programs assessed stream quality across the Midwestern United States. This Midwest Stream Quality Assessment (MSQA) simultaneously characterized watershed and stream-reach water-quality stressors along with instream biological conditions, to better understand regional stressor-effects relations. The MSQA design focused on effects from the widespread agriculture in the region and urban development because of their importance as ecological stressors of particular concern to Midwest region resource managers. A combined random stratified selection and a targeted selection based on land-use data were used to identify and select sites representing gradients in agricultural intensity across the region. During a 14-week period from May through August 2013, 100 sites were selected and sampled 12 times for contaminants, nutrients, and sediment. This 14-week water-quality “index” period culminated with an ecological survey of habitat, periphyton, benthic macroinvertebrates, and fish at all sites. Sediment was collected during the ecological survey for analysis of sediment chemistry and toxicity testing. Of the 100 sites, 50 were selected for the MSQA random stratified group from 154 NRSA sites planned for the region, and the other 50 MSQA sites were selected as targeted sites to more evenly cover agricultural and urban stressor gradients in the study area. Of the 50 targeted sites, 12 were in urbanized watersheds and 21 represented “good” biological conditions or “least disturbed” conditions. The remaining 17 targeted sites were selected to improve coverage of the agricultural intensity gradient or because of historical data collection to provide temporal context for the study. This report provides a detailed description of the MSQA study components, including surveys of ecological conditions, routine water sampling, deployment of passive polar organic compound integrative samplers, and stream sediment sampling at all sites. Component studies that were completed to provide finer scale temporal data or more extensive analysis at selected sites, included continuous water-quality monitoring, daily pesticide sampling, laboratory and in-stream water toxicity testing efforts, and deployment of passive suspended-sediment samplers.

Illinois, Indiana, Iowa, Kansas, Kentucky, Michiga↗

Ground-water quality data in the Central Eastside San Joaquin Basin 2006: Results from the California GAMA program

Ground-water quality in the approximately 1,695-square-mile Central Eastside study unit (CESJO) was investigated from March through June 2006 as part of the Statewide Basin Assessment Project of the Groundwater Ambient Monitoring and Assessment (GAMA) Program. The GAMA Statewide Basin Assessment project was developed in response to the Groundwater Quality Monitoring Act of 2001 and is being conducted by the California State Water Resources Control Board (SWRCB) in collaboration with the U.S. Geological Survey (USGS) and the Lawrence Livermore National Laboratory (LLNL). The study was designed to provide a spatially unbiased assessment of raw ground-water quality within CESJO, as well as a statistically consistent basis for comparing water quality throughout California. Samples were collected from 78 wells in Merced and Stanislaus Counties. Fifty-eight of the 78 wells were selected using a randomized grid-based method to provide statistical representation of the study unit (grid wells). Twenty of the wells were selected to evaluate changes in water chemistry along selected lateral or vertical ground-water flow paths in the aquifer (flow-path wells). The ground-water samples were analyzed for a large number of synthetic organic constituents [volatile organic compounds (VOCs), gasoline oxygenates and their degradates, pesticides and pesticide degradates], constituents of special interest [perchlorate, N-nitrosodimethylamine (NDMA), and 1,2,3-trichloropropane (1,2,3-TCP)], inorganic constituents that can occur naturally [nutrients, major and minor ions, and trace elements], radioactive constituents, and microbial indicators. Naturally occurring isotopes [tritium, carbon-14, and uranium isotopes and stable isotopes of hydrogen, oxygen, nitrogen, sulfur, and carbon], and dissolved noble and other gases also were measured to help identify the source and age of the sampled ground water. Quality-control samples (blanks, replicates, samples for matrix spikes) were collected for approximately one-sixth of the wells, and the results for these samples were used to evaluate the quality of the data for the ground-water samples. Assessment of the quality-control results showed that the environmental data were of good quality, with low bias and low variability, and resulted in censoring of less than 0.3 percent of the detections found in ground-water samples. This study did not attempt to evaluate the quality of water delivered to consumers; after withdrawal from the ground, water typically is treated, disinfected, and (or) 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 health-based thresholds established by the U.S. Environmental Protection Agency (USEPA) and California Department of Public Health (CADPH) and thresholds established for aesthetic concerns (secondary maximum contaminant levels, SMCL-CA) by CADPH. VOCs and pesticides were detected in approximately half of the grid wells, and all detections in samples from CESJO wells were below health-based thresholds. All detections of nutrients and major elements in grid wells also were below health-based thresholds. Most detections of constituents of special interest, trace elements, and radioactive constituents in samples from grid wells were below health-based thresholds. Exceptions included two detections of arsenic that were above the USEPA maximum contaminant level (MCL-US), one detection of lead above the USEPA action level (AL-US), and one detection of vanadium and three detections of 1,2,3-TCP that were above the CADPH notification levels (NL-CA). All detections of radioactive constituents were below health-based thresholds, although fourteen samples had activities of radon-222 above the lower proposed MCL-US. Most of the samples from CESJO grid wells had concentrations of major elements, total dissolved solids, and trace elements below the non-enforceable thresholds set for aesthetic concerns. A few samples contained manganese or total dissolved solids at concentrations above the SMCL-CA thresholds.

California↗

Simulation of nitrogen attenuation in a subterranean estuary, representative of the southern coast of Cape Cod, Massachusetts

A two-dimensional model was developed by the U.S. Geological Survey, in cooperation with the U.S. Environmental Protection Agency, to assess flow and chemical reaction associated with groundwater discharge through the subterranean estuary representative of coastal salt ponds of southern Cape Cod. The model simulated both the freshwater and saltwater flow systems and accounted for density-dependent flow, tidal fluctuation, and chemical reactivity among oxygen, dissolved organic carbon, nitrate, and ammonia. Not previously incorporated into one model, the interaction of these effects can now be simulated in the subterranean estuary context. An analysis of the flow system under mean-tide conditions was conducted first to provide the initial conditions for a subsequent analysis that included the effects of tidal fluctuations. Tidal fluctuations were simulated with a repeated couplet that represented a high tide-low tide sequence and alternating locations of head-dependent flux boundaries placed along the simulated seabed, above and below the levels of the respective high and low tides. Boundary conditions for chemical species included nitrate in recharge, and oxygen and organic matter (including organic nitrogen) in infiltrating solutions of head-dependent boundaries. Reaction chemistry was limited to oxidative degradation of organic matter (including remineralization of ammonia) with oxygen or nitrate as electron acceptors and nitrification of ammonia in the presence of oxygen. Simulations using the SEAWAT-2000 computer program resulted in two mixing zones-between freshwater and saltwater in a deep saltwater wedge and in an intertidal salt zone, which results from tidal fluctuation. The mixing zones are the principal locations where nitrogen attenuation reactions occurred-between organic matter in the saltwater zones of the aquifer and nitrate in the freshwater zone. In mean-tide PHT3D model simulations, 15 percent of nitrogen that is recharged was attenuated because of reaction with dissolved organic matter, a denitrification reaction that reduces nitrate to nitrogen gas. When a fluctuating tide was simulated, the amount of recharged nitrogen that was denitrified increased to 20 percent. Chemical reaction was controlled by the rate of mixing of freshwater and saltwater, which contained the reactants nitrate and dissolved organic matter, respectively, necessary for nitrogen attenuation reactions to take place. Reaction occurred in both the deep saltwater wedge and in an increased denitrification. However, mixing may also have been enhanced partly by numerical dispersion.

Massachusetts↗

Contaminants of emerging concern presence and adverse effects in fish: A case study in the Laurentian Great Lakes

The Laurentian Great Lakes are a valuable natural resource that is affected by contaminants of emerging concern (CECs), including sex steroid hormones, personal care products, pharmaceuticals, industrial chemicals, and new generation pesticides. However, little is known about the fate and biological effects of CECs in tributaries to the Great Lakes. In the current study, 16 sites on three rivers in the Great Lakes basin (Fox, Cuyahoga, and Raquette Rivers) were assessed for CEC presence using polar organic chemical integrative samplers (POCIS) and grab water samplers. Biological activity was assessed through a combination of in vitro bioassays (focused on estrogenic activity) and in vivo assays with larval fathead minnows. In addition, resident sunfish, largemouth bass, and white suckers were assessed for changes in biological endpoints associated with CEC exposure. CECs were present in all water samples and POCIS extracts. A total of 111 and 97 chemicals were detected in at least one water sample and POCIS extract, respectively. Known estrogenic chemicals were detected in water samples at all 16 sites and in POCIS extracts at 13 sites. Most sites elicited estrogenic activity in bioassays. Ranking sites and rivers based on water chemistry, POCIS chemistry, or total in vitro estrogenicity produced comparable patterns with the Cuyahoga River ranking as most and the Raquette River as least affected by CECs. Changes in biological responses grouped according to physiological processes, and differed between species but not sex. The Fox and Cuyahoga Rivers often had significantly different patterns in biological response Our study supports the need for multiple lines of evidence and provides a framework to assess CEC presence and effects in fish in the Laurentian Great Lakes basin.

Environmental Pollution↗

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↗

External quality assurance project report for the National Atmospheric Deposition Program’s National Trends Network and Mercury Deposition Network, 2017–18

The U.S. Geological Survey (USGS) Precipitation Chemistry Quality Assurance project (PCQA) operated five distinct programs to provide external quality-assurance monitoring for the National Atmospheric Deposition Program’s (NADP) National Trends Network and Mercury Deposition Network during 2017–18. The National Trends Network programs included (1) a field audit program to evaluate sample contamination and stability, (2) an interlaboratory comparison program to evaluate analytical laboratory performance, and (3) a colocated sampler program to evaluate variability attributed to automated precipitation samplers. The Mercury Deposition Network programs include the (4) system blank program and (5) an interlaboratory comparison program. The results indicate consistently low levels of sample contamination, generally strong analytical laboratory performance, and low overall variability in concentration data imparted by field equipment. The NADP operations moved from its 40-year home at the Illinois State Water Survey to the Wisconsin State Laboratory of Hygiene in June 2018. The PCQA programs were modified and (or) temporarily curtailed during the transition in 2018. Bias and variability of sample analysis results were evaluated for the two Central Analytical Laboratories, and ongoing monitoring will be helpful to differentiate true environmental signals from the effects of changing laboratory conditions and performance. Results of quality assurance sample analyses are provided to document that NADP data continue to be of sufficient quality for the analysis of spatial distributions and time trends for chemical constituents in wet deposition.

Scientific Investigations Report↗

Normalized rare earth elements in water, sediments, and wine: identifying sources and environmental redox conditions

The concentrations of the rare earth elements (REE) in surface waters and sediments, when normalized on an element-by-element basis to one of several rock standards and plotted versus atomic number, yield curves that reveal their partitioning between different sediment fractions and the sources of those fractions, for example, between terrestrial-derived lithogenous debris and seawater-derived biogenous detritus and hydrogenous metal oxides. The REE of ancient sediments support their partitioning into these same fractions and further contribute to the identification of the redox geochemistry of the sea water in which the sediments accumulated. The normalized curves of the REE that have been examined in several South American wine varietals can be interpreted to reflect the lithology of the bedrock on which the vines may have been grown, suggesting limited fractionation during soil development.

American Journal of Analytical Chemistry↗

Petrology and chemistry of Permian coals from the Paraná Basin: 1. Santa Terezinha, Leão-Butiá and Candiota Coalfields, Rio Grande do Sul, Brazil

The current paper presents results on petrological and geochemical coal seam characterization in Permian coal-bearing strata from the Paraná Basin, southern Brazil. Sequence stratigraphic analysis shows that peat accumulation in Permian time was closely linked to transgressive/regressive cycles, with peat accumulation occurring in a predominantly back barrier/lagoonal setting. Coal petrographic analysis indicates subbituminous coals at Candiota and Leão-Butiá and high volatile bituminous coals at Santa Terezinha, where locally the coal seams are thermally altered by volcanic intrusions. Petrographic composition is highly variable, with seams at Candiota and Santa Terezinha frequently enriched in inertinite. Chemical analyses indicate that all coals are mineral matter-rich (mean 49.09 wt.%), with SiO 2 and Al 2 O 3 dominating as determined by ICP-AES. Quartz is also the predominant mineral detected by X-ray diffraction, where it is associated with feldspar, kaolinite and hematite and iron-rich carbonates. The results from Scanning Electron Microscopy are broadly consistent with the bulk chemical and mineralogical analysis. Quartz and clays are common in all samples analyzed. Other minerals observed were, amongst others, carbonates (calcite, siderite, ankerite), pyrite, monazite, kaolinite, barite, sphalerite, rutile and quartz of volcanic origin. The distribution of trace elements is well within the range typical for coal basins of other areas despite the fact that the Paraná Basin coals are very high in ash yields. The average concentrations for elements of environmental concern (As, B, Be, Cd, Co, Cr, Cu, Hg, Li, Mn, Mo, Ni, Pb, Sb, Se, Tl, U, V, Zn) are similar to or less than the mean values for U.S. coal. However, considered on an equal energy basis, Paraná Basin coals will produce in combustion 5 to 10 times the amount of most elements compared to an equal weight US coal. Concentrations of major and trace elements, such as Fe, B and S, appear to be controlled by depositional setting, with increasing values in coal seams overlain by brackish/marine strata. Hierarchical cluster analysis identified three groups of major minerals and seven groups of trace elements based on similarity levels. On a regional scale, the coalfields can be separated by the differences in rank (Candiota and Leão-Butiá versus Santa Terezinha) and by applying discriminant analysis based on 4 trace elements (Li, As, Sr, Sb). Highest Rb and Sr values occur at Candiota and are linked to syngenetic volcanism of the area, whereas high Y and Sr values at Santa Terezinha can be related to the frequent diabase intrusions in that area.

International Journal of Coal Geology↗