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At least 469 records · Page 26Linked to original sources

Geochemistry of amino acids in shells of the clam Saxidomus

Concentrations of amino acids and their corresponding d l "> dl enantiomeric ratios have been measured in shells of the bivalve mollusk Saxidomus from eleven localities, ranging in age from modern to probably more than 500,000 yr, along the Pacific coast of North America. Natural logarithms of amino acid concentrations correlate well with d l "> dl ratios, and the relationship provides a possible guide to the selection of fossils for use in amino acid dating. The relative order of the extents of racemization of amino acids at any given time appears to change with increasing sample age. Application of the amino acid dating method to shells from Whidbey Island, Washington, yields an age of about 80,000 yr, in contrast to the previously determined radiocarbon age of 36,000 yr which was measured on some shell carbonate and considered a minimum age. The amino acid age is compatible with the geologic record in the area.

Alaska, Washington↗

Analyzing cloud base at local and regional scales to understand tropical montane cloud forest vulnerability to climate change

The degree to which cloud immersion provides water in addition to rainfall, suppresses transpiration, and sustains tropical montane cloud forests (TMCFs) during rainless periods is not well understood. Climate and land use changes represent a threat to these forests if cloud base altitude rises as a result of regional warming or deforestation. To establish a baseline for quantifying future changes in cloud base, we installed a ceilometer at 100 m altitude in the forest upwind of the TMCF that occupies an altitude range from ∼ 600 m to the peaks at 1100 m in the Luquillo Mountains of eastern Puerto Rico. Airport Automated Surface Observing System (ASOS) ceilometer data, radiosonde data, and Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation (CALIPSO) satellite data were obtained to investigate seasonal cloud base dynamics, altitude of the trade-wind inversion (TWI), and typical cloud thickness for the surrounding Caribbean region. Cloud base is rarely quantified near mountains, so these results represent a first look at seasonal and diurnal cloud base dynamics for the TMCF. From May 2013 to August 2016, cloud base was lowest during the midsummer dry season, and cloud bases were lower than the mountaintops as often in the winter dry season as in the wet seasons. The lowest cloud bases most frequently occurred at higher elevation than 600 m, from 740 to 964 m. The Luquillo forest low cloud base altitudes were higher than six other sites in the Caribbean by ∼ 200–600 m, highlighting the importance of site selection to measure topographic influence on cloud height. Proximity to the oceanic cloud system where shallow cumulus clouds are seasonally invariant in altitude and cover, along with local trade-wind orographic lifting and cloud formation, may explain the dry season low clouds. The results indicate that climate change threats to low-elevation TMCFs are not limited to the dry season; changes in synoptic-scale weather patterns that increase frequency of drought periods during the wet seasons (periods of higher cloud base) may also impact ecosystem health.

Atmospheric Chemistry and Physics↗

Predicting CH4 adsorption capacity of microporous carbon using N2 isotherm and a new analytical model

A new analytical pore size distribution (PSD) model was developed to predict CH4 adsorption (storage) capacity of microporous adsorbent carbon. The model is based on a 3-D adsorption isotherm equation, derived from statistical mechanical principles. Least squares error minimization is used to solve the PSD without any pre-assumed distribution function. In comparison with several well-accepted analytical methods from the literature, this 3-D model offers relatively realistic PSD description for select reference materials, including activated carbon fibers. N2 and CH4 adsorption data were correlated using the 3-D model for commercial carbons BPL and AX-21. Predicted CH4 adsorption isotherms, based on N2 adsorption at 77 K, were in reasonable agreement with the experimental CH4 isotherms. Modeling results indicate that not all the pores contribute the same percentage Vm/Vs for CH4 storage due to different adsorbed CH4 densities. Pores near 8-9 A?? shows higher Vm/Vs on the equivalent volume basis than does larger pores.

ACS Division of Fuel Chemistry, Preprints↗

Widespread detection of N, N-diethyl-m-toluamide in U.S. streams: Comparison with concentrations of pesticides, personal care products, and other organic wastewater compounds

One of the most frequently detected organic chemicals in a nationwide study concerning the effects of wastewater on stream water quality conducted in the year 2000 was the widely used insect repellant N , N -diethyl- m -toluamide (DEET). It was detected at levels of 0.02 μg/L or greater in 73% of the stream sites sampled, with the selection of sampling sites being biased toward streams thought to be subject to wastewater contamination (i.e., downstream from intense urbanization and livestock production). Although DEET frequently was detected at all sites, the median concentration was low (0.05 μg/L). The highest concentrations of DEET were found in streams from the urban areas (maximum concentration, 1.1 μg/L). The results of the present study suggest that the movement of DEET to streams through wastewater-treatment systems is an important mechanism that might lead to the exposure of aquatic organisms to this chemical.

Environmental Toxicology and Chemistry↗

Catalytic determination of vanadium in water

A kinetic determination of V(V) as a catalyst was spectrophotometrically performed by using the indicator reaction of Gallamine blue (GB + ) and bromate at pH 2.0. The reaction was followed by measuring absorbance change for a fixed-time of 3 min at 537 nm. The variables such as reagent concentration, pH, buffer concentration, ionic strength and temperature were optimized to improve the selectivity and sensitivity. Under the optimized conditions, the determination of V(V) was performed in the range 1–100 μg L −1 with limits of detection and quantification of 0.31 and 0.94 μg L −1 . The developed kinetic method is sufficiently sensitive, selective and simple. It was successfully applied to the speciative determination of total V and inorganic dissolved vanadium species, V(V) and V(IV) in environmental water samples. The oxidizing property of permanganate is used to differentiate between V(IV) and V(V) species. The V(IV) content was found by subtracting the V(V) content from those of total V. The recovery is above 95% for V(V) spiked samples. Additionally, the accuracy was validated by analysis of a certified water sample, CRM TMDA-53.3, and the results were in good agreement with the certified value.

Analytical Chemistry↗

Summary of the San Juan structural basin regional aquifer-system analysis, New Mexico, Colorado, Arizona, and Utah

Ground-water resources are the only source of water in most of the San Juan structural basin and are mainly used for municipal, industrial, domestic, and stock purposes. Industrial use increased dramatically during the late 1970's and early 1980's because of increased exploration and development of uranium and coal resources. The San Juan structural basin is a northwest-trending, asymmetric structural depression at the eastern edge of the Colorado Plateau. The basin contains as much as 14,000 feet of sedimentary rocks overlying a Precambrian basement complex. The sedimentary rocks dip basinward from the basin margins toward the troughlike structural center, or deepest part of the basin. Rocks of Triassic age were selected as the lower boundary for the study. The basin is well defined by structural boundaries in many places with structural relief of as much as 20,000 feet reported. Faulting is prevalent in parts of the basin with displacement of several thousand feet along major faults. The regional aquifers in the basin generally are coincident with the geologic units that have been mapped. Data on the hydrologic properties of the regional aquifers are minimal. Most data were collected on those aquifers associated with uranium and coal resource production. These data are summarized in table format in the report. The regional flow system throughout most of the basin has been affected by the production of oil or gas and subsequent disposal of produced brine. To date more than 26,000 oil- or gas- test holes have been drilled in the basin, the majority penetrating no deeper than the bottom of the Cretaceous rocks. The general water chemistry of the regional aquifers is based on available data. The depositional environments are the major factor controlling the quality of water in the units. The dominant ions are generally sodium, bicarbonate, and sulfate. A detailed geochemical study of three sandstone aquifers--Morrison, Dakota, and Gallup--was undertaken in the northwestern part of the study area. Results of this study indicate that water chemistry changed in individual wells over short periods of time, not expected in a regional flow system. The chemistry of the water is affected by mixing of recharge, ion filtrate, or very dilute ancient water, and by leakage of saline water. The entire system of ground-water flow and its controlling factors has been defined as the conceptual model. A steady-state, three-dimensional ground-water flow model was constructed to simulate modern predevelopment flow in the post-Jurassic rocks of the regional flow system. In the ground-water flow model, 14 geologic units or combinations of geologic units were considered to be regional aquifers, and 5 geologic units or combinations of geologic units were considered to be regional confining units. The model simulated flow in 12 layers (hydrostratigraphic units) and used harmonic-mean vertical leakance to indirectly simulate aquifer connection across 3 other hydrostratigraphic confining units in addition to coupling the 12 units.

Water-Resources Investigations Report↗

Sediment studies in the Assabet River, central Massachusetts, 2003

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

Scientific Investigations Report↗

Performance and application of a fluidized bed limestone reactor designed for control of alkalinity, hardness and pH at the Warm Springs Regional Fisheries Center

Springs serving the Warm Springs Regional Fisheries Center, Warm Springs, Georgia, have pH, alkalinity, and hardness levels thatlie under the range required for successful fish propagation while free CO 2 is well above allowable targets. We evaluate a pretreatment process that exploits limestone’s (CaCO 3 ) ability to react away hydrogen ions (H + ) and carbon dioxide (CO 2 ) while increasing alkalinity (HCO 3 − ) and calcium (Ca2+) concentrations, i.e. CaCO 3 + H + ↔ HCO 3 − + Ca 2+ CaCO 3 + CO 2 + H 2 O ↔ Ca 2+ + 2HCO 3 − Limestone sand was tested in both pilot and full scale fluidized bed reactors (CycloBio®). We first established the bed expansion characteristics of three commercial limestone products then evaluated the effect of hydraulic flux and bed height on dissolution rate of a single selected product (Type A16 × 120). Pilot scale testing at 18C showed limestone dissolution rates were relatively insensitive to flux over the range 1.51–3.03 m 3 /min/m 2 but were sensitive (P < 0.001; R 2 = 0.881) to changes in bed height (BH, cm) over the range 83–165 cm following the relation: (Alkalinity, mg/L) = 123.51 − (3788.76 (BH)). Differences between filtered and non-filtered alkalinity were small(P > 0.05) demonstrating that limestone was present in the reactor effluent primarily in the form of dissolved Ca(HCO 3 ) 2 . Effluent alkalinity exceeded our target level of 50 mg/L under most operating conditions evaluated with typical pilot scale values falling within the range of 90–100 mg/L despite influent concentrations of about 4 mg/L. Concurrently, CO 2 fell from an average of 50.6 mg/L to 8.3 mg/L (90%), providing for an increase in pH from 5.27 to a mean of 7.71. The ability of the test reactor to provide changes in water chemistry variables that exceeded required changes allowed for a dilution ratio of 0.6. Here, alkalinity still exceeded 50 mg/L, the CO 2 concentration remained well below our limit of 20 mg/L (15.4 mg/L) and the pH was near neutral (7.17). Applying the dilution ratio of 0.6 in a full scale treatment plant at the site reduced by 40% the volume of spring water that is directed through each of three parallel reactors that combined react away 49,000 kg of limestone/yr.

Aquacultural Engineering↗

Water-chemistry data collected in and near Kaloko-Honokohau National Historical Park, Hawaii, 2012–2014

Kaloko-Honokōhau National Historical Park (KAHO) on western Hawaiʻi was established in 1978 to preserve, interpret, and perpetuate traditional Native Hawaiian culture and activities, including the preservation of a variety of culturally and ecologically significant water resources that are vital to this mission. KAHO water bodies provide habitat for 1 threatened, 11 endangered, and 3 candidate threatened or endangered species. These habitats are sustained by, and in the case of ʻAimakapā Fishpond and the anchialine pools, entirely dependent on, groundwater from the Keauhou aquifer system. Development of inland impounded groundwater in the Keauhou aquifer system may affect the coastal freshwater-lens system on which KAHO depends, if the inland impounded-groundwater and coastal freshwater-lens systems are hydrologically connected. This report documents water-chemistry results from a U.S. Geological Survey study that collected and analyzed water samples from 2012 to 2014 from 25 sites in and near KAHO to investigate potential geochemical indicators in water that might indicate the presence or absence of a hydrologic connection between the inland impounded-groundwater and coastal freshwater-lens systems in the area. Samples were collected under high-tide and low-tide conditions for KAHO sites, and in dry-season and wet-season conditions for all sites. Samples were collected from two ocean sites, two fishponds, three anchialine pools, and three monitoring wells within KAHO. Two additional nearshore wells were sampled on property adjacent to and north of KAHO. Additional samples from the freshwater-lens system were collected from six inland wells located upslope from KAHO, including three production wells. Seven production wells in the inland impounded-groundwater system also were sampled. Water samples were analyzed for major ions, selected trace elements, rare-earth elements, strontium-isotope ratio, and stable isotopes of water. Precipitation samples from five sites were collected roughly along a transect upslope from KAHO. All precipitation samples were analyzed for stable isotopes of water and some precipitation samples were analyzed for rare-earth and selected trace elements.

Hawai'i↗

Selective precipitation of thorium iodate from a tartaric acid-hydrogen peroxide medium application to rapid spectrophotometric determination of thorium in Silicate Rocks and in Ores

This paper presents a selective iodate separation of thorium from nitric acid medium containing d-tartaric acid and hydrogen peroxide. The catalytic decomposition of hydrogen peroxide is prevented by the use of 8quinolinol. A few micrograms of thorium are separated sufficiently clean from 30 mg. of such oxides as cerium, zirconium, titanium, niobium, tantalum, scandium, or iron with one iodate precipitation to allow an accurate determination of thorium with the thoronmesotartaric acid spectrophotometric method. The method is successful for the determination of 0.001% or more of thorium dioxide in silicate rocks and for 0.01% or more in black sand, monazite, thorite, thorianite, eschynite, euxenite, and zircon.

Analytical Chemistry↗

Metal Mixture Modeling Evaluation project: 2. Comparison of four modeling approaches

As part of the Metal Mixture Modeling Evaluation (MMME) project, models were developed by the National Institute of Advanced Industrial Science and Technology (Japan), the U.S. Geological Survey (USA), HDR⎪HydroQual, Inc. (USA), and the Centre for Ecology and Hydrology (UK) to address the effects of metal mixtures on biological responses of aquatic organisms. A comparison of the 4 models, as they were presented at the MMME Workshop in Brussels, Belgium (May 2012), is provided herein. Overall, the models were found to be similar in structure (free ion activities computed by WHAM; specific or non-specific binding of metals/cations in or on the organism; specification of metal potency factors and/or toxicity response functions to relate metal accumulation to biological response). Major differences in modeling approaches are attributed to various modeling assumptions (e.g., single versus multiple types of binding site on the organism) and specific calibration strategies that affected the selection of model parameters. The models provided a reasonable description of additive (or nearly additive) toxicity for a number of individual toxicity test results. Less-than-additive toxicity was more difficult to describe with the available models. Because of limitations in the available datasets and the strong inter-relationships among the model parameters (log KM values, potency factors, toxicity response parameters), further evaluation of specific model assumptions and calibration strategies is needed.

Environmental Toxicology and Chemistry↗

Limited occurrence of denitrification in four shallow aquifers in agricultural areas of the United States

The ability of natural attenuation to mitigate agricultural nitrate contamination in recharging aquifers was investigated in four important agricultural settings in the United States. The study used laboratory analyses, field measurements, and flow and transport modeling for monitoring well transects (0.5 to 2.5 km in length) in the San Joaquin watershed, California, the Elkhorn watershed, Nebraska, the Yakima watershed, Washington, and the Chester watershed, Maryland. Ground water analyses included major ion chemistry, dissolved gases, nitrogen and oxygen stable isotopes, and estimates of recharge date. Sediment analyses included potential electron donors and stable nitrogen and carbon isotopes. Within each site and among aquifer-based medians, dissolved oxygen decreases with ground water age, and excess N 2 from denitrification increases with age. Stable isotopes and excess N 2 imply minimal denitrifying activity at the Maryland and Washington sites, partial denitrification at the California site, and total denitrification across portions of the Nebraska site. At all sites, recharging electron donor concentrations are not sufficient to account for the losses of dissolved oxygen and nitrate, implying that relict, solid phase electron donors drive redox reactions. Zero-order rates of denitrification range from 0 to 0.14 μmol N L −1 d −1 , comparable to observations of other studies using the same methods. Many values reported in the literature are, however, orders of magnitude higher, which is attributed to a combination of method limitations and bias for selection of sites with rapid denitrification. In the shallow aquifers below these agricultural fields, denitrification is limited in extent and will require residence times of decades or longer to mitigate modern nitrate contamination.

Journal of Environmental Quality↗

Comparison of methods for determining streamflow requirements for aquatic habitat protection at selected sites on the Assabet and Charles Rivers, Eastern Massachusetts, 2000-02

Four methods used to determine streamflow requirements for habitat protection at nine critical riffle reaches in the Assabet River and Charles River Basins were compared. The methods include three standard setting techniques?R2Cross, Wetted Perimeter, and Tennant?and a diagnostic method, the Range of Variability Approach. One study reach is on the main stem of the Assabet River, four reaches are on tributaries to the Assabet River (Cold Harbor Brook, Danforth Brook, Fort Meadow Brook, and Elizabeth Brook), three are on the main stem of the Charles River, and one is on a tributary to the Charles River (Mine Brook). The strength of the R2Cross and Wetted-Perimeter methods is that they may be applied at ungaged locations whereas the Tennant method and the Range of Variability Approach require a period of streamflow record for analysis. Fish community assessments conducted at or near riffle sites in flowing reaches of the Assabet River and Charles River Basins were used to indicate ecological conditions. The fish communities in the main stem and tributary reaches of both the Assabet and Charles River Basins indicated degraded aquatic ecosystems. However, the degree of degradation differs between the two basins. The extreme predominance of tolerant, generalist species in the Charles River fish community demon-strates the cumulative impacts of flow, habitat, and water-chemistry degradation, combined with the effects of nearby impoundments and changing land use. The range of discharges for nine ungaged riffle reaches defined by the median R2Cross 3-of-3 criteria, R2Cross 2-of-3 criteria, and Wetted-Perimeter streamflow requirements, was 0.86 cubic foot per second per square mile, 0.18 cubic foot per second per square mile, and 0.23 cubic foot per second per square mile, respectively. Application of R2Cross and Wetted-Perimeter methods to sites with altered streamflows or at sites that are riffles only at low to moderate flows can result in a greater variability of streamflow requirements than would result if the methods were applied to riffles on natural channels with unaltered streamflows. The R2Cross 2-of-3 criteria and the Wetted-Perimeter streamflow requirements for the Assabet and Charles River sites show narrower interquartile ranges and lower median streamflow requirements than for 10 index streamflow-gaging stations in southern New England. This is especially evident for the R2Cross 2-of-3 criteria and Wetted-Perimeter results that were close to half of the flow requirements determined at the 10 southern New England stations. The R2Cross and Wetted-Perimeter methods were also compared to the Range of Variability Approach analysis and the Tennant Method. The median R2Cross 3-of-3 criteria streamflow requirement for the nine riffles is close to the 75th percentile of the monthly mean flows during the summer low-flow period from six streamflow-gaging stations near the Assabet and Charles River Basins having mostly unaltered flow. This streamflow requirement is close to the median Tennant 40-percent-flow requirement for good habitat condi-tion for the same six nearby stations. The R2Cross 2-of-3 criteria and Wetted-Perimeter results were less than the 25th-percentile of monthly mean flows during the summer months for the six stations. These streamflow requirements are in the poor habitat range as indicated by a Tennant analysis of the same six stations. These comparisons indicate that the R2Cross and Wetted-Perimeter methods underestimate streamflow requirements when applied to sites in smaller drainage areas and channels that are runs at higher flows.

Scientific Investigations Report↗

Investigation of water quality and aquatic-community structure in Village and Valley Creeks, City of Birmingham, Jefferson County, Alabama, 2000-01

The U.S. Geological Survey conducted a 16-month investigation of water quality, aquatic-community structure, bed sediment, and fish tissue in Village and Valley Creeks, two urban streams that drain areas of highly intensive residential, commercial, and industrial land use in Birmingham, Alabama. Water-quality data were collected between February 2000 and March 2001 at four sites on Village Creek, three sites on Valley Creek, and at two reference sites near Birmingham—Fivemile Creek and Little Cahaba River, both of which drain less-urbanized areas. Stream samples were analyzed for major ions, nutrients, fecal bacteria, trace and major elements, pesticides, and selected organic constituents. Bed-sediment and fish-tissue samples were analyzed for trace and major elements, pesticides, polychlorinated biphenyls, and additional organic compounds. Aquatic-community structure was evaluated by conducting one survey of the fish community and in-stream habitat and two surveys of the benthic-invertebrate community. Bed-sediment and fish-tissue samples, benthic-invertebrates, and habitat data were collected between June 2000 and October 2000 at six of the nine water-quality sites; fish communities were evaluated in April and May 2001 at the six sites where habitat and benthic-invertebrate data were collected. The occurrence and distribution of chemical constituents in the water column and bed sediment provided an initial assessment of water quality in the streams. The structure of the aquatic communities, the physical condition of the fish, and the chemical analyses of fish tissue provided an indication of the cumulative effects of water quality on the aquatic biota. Water chemistry was similar at all sites, characterized by strong calcium-bicarbonate component and magnesium components. Median concentrations of total nitrogen and total phosphorus were highest at the headwaters of Valley Creek and lowest at the reference site on Fivemile Creek. In Village Creek, median concentrations of nitrite and ammonia increased in a downstream direction. In Valley Creek, median concentrations of nitrate, nitrite, ammonia, organic nitrogen, suspended phosphorus, and orthophosphate decreased in a downstream direction. Median concentrations of Escherichia coli and fecal coliform bacteria were highest at the most upstream site of Valley Creek and lowest at the reference site on Fivemile Creek. Concentrations of enterococci exceeded the U.S. Environmental Protection Agency criterion in 80 percent of the samples; concentrations of Escherichia coli exceeded the criterion in 56 percent of the samples. Concentrations of bacteria at the downstream sites on Village and Valley Creeks were elevated during high flow rather than low flow, indicating the presence of nonpoint sources. Surface-water samples were analyzed for chemical compounds that are commonly found in wastewater and urban runoff. The median number of wastewater indicators was highest at the most upstream site on Valley Creek and lowest at the reference site on Fivemile Creek. Concentrations of total recoverable cadmium, copper, lead, and zinc in surface water exceeded acute and chronic aquatic life criteria in up to 24 percent of the samples that were analyzed for trace and major elements. High concentrations of trace and major elements in the water column were detected most frequently during high flow, indicating the presence of nonpoint sources. Of the 24 pesticides detected in surface water, 17 were herbicides and 7 were insecticides. Atrazine, simazine, and prometon were the most commonly detected herbicides; diazinon, chlorpyrifos, and carbaryl were the most commonly detected insecticides. Concentrations of atrazine, carbaryl, chlorpyrifos, diazinon, and malathion periodically exceeded criteria for the protection of aquatic life. Trace-element priority pollutants, pesticides, and other organic compounds were detected in higher concentrations in bed sediment at the Village and Valley Creek sites than at the reference site on Fivemile Creek. Bed-sediment concentrations of chromium, copper, lead, mercury, and silver were highest at the most upstream site on Valley Creek; and concentrations of cadmium, nickel, selenium, and zinc were highest at the second downstream site on Village Creek. Bed-sediment concentrations of arsenic, cadmium, chromium, copper, lead, mercury, nickel, selenium, and zinc from the Village and Valley Creek sites exceeded median concentrations observed nationwide. Concentrations of cadmium, selenium, and zinc were highest in fish-liver tissue samples collected from the second downstream site on Village Creek — concentrations of copper and mercury in fish-liver samples were highest at the most downstream site on Village Creek. The highest total concentration of organic compounds detected in bed-sediment samples occurred at the most upstream site on Valley Creek and the lowest total concentration occurred at Fivemile Creek. In Village Creek, concentrations of 75 percent of the detected organic compounds increased in a downstream direction; in Valley Creek, concentrations of about 70 percent of the detected organic compounds decreased in a downstream direction. Concentrations of 10 organic compounds in bed-sediment samples, including chlordane and p,p'-DDE, exceeded levels considered harmful to aquatic organisms at sites on Village and Valley Creeks. Concentrations of dieldrin, chlordane, and polychlorinated biphenyls in fish-tissue samples exceeded National Academy of Science/National Academy of Engineering guidelines for the protection of fish-eating wildlife. Fish and benthic-invertebrate community structure differed between Village and Valley Creeks and the reference streams. Multiple lines of evidence, including the richness and density of benthic invertebrates as well as fish-community structure, indicate that the aquatic community in Village Creek is similar to that of Valley Creek, but that the integrity of the aquatic communities in both creeks is poor in comparison to that observed at the two reference sites. The abundance of mayflies and the number of EPT (Ephemeroptera, Plecoptera, Trichoptera) taxa (two well-known indicators of good water quality) were negatively correlated with industrial land use. The abundance of midges (an indicator of poor water quality) was positively correlated with industrial land use — and midge density was positively correlated with commercial land use, providing additional evidence that these streams have been negatively affected by urbanization in the basins. The percentage of mosquitofishes (a tolerant species) was positively correlated with commercial land use. In contrast, the numbers of fish species, fish families, and the percentage of sunfishes (intolerant species) were positively correlated with forested land use, indicating that the more diverse fish communities were found in basins with a higher percentage of forested land. The concentrations of 12 water-quality constituents (including several nitrogen species, chloride, copper, and molybdenum, and the detection frequency of wastewater indicators) and 18 organic compounds detected in bed sediment were positively correlated with industrial land use. Mercury and molybdenum concentrations detected in fish-liver tissue also were positively correlated with industrial land use. Bed-sediment and water-quality constituents that were found to have significant correlations with land use often were found to be correlated with many biological indicators, further supporting the link between increased urbanization and changes in aquatic-community structure. The water quality and aquatic-community structure in Village and Valley Creeks are degraded in comparison to streams flowing through less-urbanized areas. Low community richness and increased density of certain species within the fish and benthic-invertebrate communities indicate that degradation has occurred during an extended period of time. Decreased diversity in the aquatic communities and elevated concentrations of trace elements and organic contaminants in the water column, bed sediment, and fish tissues at Village and Valley Creeks are indicative of the effects of urbanization. The degree of degradation may be related to point and nonpoint sources of contamination originating within the basins. Industrial land use, in particular, was significantly correlated to elevated contaminant levels in the water column, in bed sediment, in fish tissue, and to the declining health of the benthic-invertebrate communities. The results of the 16-month study have long-range watershed management implications, demonstrating the association of urban development and stream degradation. These data can serve as a baseline from which to determine the effectiveness of stream-restoration programs.

Alabama↗

Arsenic, chromium, uranium, and vanadium in rock, alluvium, and groundwater, Mojave River and Morongo Areas, western Mojave Desert, southern California

Trace elements within groundwater that originate from aquifer materials and pose potential public-health hazards if consumed are known as geogenic contaminants. The geogenic contaminants arsenic, chromium, and vanadium can form negatively charged ions with oxygen known as oxyanions. Uranium complexes with bicarbonate and carbonate to form negatively charged ions having aqueous chemistry similar to oxyanions. The concentrations of arsenic, chromium, uranium, and vanadium in groundwater result from the combined effects of (1) geologic abundance within aquifer materials; (2) the fraction of these elements that have weathered from and sorbed to the surfaces of mineral grains and are potentially available to groundwater; and (3) the aqueous chemistry of dissolved oxyanions in groundwater during different redox conditions and pH, both of which are affected by hydrogeology, including the length of time groundwater has been in contact with aquifer materials. Concentrations of arsenic, chromium, uranium, and vanadium were measured in samples of (1) rock, surficial alluvium, and drill cuttings using portable (handheld) X-ray fluorescence (pXRF); (2) operationally defined fractions extractable from these materials; and (3) water from wells sampled between 2000 and 2018 within the 3,500 square mile Mojave River area and Morongo area of the western Mojave Desert, southern California. Regionally, rock and surficial alluvium in the Mojave River and Morongo areas are high in arsenic, low in chromium and uranium, and near the average bulk continental crust concentration for vanadium. Locally, high chromium concentrations are present in mafic rock within the San Gabriel Mountains; high uranium concentrations are present in felsic rock within the San Bernardino Mountains; and high arsenic, uranium, and vanadium concentrations are present in extrusive (volcanic) felsic rock within uplands surrounding groundwater basins along the Mojave River downstream from Barstow, California. Elemental assemblages identified using principal component analyses (PCA) of pXRF data were used to characterize felsic, mafic, and felsic volcanic source terranes in rock, surficial alluvium, and in geologic material penetrated by selected monitoring wells drilled between 1994 and 2018. Highly felsic alluvium associated with recent deposition from the Mojave River was identified along the 90-mile length of the floodplain aquifer along the river. The thickness of these highly felsic alluvial deposits ranged from 200 feet (ft) near Victorville and near Barstow to a thin veneer about 30 ft thick downstream from Victorville and downstream portions of the floodplain aquifer within the Mojave Valley. Groundwater in the Mojave River and Morongo areas was generally oxic and alkaline (pH≥7.5). Maximum concentrations of arsenic, hexavalent chromium [Cr(VI)], uranium, and vanadium in water from as many as 498 wells sampled between 2000 and 2018 were 360, 140, 1,470, and 690 micrograms per liter (μg/L), respectively. Water from 22 percent of sampled wells exceeded the U.S. Environmental Protection Agency (EPA) maximum contaminant level (MCL) for arsenic of 10 μg/L, with arsenic concentrations commonly exceeding the MCL in water from wells east of Barstow, deep wells in the Victorville fan, and in suboxic or reduced groundwater within the floodplain aquifer. Water from about 1 percent of sampled wells had Cr(VI) concentrations greater than the California MCL for total chromium of 50 μg/L, whereas 13 percent of sampled wells had Cr(VI) concentrations greater than the former California MCL of 10 μg/L. Hexavalent chromium concentrations were highest in water from wells in the Sheep Creek alluvial fan, eroded from mafic rock in the San Gabriel Mountains, although Cr(VI) concentrations greater than the former California MCL also were present elsewhere in the study area where mafic materials or older groundwater were present. Water from about 9 percent of sampled wells exceeded the EPA MCL for uranium of 30 μg/L, with concentrations exceeding the MCL commonly associated with irrigation return from agricultural land overlying the floodplain aquifer. Water from about 7 percent of sampled wells had vanadium concentrations greater than the California notification level of 50 μg/L; most of these wells were in the Victorville fan within the Mojave River area. In general, arsenic concentrations were higher in suboxic or reduced water; chromium concentrations were higher in oxic, alkaline (pH≥7.5) water; uranium concentrations were higher in circumneutral to slightly alkaline water (pH≤7.4); and vanadium concentrations were higher in highly alkaline (pH≥8.0) water, independent of redox status. Concentrations within geologic source terranes are not the sole factor controlling the concentrations of geogenic elements in groundwater. Differences in mineral weathering, pH-dependent sorption to surface-exchange sites on mineral grains, and aqueous geochemistry (especially redox status and pH) affect geogenic element concentrations in groundwater. Consequently, the relative abundances of arsenic, Cr(VI), uranium, and vanadium in groundwater differ from their relative abundances in the average bulk continental crust and their regional abundances in rock and surficial alluvium within groundwater basins of the western Mojave Desert. Processes that control the concentrations of arsenic, chromium, uranium, and vanadium in groundwater operate at the mineral-grain and aquifer scale. At the mineral-grain scale, sequential chemical extraction data show arsenic and uranium are more available to groundwater (under specific geochemical conditions) than chromium or vanadium, which largely are unavailable within unweathered mineral grains. Additionally, chromium and vanadium form few aqueous complexes and bind tightly with iron minerals within surface coatings on mineral grains making them less available to groundwater, whereas complexation with other dissolved ions enhances the solubility of uranium and, to a lesser extent, arsenic. Complexation also increases the valence (less negative charge) and increases the size of dissolved oxyanions and uranium complexes with bicarbonate and carbonate making them less readily sorbed to aquifer materials. At the aquifer scale, hydrogeology (including isolation of water in aquifers from surface sources of recharge, older groundwater age, and long contact times between groundwater and aquifer materials) combined with geochemical processes (such as silicate weathering) to produce alkaline groundwater. Desorption from sorption sites on the surfaces of mineral grains with increasing pH increases arsenic, chromium, and vanadium concentrations in water from wells and increases Cr(VI) concentrations as long as water remains oxic. Aqueous geochemistry and concentrations of geogenic contaminants also are affected by anthropogenic activities including (1) discharge of treated municipal wastewater, which may change the redox status of groundwater; (2) return from irrigated agriculture, which may alter the chemistry of groundwater and increase the solubility of trace elements such as uranium; and (3) groundwater pumping and subsequent water-level declines, which may change the source of water yielded by wells. The quality of water imported from northern California and infiltrated from ponds for groundwater recharge may be altered by naturally present trace elements, especially uranium in areas of agricultural land use or chromium within mafic alluvium.

California↗

Development of a passive, in situ, integrative sampler for hydrophilic organic contaminants in aquatic environments

Increasingly it is being realized that a holistic hazard assessment of complex environmental contaminant mixtures requires data on the concentrations of hydrophilic organic contaminants including new generation pesticides, pharmaceuticals, personal care products, and many chemicals associated with household, industrial, and agricultural wastes. To address this issue, we developed a passive in situ sampling device (the polar organic chemical integrative sampler [POCIS]) that integratively concentrates trace levels of complex mixtures of hydrophilic environmental contaminants, enables the determination of their time-weighted average water concentrations, and provides a method of estimating the potential exposure of aquatic organisms to the complex mixture of waterborne contaminants. Using a prototype sampler, linear uptake of selected herbicides and pharmaceuticals with log K ow S < 4.0 was observed for up to 56 d. Estimation of the ambient water concentrations of chemicals of interest is achieved by using appropriate uptake models and determination of POCIS sampling rates for appropriate exposure conditions. Use of POCIS in field validation studies targeting the herbicide diuron in the United Kingdom resulted in the detection of the chemical at estimated concentrations of 190 to 600 ng/L. These values are in agreement with reported levels found in traditional grab samples taken concurrently.

Environmental Toxicology and Chemistry↗

Design and methods of the U.S. Geological Survey Northeast Stream Quality Assessment (NESQA), 2016

During 2016, as part of the National Water-Quality Assessment Project (NAWQA), the U.S. Geological Survey conducted the Northeast Stream Quality Assessment (NESQA) to investigate stream quality in the northeastern United States. The goal of the NESQA was to assess the health of wadeable streams in the region by characterizing multiple water-quality factors that are stressors to aquatic life and by evaluating the relation between these stressors and the condition of biological communities. Urbanization, agriculture, and human modifications to streamflow are anthropogenic changes that greatly affect water quality in the region; consequently, the study design primarily selected sites and targeted stressors associated with these activities. The NESQA built on a prior NAWQA study conducted in the region in 2014, the Atlantic Highlands flow-ecology study, which investigated the effects of anthropogenically modified flows on aquatic biological communities in primarily forested watersheds. Land-cover data for the NESQA were used to identify and select sites within the region that had watersheds ranging in levels of urban and agricultural development. A total of 95 sites were selected: 67 on streams in watersheds representing a range of urban land use, 13 on streams in watersheds with some degree of agricultural land use, and 15 on streams in predominantly forested watersheds with little development. Depending on land-cover characteristics, sites were sampled weekly for metal and organic contaminants, nutrients, and sediment for either a 9-week period that began the week of June 6, 2016, or a 4-week period that begin the week of July 11, 2016. Beginning August 1, 2016, and for about 2 weeks, an ecological survey was conducted at every site to assess stream habitat, and algal, benthic invertebrate, and fish communities. Additional samples collected during the ecological surveys were streambed sediment for chemical analysis and toxicity testing, and fish tissue for mercury analysis. This report describes the various study components and methods of the NESQA and describes a precursor effort for the Atlantic Highlands flow-ecology study. Details are presented for measurements of water quality, sediment chemistry, streamflow, and ecological surveys of stream biota and habitat, as well as processes of sample analysis, quality assurance and quality control, and data management.

Open-File Report↗

Chapter 21 Western phosphate field - Depositional and economic deposit models

The Western Phosphate Field (WPF), composed of Permian marine sedimentary strata that cover over 300,000 km 2 in the middle Rocky Mountains of Idaho, Montana, Utah, and Wyoming in the United States, contains vast resources of phosphate mined for fertilizer and a range of other industrial applications. The richest deposits of phosphate in the WPF occur in the Meade Peak Phosphatic Shale Member of the Phosphoria Formation in southeast Idaho. Phosphate is an essential and even limiting nutrient of algal production, which occurs at the bottom of the marine food web in the oceanic photic zone. The high concentrations of phosphate and trace elements in the Phosphoria Formation reflect a low accumulation rate of diluting phases, such as terrigenous siliciclastic debris and carbonate, rather than an unusually high level of primary productivity at the time of deposition. Indeed, the mean rate of accumulation of PO 4 3 required a continuous flux of PO 4 3 into the basin and the photic zone of the water column, but only at a moderate level. This flux was maintained by upwelling of nutrient-rich seawater, imported at depth from the open ocean. Although only a fraction of the organic matter that hosted the PO 4 3 and other nutrients (NO 3 , Cd, Cu, Mo, Ni, and Zn) actually escaped oxidation in the water column, their rate of accu- mulation on the sea floor defined the basin hydrography. Rates of accumulation of Cr, U, V, and rare-earth elements by precipitation and adsorp- tion reactions identify redox conditions in the bottom water as having been denitrifying, maintained by a balance between the rate of oxidation of organic matter settling through the water column and the flux of open-ocean seawater at depth. Atmospheric mixing maintained oxygen respiration in the uppermost several tens of meters of the water column. This hydrography and seawater chemistry are present in several sedimentary envi- ronments in the ocean today. In the WPF, there is an estimated surface mineable reserve base and subeconomic resource of 7.6 billion mt, at an average grade of 24% P 2 O 5 ; a subeconomic underground- mineable resource of 17 billion mt, at a grade of 28%; and 507 billion mt of subresource- grade phosphatic material that underlie the WPF at a depth greater than 305 m. The relationship between phosphate-ore specifications and weathering suggests that significant changes in processing, with associated cost increases, will be required to extend recovery of ore below the relatively strongly weathered zone near the surface. Four open pit mines currently extract phosphate from two moderately to steeply dipping ore zones that typically contain between 20% and 35% P 2 O 5 . Although the shales are enriched in trace elements, especially As, Cd, Cr, Cu, Mo, Se, U, V, Zn, and rare-earth elements, the relative concentration of organic carbon and selected major element oxides determines the suitability of phosphate-rich rock for feed to processing plants and its other applications. Selected specifications from the four operating mines include the following: minimum P 2 O 5 of 18-20% and average of 26-27%; maximum A1 2 O 3 of 1.6-5.0%; maximum MgO of 0.3-0.6%; a CaO/P 2 O 5 ratio of 1.5-1.6; and total carbon content of 4%-5%. Weathering to a depth of as much as 100 m significantly enhances ore quality by decreasing the proportions of calcite, dolomite, and organic matter relative to carbonate fluorapatite, the primary ore mineral

Colorado, Idaho, Montana, Nebraska, North Dakota, ↗