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Analysis and detection of the herbicides dimethenamid and flufenacet and their sulfonic and oxanilic acid degradates in natural water

Dimethenamid [2-chloro-N-(2,4-dimethyl-3-thienyl)-N-(2-methoxy-1-methylethyl)acetamide] and flufenacet [N-(4-fluorophenyl)-N-(1-methylethyl)-2-(5-(trifluoromethyl)-1,3,4- thiadiazol-2-yl)oxy] were isolated by C-18 solid-phase extraction and separated from their ethanesulfonic acid (ESA) and oxanilic acid (OXA) degradates during their elution using ethyl acetate for the parent compound, followed by methanol for the polar degradates. The parent compounds were detected using gas chromatography-mass spectrometry in selected-ion mode. The ESA and OXA degradates were detected using high-performance liquid chromatography-electrospray mass spectrometry (HPLC-ESPMS) in negative-ion mode. The method detection limits for a 123-mL sample ranged from 0.01 to 0.07 μg/L. These methods are compatible with existing methods and thus allow for analysis of 17 commonly used herbicides and 18 of their degradation compounds with one extraction. In a study of herbicide transport near the mouth of the Mississippi River during 1999 and 2000, dimethenamid and its ESA and OXA degradates were detected in surface water samples during the annual spring flushes. For flufenacet, the only detections at the study site were for the ESA degradates in samples collected at the peak of the herbicide spring flush in 2000. The low frequency of detections in surface water likely is due to dimethenamid and flufenacet being relatively new herbicides. In addition, detectable amounts of the stable degradates have not been detected in ground water.

Journal of Agricultural and Food Chemistry

Input, flux, and persistence of six select pesticides in San Francisco Bay

Temporal patterns of pesticide inputs to San Francisco Bay were identified and correlated with timing of application and transport mechanism. Fluxes were calculated from measured concentrations and estimated flow. Persistence of the pesticides under typical riverine or estuarine conditions were estimated from laboratory experiments. Simazine was detected most frequently and had the highest flux into the Bay, which could be explained by its continuous use and long half-life. In comparison, diazinon was detected at lower concentrations and had a lower flux which corresponded to its lower use and shorter half-life. The order-of-magnitude lower fluxes of carbofuran and methidathion corresponded to their lower use and expected hydrolysis. Molinate was detected at the highest concentration but its flux was lower than expected, considering its very high use and persistence in the laboratory experiments. Additional loss of molinate is likely to occur from volatilization and photodegradation on the rice fields. Although thiobencarb had the second highest use, it had the lowest flux of the six pesticides, which can be attributed to its loss via hydrolysis, photodegradation, volatilization, and sorption to sediments. Fluxes into San Francisco Bay were equal to or greater than those reported for other estuaries, except for the Gulf of Mexico.

California

Water-quality assessment of the Ozark Plateaus study unit, Arkansas, Kansas, Missouri, and Oklahoma- fish communities in streams of the Ozark Plateaus and their relations to selected environmental factors

Fish communities from 22 reaches at 18 stations in the Ozark Plateaus were sampled in 1993, 1994, and 1995. The 18 stations were chosen to represent selected combinations of major environmental factors (geology/physiographic area, land use, and basin size). Additional physical, chemical, and biological factors also were measured for each of the 22 reaches and the influence of these factors upon the fish communities was investigated. Fish community samples collected at the 22 reaches identified differences in these communities that can be attributed to differences in land use and related water-quality and habitat characteristics. Communities from agriculture reaches tended to have more species, increased relative abundance of stonerollers and members of the sucker family, and decreased relative abundance of members of the sunfish and darter families. Several groups of environmental factors (concentrations of nutrients, organic carbon, suspended sediment, and dissolved oxygen; measures related to ionic strength; measures related to riparian vegetation; measures related to substrate; and measures related to stream size) appear to be related to land-use differences and fish community differences. Three multivariate analysis techniques (two ordination techniques and a classification technique) yielded similar results when applied to the fish community data. Fish communities from reaches with more similar land use in their basins and with similar drainage areas generally were grouped closer together in the analysis. Water quality, substrate, stream morphology, and riparian measures appear to be affecting fish communities at these reaches. The relations between land use, stream size, and fish communities have implications for water quality assessments of Ozark streams. Compared to other parts of the United States, many fish species live in the Ozark Plateaus. At least 19 of these species are endemic to the Ozarks area. Many of these species are intolerant of habitat or water chemistry degradation. This characteristic makes fish a useful tool for assessing water-chemistry and other habitat conditions of streams. Several environmental factors can contribute to differences in fish communities. Elevated nutrient concentrations and greater canopy angles can increase periphyton production. Greater canopy angles can raise water temperatures and, if they reflect less woody vegetation along the banks of streams, can be associated with greater streambank erosion. Elevated suspended sediment concentrations and finer and more embedded substrates can reduce benthic macroinvertebrate populations, decrease spawning success of many fish species, and decrease protection of benthic fish from water velocities and predators.

Arkansas, Kansas, Missouri, Oklahoma

Design and methods of the California stream quality assessment (CSQA), 2017

During 2017, as part of the National Water-Quality Assessment Project, the U.S. Geological Survey conducted the California Stream Quality Assessment to investigate the quality of streams in the Central California Foothills and Coastal Mountains ecoregion, United States. The goal of the California Stream Quality Assessment study was to assess the health of wadeable streams in the region by characterizing multiple water-quality factors that are stressors to aquatic biota and by evaluating the relation between these stressors and biological indicators of stream health. Urbanization, agriculture, and modifications to streamflow are anthropogenic changes that affect water quality in the region; consequently, the study design primarily targeted sites and specific stressors associated with these activities. For the study, 85 stream sites were selected to represent the types and intensity of land use in the watershed; categories of site types were undeveloped, urban (low, medium, high), agriculture (low, high), and mixed (urban and agriculture). Most sites (about 70 percent) represent a gradient of urbanization from undeveloped to 99-percent urbanized. At most of the sites, streamgages or pressure transducers were used to monitor stream discharge and stage, as well as temperature. Water-quality samples were collected routinely at all sites and were analyzed for major ions, organic contaminants, nutrients, and suspended sediment. Sampling frequency varied on the basis of site type and location. Discrete water samples were collected weekly and generally 6 times per site, except for 11 undeveloped sites that were sampled only 4 times (during the last 4 weeks). Water sampling began at sites in the southern part of the study on March 13, 2017, and at sites in the northern part of the study on April 3, 2017. Passive samplers were deployed at most sites for measurement of polar organic contaminants (pesticides and pharmaceuticals). In May 2017, coincident with completion of water-quality sampling, an ecological survey was conducted at each site to assess benthic algal and macroinvertebrate communities and instream habitat. During the ecological surveys, a single composite streambed-sediment sample was collected for chemical analysis and toxicity testing. In addition, a few focused studies were done at subsets of sites, namely, measuring pesticides using small-volume automated samplers, measuring pesticides in biofilms, and sampling suspended sediments using passive samplers. This report describes the various study components and methods of the California Stream Quality Assessment, including measurements of water quality, sediment chemistry, habitat assessments, and ecological surveys, as well as procedures for sample analysis, quality assurance and quality control, and data management.

California

Laboratory-derived bioaccumulation kinetic parameters for four per- and polyfluoroalkyl substances in freshwater mussels

Although freshwater mussels are imperiled and identified as key conservation priorities, limited bioaccumulation information is available on these organisms for contaminants of emerging concern. In the present study we investigated the bioaccumulation of per- and polyfluoroalkyl substances (PFAS) in the model freshwater pond mussel Sagittunio subrostratus because mussels provide important ecosystem services and are important components of aquatic systems where PFAS occur. In the present study we selected four representative perfluorinated carboxylic acids and sulfonic acids, then determined the bioaccumulation kinetics of freshwater mussels in a controlled laboratory study. Because uptake ( k u ) and elimination ( k e ) rate constants and time to steady state are important parameters for food web bioaccumulation models, we derived bioaccumulation kinetic parameters following exposure to perfluorohexane sulfonic acid (PFHxS), perfluorooctane sulfonic acid (PFOS), and perfluorodecanoic acid (PFDA) at 10 µg/L and perfluoroundecanoic acid (PFUnDA) at 1 µg/L during a 14-day uptake period followed by a 7-day elimination period. Kinetic and ratio-based bioaccumulation factors (BAFs) were subsequently calculated, for example ratio-based BAFs for mussel at day 7 were determined for PFHxS (0.24 ± 0.08 L/kg), PFOS (7.73 ± 1.23 L/kg), PFDA (4.80 ± 1.21 L/kg), and PFUnDA (84.0 ± 14.4 L/kg). We generally observed that, for these four model PFAS, freshwater mussels have relatively low BAF values compared with other aquatic invertebrates and fish.

Environmental Toxicology and Chemistry

Profiles of polychlorinated biphenyl congeners, organochlorine pesticides and butlyns in southern sea otters and their prey

Concentrations of organochlorine pesticides, polychlorinated biphenyl (PCB)congeners, and butyltins were measured in sea otters and selected prey species (invertebrates) collected from the California (USA) coast. Polychlorinated biphenyls, DDTs (sum of p,p ′-dichlorodiphenyldichloroethylene [ p,p -DDE], p,p ′-dichlorodiphenyldichloroethane [ p,p -DDD], and p,p ′-DDT), and butyltins were the major contaminants found in sea otters and their prey. Lipid-normalized concentrations of PCBs and DDT in sea otter livers were 60- and 240-fold greater than those found in the prey. Great biomagnification of PCBs and DDT in sea otters is suggested to result from their high per-capita intake of diet compared with those of other marine mammals. Profiles of PCB congeners in sea otters and prey species suggest a great capacity of sea otters to biotransform lower-chlorinated congeners. Sea otters seem to possess a greater ability than cetaceans to metabolize PCBs. The 2,3,7,8-tetrachlorodibenzo- p -dioxin equivalents of non- and mono- ortho PCBs in sea otters and certain prey species were at or above the theoretical threshold for toxic effects.

California

Mg isotope constraints on soil pore-fluid chemistry: Evidence from Santa Cruz, California

Mg isotope ratios ( 26 Mg/ 24 Mg) are reported in soil pore-fluids, rain and seawater, grass and smectite from a 90 kyr old soil, developed on an uplifted marine terrace from Santa Cruz, California. Rain water has an invariant 26 Mg/ 24 Mg ratio (expressed as δ26 Mg> δ26 Mg ) at −0.79 ± 0.05‰, identical to seawater δ26 Mg> δ26 Mg . Detrital smectite (from the base of the soil profile, and therefore unweathered) has a δ26Mg"> δ26Mg value of 0.11‰, potentially enriched in 26 Mg by up to 0.3‰ compared to the bulk silicate Earth Mg isotope composition (although within the range of all terrestrial silicates). The soil pore-waters show a continuous profile with depth for δ26 Mg> δ26 Mg , ranging from −0.99‰ near the surface to −0.43‰ at the base of the profile. Shallow pore-waters (<1 m) have δ26 Mg> δ26 Mg values that are similar to, or slightly lower than the rain waters. This implies that the degree of biological cycling of Mg in the pore-waters is relatively small and is quantified as <32%, calculated using the average Mg isotope enrichment factor between grass and rain ( δ26 Mggrass- δ26 Mgrain> δ26 Mggrass- δ26 Mgrain ) of 0.21‰. The deep pore-waters (1–15 m deep) have δ26 Mg> δ26 Mg values that are intermediate between the smectite and rain, ranging from −0.76‰ to −0.43‰, and show a similar trend with depth compared to Sr isotope ratios. The similarity between Sr and Mg isotope ratios confirms that the Mg in the pore-waters can be explained by a mixture between rain and smectite derived Mg, despite the fact that Mg and Sr concentrations may be buffered by the exchangeable reservoir. However, whilst Sr isotope ratios in the pore-waters span almost the complete range between mineral and rain inputs, Mg isotopes compositions are much closer to the rain inputs. If Mg and Sr isotope ratios are controlled uniquely by a mixture, the data can be used to estimate the mineral weathering inputs to the pore-waters, by correcting for the rain inputs. This isotopic correction is compared to the commonly used chloride correction for precipitation inputs. A consistent interpretation is only possible if Mg isotope ratios are fractionated either by the precipitation of a secondary Mg bearing phase, not detected by conventional methods, or selective leaching of 24 Mg from smectite. There is therefore dual control on the Mg isotopic composition of the pore-waters, mixing of two inputs with distinct isotopic compositions, modified by fractionation. The data provide (1) further evidence for Mg isotope fractionation at the surface of the Earth and (2) the first field evidence of Mg isotope fractionation during uptake by natural plants. The coherent behaviour of Mg isotope ratios in soil environments is encouraging for the development of Mg isotope ratios as a quantitative tracer of both weathering inputs of Mg to waters, and the physicochemical processes that cycle Mg, a major cation linked to the carbon cycle, during continental weathering.

California

Environmental setting and natural factors and human influences affecting water quality in the White River Basin, Indiana

The White River Basin drains 11,349 square miles of central and southern Indiana and is one of 59 Study Units selected for water-quality assessment as part of the U.S. Geological Survey's National WaterQuality Assessment Program. Defining the environmental setting of the basin and identifying the natural factors and human influences that affect water quality are important parts of the assessment. Interrelated natural factors help determine the quality of surface and ground water in a river basin. The White River Basin has a humid continental climate, characterized by well-defined winter and summer seasons. Geologic features in the basin include glaciated and nonglaciated areas; a region of karst geomorphology that is characterized by caves and sinkholes; and a thick, sedimentary bedrock sequence underlying the entire basin. Unconsolidated glacial deposits of clay, silt, sand and gravel cover more than 60 percent of the basin. Soils developed in unconsolidated glacial deposits are typically fertile, naturally or artificially well drained, and farmed. Soils in the unglaciated south-central part of the basin are thin, have low fertility, and are best suited for forest or pasture. Agriculture is the principal land use in the White River Basin. Approximately 70 percent of the basin is used for agriculture, and about 50 percent of the basin is cropland. Corn and soybeans are the major crops. Other significant land uses are forest (22 percent) and urban and residential (7 percent). The population of the basin was 2.1 million in 1990. Water use in the White River Basin totaled 1,284 million gallons per day in 1995, of which 84.5 percent was surface water and 15.5 percent was ground water. Despite the predominant use of surface water, ground water was the primary source of drinking water for approximately 56 percent of the population. The general water chemistry in the White River Basin is determined by natural factors such as soils and geologic materials that water contacts as it moves through the hydrologic system. In the southern part of the basin, bedrock upland areas are dominated by non-carbonate bedrock, thin soils, and high runoff-rainfall ratios. These areas have small chemical concentrations in streamwater. Conversely, in the northern part of the basin where glacial deposits are thick and in the southwestern part of the basin where loess deposits are thick, water has longer periods of time to react with soils and aquifers and to acquire substantial quantities of dissolved constituents. As a result, streams in the till plain and glacial lowland have higher concentrations of most constituents than streams in the unglaciated parts of the basin. Water quality is significantly modified by human influences. Water quality is affected locally by point sources of contamination that include combined-sewer overflows, power-generation-plant cooling stations, and wastewater-treatment-plant effluents that are generally associated with densely populated areas. Water quality is additionally affected by non-point sources of contamination related to agriculture, urban runoff, and mining. Six hydrogeomorphic regions of the White River Basin are delineated on the basis of distinct and relatively homogeneous natural characteristics. These six regions are used in the White River Basin study as a framework for examining the effects of natural factors on water quality in the basin. Bedrock is exposed or near the surface in three hydrogeomorphic regions the bedrock uplands, bedrock lowland and plain, and karst plain; streams and shallow aquifers in these regions are susceptible to contamination, especially in the karst plain, and show rapid response to rainfall. The other three hydrogeomorphic regions the fluvial deposits, till plain, and glacial lowland are in the glaciated part of the basin. Where thick fine-grained unconsolidated sediments are present, primarily in the till plain, ground-water supplies are protected from contamination, and extreme high and low streamflows are moderated.

Indiana

Selected resin acids in effluent and receiving waters derived from a bleached and unbleached kraft pulp and paper mill

Water samples were collected on three dates at 24 sites influenced by effluent from Georgia-Pacific's Palatka Pulp and Paper Mill Operation, a bleached and unbleached kraft mill near Palatka, Florida, USA. The sampling sites were located within the mill retention ponds, Rice Creek, and the St. John's River. Samples were analyzed by gas chromatography-mass spectrometry for abietic, dehydroabietic, and isopimaric acids, all of which are potentially toxic by-products of pulp production. Isopimaric acid concentrations greater than 12 mg/L were measured at the mill's effluent outfall but were less than 20 μg/L at the end of Rice Creek. This result indicates that the waters of Rice Creek provide dilution or conditions conducive for degradation or sorption of these compounds. Large differences in resin acid concentrations were observed between sampling events. In two sampling events, the maximum observed concentrations were less than 2 mg/L for each analyte. In a third sampling event, all of the compounds were detected at concentrations greater than 10 mg/L. Data from the three sample dates showed that resin acid concentrations were below 20 μg/L before the confluence of Rice Creek and the St. John's River in all cases.

Florida

Biogeochemical transport in the Loxahatchee River estuary, Florida: The role of submarine groundwater discharge

The distributions of dissolved organic carbon (DOC), Ba, U, and a suite of naturally occurring radionuclides in the U/Th decay series (222Rn, 223,224,226,228Ra) were studied during high- and low-discharge conditions in the Loxahatchee River estuary, Florida to examine the role of submarine groundwater discharge in estuarine transport. The fresh water endmember of this still relatively pristine estuary may reflect not only river-borne constituents, but also those advected during active groundwater/surface water (hyporheic) exchange. During both discharge conditions, Ba concentrations indicated slight non-conservative mixing. Such Ba excesses could be attributed either to submarine groundwater discharge or particle desorption processes. Estuarine dissolved organic carbon concentrations were highest at salinities closest to zero. Uranium distributions were lowest in the fresh water sites and mixed mostly conservatively with an increase in salinity. Suspended particulate matter (SPM) concentrations were generally lowest (< 5??mg L- 1) close to zero salinity and increased several-fold (??? 18??mg L- 1; low discharge) toward the seaward endmember, which may be attributed to dynamic resuspension of bottom sediments within Jupiter Inlet. Surface water-column 222Rn activities were most elevated (> 28??dpm L- 1) at the freshwater endmember of the estuary and appear to identify regions of the river most influenced by the discharge of fresh groundwater. Activities of four naturally occurring isotopes of Ra (223,224,226,228Ra) in this estuary and select adjacent shallow groundwater wells yield mean estuarine water-mass transit times of less than 1 day; these values are in close agreement to those calculated by tidal prism and tidal frequency. Submarine groundwater discharge rates to the Loxahatchee River estuary were calculated using a tidal prism approach, an excess 226Ra mass balance, and an electromagnetic seepage meter. Average SGD rates ranged from 1.0 to 3.8 ?? 105??m3 d- 1 (20-74??L m- 2 d- 1), depending on river-discharge stage. Such calculated SGD estimates, which must include both a recirculated as well as fresh water component, are in close agreement with results obtained from a first-order watershed mass balance. Average submarine groundwater discharge rates yield NH4+ and PO4- 3 flux estimates to the Loxahatchee River estuary that range from 62.7 to 1063.1 and 69.2 to 378.5????mol m- 2 d- 1, respectively, depending on river stage. SGD-derived nutrient flux rates are compared to yearly computed riverine total N and total P load estimates. ?? 2006 Elsevier B.V. All rights reserved.

Marine Chemistry

The Japanese Quail as an avian model for testing endocrine disrupting chemicals: endocrine and behavioral end points

Birds have extremely varied reproductive strategies. As such, the impact of endocrine disrupting chemicals (EDCs) can greatly differ across avian species. Precocial species, such as Japanese quail appear to be most sensitive to EDC effects during embryonic development, particularly sexual differentiation. A great deal is known about the ontogeny of Japanese quail (Coturnix japonica) relative to endocrine, neuro-endocrine, and behavioral components of reproduction. Therefore, this species provides an excellent model for understanding effects of EDCs on reproductive biology with exposure at specific stages of the life cycle. The purpose of these experiments was to conduct a 1- or 2- generation experiment with positive or negative control chemicals and to determine changes in selected end points. Japanese quail embryos were exposed to estradiol benzoate (EB; positive control) in a 2-generation design or to fadrozole (FAD; negative control) in a 1-generation design. Embryonic EB treatment resulted in significant reductions (p< 0.5) in hen day production (90.2 vs 54.1; control vs EB, resp.) and fertility (85.3 vs 33.4%, control vs EB, resp.). Males showed sharply reduced courtship and mating behaviors as well as increased lag time (26 vs 148 sec; control vs EB) in behavioral tests. Fadrozole exposure resulted in reduced hatchability of fertile eggs, particularly at higher doses. There were no significant effects on courtship and mating behavior of males although males showed an increased lag time in their responses, nally, a behavioral test for studying motor and fear responses in young chicks was used; chicks exposed to an estrogenic pesticide (methoxychlor) showed some deficits. In summary, the use of appropriate and reliable end points that are responsive to endocrine disruption are critical for assessment of EDCs. Supported in part by EPA grant R826134.

Society of Environmental Toxicology and Chemistry,

Study and interpretation of the chemical characteristics of natural water

The chemical composition of natural water is derived from many different sources of solutes, including gases and aerosols from the atmosphere, weathering and erosion of rocks and soil, solution or precipitation reactions occurring below the land surface, and cultural effects resulting from human activities. Broad interrelationships among these processes and their effects can be discerned by application of principles of chemical thermodynamics. Some of the processes of solution or precipitation of minerals can be closely evaluated by means of principles of chemical equilibrium, including the law of mass action and the Nernst equation. Other processes are irreversible and require consideration of reaction mechanisms and rates. The chemical composition of the crustal rocks of the Earth and the composition of the ocean and the atmosphere are significant in evaluating sources of solutes in natural freshwater. The ways in which solutes are taken up or precipitated and the amounts present in solution are influenced by many environmental factors, especially climate, structure and position of rock strata, and biochemical effects associated with life cycles of plants and animals, both microscopic and macroscopic. Taken together and in application with the further influence of the general circulation of all water in the hydrologic cycle, the chemical principles and environmental factors form a basis for the developing science of natural-water chemistry. Fundamental data used in the determination of water quality are obtained by the chemical analysis of water samples in the laboratory or onsite sensing of chemical properties in the field. Sampling is complicated by changes in the composition of moving water and by the effects of particulate suspended material. Some constituents are unstable and require onsite determination or sample preservation. Most of the constituents determined are reported in gravimetric units, usually milligrams per liter or milliequivalents per liter. More than 60 constituents and properties are included in water analyses frequently enough to provide a basis for consideration of the sources from which each is generally derived, the most probable forms of elements and ions in solution, solubilitycontrols, expected concentration ranges, and other chemical factors. Mechanisms that control concentrations of elements commonly present in amounts less than a few tens of micrograms per liter cannot always be easily ascertained, but present information suggests that many are controlled by solubility of their hydroxides or carbonates or by sorption on solid particles. Many dissolved organic compounds can now be specifically determined. Chemical analyses may be grouped and statistically evaluated by means, medians, frequency distributions, or ion correlations to summarize large volumes of data. Graphing of analyses or of groups of analyses aids in showing chemical relationships among water, probable sources of solutes, areal water-quality regimen, temporal and spatial variation, and water-resources evaluation. Graphs may show water type based on chemical composition, relationships among ions, or groups of ions in individual waters or many waters considered simultaneously. The relationships of water quality to hydrogeologic characteristics, such as stream discharge rate or ground-water flow patterns, can be shown by mathematical equations, graphs, and maps. About 80 water analyses selected from the literature are tabulated to illustrate the relationships described, and some of these, along with many others that are not tabulated, are also used in demonstrating graphing and mapping techniques. Relationships of water composition to source rock type are illustrated by graphs of some of the tabulated analyses. Human activities may modify water composition extensively through direct effects of pollution and indirect results of water development, such as intrusion of seawater in groundwater aquifers. Water-quality standards for domestic, agricultural, and industrial use have been published by various agencies. Irrigation project requirements for water quality are particularly intricate. Fundamental knowledge of processes that control natural-water composition is required for rational management of water quality.

Water Supply Paper

Reconnaissance of ground-water quality in the Papio-Missouri River Natural Resources District, eastern Nebraska, July through September 1992

A reconnaissance of ground-water quality was conducted in the Papio-Missouri River Natural Resources District of eastern Nebraska. Sixty-one irrigation, municipal, domestic, and industrial wells completed in the principal aquifers--the unconfined Elkhorn, Missouri, and Platte River Valley alluvial aquifers, the upland area alluvial aquifers, and the Dakota aquifer--were selected for water-quality sampling during July, August, and September 1992. Analyses of water samples from the wells included determination of dissolved nitrate as nitrogen and triazine and acetanilide herbicides. Waterquality analyses of a subset of 42 water samples included dissolved solids, major ions, metals, trace elements, and radionuclides. Concentrations of dissolved nitrate as nitrogen in water samples from 2 of 13 wells completed in the upland area alluvial aquifers exceeded the U.S. Environmental Protection Agency Maximum Contaminant Level for drinking water of 10 milligrams per liter. Thirty-nine percent of the dissolved nitrate-as-nitrogen concentrations were less than the detection level of 0.05 milligram per liter. The largest median dissolved nitrate-as-nitrogen concentrations were in water from the upland area alluvial aquifers and the Dakota aquifer. Water from all principal aquifers, except the Dakota aquifer, had detectable concentrations of herbicides. Herbicides detected included alachlor (1 detection), atrazine (13 detections), cyanazine (5 detections), deisopropylatrazine (6 detections), deethylatrazine (9 detections), metolachlor (6 detections), metribuzin (1 detection), prometon (6 detections), and simazine (2 detections). Herbicide concentrations did not exceed U.S. Environmental Protection Agency Maximum Contaminant Levels for drinking water. In areas where the hydraulic gradient favors loss of surface water to ground water, the detection of herbicides in water from wells along the banks of the Platte River indicates that the river could act as a line source of herbicides. Water from the alluvial and bedrock aquifers generally was a calcium bicarbonate type and was hard. Two of nine water samples collected from the Dakota aquifer contained calcium sulfate type water. Results of analyses of 42 groundwater samples for major ions, metals, trace elements, and radionuclide constituents indicated that statistically at least one principal aquifer had significant differences in its water chemistry. In general, the water chemistry of the Dakota aquifer was similar to the water chemistry of the upland area alluvial aquifers in areas where there was a hydraulic connection. The water from the Dakota aquifer had large dissolved-solids, calcium, sulfate, chloride, iron, lithium, manganese, and strontium concentrations in areas where the aquifer is thought not to be in hydraulic connection with the Missouri River Valley and upland area alluvial aquifers. Ground-water quality in the Papio-MissouriRiver Natural Resources District is generally suitable for most uses. However, the numerous occurrences of herbicides in water of the Elkhorn and Platte River Valley alluvial aquifers, especially near the Platte River, are of concern because U.S. Environmental Protection Agency Maximum Contaminant Levels could be exceeded. Concentrations in three of nine water samples collected from wells completed in the Dakota aquifer exceeded the U.S. Environmental Protection Agency Maximum Contaminant Levels or Secondary Maximum Contaminant Levels for gross alpha activity, radon-222 activity, dissolved solids, sulfate, or iron. Also of concern are the exceedances of the U.S Environmental Protection Agency proposed Maximum Contaminant Level for radon-222 activity.

Water-Resources Investigations Report

Results of mineral, chemical, and sulfate isotopic analyses of water, soil, rocks, and soil extracts from the Pariette Draw Watershed, Uinta Basin, Utah

In 2010, Utah Department of Environmental Quality (DEQ) Division of Water Quality (UDWQ, 2010) determined that water quality in Pariette Draw was in violation of Federal and State water quality criteria for total dissolved solids (TDS), selenium (Se), and boron (B). The measure of total dissolved solids is the sum of all the major ion concentrations in solution and in this case, the dominant ions are sodium (Na) and sulfate (SO4), which can form salts like thenardite (Na2SO4) and mirabilite (Na2SO4&sdot;H2O). The Utah Department of Environmental Quality (2010) classified the contamination as natural background and from nonpoint sources related to regional lithology and irrigation practices. Although the daily loads of the constituents of concern and water chemistry have been characterized for parts of the watershed, little is known about the controls that bedrock and soil mineralogy have on salt, Se, and B storage and the water-rock interactions that influence the mobility of these components in ground and surface waters. Studies in the Uncompahgre River watershed in Colorado by Tuttle and others (2014a, 2014b) show that salt derived from weathering of shale in a semiarid climate is stored in a variety of minerals that contribute solutes to runoff and surface waters based on a complex set of conditions such as water availability, geomorphic position (for example, topography controls the depth of salt accumulation in soils), water-table fluctuations, redox conditions, mineral dissolution kinetics, ion-exchange reactions, and secondary mineral formation. Elements like Se and B commonly reside in soluble salt phases, so knowledge of the behavior of salt minerals also sheds light on the behavior of associated contaminants. The goal of this study was to establish a process-based understanding of salt, Se, and B behavior to address whether these contaminants can be better managed, or if uncontrollable natural processes will overwhelm any attempts to bring Pariette Draw into compliance with respect to recently established total maximum daily limits (TMDLs). We collected data to refine our knowledge about the role of rock weathering and soil formation in the transport and storage of salt in the watershed and to show how salt is cycled under irrigated and natural conditions. Our approach was to sample rock, soils, and sediment on irrigated and natural terrain for mineralogical analysis to determine the residence of salt and associated Se and B, classify minerals as primary (related to rock formation) or secondary weathering products, and characterize mineral dissolution kinetics. Mineral and chemical analyses and selective extractions of rocks and soils provide useful information in understanding solute movement and mineral dissolution/ formation. The resulting data are critical in determining residence of salt, Se, and B in weathered rock and soil and understanding the mobility during water-rock-soil interactions. This report summarizes our methods for sample and data collection and tabulates the mineral, chemical, and isotopic data collected.

Utah

Toxic effects of dietary methylmercury on immune function and hematology in American kestrels (Falco sparverius)

Fifty-nine adult male American kestrels ( Falco sparverius ) were assigned to one of three diet formulations including 0 (control), 0.6, and 3.9 &mu;g/g (dry wt) methylmercury (MeHg). Kestrels received their diets daily for 13 weeks to assess the effects of dietary MeHg on immunocompetence. Immunotoxic endpoints included assessment of cell-mediated immunity (CMI) using the phytohemagglutinin (PHA) skin-swelling assay and primary and secondary antibody-mediated immune responses (IR) via the sheep red blood cell (SRBC) hemagglutination assay. Select hematology and histology parameters were evaluated to corroborate the results of functional assays and to assess immunosuppression of T and B cell-dependent components in spleen tissue. Kestrels in the 0.6 and 3.9 &mu;g/g MeHg groups exhibited suppression of CMI, including lower PHA stimulation indexes ( p = 0.019) and a 42 to 45% depletion of T cell-dependent splenic lymphoid tissue ( p = 0.006). Kestrels in the 0.6 &mu;g/g group exhibited suppression of the primary IR to SRBCs ( p = 0.014). MeHg did not have a noticeable effect on the secondary IR ( p = 0.166). Elevation of absolute heterophil counts ( p < 0.001), the heterophil to lymphocyte ratio ( p < 0.001), and total white blood cell counts ( p = 0.003) was apparent in the 3.9 &mu;g/g group at week 12. Heterophilia, or the excess of heterophils in peripheral blood above normal ranges, was apparent in seven of 17 (41%) kestrels in the 3.9 &mu;g/g group and was indicative of an acute inflammatory response or physiological stress. This study revealed that adult kestrels were more sensitive to immunotoxic effects of MeHg at environmentally relevant dietary concentrations than they were to reproductive effects as previously reported.

Environmental Toxicology and Chemistry

Regional ground-water flow and geochemistry in the midwestern Basins and Arches aquifer system in parts of Indiana, Ohio, Michigan, and Illinois

This report synthesizes information on the regional ground-water flow and geochemistry in the Midwestern Basins and Arches aquifer system in parts of Indiana, Ohio, Michigan, and Illinois. Aquifers that compose this water-table aquifer system include glacial aquifers and an underlying, areally extensive carbonate-rock aquifer. Water within the aquifers is most commonly a Ca-Mg-HCO 3 type or a Ca-Mg-SO 4 type. In general, the distribution of hydrochemical facies within the aquifer system is controlled by the mineralogy of the aquifer material, rather than by a chemical evolution of water along general directions of regional ground-water flow. Some ground-water flow systems within the aquifer system provide base flow to streams in response to ground-water recharge events. Other (often deeper) ground-water flow systems respond minimally to variations in ground-water recharge from precipitation and provide a fairly constant supply of water to streams. Streamflow hydrographs and base-flow duration curves were used to estimate such components of base flow in selected streams for long-term steady-state conditions in the aquifer system. Mean sustained ground-water discharge (discharge from fairly stable ground-water flow systems) ranges from 3 to 50 percent of mean ground-water discharge (discharge from all ground-water flow systems) to the selected stream reaches. These percentages indicate that 50 to 97 percent of base flow in the streams within the study area can be attributed to transient ground-water flow systems, which typically have a major component of local-scale flow. Because ground-water flow across the external boundaries of the aquifer system is minimal, such percentages indicate that most ground-water flow in the aquifer system is associated with seasonally transient local flow systems. Results of a ground-water flow model that was calibrated by use of regression methods and that simulates regional flow systems within the aquifer system (approximately 10 percent of total ground-water flow in the aquifer system) indicate that most water (99 percent) in simulated regional flow systems is from recharge at the water table. Most water (78 percent) discharges from simulated regional flow systems to the principal streams. Less than 3 percent of water in simulated regional flow systems discharges to the Ohio River, Lake Erie, or downdip areas in the Illinois (structural) Basin. Simulations also indicate that most of the Midwestern Basins and Arches aquifer system is characterized by alternating regional recharge and discharge areas at intervals of less than every 10 miles along the dominant regional trends of the potentiometric surfaces in the aquifers. Such alternating regional recharge and discharge areas result in the absence of long flow paths from the very highest regional potentiometric levels to the very lowest regional potentiometric levels. The presence of tritiated ground water (less than 50 years old) across most of the aquifer system also indicates that the aquifer system receives recharge across most of the study area. The northeastern part of the aquifer system near Lake Erie differs from the rest of the system with respect to regional ground-water flow and chemistry. Specifically, part of the northeastern part of the aquifer system can be characterized as a broad area (tens of miles) of weak regional discharge (less than 0.5 inch per year). Results of the regional ground-water flow model indicate that regional flow systems have a limited ability to carry ground water away from this area; thus precipitation is prevented from recharging the regional flow systems in this part of the aquifer system. Some ground water recharged during Pleistocene glaciation was found in this area.

Illinois, Indiana, Michigan, Ohio

Estimates of groundwater recharge rates and sources in the East Mountain area, Eastern Bernalillo County, New Mexico, 2005-12

The U.S. Geological Survey, in cooperation with the Bernalillo County Public Works Division, has conducted a monitoring program in the East Mountain area of eastern Bernalillo County, New Mexico, since 2000 to better define the hydrogeologic characteristics of the East Mountain area and to provide scientific information that will assist in the sustainable management of water resources. This report presents estimates of groundwater recharge to the aquifers that supply water to a network of springs that discharged within the East Mountain area of eastern Bernalillo County during 2005&ndash;12. Chloride concentration, the mass ratio of chloride to bromide, and the stable isotope ratios of hydrogen and oxygen were used to estimate annual groundwater recharge rates and to identify the sources and timing of recharge to the aquifers in the East Mountain area. Groundwater recharge rates were estimated by using a chloride mass-balance (CMB) method applied to data from selected springs located in the study area. Eleven springs and four downgradient monitoring wells were sampled for this study. On the basis of chloride concentrations and the mass ratio of chloride to bromide, eight of the eleven sampled springs are considered representative of dilute groundwater recharged by meteoric water in the Sandia Mountains. Eight of the eleven springs sampled as part of this investigation are considered representative of dilute groundwater not influenced by nonmeteoric chloride sources on the basis of analysis of chloride concentrations and the mass ratio of chloride to bromide. Chloride concentrations at three of the sampled springs were likely affected by nonmeteoric chloride sources. Results of CMB calculations for the eight springs with Cl:Br ratios and chloride concentrations within the range of dilute groundwater (not influenced by nonmeteoric chloride sources) indicated that between about 5.5 and 23 percent of annual precipitation recharges the groundwater system. The variation in estimated recharge rates indicated that the mechanisms for recharge and groundwater movement in the East Mountain area are complex and that factors such as climate variability, the extent and interconnection of structural features such as faults and fractures, and potential solution enhancement of the aquifers all play important roles in the rates and timing of recharge. Stable isotope data from springs and snowpacks sampled in the East Mountain area were compared with local, regional, and global meteoric water lines and were analyzed along with values representing the stable isotope composition of winter precipitation and summer monsoonal rains. Results of the stable isotope analysis from springs in this study suggested that winter precipitation is the primary source of groundwater recharge to the aquifers supplying the springs, but there is a component of more isotopically enriched precipitation being recharged as well, likely from summer monsoonal rains. Specific conductance, groundwater-level hydrographs, snowpack chemistry, and snow-water equivalent data were used to inform the analyses and corroborate the findings of the CMB and stable isotope results.

New Mexico

Rapid toxicity assessment of sediments from estuarine ecosystems: A new tandem in vitro testing approach

Microtox® and Mutatox® were used to evaluate the acute toxicity and genotoxicity, respectively, of organic sediment extracts from Pensacola Bay and St. Andrew Bay, two estuaries that cover about 273 and 127 km 2 , respectively, along the Gulf coast of Florida, USA. The sensitivity and selectivity of these two bioluminescent toxicity assays were demonstrated in validation studies with over 50 pesticides, genotoxins, and industrial pollutants, both as single compounds and in complex mixtures. The 50% effective concentration (EC50) values of insecticides, petroleum products, and polychlorinated biphenyls determined by Microtox all tended to group around the mean EC50 value of 1.2 (0.8) mg/L. The polycyclic aromatic hydrocarbon sensitivity of Mutatox was in general similar to that reported in the Ames test. Surficial sediment samples were collected, extracted with dichloromethane, evaporated and concentrated under nitrogen, dissolved in dimethyl sulfoxide, assayed for acute toxicity and genotoxicity, and compared with reference sediments. Samples with low EC50 values, and determined to be genotoxic, were detected in Massalina Bayou, Watson Bayou, East Bay, and St. Andrew Bay–East in St. Andrew Bay as well as Bayou Grande, Bayou Chico, and Bayou Texar in Pensacola Bay. An overview of these data sets analyzed by Spearman rank correlation showed a significant correlation between acute toxicity and genotoxicity ( p < 0.05). Microtox and Mutatox in tandem was a sensitive, cost‐effective, and rapid (<24 h) screening tool that identified troublesome areas of pollution and assessed the potential sediment toxicity of lipophilic contaminants in aquatic ecosystems.

Environmental Toxicology and Chemistry