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

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

Illinois, Indiana, Iowa, Kansas, Kentucky, Michiga

Hydrologic landscapes on the Delmarva Peninsula - Part 2: Estimates of base-flow nitrogen load to Chesapeake Bay

ABSTRACT: The relation between landscape characteristics and water chemistry on the Delmarva Peninsula can be determined through a principal-component analysis of basin characteristics. Two basin types were defined by factor scores: (1) well-drained basins, characterized by combinations of a low percentage of forest cover, a low percentage of poorly drained soil, and elevated channel slope; and (2) poorly drained basins, characterized by a combinations of an elevated percentage of forest cover, an elevated percentage of poorly drained soil, and low channel slopes. Results from base-flow sampling of 29 basins during spring 1991 indicate that water chemistry of the two basin types differ significantly. Concentrations of calcium, magnesium, potassium, alkalinity, chloride, and nitrate are elevated in well-drained basins, and specific conductance is elevated. Concentrations of aluminum, dissolved organic carbon, sodium, and silica are elevated in poorly drained basins whereas specific conductance is low. The chemical patterns found in well-drained basins can be attributed to the application of agricultural chemicals, and those in poorly drained basins can be attributed to ground-water flowpaths. These results indicate that basin types determined by a quantitative analysis of basin characteristics can be related statistically to differences in base-flow chemistry, and that the observed statistical differences can be related to major processes that affect water chemistry.

Journal of the American Water Resources Associatio

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

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

Potomac River Basin

Report of committee on the chemistry of natural waters, 1941–42

The membership of the Committee during the past year was as follows: I. A. Dennison, National Bureau of Standards; C S. Howard (Chairman), Geological Survey; C. S. Scofield, Department of Agriculture; D. G. Thompson, Geological Survey; and T. G. Thompson, University of Washington, Seattle, Washington. SCOFIELD has continued his studies in connection with the salt balance in irrigated areas and has made progress‐reports to interested parties concerning the salt balance on the El Paso Project, Wapato Project, and the Yuma Project. These studies are of great interest to those responsible for the operation of the projects and should be of considerable value to other projects in indicating the volumes of water that may be necessary under certain conditions to insure proper drainage of the project.

Eos, Transactions, American Geophysical Union

Physiography, geology, and land cover of four watersheds in eastern Puerto Rico: Chapter A in Water quality and landscape processes of four watersheds in eastern Puerto Rico

Four watersheds with differing geology and land cover in eastern Puerto Rico have been studied on a long-term basis by the U.S. Geological Survey to evaluate water, energy, and biogeochemical budgets. These watersheds are typical of tropical, island-arc settings found in many parts of the world. Two watersheds are located on coarse-grained granitic rocks that weather to quartz- and clay-rich, sandy soils, and two are located on fine-grained volcanic rocks and volcaniclastic sedimentary rocks that weather to quartz-poor, fine-grained soils. For each bedrock type, one watershed is covered with mature forest, and the other watershed, like most of Puerto Rico, has transformed from relatively undisturbed pre-European forest to intensive agriculture in the 19th and early 20th centuries, and further to ongoing reforestation that began in the middle of the 20th century. The comparison of water chemistry and hydrology in these watersheds allows an evaluation of the effects of land-use history and geology on hydrologic regimes and erosion rates. This chapter describes the physiography, geology, and land cover of the four watersheds and provides background information for the remaining chapters in this volume.

Professional Paper

The effects of land use on fluvial sediment chemistry for the conterminous U.S. - Results from the first cycle of the NAWQA Program: Trace and major elements, phosphorus, carbon, and sulfur

In 1991, the U.S. Geological Survey (USGS) began the first cycle of its National Water Quality Assessment (NAWQA) Program. The Program encompassed 51 river basins that collectively accounted for more than 70% of the total water use (excluding power generation), and 50% of the drinking water supply in the U.S. The basins represented a variety of hydrologic settings, rock types (geology), land-use categories, and population densities. One aspect of the first cycle included bed sediment sampling; sites were chosen to represent baseline and important land-use categories (e.g., agriculture, urban) in each basin. In total, over 1200 bed sediment samples were collected. All samples were size-limited (< 63????m) to facilitate spatial and/or temporal comparisons, and subsequently analyzed for a variety of chemical constituents including major (e.g., Fe, Al,) and trace elements (e.g., Cu, Zn, Cd), nutrients (e.g., P), and carbon. The analyses yielded total (??? 95% of the concentrations present), rather than total-recoverable chemical data. Land-use percentages, upstream underlying geology, and population density were determined for each site and evaluated to asses their relative influence on sediment chemistry. Baseline concentrations for the entire U.S. also were generated from a subset of all the samples, and are based on material collected from low population (??? 27??p km- 2) density, low percent urban (??? 5%), agricultural or undeveloped areas. The NAWQA baseline values are similar to those found in other national and global datasets. Further, it appears that upstream/underlying rock type has only a limited effect (mostly major elements) on sediment chemistry. The only land-use category that appears to substantially affect sediment chemistry is percent urban, and this result is mirrored by population density; in fact, the latter appears more consistent than the former.

Science of the Total Environment

Assessing background ground water chemistry beneath a new unsewered subdivision

Previous site-specific studies designed to assess the impacts of unsewered subdivisions on ground water quality have relied on upgradient monitoring wells or very limited background data to characterize conditions prior to development. In this study, an extensive monitoring program was designed to document ground water conditions prior to construction of a rural subdivision in south-central Wisconsin. Previous agricultural land use has impacted ground water quality; concentrations of chloride, nitrate-nitrogen, and atrazine ranged from below the level of detection to 296 mg/L, 36 mg/L, and 0.8 ??g/L, respectively, and were highly variable from well to well and through time. Seasonal variations in recharge, surface topography, aquifer heterogeneities, surficial loading patterns, and well casing depth explain observed variations in ground water chemistry. This variability would not have been detected if background conditions were determined from only a few monitoring wells or inferred from wells located upgradient of the subdivision site. This project demonstrates the importance of characterizing both ground water quality and chemical variability prior to land-use change to detect any changes once homes are constructed. Copyright ?? 2005 National Ground Water Association.

Ground Water

Geohydrology and water chemistry of the Alexander Valley, Sonoma County, California

This study of the geohydrology and water chemistry of the Alexander Valley, California, was done to provide an improved scientific basis for addressing emerging water-management issues, including potential increases in water demand and changes in flows in the Russian River. The study tasks included (1) evaluation of existing geohydrological, geophysical, and geochemical data; (2) collection and analysis of new geohydrologic data, including subsurface lithologic data, ground-water levels, and streamflow records; and (3) collection and analysis of new water-chemistry data. The estimated total water use for the Alexander Valley for 1999 was approximately 15,800 acre-feet. About 13,500 acre-feet of this amount was for agricultural use, primarily vineyards, and about 2,300 acre-feet was for municipal/industrial use. Ground water is the main source of water supply for this area. The main sources of ground water in the Alexander Valley are the Quaternary alluvial deposits, the Glen Ellen Formation, and the Sonoma Volcanics. The alluvial units, where sufficiently thick and saturated, comprise the best aquifer in the study area. Average recharge to the Alexander Valley is estimated from a simple, basinwide water budget. On the basis of an estimated annual average of 298,000 acre-feet of precipitation, 160,000 acre-feet of runoff, and 113,000 to 133,000 acre-feet of evapotranspiration, about 5,000 to 25,000 acre-feet per year is available for ground-water recharge. Because this estimate is based on differences between large numbers, there is significant uncertainty in this recharge estimate. Long-term changes in ground-water levels are evident in parts of the study area, but because of the sparse network and lack of data on well construction and lithology, it is uncertain if any significant changes have occurred in the northern part of the study area since 1980. In the southern half of the study area, ground-water levels generally were lower at the end of the 2002 irrigation season than at the end of the 1980 season, which suggests that a greater amount of ground water is being pumped in the southern half of the study area in recent years compared with that pumped in the early 1980s. Water-chemistry data for samples collected from 11 wells during 2002-04 indicate that water quality in the study area generally is acceptable for potable use. Two wells, however, each contained one constituent (241 ?g/L of manganese and 1,350 ?g/L of boron) in excess of the recommended standards for drinking water (50 ?g/L and 1,000 ?g/L, respectively). The chemical composition of water from most of the wells sampled for major ions plot as a mixed cation-bicarbonate, magnesium-bicarbonate, or calcium-bicarbonate type water. The ionic composition of the historical and recent samples from wells in the Alexander Valley is similar to that of the historical surface-water samples collected from the Russian River near Healdsburg. This suggests a similar source of water, particularly for wells that are less than 200 feet total depth and perforated in Quaternary alluvial deposits. Water from deeper, non-alluvial wells may contain slightly higher concentrations of sodium as a result of cation exchange. Water samples collected from several wells over an approximately 30-year period suggest a progressive change in water chemistry over time. Samples from the southern part of the valley show a trend towards higher ionic concentrations and increasing concentrations of particular constituents such as sulfate.

California

Prioritizing US Geological Survey science on salinization and salinity in candidate and selected priority river basins

The US Geological Survey (USGS) is selecting and prioritizing basins, known as Integrated Water Science basins, for monitoring and intensive study. Previous efforts to aid in this selection process include a scientifically defensible and quantitative assessment of basins facing human-caused water resource challenges (Van Metre et al. in Environmental Monitoring and Assessment , 192(7), 458 2020). In the present work, we explore this ranking process based on water quality considerations, specifically salinity and salinization. We selected top candidate basins to study salinity and salinization issues in 18 hydrologic regions that include 163 candidate basins. Our prioritization is based on quantitative assessment of sources of salinity, drivers of change, and receptors that must respond to those sources and drivers. Source terms represented in the prioritization include geology, depth to brackish groundwater, stream conductivity, chloride in precipitation, urban and agricultural land use, application of road salt as a deicer, and irrigation. Drivers represented in prioritization include changes in chemical weathering as a result of changes in rainwater chemistry. Receptors include measures of water stress, measurements of stream ecological health, and socioeconomic factors. In addition, we present research activities for the USGS on salinity and salinization that can be pursued in these basins including assessment of sources, pathways, and loadings; predicting and understanding changes in sources, peaks, and trends; understanding the components of salinity and mobilization of contaminants; understanding the relationship between salinization and changing ecosystems; and developing knowledge on the causes and distribution of groundwater salinity, brackish water resources, and challenges related to desalination.

Enviornmental Monitoring and Assessment

Seasonal/yearly salinity variations in San Francisco Bay

The ability of resource agencies to manage fish, wildlife and freshwater supplies of San Francisco Bay estuary requires an integrated knowledge of the relations between the biota and their physical environment. A key factor in these relations is the role of salinity in determining both the physical and the biological character of the estuary. The saltiness of the water, and particularly its seasonal and interannual patterns of variability, affects which aquatic species live where within the estuary. Salinity also determines where water can and cannot be diverted for human consumption and irrigated agriculture, and plays a role in determining the capacity of the estuary to cleanse itself of wastes. In short, salinity is a fundamental property of estuarine physics and chemistry that, in turn, determines the biological characteristics of each estuary. Freshwater is a major control on estuarine salinity. Most freshwater supplied to the Bay is from river flow through the Delta, which is primarily runoff from the Sierra Nevada. Most contaminants in San Francisco Bay are from the Sacramento/San Joaquin Valley and the local watershed around the Bay rather than the sea or atmosphere. Land is the primary source of freshwater and freshwater serves as a tracer of land-derived substances such as the trace metals (copper, lead and selenium), pesticides and plant nutrients (nitrate and phosphate). The U.S. Geological Survey is collaborating with other agencies and institutions in studying San Francisco Bay salinity using field observations and numerical simulations to define the physical processes that control salinity. The issues that arise from salinity fluctuations, however, differ in the northern and southern parts of the bay. In North Bay we need to know how salinity responds to freshwater flow through the Sacramento/San Joaquin Delta; this knowledge will benefit water managers who determine how much delta flow is needed a) to protect freshwater supplies for municipal water use and b) modulate salinity for a healthy estuary. In South Bay we need to know where the freshwater comes from (the distant Delta or local streams) to sort out the sources of a) contamination or b) dilution.

California

The Beaver Creek story

Beaver Creek watershed in West Tennessee includes about 95,000 acres of the Nation's most productive farmland and most highly erodible soils. In 1989 the U.S. Geological Survey, in cooperation with the Tennessee Department of Agriculture, began a study to evaluate the effect of agricultural activities on water quality in the watershed and for best management practices designed to reduce agricultural nonpoint-source pollution. Agrichemical monitoring included testing the soils, ground water, and streams at four farm sites ranging from 27 to 420 acres. Monitoring stations were operated downstream to gain a better understanding of the water chemistry as runoff moved from small ditches into larger streams to the outlet of the Beaver Creek watershed. Prior to the implementation of best management practices at one of the farm study sites, some storms produced an average suspended-sediment concentration of 70,000 milligrams per liter. After the implementation of BMP's, however, the average value never exceeded 7,000 milligrams per liter. No-till crop production was the most effective best management practice for conserving soil on the farm fields tested. A natural bottomland hardwood wetland and a constructed wetland were evaluated as instream resource-management systems. The wetlands improved water quality downstream by acting as a filter and removing a significant amount of nonpoint-source pollution from the agricultural runoff. The constructed wetland reduced the sediment, pesticide, and nutrient load by approximately 50 percent over a 4-month period. The results of the Beaver Creek watershed study have increased the understanding of the effects of agriculture on water resources. Study results also demonstrated that BMP's do protect and improve water quality.

Open-File Report

Use of biological characteristics of common carp ( Cyprinus carpio ) to indicate exposure to hormonally active agents in selected Minnesota streams, 1999

The presence of hormonally active agents (HAAs) was determined in selected Minnesota streams using biological characteristics (measures of endocrine disruption) of common carp ( Cyprinus carpio ) exposed to wastewater treatment plant (WWTP) effluent and runoff from agricultural and forested land. Four biological characteristics of common carp were used as indicators of HAAs in the streams selected for this study: (1) high concentrations of vitellogenin in male fish and low concentrations in female fish, (2) high or low plasma concentrations of the sex steroid hormones (17&beta;-estradiol and 11-ketotestosterone), (3) low gonado-somatic index (GSI) (gonad weight divided by total body weight multiplied by 100) values, and (4) abnormal gonad histopathology (high percent of atretic oocytes in female ovaries and high percent ceroid/lipofuscin tissue in male or female gonads). The study design was a paired site approach targeting sites downstream and upstream of WWTP discharges on different streams. Male (221 individuals) and female (201 individuals) common carp were collected using electrofishing techniques from seven streams with sites at two locations (upstream and downstream of WWTPs), and eight sites located downstream of WWTPs with no upstream-paired sites. Samples were collected between August 3 and September 13, 1999. The presence of HAAs in selected Minnesota streams was indicated by biological characteristics in common carp. Biological characteristics used in this study identified WWTP effluent as a potential source of HAAs. Additionally, fish located at sites upstream of WWTP effluent primarily draining agricultural land show indications of HAAs, which may be the result of agricultural runoff or other sources of HAAs. There was variability among all sites and among sites within each site group. Differences among sites may be due to differences in water chemistry or fish exposure time. Natural variation in the biological characteristics may account for some of the differences observed in this study. This study and others indicate the presence of HAAs in surface water and the potential signs of endocrine disruption in resident fish populations. Detailed controlled studies could confirm the effects of particular chemicals such as pesticides or components of WWTPs on fish reproduction and population structure.

Minnesota

Geohydrological characterization, water-chemistry, and ground-water flow simulation model of the Sonoma Valley area, Sonoma County, California

The Sonoma Valley, located about 30 miles north of San Francisco, is one of several basins in Sonoma County that use a combination of ground water and water delivered from the Russian River for supply. Over the past 30 years, Sonoma Valley has experienced rapid population growth and land-use changes. In particular, there has been a significant increase in irrigated agriculture, predominantly vineyards. To provide a better understanding of the ground-water/surface-water system in Sonoma Valley, the U.S. Geological Survey compiled and evaluated existing data, collected and analyzed new data, and developed a ground-water flow model to better understand and manage the ground-water system. The new data collected include subsurface lithology, gravity measurements, groundwater levels, streamflow gains and losses, temperature, water chemistry, and stable isotopes. Sonoma Valley is drained by Sonoma Creek, which discharges into San Pablo Bay. The long-term average annual volume of precipitation in the watershed is estimated to be 269,000 acre-feet. Recharge to the ground-water system is primarily from direct precipitation and Sonoma Creek. Discharge from the ground-water system is predominantly outflow to Sonoma Creek, pumpage, and outflow to marshlands and to San Pablo Bay. Geologic units of most importance for groundwater supply are the Quaternary alluvial deposits, the Glen Ellen Formation, the Huichica Formation, and the Sonoma Volcanics. In this report, the ground-water system is divided into three depth-based geohydrologic units: upper (less than 200 feet below land surface), middle (between 200 and 500 feet), and lower (greater than 500 feet). Synoptic streamflow measurements were made along Sonoma Creek and indicate those reaches with statistically significant gains or losses. Changes in ground-water levels in wells were analyzed by comparing historical contour maps with the contour map for 2003. In addition, individual hydrographs were evaluated to assess temporal changes by region. In recent years, pumping depressions have developed southeast of Sonoma and southwest of El Verano. Water-chemistry data for samples collected from 75 wells during 2002-04 indicate that the ground-water quality in the study area generally is acceptable for potable use. The water from some wells, however, contains one or more constituents in excess of the recommended standards for drinking water. The chemical composition of water from creeks, springs, and wells sampled for major ions plot within three groups on a trilinear diagram: mixed-bicarbonate, sodium-mixed anion, and sodium-bicarbonate. An area of saline ground water in the southern part of the Sonoma Valley appears to have shifted since the late 1940s and early 1950s, expanding in one area, but receding in another. Sparse temperature data from wells southwest of the known occurrence of thermal water suggest that thermal water may be present beneath a larger part of the valley than previously thought. Thermal water contains higher concentrations of dissolved minerals than nonthermal waters because mineral solubilities generally increase with temperature. Geohydrologic Characterization, Water-Chemistry, and Ground-Water Flow Simulation Model of the Sonoma Valley Area, Sonoma County, California Oxygen-18 (d18 O) and deuterium (dD) values for water from most wells plot along the global meteoric water line, indicating that recharge primarily is derived from the direct infiltration of precipitation or the infiltration of seepage from creeks. Samples from shallow- and intermediate-depth wells located near Sonoma Creek and (or) in the vicinity of Shellville plot to the right of the global meteoric water line, indicating that these waters are partly evaporated. The d18 O and dD composition of water from sampled wells indicates that water from wells deeper than 200 feet is isotopically lighter (more negative) than water from wells less than 200 feet deep, possibly indicating that older ground wate

California

Identifying chemicals and mixtures of potential biological concern detected in passive samplers from Great Lakes tributaries using high-throughput data and biological pathways

Waterborne contaminants were monitored in 69 tributaries of the Laurentian Great Lakes in 2010 and 2014 using semipermeable membrane devices (SPMDs) and polar organic chemical integrative samplers (POCIS). A risk-based screening approach was used to prioritize chemicals and chemical mixtures, identify sites at greatest risk for biological impacts, and identify potential hazards to monitor at those sites. Analyses included 185 chemicals (143 detected) including polycyclic aromatic hydrocarbons (PAHs), legacy and current-use pesticides, fire retardants, pharmaceuticals, and fragrances. Hazard quotients were calculated by dividing detected concentrations by biological effect concentrations reported in the ECOTOX Knowledgebase (toxicity quotients) or ToxCast database (exposure–activity ratios [EARs]). Mixture effects were estimated by summation of EAR values for chemicals that influence ToxCast assays with common gene targets. Nineteen chemicals—atrazine, N,N -diethyltoluamide, di(2-ethylhexyl)phthalate, dl-menthol, galaxolide, p-tert-octylphenol, 3 organochlorine pesticides, 3 PAHs, 4 pharmaceuticals, and 3 phosphate flame retardants—had toxicity quotients >0.1 or EARs for individual chemicals >10 –3 at 10% or more of the sites monitored. An additional 4 chemicals (tributyl phosphate, triethyl citrate, benz[ a ]anthracene, and benzo[ b ]fluoranthene) were present in mixtures with EARs >10 –3 . To evaluate potential apical effects and biological endpoints to monitor in exposed wildlife, in vitro bioactivity data were compared to adverse outcome pathway gene ontology information. Endpoints and effects associated with endocrine disruption, alterations in xenobiotic metabolism, and potentially neuronal development would be relevant to monitor at the priority sites. The EAR threshold exceedance for many chemical classes was correlated with urban land cover and wastewater effluent influence, whereas herbicides and fire retardants were also correlated to agricultural land cover. Environ Toxicol Chem 2021;40:2165–2182. Published 2021. This article is a U.S. Government work and is in the public domain in the USA. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Great Lakes

Use of spatial statistics and isotopic tracers to measure the influence of arsenical pesticide use on stream sediment chemistry in New England, USA

Arsenical pesticides and herbicides, principally Pb arsenate, Ca arsenate, and Na arsenate with lesser use of other metal-As pesticides, were widely applied on apple, blueberry, and potato crops in New England during the first half of the twentieth century. Agricultural census data for this time period is used to define an agricultural index that identifies areas that are inferred to have used arsenical pesticides extensively. Factor analysis on metal concentrations in 1597 stream sediment samples collected throughout New England, grouped by agricultural-index categories, indicate a positive association of areas with stream sediment sample populations that contain higher As and Pb concentrations than samples from the region as a whole with sample site settings having high agricultural-index values. Population statistics for As and Pb concentrations and factor scores for an As-Pb factor all increase systematically and significantly with increasing agricultural-index intensity in the region, as tested by Kruskal-Wallis analysis. Lead isotope compositions for 16 stream sediments from a range of agricultural-index settings generally overlap the observed variation in rock sulfides and their weathering products; however, sediments collected from high agricultural-index settings have slightly more radiogenic Pb compositions, consistent with an industrial Pb contribution to these samples. Although weathering products from rocks are likely to be the dominant source of As and metals to most of the stream sediment samples collected in the region, the widespread use of arsenical pesticides and herbicides in New England during the early 1900-1960s appears to be a significant anthropogenic source of As and metals to many sediments in agricultural areas in the region and has raised background levels of As in some regions. Elevated concentrations of As in stream sediments are of concern for two reasons. Stream sediments with elevated As concentrations delineate areas with elevated background concentrations of As from both natural rock and anthropogenic sources that may contribute As to groundwater systems used for drinking water supplies. Conversion of agricultural land contaminated with arsenical pesticide residues to residential development may increase the likelihood that humans will be exposed to As. In addition, many stream sediment sites have As concentrations that exceed sediment quality guidelines established for freshwater ecosystems. Thirteen percent of the New England sediment sample sites exceed 9.79 mg/kg As, the threshold effects concentration (TEC), below which harmful effects are unlikely to be observed. Arsenic concentrations exceed 33 mg/kg, the probable effects concentration (PEC), above which harmful effects on sediment-dwelling organisms are expected to occur frequently, at 1.25% of the sediment sample sites. The sample sites that exceed the PEC value occur predominately in agricultural areas that used arsenical pesticides.

Conference Paper

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

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

Open-File Report

Availability and chemistry of ground water on the Bruneau Plateau and adjacent eastern plain in Twin Falls County, south-central Idaho

The Bruneau plateau in south-central Idaho consists of about 889 ,600 acres of potentially irrigable land. About 112,200 of these acres have been developed for agriculture; 11,200 acres are irrigated with ground water, and the remaining acreage is irrigated with water from the Snake and Bruneau rivers and Salmon Falls Creek. On the basis of present usage, about 158,000 acre-feet of water per year are needed to develop an additional 63,000 acres. About 438,000 acre-feet per year are needed to irrigate existing and newly developed lands in dry years when streamflow in the Snake River at Milner Dam is inadequate to meet appropriated needs. Pumping lifts of about 400-600 feet and low well yields on the Bruneau plateau probably preclude large-scale irrigation development solely from local ground-water resources. However, supplemental sources of irrigation water are available from a perched-water aquifer, a thermal aquifer, and the regional aquifer adjacent to the plateau. About 100,000-115,000 acre-feet per year of water probably could be withdrawn from the perched and regional aquifers and conveyed to the plateau without serious impact on local ground-water resources. The amount of water that could be safely withdrawn from the thermal aquifer was not determined. (USGS)

Water-Resources Investigations Report

Seasonal and spatial patterns of nitrate and silica concentrations in Canajoharie Creek, New York

The impact of nonpoint-source pollution on surface waters in agricultural watersheds is an emerging environmental issue. As part of the U.S. Geological Survey National Water Quality Assessment program in the Hudson River Basin, Canajoharie Creek was monitored for seasonal and spatial patterns of nutrient chemistry from March 1993 to January 1996. Nitrate and silica concentrations in Canajoharie Creek suggest that seasonal and spatial variations of these nutrients are dominated by biological processes, particularly uptake by phytoplankton. Observed concentration patterns were more typical of those observed in much larger, low-gradient streams. The median nitrate and silica concentrations in Canajoharie Creek were significantly lower from April through November than during winter. Concentrations of both constituents declined downstream from the headwaters during base-flow conditions in June 1995. Groundwater and surface water chemistry data support biological causes for downstream decreases in silica. The strong correlation between nitrate and silica in samples collected along the mainstem suggests that most of the nitrate decrease is due to uptake by diatoms. Downstream patterns of chlorophyll-a in phytoplankton strongly suggest the conversion of in-stream nutrients to algal biomass. Data collected from Canajoharie Creek outlet during the northeast drought of 1995 indicate that silica concentrations in May had possibly declined to a level that adversely affected the diatom community. This decline in the diatom population and subsequent resurgence is inferred from a sharp rise in silica concentrations between May and July and a reversal of this trend from mid-July through October without associated changes in hydrology.

Journal of Environmental Quality