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Comparison of enzyme-linked immunosorbent assay and gas chromatography procedures for the detection of cyanazine and metolachlor in surface water samples

Enzyme-linked immunosorbent assay (ELISA) data from surface water reconnaissance were compared to data from samples analyzed by gas chromatography for the pesticide residues cyanazine (2-[[4-chloro-6-(ethylamino)-l,3,5-triazin-2-yl]amino]-2-methylpropanenitrile ) and metolachlor (2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide). When ELISA analyses were duplicated, cyanazine and metolachlor detection was found to have highly reproducible results; adjusted R2s were 0.97 and 0.94, respectively. When ELISA results for cyanazine were regressed against gas chromatography results, the models effectively predicted cyanazine concentrations from ELISA analyses (adjusted R2s ranging from 0.76 to 0.81). The intercepts and slopes for these models were not different from 0 and 1, respectively. This indicates that cyanazine analysis by ELISA is expected to give the same results as analysis by gas chromatography. However, regressing ELISA analyses for metolachlor against gas chromatography data provided more variable results (adjusted R2s ranged from 0.67 to 0.94). Regression models for metolachlor analyses had two of three intercepts that were not different from 0. Slopes for all metolachlor regression models were significantly different from 1. This indicates that as metolachlor concentrations increase, ELISA will over- or under-estimate metolachlor concentration, depending on the method of comparison. ELISA can be effectively used to detect cyanazine and metolachlor in surface water samples. However, when detections of metolachlor have significant consequences or implications it may be necessary to use other analytical methods.

Journal of Agricultural and Food Chemistry

Herbicides and nitrate in near-surface aquifers in the midcontinental United States, 1991

The occurrence and distribution of selected herbicides, atrazine metabolites, and nitrate were determined for near-surface aquifers (within 50 feet of land surface) in the corn- and soybean-producing region of the midcontinental United States. The study region included all or parts of Illinois, Indiana, Iowa, Kansas, Michigan, Minnesota, Missouri, Nebraska, North Dakota, Ohio, South Dakota, and Wisconsin. Water samples were collected during the spring and summer of 1991 from 303 wells completed in near-surface unconsolidated and near-surface bedrock aquifers. At least one herbicide or atrazine metabolite was detected in 24 percent of 579 water samples analyzed for herbicides, based on a reporting limit of 0.05 microgram per liter. However, no herbicide concentration exceeded the U.S. Environmental Protection Agency's maximum contaminant levels or health advisory levels for drinking water. The most frequently detected herbicide compound was desethylatrazine, an atrazine metabolite (18.1 percent), followed by atrazine (17.4 percent); deisopropylatrazine, an atrazine metabolite (5.7 percent); prometon (5.0 percent); metolachlor (2.7 percent); alachlor (1.7 percent); simazine (1.0 percent); metribuzin (1.0 percent); and cyanazine (0.7 percent). The herbicides ametryn, prometryn, propazine, and terbutryn were not detected during this study. Nitrate concentrations equal to or greater than 3.0 milligrams per liter (excess nitrate) were detected in 29 percent of the 599 nitrate analyses, and ammonium concentrations equal to or greater than 0.01 milligram per liter were detected in 78 percent of the 584 ammonium analyses. Nitrate concentrations equal to or greater than the U.S. Environmental Protection Agency's maximum contaminant level for drinking water of 10 milligrams per liter were found in 6 percent of the samples. The frequency of herbicide detection was, in part, affected by the analytical method's reporting limit. Results from this study show that the frequency of atrazine detection increases as the reporting limit decreases. Herbicide metabolite concentrations are critical to understanding the detection of herbicide residues. The frequency of detection of atrazine residue (atrazine + desethylatrazine + deisopropylatrazine) was 22.1 percent, which was more than the frequency of detection of atrazine alone (17.4 percent). Prometon was detected more frequently than every other herbicide except atrazine. The prometon appears to be derived from areas of nonagricultural land use, such as golf courses and residential areas. Herbicides and excess nitrate were both rarely detected in the eastern part of the study region, even though this is an area of intense herbicide and nitrogen-fertilizer use. Hydrogeologic factors, land use, agricultural practices, local features, and water chemistry were analyzed for possible relation to herbicide and excess-nitrate detections. Herbicides and excess nitrate were detected more frequently in near-surface unconsolidated aquifers than in nearsurface bedrock aquifers. The depth to the top of the aquifer was inversely related to the frequency of detection of herbicides and excess nitrate. The proximity of streams to sampled wells also affected the frequency of herbicide detection. Significant seasonal differences were determined for the frequency of herbicide detection, but not for the frequency of excess nitrate.

Illinois, Indiana, Iowa, Kansas, Michigan, Minneso

Comprehensive water quality of the Boulder Creek Watershed, Colorado, during high-flow and low-flow conditions, 2000

Executive Summary The Boulder Creek Watershed, Colorado, is 1160 square kilometers in area and ranges in elevation from 1480 to 4120 meters above sea level. Streamflow originates primarily as snowmelt near the Continental Divide, and thus discharge varies seasonally and annually (Chapter 1). Most of the water in Boulder Creek is diverted for domestic, agricultural, and industrial use. Some diverted water is returned to the creek as wastewater effluent and by ditch returns, and additional water enters as groundwater and by transbasin diversions. These diversions and returns lead to complex temporal and spatial variations in discharge. The variations in discharge, along with natural factors such as geology and climate, and anthropogenic factors such as wastewater treatment, agriculture, mining, and urbanization, can affect water chemistry. As with many watersheds in the American West, dependable water quality and sufficient water supply are issues facing local water managers and users. Detailed water-quality and sediment sampling allows the identification of sources and sinks of chemical constituents and an understanding of the processes at work in a river system. This study, the most comprehensive water-quality analysis performed for Boulder Creek to date, was a cooperative effort of the U.S. Geological Survey (USGS) and the city of Boulder. Geographic information systems and modeling programs were used to delineate watershed boundaries, land cover, and geology (Chapter 2). During high-flow (June 2000) and low-flow (October 2000) conditions, researchers evaluated 226 water-quality variables, including basic water-quality indicators (Chapter 3), major ions and trace elements (Chapter 4), wastewater-derived organic compounds (Chapter 5), and pesticides (Chapter 6). Discharge (Chapter 1) and bed-sediment particle size and mineralogy (Chapter 7) were also evaluated. This cooperative study was facilitated by the Boulder Area Sustainability Information Network (BASIN), which provides public access to environmental information about the Boulder Creek Watershed on a website, www.basin.org. In addition to the USGS and city of Boulder data, researchers at the Institute of Arctic and Alpine Research at the University of Colorado provided water chemistry data for the headwaters of North Boulder Creek, upstream of the reach of the USGS/city of Boulder sampling sites (Chapter 8). Snowmelt produces high flows in Boulder Creek in late spring to early summer (Chapter 1). Because precipitation falling in the headwaters is very dilute (specific conductance about 5 microsiemens per centimeter), most chemical constituents are present in lower concentrations during high flows (Chapters 3, 4, 5, 6, and 8). However, concentrations of some constituents, such as total suspended solids (Chapter 3) and organic carbon (Chapter 5), increase during the spring snowmelt flush. The upper basin, which consists of alpine, subalpine, montane, and foothills regions west of the mouth of Boulder Canyon, is underlain by Precambrian igneous and metamorphic rocks (Chapter 1). Major dissolved inorganic constituents in headwater sites were found to be enriched by factors of 10 to 20 relative to precipitation; this is consistent with minor weathering of the local crystalline bedrock (Chapter 4). Some anthropogenic input is observed in the headwaters; precipitation introduces nitrogen derived from fossil fuel combustion and agricultural activities (Chapter 8). The lower basin, which consists of the plains region east of the mouth of Boulder Canyon, is underlain by Mesozoic sedimentary rock and Quaternary alluvium, and has substantially more anthropogenic sources. Concentrations of most dissolved inorganic constituents increased in the lower basin. Differentiation between natural and anthropogenic sources of some dissolved constituents is difficult because both sources contribute to the water composition in this region. The increase of most major constituents (bicarbonate, calcium, chloride, magnesium, sodium, and sulfate) is consistent with weathering of the underlying sedimentary bedrock (Chapter 4). It is likely that anthropogenic loading of constituents in this reach occurs during storm events. Fecal coliform concentrations were variable and in some cases exceeded state standards, primarily during low-flow conditions (Chapter 3). Effluent from Boulder’s 75th Street Wastewater Treatment Plant (WWTP) has a substantial impact on the water chemistry of lower Boulder Creek. The WWTP increases the concentrations of nutrients such as nitrogen and phosphorus (Chapter 3), major ions and trace metals (Chapter 4), and organic carbon (Chapter 5) in Boulder Creek. The effluent contained a spike in gadolinium, a rare earth element that is ingested for magnetic resonance imaging as a contrasting agent and then excreted to the urban wastewater system. The effluent also contained trace organic compounds such as surfactants, pharmaceuticals, hormones (Chapter 5), and pesticides (Chapter 6), which also were detected at downstream Boulder Creek sites. Water chemistry of Boulder Creek downstream of the WWTP is largely controlled by the degree of dilution of the wastewater effluent, which varies depending on the baseflow of Boulder Creek, the volume of wastewater effluent, and depletion by agricultural diversions. Coal Creek, a tributary of Boulder Creek, contains wastewater effluent from four additional WWTPs, and increases the load of many constituents in Boulder Creek. In addition to the impact from wastewater effluent, lower Boulder Creek is affected by agricultural land use. Eleven of 84 analyzed pesticides were detected in Boulder Creek or its inflows, primarily in the eastern section of the watershed (Chapter 6). This collaborative study provides an in-depth evaluation of the hydrology, water chemistry, and sediment mineralogy of North Boulder Creek, Middle Boulder Creek, Boulder Creek, and major inflows. The detailed sampling and analysis in this report provide a baseline for future reference, as well as information on the effect of land use and geology on water chemistry.

Colorado

Responses of benthic macroinvertebrates to urbanization in nine metropolitan areas of the conterminous United States

The effects of urbanization on benthic macroinvertebrates were investigated in nine metropolitan areas (Boston, MA; Raleigh, NC; Atlanta, GA; Birmingham, AL; Milwaukee–Green Bay, WI; Denver, CO; Dallas–Fort Worth, TX; Salt Lake City, UT; and Portland, OR) as a part of the U.S. Geological Survey National Water Quality Assessment Program. Several invertebrate metrics showed strong, linear responses to urbanization when forest or shrublands were developed. Responses were difficult to discern in areas where urbanization was occurring on agricultural lands because invertebrate assemblages were already severely degraded. There was no evidence that assemblages showed any initial resistance to urbanization. Ordination scores, EPT taxa richness, and the average tolerance of organisms were the best indicators of changes in assemblage condition at a site. Richness metrics were better indicators than abundance metrics, and qualitative samples were as good as quantitative samples. A common set of landscape variables (population density, housing density, developed landcover, impervious surface, and roads) were strongly correlated with urbanization and invertebrate responses in all non-agricultural areas. The instream environmental variables (hydrology, water chemistry, habitat, and temperature) that were strongly correlated with urbanization and invertebrate responses were influenced by environmental setting (e.g., dominant ecoregion) and varied widely among metropolitan areas. Multilevel hierarchical regression models were developed that predicted invertebrate responses using only two landcover variables—basinscale landcover (percentage of basin area in developed land) and regional-scale landcover (antecedent agricultural land).

Conference Paper

Residence time, chemical and isotopic analysis of nitrate in the groundwater and surface water of a small agricultural watershed in the Coastal Plain, Bucks Branch, Sussex County, Delaware

Nitrate is a common contaminant in groundwater and surface water throughout the Nation, and water-resource managers need more detailed small-scale watershed research to guide conservation efforts aimed at improving water quality. Concentrations of nitrate in Bucks Branch are among the highest in the state of Delaware and a scientific investigation was performed to provide water-quality information to assist with the management of agriculture and water resources. A combination of major-ion chemistry, nitrogen isotopic composition and age-dating techniques was used to estimate the residence time and provide a chemical and isotopic analysis of nitrate in the groundwater in the surficial aquifer of the Bucks Branch watershed in Sussex County, Delaware. The land use was more than 90 percent agricultural and most nitrogen inputs were from manure and fertilizer. The apparent median age of sampled groundwater is 18 years and the estimated residence time of groundwater contributing to the streamflow for the entire Bucks Branch watershed at the outlet is approximately 19 years. Concentrations of nitrate exceeded the U.S. Environmental Protection Agency drinking-water standard of 10 milligrams per liter (as nitrogen) in 60 percent of groundwater samples and 42 percent of surface-water samples. The overall geochemistry in the Bucks Branch watershed indicates that agriculture is the predominant source of nitrate contamination and the observed patterns in major-ion chemistry are similar to those observed in other studies on the Mid-Atlantic Coastal Plain. The pattern of enrichment in nitrogen and oxygen isotopes (δ15N and δ18O) of nitrate in groundwater and surface water indicates there is some loss of nitrate through denitrification, but this process is not sufficient to remove all of the nitrate from groundwater discharging to streams, and concentrations of nitrate in streams remain elevated.

Delaware

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

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

Water-Resources Investigations Report

Per- and polyfluorinated alkyl substances (PFAS) in Pennsylvania surface waters: A statewide assessment, associated sources, and land-use relations

The objectives of this study are to identify per- and polyfluoroalkyl substances (PFAS) in Pennsylvania surface waters, corresponding associations with potential sources of PFAS contamination (PSOC) and other parameters, and compare raw surface water concentrations to human and ecological benchmarks. Surface water samples from 161 streams were collected in September 2019 and were analyzed for 33 target PFAS and water chemistry. Land use and physical attributes in upstream catchments and geospatial counts of PSOC in local catchments are summarized. The hydrologic yield of the sum of 33 PFAS (∑PFAS) for each stream was computed by normalizing each site's load by the drainage area of the upstream catchment. Utilizing conditional inference tree analysis, the percentage of development (>7.58 %) was identified as a primary driver of the ∑PFAS hydrologic yields. When percentage of development was removed from analysis, ∑PFAS yields were closely related to surface water chemistry associated with landscape alteration (e.g., development or agricultural cropland), such as concentrations of total nitrogen, chloride, and ammonia, but also to count of water pollution control facilities (agricultural, industrial, stormwater, and/or municipal waste pollution abatement facilities). In oil and gas development regions, ∑PFAS yields were associated with combined sewage outfalls. Sites surrounded by ≥2 electronic manufacturing facilities had elevated ∑PFAS yields (median = 241 ng/s/km 2 ). Study results are critical to guide future research, regulatory policy, best practices that will mitigate PFAS contamination, and the communication of human health and ecological risks associated with PFAS exposure from surface waters.

Pennsylvania

Influence of sediment chemistry and sediment toxicity on macroinvertebrate communities across 99 wadable streams of the Midwestern USA

Simultaneous assessment of sediment chemistry, sediment toxicity, and macroinvertebrate communities can provide multiple lines of evidence when investigating relations between sediment contaminants and ecological degradation. These three measures were evaluated at 99 wadable stream sites across 11 states in the Midwestern United States during the summer of 2013 to assess sediment pollution across a large agricultural landscape. This evaluation considers an extensive suite of sediment chemistry totaling 274 analytes (polycyclic aromatic hydrocarbons, organochlorine compounds, polychlorinated biphenyls, polybrominated diphenyl ethers, trace elements, and current-use pesticides) and a mixture assessment based on the ratios of detected compounds to available effects-based benchmarks. The sediments were tested for toxicity with the amphipod Hyalella azteca (28-d exposure), the midge Chironomus dilutus (10-d), and, at a few sites, with the freshwater mussel Lampsilis siliquoidea (28-d). Sediment concentrations, normalized to organic carbon content, infrequently exceeded benchmarks for aquatic health, which was generally consistent with low rates of observed toxicity. However, the benchmark-based mixture score and the pyrethroid insecticide bifenthrin were significantly related to observed sediment toxicity. The sediment mixture score and bifenthrin were also significant predictors of the upper limits of several univariate measures of the macroinvertebrate community (EPT percent, MMI (Macroinvertebrate Multimetric Index) Score, Ephemeroptera and Trichoptera richness) using quantile regression. Multivariate pattern matching (Mantel-like tests) of macroinvertebrate species per site to identified contaminant metrics and sediment toxicity also indicate that the sediment mixture score and bifenthrin have weak, albeit significant, influence on the observed invertebrate community composition. Together, these three lines of evidence (toxicity tests, univariate metrics, and multivariate community analysis) suggest that elevated contaminant concentrations in sediments, in particular bifenthrin, is limiting macroinvertebrate communities in several of these Midwest streams.

Science of the Total Environment

Ground-water quality data in the middle Sacramento Valley study unit, 2006— Results from the California GAMA program

Ground-water quality in the approximately 3,340 mi 2 Middle Sacramento Valley study unit (MSACV) was investigated from June through September, 2006, as part of the California Groundwater Ambient Monitoring and Assessment (GAMA) program. The GAMA Priority Basin Assessment project was developed in response to the Groundwater Quality Monitoring Act of 2001 and is being conducted by the U.S. Geological Survey (USGS) in cooperation with the California State Water Resources Control Board (SWRCB). The Middle Sacramento Valley study was designed to provide a spatially unbiased assessment of raw ground-water quality within MSACV, as well as a statistically consistent basis for comparing water quality throughout California. Samples were collected from 108 wells in Butte, Colusa, Glenn, Sutter, Tehama, Yolo, and Yuba Counties. Seventy-one wells were selected using a randomized grid-based method to provide statistical representation of the study unit (grid wells), 15 wells were selected to evaluate changes in water chemistry along ground-water flow paths (flow-path wells), and 22 were shallow monitoring wells selected to assess the effects of rice agriculture, a major land use in the study unit, on ground-water chemistry (RICE wells). The ground-water samples were analyzed for a large number of synthetic organic constituents (volatile organic compounds [VOCs], gasoline oxygenates and degradates, pesticides and pesticide degradates, and pharmaceutical compounds), constituents of special interest (perchlorate, N-nitrosodimethylamine [NDMA], and 1,2,3-trichloropropane [1,2,3-TCP]), inorganic constituents (nutrients, major and minor ions, and trace elements), radioactive constituents, and microbial indicators. Naturally occurring isotopes (tritium, and carbon-14, and stable isotopes of hydrogen, oxygen, nitrogen, and carbon), and dissolved noble gases also were measured to help identify the sources and ages of the sampled ground water. Quality-control samples (blanks, replicates, laboratory matrix spikes) were collected at approximately 10 percent of the wells, and the results for these samples were used to evaluate the quality of the data for the ground-water samples. Field blanks rarely contained detectable concentrations of any constituent, suggesting that contamination was not a noticeable source of bias in the data for the ground-water samples. Differences between replicate samples were within acceptable ranges, indicating acceptably low variability. Matrix spike recoveries were within acceptable ranges for most constituents. This study did not attempt to evaluate the quality of water delivered to consumers; after withdrawal from the ground, water typically is treated, disinfected, or blended with other waters to maintain acceptable water quality. Regulatory thresholds apply to treated water that is served to the consumer, not to raw ground water. However, to provide some context for the results, concentrations of constituents measured in the raw ground water were compared with health-based thresholds established by the U.S. Environmental Protection Agency (USEPA) and California Department of Public Health (CDPH) and thresholds established for aesthetic concerns (secondary maximum contaminant levels, SMCL-CA) by CDPH. Comparisons between data collected for this study and drinking-water thresholds are for illustrative purposes only and are not indicative of compliance or noncompliance with regulatory thresholds. Most constituents that were detected in ground-water samples were found at concentrations below drinking-water thresholds. VOCs were detected in less than one-third and pesticides and pesticide degradates in just over one-half of the grid wells, and all detections of these constituents in samples from all wells of the MSACV study unit were below health-based thresholds. All detections of trace elements in samples from MSACV grid wells were below health-based thresholds, with the exceptions of arsenic and boron. Arsenic concentrations were above the USEPA maximum contaminant level (MCL-US) threshold in eight grid wells, and boron concentrations were above the CDPH notification level (NL-CA) in two grid wells. Arsenic was detected above the MCL-US in two flow-path wells. Arsenic, barium, boron, molybdenum, strontium, and vanadium were detected above health-based thresholds in a few of the RICE wells; these wells are not used to supply drinking water. All detections of radioactive constituents were below health-based thresholds, although six samples had activities of radon-222 above the lower proposed MCL-US threshold. Most of the samples from the MSACV wells had concentrations of major elements, total dissolved solids, and trace elements below the non-enforceable thresholds set for aesthetic concerns. Chloride and sulfate concentrations exceeded SMCL-CA thresholds in two and one grid well, respectively. Iron, manganese, and total dissolved solids concentrations were above the SMCL-CA thresholds in 1, 12, and 6 grid wells, respectively. Nitrate (nitrite plus nitrate, as dissolved nitrogen) concentrations from two grid wells were above the MCL-US threshold. There were no detections of microbial indicators in MSACV.

California

Benthic invertebrate communities and their responses to selected environmental factors in the Kanawha River basin, West Virginia, Virginia, and North Carolina

The effects of selected environmental factors on the composition and structure of benthic invertebrate communities in the Kanawha River Basin of West Virginia, Virginia and North Carolina were investigated in 1997 and 1998. Environmental factors investigated include physiography, land-use pattern, streamwater chemistry, streambed- sediment chemistry, and habitat characteristics. Land-use patterns investigated include coal mining, agriculture, and low intensity rural-residential patterns, at four main stem and seven tributary sites throughout the basin. Of the 37 sites sampled, basin size and physiography most strongly affected benthic invertebrate-community structure. Land-use practices also affected invertebrate community structure in these basins. The basins that differed most from the minimally affected reference condition were those basins in which coal mining was the dominant nonforest land use, as determined by comparing invertebrate- community metric values among sites. Basins in which agriculture was important were more similar to the reference condition. The effect of coal mining upon benthic invertebrate communities was further studied at 29 sites and the relations among invertebrate communities and the selected environmental factors of land use, streamwater chemistry, streambed- sediment chemistry, and habitat characteristics analyzed. Division of coal-mining synoptic-survey sites based on invertebrate-community composition resulted in two groups?one with more than an average production of 9,000 tons of coal per square mile per year since 1980, and one with lesser or no recent coal production. The group with significant recent coal production showed higher levels of community impairment than the group with little or no recent coal production. Median particle size of streambed sediment, and specific conductance and sulfate concentration of streamwater were most strongly correlated with effects on invertebrate communities. These characteristics were related to mining intensity, as measured by thousands of tons of coal produced per square mile of drainage area.

North Carolina, Virginia, West Virginia

Effects of Groundwater Development on Uranium: Central Valley, California, USA

Uranium (U) concentrations in groundwater in several parts of the eastern San Joaquin Valley, California, have exceeded federal and state drinking water standards during the last 20 years. The San Joaquin Valley is located within the Central Valley of California and is one of the most productive agricultural areas in the world. Increased irrigation and pumping associated with agricultural and urban development during the last 100 years have changed the chemistry and magnitude of groundwater recharge, and increased the rate of downward groundwater movement. Strong correlations between U and bicarbonate suggest that U is leached from shallow sediments by high bicarbonate water, consistent with findings of previous work in Modesto, California. Summer irrigation of crops in agricultural areas and, to lesser extent, of landscape plants and grasses in urban areas, has increased Pco2 concentrations in the soil zone and caused higher temperature and salinity of groundwater recharge. Coupled with groundwater pumping, this process, as evidenced by increasing bicarbonate concentrations in groundwater over the last 100 years, has caused shallow, young groundwater with high U concentrations to migrate to deeper parts of the groundwater system that are tapped by public-supply wells. Continued downward migration of U-affected groundwater and expansion of urban centers into agricultural areas will likely be associated with increased U concentrations in public-supply wells. The results from this study illustrate the potential longterm effects of groundwater development and irrigation-supported agriculture on water quality in arid and semiarid regions around the world.

California

Response of lake chemistry to atmospheric deposition and climate in selected Class I wilderness areas in the western United States, 1993-2009

The U.S. Geological Survey, in cooperation with the U.S. Department of Agriculture Forest Service, Air Resource Management, conducted a study to evaluate long-term trends in lake-water chemistry for 64 high-elevation lakes in selected Class I wilderness areas in Colorado, Idaho, Utah, and Wyoming during 1993 to 2009. Understanding how and why lake chemistry is changing in mountain areas is essential for effectively managing and protecting high-elevation aquatic ecosystems. Trends in emissions, atmospheric deposition, and climate variables (air temperature and precipitation amount) were evaluated over a similar period of record. A main objective of the study was to determine if changes in atmospheric deposition of contaminants in the Rocky Mountain region have resulted in measurable changes in the chemistry of high-elevation lakes. A second objective was to investigate linkages between lake chemistry and air temperature and precipitation to improve understanding of the sensitivity of mountain lakes to climate variability.

Colorado;Idaho;Utah;Wyoming

Algal and Invertebrate Community Composition along Agricultural Gradients: A Comparative Study from Two Regions of the Eastern United States

Benthic algal and invertebrate communities in two Coastal Plain regions of the Eastern United States?the Delmarva Peninsula (27 sites) and Georgia Upper Coastal Plain (29 sites)?were assessed to determine if aspects of agricultural land use and nutrient conditions (dissolved and whole-water nitrogen and phosphorus) could be linked to biological community compositions. Extensive effort was made to compile land-use data describing the basin and riparian conditions at multiple scales to determine if scale played a role in these relations. Large differences in nutrient condition were found between the two study areas, wherein on average, the Delmarva sites had three times the total phosphorus and total nitrogen as did the sites in the Georgia Upper Coastal Plain. A statistical approach was undertaken that included multivariate correlations between Bray-Curtis similarity matrices of the biological communities and Euclidean similarity matrices of instream nutrients and land-use categories. Invertebrate assemblage composition was most associated with land use near the sampled reach, and algal diatom assemblage composition was most associated with land use farther from the streams and into the watersheds. Link tree analyses were conducted to isolate portions of nonmetric multidimensional scaling ordinations of community compositions that could be explained by break points in abiotic datasets. Invertebrate communities were better defined by factors such as agricultural land use near streams and geographic position. Algal communities were better defined by agricultural land use at the basin scale and instream nutrient chemistry. Algal autecological indices were more correlated with gradients of nutrient condition than were typically employed invertebrate metrics and may hold more promise in indicating nutrient impairment in these regions. Nutrient conditions in the respective study areas are compared to draft nutrient criteria established by the U.S. Environmental Protection Agency. Substantial reductions in some nutrients would be required to meet proposed reference conditions on the Delmarva Peninsula.

Scientific Investigations Report

Meteoric precipitation at Yucca Mountain, Nevada: Chemical and stable isotope analyses, 2006-09

Meteoric precipitation samples collected in 2006-09 at Yucca Mountain, Nevada, were analyzed for chemistry and stable isotope composition. Precipitation is the major source of infiltration to the unsaturated zone and of recharge to the saturated zone at Yucca Mountain. On February 28, 2005, seepage of water was observed about 40 to 80 meters below the ground surface within the Tiva Canyon Tuff in the South Ramp of the Exploratory Studies Facility tunnel within Yucca Mountain. This seepage was preceded by a 5-month period of above-average precipitation. Chemical and isotopic analysis of this seepage could not be used to estimate travel time, extent of water-rock interaction, and (or) evaporative water loss during percolation through the unsaturated zone due to the lack of corresponding chemical and isotopic analyses of precipitation inputs to the infiltration events that produced the seepage. In February 2006, collection of precipitation samples for chemical (major ions), delta oxygen-18 (&delta 18 O), and delta deuterium (&deltaD) analyses began at seven meteorological monitoring stations to provide baseline isotopic and chemical analyses. The sampling stations range in elevation from 1,131 to 1,562 meters. Each site has two collectors-one for chemical analysis and the other for isotopic analysis of precipitation. The collectors were sampled and emptied after each precipitation event. In 2006-09, 36 distinct precipitation events, with an average 3- to 4-day duration and an average 9.9 millimeters of accumulation, have been analyzed. The chemical composition of these samples of Yucca Mountain precipitation is relatively dilute but contains measurable and variable concentrations of Na + , Ca 2+ , NH + , NO 3 - , and SO 4 2- . Dust transported by typical winter storms and generated from soil carbonates is the main contributor to this precipitation chemistry. Elevated nitrate and ammonium concentrations may be linked to agriculture in the nearby Amargosa River valley to the south and west of Yucca Mountain. Cumulatively, &delta 18 O values range from 3.0 to -20.4 per mil (%o) and &deltaD values range from 10 to -14%o. Winter-season precipitation commonly has isotopically lighter compositions. The cumulative &delta18O plotted against &deltaD shows that precipitation samples define a line with slope of 6.4, less than the 8 of the Global Meteoric Water Line. This difference in slope, typical of arid environments, is chiefly the result of evaporation of falling raindrops due to warmer air temperatures. ;

Scientific Investigations Report

Vertical gradients in water chemistry in the central High Plains aquifer, southwestern Kansas and Oklahoma panhandle, 1999

The central High Plains aquifer is the primary source of water for domestic, industrial, and irrigation uses in parts of Colorado, Kansas, New Mexico, Oklahoma, and Texas. Water-level declines of more than 100 feet in some areas of the aquifer have increased the demand for water deeper in the aquifer. The maximum saturated thickness of the aquifer ranged from 500 to 600 feet in 1999. As the demand for deeper water increases, it becomes increasingly important for resource managers to understand how the quality of water in the aquifer changes with depth. In 1998?99, 18 monitoring wells at nine sites in southwestern Kansas and the Oklahoma Panhandle were completed at various depths in the central High Plains aquifer, and one monitoring well was completed in sediments of Permian age underlying the aquifer. Water samples were collected once from each well in 1999 to measure vertical gradients in water chemistry in the aquifer. Tritium concentrations measured in ground water indicate that water samples collected in the upper 30 feet of the aquifer were generally recharged within the last 50 years, whereas all of the water samples collected at depths more than 30 feet below the water table were recharged more than 50 years ago. Dissolved oxygen was present throughout the aquifer, with concentrations ranging from 1.7 to 8.4 mg/L. Water in the central High Plains aquifer was predominantly a calcium-bicarbonate type that exhibited little variability in concentrations of dissolved solids with depth (290 to 642 mg/L). Exceptions occurred in some areas where there had been upward movement of mineralized water from underlying sediments of Permian age and areas where there had been downward movement of mineralized Arkansas River water to the aquifer. Calcium-sulfate and sodium-chloride waters dominated and concentrations of dissolved solids were elevated (862 to 4,030 mg/L) near the base of the aquifer in the areas of upward leakage. Dissolution of gypsum or anhydrite and halite in sediments of Permian age by ground water was the likely source of calcium, sulfate, sodium, and chloride in those waters. Calcium-sodium-sulfate waters dominated, and concentrations of dissolved solids were as large as 4,916 mg/L near the water table in the area of downward leakage. Dissolution of minerals in sedimentary deposits of marine origin in upstream areas of the Arkansas River drainage were the likely sources of calcium, sodium, and sulfate in those waters. Nitrate was detected throughout the aquifer and the background concentration was estimated to be 2.45 mg/L as N. The largest nitrate concentrations (8.28, 22, and 54.4 mg/L as N) occurred in recently recharged water collected adjacent to irrigated fields. Three pesticides (atrazine, metolachlor, simazine) and five pesticide degradation products (alachlor ethanesulfonic acid, alachlor oxanilic acid, deethylatrazine, metolachlor ethanesulfonic acid, metolachlor oxanilic acid) were detected in recently recharged water from six water-table wells. Five of the six wells were adjacent to irrigated fields. These data indicate that concentrations of nitrate and pesticides increased over time in some areas of the aquifer as a result of agricultural activities. Results from this study indicate that vertical gradients in water chemistry existed in the central High Plains aquifer. The chemical gradients resulted from chemical inputs to the aquifer from underlying sediments of Permian age, from the Arkansas River, and from agricultural activities. In areas where those chemical inputs occurred, water quality in the aquifer was impaired and may not have been suitable for some intended uses.

Water-Resources Investigations Report

Trends in lake chemistry in response to atmospheric deposition and climate in selected Class I wilderness areas in Colorado, Idaho, Utah, and Wyoming, 1993-2009

In 2010, the U.S. Geological Survey, in cooperation with the U.S. Department of Agriculture Forest Service, Air Resource Management, began a study to evaluate long-term trends in lake-water chemistry for 64 high-elevation lakes in selected Class I wilderness areas in Colorado, Idaho, Utah, and Wyoming during 1993 to 2009. The purpose of this report is to describe trends in the chemical composition of these high-elevation lakes. Trends in emissions, atmospheric deposition, and climate variables (air temperature and precipitation amount) are evaluated over a similar period of record to determine likely drivers of changing lake chemistry. Sulfate concentrations in precipitation decreased over the past two decades at high-elevation monitoring stations in the Rocky Mountain region. The trend in deposition chemistry is consistent with regional declines in sulfur dioxide emissions resulting from installation of emission controls at large stationary sources. Trends in nitrogen deposition were not as widespread as those for sulfate. About one-half of monitoring stations showed increases in ammonium concentrations, but few showed significant changes in nitrate concentrations. Trends in nitrogen deposition appear to be inconsistent with available emission inventories, which indicate modest declines in nitrogen emissions in the Rocky Mountain region since the mid-1990s. This discrepancy may reflect uncertainties in emission inventories or changes in atmospheric transformations of nitrogen species that may be affecting deposition processes. Analysis of long-term climate records indicates that average annual mean air temperature minimums have increased from 0.57 to 0.75 °C per decade in mountain areas of the region with warming trends being more pronounced in Colorado. Trends in annual precipitation were not evident over the period 1990 to 2006, although wetter than average years during 1995 to 1997 and drier years during 2001 to 2004 caused a notable decline in precipitation in the middle part of the record.

Colorado;Idaho;Utah;Wyoming