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David K. Mueller

Publications and source records attributed to David K. Mueller.

At least 19 recordsLinked to original sources

Quality-control design for surface-water sampling in the National Water-Quality Network

The data-quality objectives for samples collected at surface-water sites in the National Water-Quality Network include estimating the extent to which contamination, matrix effects, and measurement variability affect interpretation of environmental conditions. Quality-control samples provide insight into how well the samples collected at surface-water sites represent the true environmental conditions. Quality-control samples used in this program include field blanks, replicates, and field matrix spikes. This report describes the design for collection of these quality-control samples and the data management needed to properly identify these samples in the U.S. Geological Survey’s national database.

Open-File Report

Design, analysis, and interpretation of field quality-control data for water-sampling projects

The process of obtaining and analyzing water samples from the environment includes a number of steps that can affect the reported result. The equipment used to collect and filter samples, the bottles used for specific subsamples, any added preservatives, sample storage in the field, and shipment to the laboratory have the potential to affect how accurately samples represent the environment from which they were collected. During the early 1990s, the U.S. Geological Survey implemented policies to include the routine collection of quality-control samples in order to evaluate these effects and to ensure that water-quality data were adequately representing environmental conditions. Since that time, the U.S. Geological Survey Office of Water Quality has provided training in how to design effective field quality-control sampling programs and how to evaluate the resultant quality-control data. This report documents that training material and provides a reference for methods used to analyze quality-control data. Quality-control data are those generated from the collection and analysis of quality-control samples, and are used to estimate the magnitude of errors in the process of obtaining environmental data. “Bias” and “variability” are the terms used in this report for the two types of errors in environmental data that are quantified by the data from quality-control samples. Bias is the systematic error inherent in a method or measurement system. Variability is the random error that occurs in independent measurements. The types of field quality-control samples discussed in this report include blanks, spikes, and replicates. Blanks are samples prepared with water that is intended to be free of measurable constituents that will be analyzed by the laboratory; blanks are used to estimate bias caused by contamination. Spiked samples are modified by addition of specific analytes; spikes are used to determine the performance of analytical methods and to estimate the potential bias due to matrix interference or analyte degradation. Replicate samples are two or more samples that are considered to be essentially identical in composition. Replicates are used to evaluate variability in analytical results. Various sub-types of these quality-control samples are defined and discussed in this report, and guidance is provided for incorporating the proper samples into the design for a project. The concept of inference space is introduced to help determine where and when quality-control samples should be collected as well as which environmental samples are related to a set of quality-control samples. The recommended basic quality-control design incorporates project-specific considerations, such as the objectives and scale of the study, and hydrologic and chemical conditions within the study area. The report provides extensive information about statistical methods used to analyze quality-control data in order to estimate potential bias and variability in environmental data. These methods include construction of confidence intervals on various statistical measures, such as the mean, percentiles and percentages, and standard deviation. The methods are used to compare quality-control results with the larger set of environmental data in order to determine whether the effects of bias and variability might interfere with interpretation of these data. Examples from published reports are presented to illustrate how the methods are applied, how bias and variability are reported, and how the interpretation of environmental data can be qualified based on the quality-control analysis.

Techniques and Methods

County-level estimates of nitrogen and phosphorus from animal manure for the conterminous United States, 2002

County-level nitrogen and phosphorus inputs from animal manure for the conterminous United States for 2002 were estimated from animal populations from the 2002 Census of Agriculture by using methods described in U.S. Geological Survey Scientific Investigations Report 2006–5012. These estimates of nitrogen and phosphorus from animal manure were compiled in support of the U.S. Geological Survey’s National Water-Quality Assessment Program.

Open-File Report

Groundwater-quality and quality-control data for two monitoring wells near Pavillion, Wyoming, April and May 2012

In June 2010, the U.S. Environmental Protection Agency installed two deep monitoring wells (MW01 and MW02) near Pavillion, Wyoming, to study groundwater quality. During April and May 2012, the U.S Geological Survey, in cooperation with the Wyoming Department of Environmental Quality, collected groundwater-quality data and quality-control data from monitoring well MW01 and, following well redevelopment, quality-control data for monitoring well MW02. Two groundwater-quality samples were collected from well MW01—one sample was collected after purging about 1.5 borehole volumes, and a second sample was collected after purging 3 borehole volumes. Both samples were collected and processed using methods designed to minimize atmospheric contamination or changes to water chemistry. Groundwater-quality samples were analyzed for field water-quality properties (water temperature, pH, specific conductance, dissolved oxygen, oxidation potential); inorganic constituents including naturally occurring radioactive compounds (radon, radium-226 and radium-228); organic constituents; dissolved gasses; stable isotopes of methane, water, and dissolved inorganic carbon; and environmental tracers (carbon-14, chlorofluorocarbons, sulfur hexafluoride, tritium, helium, neon, argon, krypton, xenon, and the ratio of helium-3 to helium-4). Quality-control sample results associated with well MW01 were evaluated to determine the extent to which environmental sample analytical results were affected by bias and to evaluate the variability inherent to sample collection and laboratory analyses. Field documentation, environmental data, and quality-control data for activities that occurred at the two monitoring wells during April and May 2012 are presented.

Wyoming

Organic contaminants, trace and major elements, and nutrients in water and sediment sampled in response to the Deepwater Horizon oil spill

Beach water and sediment samples were collected along the Gulf of Mexico coast to assess differences in contaminant concentrations before and after landfall of Macondo-1 well oil released into the Gulf of Mexico from the sinking of the British Petroleum Corporation's Deepwater Horizon drilling platform. Samples were collected at 70 coastal sites between May 7 and July 7, 2010, to document baseline, or "pre-landfall" conditions. A subset of 48 sites was resampled during October 4 to 14, 2010, after oil had made landfall on the Gulf of Mexico coast, called the "post-landfall" sampling period, to determine if actionable concentrations of oil were present along shorelines. Few organic contaminants were detected in water; their detection frequencies generally were low and similar in pre-landfall and post-landfall samples. Only one organic contaminant--toluene--had significantly higher concentrations in post-landfall than pre-landfall water samples. No water samples exceeded any human-health benchmarks, and only one post-landfall water sample exceeded an aquatic-life benchmark--the toxic-unit benchmark for polycyclic aromatic hydrocarbons (PAH) mixtures. In sediment, concentrations of 3 parent PAHs and 17 alkylated PAH groups were significantly higher in post-landfall samples than pre-landfall samples. One pre-landfall sample from Texas exceeded the sediment toxic-unit benchmark for PAH mixtures; this site was not sampled during the post-landfall period. Empirical upper screening-value benchmarks for PAHs in sediment were exceeded at 37 percent of post-landfall samples and 22 percent of pre-landfall samples, but there was no significant difference in the proportion of samples exceeding benchmarks between paired pre-landfall and post-landfall samples. Seven sites had the largest concentration differences between post-landfall and pre-landfall samples for 15 alkylated PAHs. Five of these seven sites, located in Louisiana, Mississippi, and Alabama, had diagnostic geochemical evidence of Macondo-1 oil in post-landfall sediments and tarballs. For trace and major elements in water, analytical reporting levels for several elements were high and variable. No human-health benchmarks were exceeded, although these were available for only two elements. Aquatic-life benchmarks for trace elements were exceeded in 47 percent of water samples overall. The elements responsible for the most exceedances in post-landfall samples were boron, copper, and manganese. Benchmark exceedances in water could be substantially underestimated because some samples had reporting levels higher than the applicable benchmarks (such as cobalt, copper, lead and zinc) and some elements (such as boron and vanadium) were analyzed in samples from only one sampling period. For trace elements in whole sediment, empirical upper screening-value benchmarks were exceeded in 57 percent of post-landfall samples and 40 percent of pre-landfall samples, but there was no significant difference in the proportion of samples exceeding benchmarks between paired pre-landfall and post-landfall samples. Benchmark exceedance frequencies could be conservatively high because they are based on measurements of total trace-element concentrations in sediment. In the less than 63-micrometer sediment fraction, one or more trace or major elements were anthropogenically enriched relative to national baseline values for U.S. streams for all sediment samples except one. Sixteen percent of sediment samples exceeded upper screening-value benchmarks for, and were enriched in, one or more of the following elements: barium, vanadium, aluminum, manganese, arsenic, chromium, and cobalt. These samples were evenly divided between the sampling periods. Aquatic-life benchmarks were frequently exceeded along the Gulf of Mexico coast by trace elements in both water and sediment and by PAHs in sediment. For the most part, however, significant differences between pre-landfall and post-landfall samples were limited to concentrations of PAHs in sediment. At five sites along the coast, the higher post-landfall concentrations of PAHs were associated with diagnostic geochemical evidence of Deepwater Horizon Macondo-1 oil.

Alabama, Arkansas, Florida, Georgia, Louisiana, Te

Organic contaminants, trace and major elements, and nutrients in water and sediment sampled in response to the Deepwater Horizon oil spill

Beach water and sediment samples were collected along the Gulf of Mexico coast to assess differences in contaminant concentrations before and after landfall of Macondo-1 well oil released into the Gulf of Mexico from the sinking of the British Petroleum Corporation's Deepwater Horizon drilling platform. Samples were collected at 70 coastal sites on the Gulf of Mexico between May 7 and July 7, 2010, to document baseline, "pre-landfall" conditions. A subset of these sites was resampled during October 4 to 14, 2010, after oil had made landfall on the Gulf of Mexico coast ("post-landfall") to determine if actionable concentrations of oil were present along shorelines. Few organic contaminants were detected in water; their detection frequencies were generally low and similar in pre-landfall and post-landfall samples. Only one organic contaminant, toluene, had significantly higher concentrations in post-landfall than pre-landfall water samples. No samples exceeded any human-health benchmarks, and only one sample exceeded an aquatic-life benchmark-the toxic-unit benchmark for polycyclic aromatic hydrocarbons (PAH) mixtures was exceeded in one post-landfall water sample from Louisiana. No exceedance was observed in the corresponding pre-landfall water sample at this site. In sediment, several PAHs were detected at over 20 percent of sites. Concentrations of 3 parent PAHs and 17 alkylated PAH groups were significantly higher in post-landfall samples than pre-landfall samples. One pre-landfall sample from Texas exceeded the sediment toxic-unit benchmark for PAH mixtures; this site was not sampled during the post-landfall period, so no comparison between sampling periods could be made. Twenty-seven percent of sediment samples exceeded empirical sediment-quality benchmarks (upper screening values) for PAHs, indicating these samples are in the probable-effect range. A higher percentage of post-landfall samples exceeded upper screening-value benchmarks (37 percent) than did pre-landfall samples (22 percent), but there was no significant difference in the proportion of samples exceeding one or more benchmarks between paired pre-landfall and post-landfall samples. Seven sites had the largest concentration differences between post-landfall and pre-landfall samples for fifteen alkylated PAHs. Five of these seven sites (1 site in Louisiana, 1 in Mississippi, and 3 in Alabama) were identified on the basis of diagnostic geochemical biomarkers as containing Macondo-1 oil in post-landfall sediments and tarballs, as described in a companion report by Rosenbauer and others (2010). For trace and major elements in water, analytical reporting levels for several elements were highly variable; after censoring to a common reporting threshold, concentrations were significantly different between pre-landfall and post-landfall samples for a few elements, all of which are elements in seawater. No human-health benchmarks were exceeded, although these were available for only two elements. Aquatic-life benchmarks for trace elements were exceeded in almost 50 percent of water samples. Post-landfall samples exceeded one or more acute benchmarks in 21 percent, and chronic benchmarks in 93 percent of samples, compared to 1 percent (acute) and 39 percent (chronic) for pre-landfall samples. The elements responsible for the most exceedances in post-landfall samples were boron (48 samples), copper (22), and manganese (12). Nickel and vanadium, which U.S. Environmental Protection Agency specifically identified as relevant to the oil spill, were responsible for exceedances in only one of the fifty-two post-landfall samples with exceedances. These results represent the minimum number of exceedances for several trace elements because a substantial number of samples could not be compared with benchmarks because the element was determined during only one sampling period (boron and vanadium) or the reporting level for the sample was higher than the applicable benchmark value (for example, cobalt, copper, lead, and nickel). The high and variable reporting levels for trace elements in water also precluded the statistical comparison between sampling periods of the proportion of samples exceeding benchmarks. For trace elements in whole (unsieved) sediment, 47 percent of samples exceeded empirical upper screening-value benchmarks, indicating these samples are in the probable-effect range. However, there was no significant difference in the proportion of samples exceeding one or more benchmarks between paired pre-landfall post-landfall samples. Benchmark exceedance frequencies could be conservatively high, because they are based on measurements of total trace-element concentrations, including the sediment matrix. In fine sediment (the less than 63-micrometer sediment fraction), one or more trace or major elements were anthropogenically enriched relative to national baseline values for U.S. streams for almost all sediment samples (123 of 124). Sixteen percent of sediment samples exceeded upper screening-value benchmarks for, and were enriched in, one or more of the element(s) barium (in 14 samples), vanadium (5), aluminum (3), manganese (3), arsenic (2), chromium (2), and cobalt (1). These samples, collected from Louisiana and Texas, were evenly divided between the pre-landfall (9 samples) and post-landfall (10 samples) periods. Considering all the information evaluated in this report, there were significant differences between pre-landfall and post-landfall samples for PAH concentrations in sediment. Pre-landfall and post-landfall samples did not differ significantly in concentrations or benchmark exceedances for most organics in water or trace elements in sediment. For trace elements in water, aquatic-life benchmarks were exceeded in almost 50 percent of samples, but the high and variable analytical reporting levels precluded statistical comparison of benchmark exceedances between sampling periods. Concentrations of several PAH compounds in sediment were significantly higher in post-landfall samples than pre-landfall samples, and five of seven sites with the largest differences in PAH concentrations also had diagnostic geochemical evidence of Deepwater Horizon Macondo-1 oil from Rosenbauer and others (2010).

Open-File Report

Design and evaluation of a field study on the contamination of selected volatile organic compounds and wastewater-indicator compounds in blanks and groundwater samples

The Field Contamination Study (FCS) was designed to determine the field processes that tend to result in clean field blanks and to identify potential sources of contamination to blanks collected in the field from selected volatile organic compounds (VOCs) and wastewater-indicator compounds (WICs). The VOCs and WICs analyzed in the FCS were detected in blanks collected by the U.S. Geological Survey (USGS) National Water-Quality Assessment (NAWQA) Program during 1996–2008 and 2002–08, respectively. To minimize the number of variables, the study required ordering of supplies just before sampling, storage of supplies and equipment in clean areas, and use of adequate amounts of purge-and-trap volatile-grade methanol and volatile pesticide-grade blank water (VPBW) to clean sampling equipment and to collect field blanks. Blanks and groundwater samples were collected during 2008–09 at 16 sites, which were a mix of water-supply and monitoring wells, located in 9 States. Five different sample types were collected for the FCS at each site: (1) a source-solution blank collected at the USGS National Water Quality Laboratory (NWQL) using laboratory-purged VPBW, (2) source-solution blanks collected in the field using laboratory-purged VPBW, (3) source-solution blanks collected in the field using field-purged VPBW, (4) a field blank collected using field-purged VPBW, and (5) a groundwater sample collected from a well. The source-solution blank and field-blank analyses were used to identify, quantify, and document extrinsic contamination and to help determine the sources and causes of data-quality problems that can affect groundwater samples. Concentrations of compounds detected in FCS analyses were quantified and results were stored in the USGS National Water Information System database after meeting rigorous identification and quantification criteria. The study also utilized information provided by laboratory analysts about evidence indicating the presence of selected compounds, using less rigorous identification criteria than is required for reporting data to the National Water Information System database. For the FCS, these data are considered adequate to indicate "evidence of presence," and were used only for diagnostic purposes. Evidence of VOCs and WICs at low concentrations near or less than the long-term method detection level can indicate a contamination problem that could affect future datasets if method detection levels were ever to be lowered.

Scientific Investigations Report

Quality of volatile organic compound data from groundwater and surface water for the National Water-Quality Assessment Program, October 1996–December 2008

This report describes the quality of volatile organic compound (VOC) data collected from October 1996 to December 2008 from groundwater and surface-water sites for the U.S. Geological Survey's National Water-Quality Assessment (NAWQA) Program. The VOC data described were collected for three NAWQA site types: (1) domestic and public-supply wells, (2) monitoring wells, and (3) surface-water sites. Contamination bias, based on the 90-percent upper confidence limit (UCL) for the 90th percentile of concentrations in field blanks, was determined for VOC samples from the three site types. A way to express this bias is that there is 90-percent confidence that this amount of contamination would be exceeded in no more than 10 percent of all samples (including environmental samples) that were collected, processed, shipped, and analyzed in the same manner as the blank samples. This report also describes how important native water rinsing may be in decreasing carryover contamination, which could be affecting field blanks. The VOCs can be classified into four contamination categories on the basis of the 90-percent upper confidence limit (90-percent UCL) concentration distribution in field blanks. Contamination category 1 includes compounds that were not detected in any field blanks. Contamination category 2 includes VOCs that have a 90-percent UCL concentration distribution in field blanks that is about an order of magnitude lower than the concentration distribution of the environmental samples. Contamination category 3 includes VOCs that have a 90-percent UCL concentration distribution in field blanks that is within an order of magnitude of the distribution in environmental samples. Contamination category 4 includes VOCs that have a 90-percent UCL concentration distribution in field blanks that is at least an order of magnitude larger than the concentration distribution of the environmental samples. Fifty-four of the 87 VOCs analyzed in samples from domestic and public-supply wells were not detected in field blanks (contamination category 1), and 33 VOC were detected in field blanks. Ten of the 33 VOCs had a 90-percent UCL concentration distribution in field blanks that was at least an order of magnitude lower than the concentration distribution in environmental samples (contamination category 2). These 10 VOCs may have had some contamination bias associated with the environmental samples, but the potential contamination bias was negligible in comparison to the environmental data; therefore, the field blanks were assumed to be representative of the sources of contamination bias affecting the environmental samples for these 10 VOCs. Seven VOCs had a 90-percent UCL concentration distribution of the field blanks that was within an order of magnitude of the concentration distribution of the environmental samples (contamination category 3). Sixteen VOCs had a 90-percent UCL concentration distribution in the field blanks that was at least an order of magnitude greater than the concentration distribution of the environmental samples (contamination category 4). Field blanks for these 16 VOCs appear to be nonrepresentative of the sources of contamination bias affecting the environmental samples because of the larger concentration distributions (and sometimes higher frequency of detection) in field blanks than in environmental samples. Forty-three of the 87 VOCs analyzed in samples from monitoring wells were not detected in field blanks (contamination category 1), and 44 VOCs were detected in field blanks. Eight of the 44 VOCs had a 90-percent UCL concentration distribution in field blanks that was at least an order of magnitude lower than concentrations in environmental samples (contamination category 2). These eight VOCs may have had some contamination bias associated with the environmental samples, but the potential contamination bias was negligible in comparison to the environmental data; therefore, the field blanks were assumed to be representative. Seven VOCs had a 90-percent UCL concentration distribution in field blanks that was of the same order of magnitude as the concentration distribution of the environmental samples (contamination category 3). Twenty-nine VOCs had a 90-percent UCL concentration distribution in the field blanks that was an order of magnitude greater than the distribution of the environmental samples (contamination category 4). Field blanks for these 29 VOCs appear to be nonrepresentative of the sources of contamination bias to the environmental samples. Fifty-four of the 87 VOCs analyzed in surface-water samples were not detected in field blanks (category 1), and 33 VOC were detected in field blanks. Sixteen of the 33 VOCs had a 90-percent UCL concentration distribution in field blanks that was at least an order of magnitude lower than the concentration distribution in environmental samples (contamination category 2). These 16 VOCs may have had some contamination bias associated with the environmental samples, but the potential contamination bias was negligible in comparison to the environmental data; therefore, the field blanks were assumed to be representative. Ten VOCs had a 90-percent UCL concentration distribution in field blanks that was similar to the concentration distribution of environmental samples (contamination category 3). Seven VOCs had a 90-percent UCL concentration distribution in the field blanks that was greater than the concentration distribution in environmental samples (contamination category 4). Field-blank samples for these seven VOCs appear to be nonrepresentative of the sources of contamination bias to the environmental samples. The relation between the detection of a compound in field blanks and the detection in subsequent environmental samples appears to be minimal. The median minimum percent effectiveness of native water rinsing is about 79 percent for the 19 VOCs detected in more than 5 percent of field blanks from all three site types. The minimum percent effectiveness of native water rinsing (10 percent) was for toluene in surface-water samples, likely because of the large detection frequency of toluene in surface-water samples (about 79 percent) and in the associated field-blank samples (46.5 percent). The VOCs that were not detected in field blanks (contamination category 1) from the three site types can be considered free of contamination bias, and various interpretations for environmental samples, such as VOC detection frequency at multiple assessment levels and comparisons of concentrations to benchmarks, are not limited for these VOCs. A censoring level for making comparisons at different assessment levels among environmental samples could be applied to concentrations of 9 VOCs in samples from domestic and public-supply wells, 16 VOCs in samples from monitoring wells, and 9 VOCs in surface-water samples to account for potential low-level contamination bias associated with these selected VOCs. Bracketing the potential contamination by comparing the detection and concentration statistics with no censoring applied to the potential for contamination bias on the basis of the 90-percent UCL for the 90th-percentile concentrations in field blanks may be useful when comparisons to benchmarks are done in a study. The VOCs that were not detected in field blanks (contamination category 1) from the three site types can be considered free of contamination bias, and various interpretations for environmental samples, such as VOC detection frequency at multiple assessment levels and comparisons of concentrations to benchmarks, are not limited for these VOCs. A censoring level for making comparisons at different assessment levels among environmental samples could be applied to concentrations of 9 VOCs in samples from domestic and public-supply wells, 16 VOCs in samples from monitoring wells, and 9 VOCs in surface-water samples to account for potential low-level contamination bias associated with these selected VOCs. Bracketing the potential contamination by comparing the detection and concentration statistics with no censoring applied to the potential for contamination bias on the basis of the 90-percent UCL for the 90th-percentile concentrations in field blanks may be useful when comparisons to benchmarks are done in a study.

Scientific Investigations Report

The quality of our nation's waters: Nutrients in the nation's streams and groundwater, 1992-2004

National Findings and Their Implications Although the use of artificial fertilizer has supported increasing food production to meet the needs of a growing population, increases in nutrient loadings from agricultural and, to a lesser extent, urban sources have resulted in nutrient concentrations in many streams and parts of aquifers that exceed standards for protection of human health and (or) aquatic life, often by large margins. Do NAWQA findings substantiate national concerns for aquatic and human health? National Water-Quality Assessment (NAWQA) findings indicate that nutrient concentrations in streams and groundwater in basins with significant agricultural or urban development are substantially greater than naturally occurring or “background” levels. For example, median concentrations of total nitrogen and phosphorus in agricultural streams are about 6 times greater than background levels. Findings also indicate that concentrations in streams routinely were 2 to 10 times greater than regional nutrient criteria recommended by the U.S. Environmental Protection Agency (USEPA) to protect aquatic life. Such large differences in magnitude suggest that significant reductions in sources of nutrients, as well as greater use of land management strategies to reduce the transport of nutrients to streams, are needed to meet recommended criteria for streams draining areas with significant agricultural and urban development. Nitrate concentrations above the Federal drinking-water standard—or Maximum Contaminant Level (MCL)—of 10 milligrams per liter (mg/L, as nitrogen) are relatively uncommon in samples from streams used for drinking water or from relatively deep aquifers; the MCL is exceeded, however, in more than 20 percent of shallow (less than 100 feet below the water table) domestic wells in agricultural areas. This finding raises concerns for human health in rural agricultural areas where shallow groundwater is used for domestic supply and may warn of future contamination of deeper groundwater pumped from public‑supply wells. Are levels of nutrients in water increasing or decreasing? A decadal assessment of trends in concentrations of nitrogen and phosphorus from about 1993 to 2003 shows minimal changes in those concentrations in the majority of studied streams across the Nation, and more upward than downward trends in concentrations at sites with changes. These findings underscore the need for reductions in nutrient inputs or management strategies that would reduce transport of nutrients to streams. Upward trends were evident among all land uses, including those only minimally affected by agricultural and (or) urban development, which suggests that additional protection of some of our Nation’s most pristine streams warrants consideration. The median of nitrate concentrations in groundwater from 495 wells also increased significantly from 3.2 to 3.4 mg/L (6 percent) during about the same period, and the proportion of wells with concentrations of nitrate greater than the MCL increased from 16 to 21 percent. Nitrate concentrations in water in deep aquifers are likely to increase during the next decade as shallow groundwater with elevated concentrations moves downward. The potential for future contamination of the deep aquifers requires attention because these aquifers commonly are used for public water supply, and because restoration of groundwater is costly and difficult. Long-term and consistent monitoring of nutrients, improved accounting of nutrient sources, and improved tracking and modeling of climatic and landscape changes will be essential for distinguishing trends in nutrient concentrations, understanding the causes of those trends, and accurately tracking the effectiveness of strategies implemented to manage nutrients.

Circular

Development and Application of Regression Models for Estimating Nutrient Concentrations in Streams of the Conterminous United States, 1992-2001

Data collected for the U.S. Geological Survey National Water-Quality Assessment program from 1992-2001 were used to investigate the relations between nutrient concentrations and nutrient sources, hydrology, and basin characteristics. Regression models were developed to estimate annual flow-weighted concentrations of total nitrogen and total phosphorus using explanatory variables derived from currently available national ancillary data. Different total-nitrogen regression models were used for agricultural (25 percent or more of basin area classified as agricultural land use) and nonagricultural basins. Atmospheric, fertilizer, and manure inputs of nitrogen, percent sand in soil, subsurface drainage, overland flow, mean annual precipitation, and percent undeveloped area were significant variables in the agricultural basin total nitrogen model. Significant explanatory variables in the nonagricultural total nitrogen model were total nonpoint-source nitrogen input (sum of nitrogen from manure, fertilizer, and atmospheric deposition), population density, mean annual runoff, and percent base flow. The concentrations of nutrients derived from regression (CONDOR) models were applied to drainage basins associated with the U.S. Environmental Protection Agency (USEPA) River Reach File (RF1) to predict flow-weighted mean annual total nitrogen concentrations for the conterminous United States. The majority of stream miles in the Nation have predicted concentrations less than 5 milligrams per liter. Concentrations greater than 5 milligrams per liter were predicted for a broad area extending from Ohio to eastern Nebraska, areas spatially associated with greater application of fertilizer and manure. Probabilities that mean annual total-nitrogen concentrations exceed the USEPA regional nutrient criteria were determined by incorporating model prediction uncertainty. In all nutrient regions where criteria have been established, there is at least a 50 percent probability of exceeding the criteria in more than half of the stream miles. Dividing calibration sites into agricultural and nonagricultural groups did not improve the explanatory capability for total phosphorus models. The group of explanatory variables that yielded the lowest model error for mean annual total phosphorus concentrations includes phosphorus input from manure, population density, amounts of range land and forest land, percent sand in soil, and percent base flow. However, the large unexplained variability and associated model error precluded the use of the total phosphorus model for nationwide extrapolations.

Scientific Investigations Report

Nutrient Trends in Streams and Rivers of the United States, 1993-2003

Trends in streamflow and concentrations and loads of total phosphorus, total nitrogen, and nitrate were determined for the period from 1993 to 2003 in selected streams and ricers of the United States. Flow-adjusted trends in concentration (the trends that would have occurred in the absence of natural chances in streamflow), non-flow-adjusted trends in concentration (the trends resulting from both natural and human factors), and trends in load (trends in the nutrient mass transported downstream) were determined, and the results were examined spatially to determine whether a consistent pattern of trends occurred across groups of sites at multiple locations. Relations between the trends and changes in nutrient sources and streamflow are examined. See document for complete abstract.

Scientific Investigations Report

Computer program for the Kendall family of trend tests

The Seasonal Kendall (SK) test for trend was developed by the U.S. Geological Survey and has become the most frequently used test for trend in the environmental sciences. Recently the test was modified to form the Regional Kendall (RK) test for trend. In this form, trends at numerous locations within a region are tested to determine whether the direction of trend is consistent across the entire region. Computer code developed at the USGS in the 1980s to perform the SK test is no longer widely available. Other versions written by other scientists may or may not be easily available, and may require commercial software in order to be run. These other versions do not explicitly compute the RK test. Therefore, the original code for computing the SK test has been repackaged into a program that runs under the Windows operating system. This program may be used to verify that other implementations of the test give the same results as the original. The program also provides a means for computing the RK test and the simpler Mann-Kendall test for trend.

Scientific Investigations Report

County-level estimates of nutrient inputs to the land surface of the conterminous United States, 1982-2001

Nutrient input data for fertilizer use, livestock manure, and atmospheric deposition from various sources were estimated and allocated to counties in the conterminous United States for the years 1982 through 2001. These nationally consistent nutrient input data are needed by the National Water-Quality Assessment Program for investigations of stream- and ground-water quality. For nitrogen, the largest source was farm fertilizer; for phosphorus, the largest sources were farm fertilizer and livestock manure. Nutrient inputs from fertilizer use in nonfarm areas, while locally important, were an order of magnitude smaller than inputs from other sources. Nutrient inputs from all sources increased between 1987 and 1997, but the relative proportions of nutrients from each source were constant. Farm-fertilizer inputs were highest in the upper Midwest, along eastern coastal areas, and in irrigated areas of the West. Nonfarm-fertilizer use was similar in major metropolitan areas throughout the Nation, but was more extensive in the more populated Eastern and Central States and in California. Areas of greater manure inputs were located throughout the South-central and Southeastern States and in scattered areas of the West. Nitrogen deposition from the atmosphere generally increased from west to east and is related to the location of major sources and the effects of precipitation and prevailing winds. These nutrient-loading data at the county level are expected to be the fundamental basis for national and regional assessments of water quality for the National Water-Quality Assessment Program and other large-scale programs.

conterminous United States

Review of Trace Element Blank and Replicate Data Collected in Ground and Surface Water for the National Water-Quality Assessment Program, 1991-2002

The trace elements Sb, Be, and Tl in ground water and Sb, Be, Co, Mo, and U in surface water are unaffected by contamination. Limited quality control data (blanks) for Li and V in ground water and surface water do not allow for a good assessment on the potential contamination associated with these trace elements. Potential contamination was identified for Al, As, Ba, B, Cd, Cr, Cu, Fe, Pb, Mn, Ni, Se, Ag, Sr, and Zn in ground water and surface water. Evidence of potential contamination was shown for Co, Mo, and U in ground water; potential contamination was shown for T1 in surface water. In comparing the potential contamination for these trace elements with the U.S. Environmental Protection Agency's (USEPA) drinking-water standards, the contamination for most of these trace elements is less than 10 percent of the drinking-water standard; therefore, contamination would have little or no effect when comparing trace element concentrations with the USEPA drinking-water standards. The exceptions are Al, Cd, and possibly Pb in ground water, and As and possibly Pb in surface water. Potential contamination identified for these trace elements is greater than 10 percent of the USEPA drinking-water standard, but affects only 5 percent or less of the As, Cd, and Pb samples. For most trace elements, the level of potential contamination is not large enough to significantly affect the measured concentration of the environmental sample. The exceptions may be Fe in ground water and Al in surface water, which have concentrations for at least 10 percent of the environmental samples that exceeded the USEPA drinking-water standards. Sample variability for some of the trace elements could not be determined because there were either no detected concentrations, or there were less than 10 replicate sets with detected concentrations. These trace elements are Be, Ag, and Tl for ground water and Sb, Be, Cr, Co, Pb, Ag, and Tl for surface water. For most trace elements, sample variability was less than 10 percent, which would have little or no affect on the reported concentrations. The exceptions are Al, Cd, Cu, Pb, Rn (at concentrations less than about 700 picocuries per liter), Se, and Zn in ground water and Cu, Se, and Zn in surface water, all of which have sample variability ranging from 10 to 20 percent. Sample variability should be considered when evaluating the potential error associated with a sample measurement. Collection of additional quality control samples for some of these trace elements to determine bias and variability is probably warranted particularly for those trace elements that the NAWQA Program did not begin sampling until 1998. Results obtained from the analysis of the quality control data can be applied to the interpretation of the environmental data collected from 1991 to 2002 and for water-quality data that are currently being collected as part of the NAWQA Program. More...

Scientific Investigations Report

Nutrients in streams and rivers across the nation — 1992–2001

Nutrient compounds of nitrogen and phosphorus were investigated in streams and rivers sampled as part of the U.S. Geological Survey National Water-Quality Assessment (NAWQA) Program. Nutrient data were collected in 20 NAWQA study units during 1992-95, 16 study units during 1996-98, and 15 study units during 1999-2001. To facilitate comparisons among sampling sites with variable sampling frequency, daily loads were determined by using regression models that relate constituent transport to streamflow and time. Model results were used to compute mean annual loads, yields, and concentrations of ammonia, nitrate, total nitrogen, orthophosphate, and total phosphorus, which were compared among stream and river sampling sites. Variations in the occurrence and distribution of nutrients in streams and rivers on a broad national scale reflect differences in the sources of nutrient inputs to the upstream watersheds and in watershed characteristics that affect movement of those nutrients. Sites were classified by watershed size and by land use in the upstream watershed: agriculture, urban, and undeveloped (forest or rangeland). Selection of NAWQA urban sites was intended to avoid effects of major wastewater-treatment plants and other point sources, but in some locations this was not feasible. Nutrient concentrations and yields generally increased with anthropogenic development in the watershed. Median concentrations and yields for all constituents at sites downstream from undeveloped areas were less than at sites downstream from agricultural or urban areas. Concentrations of ammonia, orthophosphate, and total phosphorus at agricultural and urban sites were not significantly different; however, concentrations of nitrate and total nitrogen were higher at agricultural than at urban sites. Total nitrogen concentrations at agricultural sites were higher in areas of high nitrogen input or enhanced transport, such as irrigation or artificial drainage that can rapidly move water from cropland to streams (Midwest, Northern Plains, and western areas of the United States). Concentrations were lower in the Southeast, where more denitrification occurs during transport of nitrogen compounds in shallow ground water. At urban sites, high concentrations of ammonia and orthophosphate were more prevalent downstream from wastewater-treatment plants. At sites with large watersheds and high mean-annual streamflow (“large-watershed” sites), concentrations of most nutrients were significantly less than at sites downstream from agricultural or urban areas. Total nitrogen concentrations at large-watershed sites were higher in Midwest agricultural areas and lower in the Western United States, where agricultural and urban development is less extensive. Total phosphorus concentrations at large-watershed sites were higher in areas of greater potential erosion and low overall runoff such as the arid areas in the West. Although not as distinct as seasonal patterns of streamflow, geographic patterns of seasonally high and low concentrations of total nitrogen and total phosphorus were identified in the data. Seasonal patterns in concentrations of total nitrogen generally mirror seasonal patterns in streamflow in the humid Eastern United States but are inverse to seasonal patterns in streamflow in the semiarid interior West. Total phosphorus concentrations typically have the opposite regional relation with streamflow; high concentrations coincide with high streamflows in the interior West. In the NAWQA Program, sites downstream from relatively undeveloped areas were selected to provide a baseline for comparison to sites with potential effects of urban development and agriculture. Concentrations of nitrate, total nitrogen, and total phosphorus at NAWQA undeveloped sites were found to be greater than values reported by other studies for conditions of essentially no development (background conditions). Concentrations at NAWQA undeveloped sites represent conditions of relatively little development and provide insight in comparison to developed areas but should not, in general, be considered to represent background status. The U.S. Environmental Protection Agency has developed nutrient criteria to assist States in setting regional water-quality standards. Regional criteria were exceeded by total nitrogen concentrations at 72 percent of NAWQA undeveloped sites and by total phosphorus concentrations at 89 percent of these sites. Exceedances were even more extensive at sites with greater anthropogenic development upstream. The nitrogen criteria were exceeded at 96 percent of NAWQA sites classified as agricultural, urban, or mixed land use, and the phosphorus criteria were exceeded at 97 percent of these sites. Nationally, outflow loads of all nutrient constituents were strongly correlated to nonpoint-source inputs in the upstream watershed. The variation in input mass explained at least 69 percent of the variation in loads. Correlations between nonpoint-source input rates and outflow yields were not quite as good; variation in input rates explained only about 22-45 percent of the variations in nutrient yields. Estimation of nutrient outflow, on the basis of these correlations, likely could be improved if nationally consistent data were available for additional watershed characteristics.

Scientific Investigations Report

Water-quality, streamflow, and ancillary data for nutrients in streams and rivers across the nation, 1992-2001

Introduction: This report is the companion data report for: Nutrients in Streams and Rivers Across the Nation - 1992-2001 (D.K. Mueller and N.E. Spahr, U.S. Geological Survey written commun., 2005). The data contained in this report were collected as part of the National Water-Quality Assessment (NAWQA) Program. Investigations were conducted in 51 large river basins and aquifer systems, which are referred to as 'study units.' Implementation of study-unit investigations were phased so that high-intensity sampling occurred in about one-third of the study units at a time. Investigations in the first 20 study units began in 1991, and stream sampling began in 1992; however, most samples were collected during water years 1993-95. (Water year is defined as the period from October through September and is identified by the year in which it ends.) A second group of 16 study-unit investigations began in 1994, with most of the sampling completed during water years 1996-98. A third group, consisting of 15 study units, began in 1997 with most of the data collected during water years 1999-2001. At some sites, additional sampling continued after the high-intensity time period. Gilliom and others (1995) provide additional information about study-unit sampling design. Additional information about the NAWQA program is available at http://water.usgs.gov/nawqa/index.html.

Data Series

Inventory of ground-water resources in the Kabul Basin, Afghanistan

In 2004, the U.S. Geological Survey began working with engineers at the Afghanistan Geological Survey to provide hydrologic training and equipment and to apply these tools to build an inventory of water wells in the Kabul Basin of Afghanistan. An inventory of 148 wells now includes information on well location, depth, and access. Water-level and water-quality measurements have been made at most of these wells. A water-level elevation map has been constructed, and general directions of ground-water flow have been defined. Ground-water flow in the Kabul Basin is primarily through saturated alluvium and other basin-fill sediments. The water-table surface generally mirrors topography, and ground water generally flows in the directions of surface-water discharge. The quality of ground water in the Kabul Basin varies widely. In some areas, ground-water quality is excellent, with low concentrations of dissolved solids and no problematic constituents. In other areas, however, high concentrations of dissolved solids and the presence of some constituents at concentrations deemed harmful to humans and crops render untreated ground water marginal or unsuitable for public supply and/or agricultural use. Of particular concern are elevated concentrations of nitrate, boron, and dissolved solids, and an indication of fecal pollution in some parts of the basin. As Afghanistan emerges from years of conflict, as institutional capacities rejuvenate and grow, and as the need for wise water-management decisions continues, adequate data and a fuller understanding of the ground-water resource in the Kabul Basin will be imperative. The work described in this report represents only a modest beginning in what will be a long-term data-collection and interpretive effort.

Scientific Investigations Report

Quality of nutrient data from streams and ground water sampled during water years 1992-2001

Proper interpretation of water-quality data requires consideration of the effects that bias and variability might have on measured constituent concentrations. In this report, methods are described to estimate the bias due to contamination of samples in the field or laboratory and the variability due to sample collection, processing, shipment, and analysis. Contamination can adversely affect interpretation of measured concentrations in comparison to standards or criteria. Variability can affect interpretation of small differences between individual measurements or mean concentrations. Contamination and variability are determined for nutrient data from quality-control samples (field blanks and replicates) collected as part of the National Water-Quality Assessment (NAWQA) Program during water years 1992-2001. Statistical methods are used to estimate the likelihood of contamination and variability in all samples. Results are presented for five nutrient analytes from stream samples and four nutrient analytes from ground-water samples. Ammonia contamination can add at least 0.04 milligram per liter in up to 5 percent of all samples. This could account for more than 22 percent of measured concentrations at the low range of aquatic-life criteria (0.18 milligram per liter). Orthophosphate contamination, at least 0.019 milligram per liter in up to 5 percent of all samples, could account for more than 38 percent of measured concentrations at the limit to avoid eutrophication (0.05 milligram per liter). Nitrite-plus-nitrate and Kjeldahl nitrogen contamination is less than 0.4 milligram per liter in 99 percent of all samples; thus there is no significant effect on measured concentrations of environmental significance. Sampling variability has little or no effect on reported concentrations of ammonia, nitrite-plus-nitrate, orthophosphate, or total phosphorus sampled after 1998. The potential errors due to sampling variability are greater for the Kjeldahl nitrogen analytes and for total phosphorus sampled before 1999. The uncertainty in a mean of 10 concentrations caused by sampling variability is within a small range (1 to 7 percent) for all nutrients. These results can be applied to interpretation of environmental data collected during water years 1992-2001 in 52 NAWQA study units.

Scientific Investigations Report