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Jeffrey D. Martin

Publications and source records attributed to Jeffrey D. Martin.

At least 19 recordsLinked to original sources
USGS2018

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↗
USGS2017

A field study of selected U.S. Geological Survey analytical methods for measuring pesticides in filtered stream water, June - September 2012

U.S. Geological Survey monitoring programs extensively used two analytical methods, gas chromatography/mass spectrometry and liquid chromatography/mass spectrometry, to measure pesticides in filtered water samples during 1992–2012. In October 2012, the monitoring programs began using direct aqueous-injection liquid chromatography tandem mass spectrometry as a new analytical method for pesticides. The change in analytical methods, however, has the potential to inadvertently introduce bias in analysis of datasets that span the change. A field study was designed to document performance of the new method in a variety of stream-water matrices and to quantify any potential changes in measurement bias or variability that could be attributed to changes in analytical methods. The goals of the field study were to (1) summarize performance (bias and variability of pesticide recovery) of the new method in a variety of stream-water matrices; (2) compare performance of the new method in laboratory blank water (laboratory reagent spikes) to that in a variety of stream-water matrices; (3) compare performance (analytical recovery) of the new method to that of the old methods in a variety of stream-water matrices; (4) compare pesticide detections and concentrations measured by the new method to those of the old methods in a variety of stream-water matrices; (5) compare contamination measured by field blank water samples in old and new methods; (6) summarize the variability of pesticide detections and concentrations measured by the new method in field duplicate water samples; and (7) identify matrix characteristics of environmental water samples that adversely influence the performance of the new method. Stream-water samples and a variety of field quality-control samples were collected at 48 sites in the U.S. Geological Survey monitoring networks during June–September 2012. Stream sites were located across the United States and included sites in agricultural and urban land-use settings, as well as sites on major rivers. The results of the field study identified several challenges for the analysis and interpretation of data analyzed by both old and new methods, particularly when data span the change in methods and are combined for analysis of temporal trends in water quality. The main challenges identified are large (greater than 30 percent), statistically significant differences in analytical recovery, detection capability, and (or) measured concentrations for selected pesticides. These challenges are documented and discussed, but specific guidance or statistical methods to resolve these differences in methods are beyond the scope of the report. The results of the field study indicate that the implications of the change in analytical methods must be assessed individually for each pesticide and method. Understanding the possible causes of the systematic differences in concentrations between methods that remain after recovery adjustment might be necessary to determine how to account for the differences in data analysis. Because recoveries for each method are independently determined from separate reference standards and spiking solutions, the differences might be due to an error in one of the reference standards or solutions or some other basic aspect of standard procedure in the analytical process. Further investigation of the possible causes is needed, which will lead to specific decisions on how to compensate for these differences in concentrations in data analysis. In the event that further investigations do not provide insight into the causes of systematic differences in concentrations between methods, the authors recommend continuing to collect and analyze paired environmental water samples by both old and new methods. This effort should be targeted to seasons, sites, and expected concentrations to supplement those concentrations already assessed and to compare the ongoing analytical recovery of old and new methods to those observed in the summer and fall of 2012.

Scientific Investigations Report↗
USGS2017

Nutrient and pesticide contamination bias estimated from field blanks collected at surface-water sites in U.S. Geological Survey Water-Quality Networks, 2002–12

Potential contamination bias was estimated for 8 nutrient analytes and 40 pesticides in stream water collected by the U.S. Geological Survey at 147 stream sites from across the United States, and representing a variety of hydrologic conditions and site types, for water years 2002–12. This study updates previous U.S. Geological Survey evaluations of potential contamination bias for nutrients and pesticides. Contamination is potentially introduced to water samples by exposure to airborne gases and particulates, from inadequate cleaning of sampling or analytic equipment, and from inadvertent sources during sample collection, field processing, shipment, and laboratory analysis. Potential contamination bias, based on frequency and magnitude of detections in field blanks, is used to determine whether or under what conditions environmental data might need to be qualified for the interpretation of results in the context of comparisons with background levels, drinking-water standards, aquatic-life criteria or benchmarks, or human-health benchmarks. Environmental samples for which contamination bias as determined in this report applies are those from historical U.S. Geological Survey water-quality networks or programs that were collected during the same time frame and according to the same protocols and that were analyzed in the same laboratory as field blanks described in this report. Results from field blanks for ammonia, nitrite, nitrite plus nitrate, orthophosphate, and total phosphorus were partitioned by analytical method; results from the most commonly used analytical method for total phosphorus were further partitioned by date. Depending on the analytical method, 3.8, 9.2, or 26.9 percent of environmental samples, the last of these percentages pertaining to all results from 2007 through 2012, were potentially affected by ammonia contamination. Nitrite contamination potentially affected up to 2.6 percent of environmental samples collected between 2002 and 2006 and affected about 3.3 percent of samples collected between 2007 and 2012. The percentages of environmental samples collected between 2002 and 2011 that were potentially affected by nitrite plus nitrate contamination were 7.3 for samples analyzed with the low-level method and 0.4 for samples analyzed with the standard-level method. These percentages increased to 14.8 and 2.2 for samples collected in 2012 and analyzed using replacement low- and standard-level methods, respectively. The maximum potentially affected concentrations for nitrite and for nitrite plus nitrate were much less than their respective maximum contamination levels for drinking-water standards. Although contamination from particulate nitrogen can potentially affect up to 21.2 percent and that from total Kjeldahl nitrogen can affect up to 16.5 percent of environmental samples, there are no critical or background levels for these substances. For total nitrogen, orthophosphate, and total phosphorus, contamination in a small percentage of environmental samples might be consequential for comparisons relative to impairment risks or background levels. At the low ends of the respective ranges of impairment risk for these nutrients, contamination in up to 5 percent of stream samples could account for at least 23 percent of measured concentrations of total nitrogen, for at least 40 or 90 percent of concentrations of orthophosphate, depending on the analytical method, and for 31 to 76 percent of concentrations of total phosphorus, depending on the time period. Twenty-six pesticides had no detections in field blanks. Atrazine with 12 and metolachlor with 11 had the highest number of detections, mostly occurring in spring or early summer. At a 99-percent level of confidence, contamination was estimated to be no greater than the detection limit in at least 98 percent of all samples for 38 of 40 pesticides. For metolachlor and atrazine, potential contamination was no greater than 0.0053 and 0.0093 micrograms per liter in 98 percent of samples. For 11 of 14 pesticides with at least one detection, the maximum potentially affected concentration of the environmental sample was less than their respective human-health or aquatic-life benchmarks. Small percentages of environmental samples had concentrations high enough that atrazine contamination potentially could account for the entire aquatic-life benchmark for acute effects on nonvascular plants, that dieldrin contamination could account for up to 100 percent of the cancer health-based screening level, or that chlorpyrifos contamination could account for 13 or 12 percent of the concentrations in the aquatic-life benchmarks for chronic effects on invertebrates or the criterion continuous concentration for chronic effects on aquatic life.

Scientific Investigations Report↗
USGS2017

A method for addressing differences in concentrations of fipronil and three degradates obtained by two different laboratory methods

In October 2012, the U.S. Geological Survey (USGS) began measuring the concentration of the pesticide fipronil and three of its degradates (desulfinylfipronil, fipronil sulfide, and fipronil sulfone) by a new laboratory method using direct aqueous-injection liquid chromatography tandem mass spectrometry (DAI LC–MS/MS). This method replaced the previous method—in use since 2002—that used gas chromatography/mass spectrometry (GC/MS). The performance of the two methods is not comparable for fipronil and the three degradates. Concentrations of these four chemical compounds determined by the DAI LC–MS/MS method are substantially lower than the GC/MS method. A method was developed to correct for the difference in concentrations obtained by the two laboratory methods based on a methods comparison field study done in 2012. Environmental and field matrix spike samples to be analyzed by both methods from 48 stream sites from across the United States were sampled approximately three times each for this study. These data were used to develop a relation between the two laboratory methods for each compound using regression analysis. The relations were used to calibrate data obtained by the older method to the new method in order to remove any biases attributable to differences in the methods. The coefficients of the equations obtained from the regressions were used to calibrate over 16,600 observations of fipronil, as well as the three degradates determined by the GC/MS method retrieved from the USGS National Water Information System. The calibrated values were then compared to over 7,800 observations of fipronil and to the three degradates determined by the DAI LC–MS/MS method also retrieved from the National Water Information System. The original and calibrated values from the GC/MS method, along with measures of uncertainty in the calibrated values and the original values from the DAI LC–MS/MS method, are provided in an accompanying data release.

Open-File Report↗
USGS2015

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↗
USGS2014

Pesticide Toxicity Index: a tool for assessing potential toxicity of pesticide mixtures to freshwater aquatic organisms

Pesticide mixtures are common in streams with agricultural or urban influence in the watershed. The Pesticide Toxicity Index (PTI) is a screening tool to assess potential aquatic toxicity of complex pesticide mixtures by combining measures of pesticide exposure and acute toxicity in an additive toxic-unit model. The PTI is determined separately for fish, cladocerans, and benthic invertebrates. This study expands the number of pesticides and degradates included in previous editions of the PTI from 124 to 492 pesticides and degradates, and includes two types of PTI for use in different applications, depending on study objectives. The Median-PTI was calculated from median toxicity values for individual pesticides, so is robust to outliers and is appropriate for comparing relative potential toxicity among samples, sites, or pesticides. The Sensitive-PTI uses the 5th percentile of available toxicity values, so is a more sensitive screening-level indicator of potential toxicity. PTI predictions of toxicity in environmental samples were tested using data aggregated from published field studies that measured pesticide concentrations and toxicity to Ceriodaphnia dubia in ambient stream water. C. dubia survival was reduced to ≤ 50% of controls in 44% of samples with Median-PTI values of 0.1–1, and to 0% in 96% of samples with Median-PTI values > 1. The PTI is a relative, but quantitative, indicator of potential toxicity that can be used to evaluate relationships between pesticide exposure and biological condition.

Science of the Total Environment↗
USGS2014

Pesticide trends in major rivers of the United States, 1992-2010

This report is part of a series of pesticide trend assessments led by the National Water-Quality Assessment Program of the U.S. Geological Survey. This assessment focuses on major rivers of various sizes throughout the United States that have large watersheds with a range of land uses, changes in pesticide use, changes in management practices, and natural influences typical of the regions being drained. Trends were assessed at 59 sites for 40 pesticides and pesticide degradates during each of three overlapping periods: 1992–2001, 1997–2006, and 2001–10. In addition to trends in concentration, trends in agricultural-use intensity (agricultural use) were also assessed at 57 of the sites for 35 parent compounds with agricultural uses during the same three periods. The SEAWAVE-Q model was used to analyze trends in concentration, and parametric survival regression for interval-censored data was used to assess trends in agricultural use. All trends are provided in downloadable electronic files. A subset of 39 sites was chosen to represent non-nested, generally independent basins for a national analysis of pesticide and agricultural-use trends for the most prevalent pesticides (15 pesticides and 2 degradation products). Graphical and numerical results are presented to provide a national overview of concentration and use trends. As another perspective on understanding pesticide concentration trends in large rivers in relation to multiple tributary watersheds, this report also presents a detailed assessment of concentration and use trends for simazine, metolachlor, atrazine, deethylatrazine, and diazinon for a set of 17 nested sites in the Mississippi River Basin (including the Ohio and Missouri River Basins), for the second and third trend periods. Pesticides strongly dominated by agricultural use—cyanazine, metolachlor, atrazine, and alachlor—had widespread agreement between concentration trends and agricultural-use trends. Pesticides with substantial use in agricultural and urban applications—simazine, tebuthiuron, Dacthal, pendimethalin, chlorpyrifos, malathion, diazinon, fipronil, carbofuran, and carbaryl—had concentration trends that were mostly explained by a combination of agricultural-use trends and concentration trends in urban streams that were evaluated in a separate companion study. The importance of the urban stream trends for explaining concentration trends in major rivers indicates the significance of nonagricultural uses of some pesticides to concentrations in major rivers despite the much smaller area of urban land use compared to agriculture. Deethylatrazine, a degradate of atrazine, was the only pesticide compound assessed that had frequent occurrences during 1997–2006 and 2001–10 of concentration trends in the opposite direction of use trends (atrazine use). The nested analysis for the Mississippi River indicates that most trends observed in the largest rivers—multiple Mississippi River sites, the Ohio River, and the Missouri River—are consistent with streamflow contributions and concentration trends observed at tributary sites. Streamflow (incorporated into the trend model and shown in the nested basin analysis), trends in agricultural use of pesticides (quantified in this report), and urban use of pesticides (represented by concentration trends in a companion study of urban streams) are all important influences on pesticide concentrations in streams and rivers. Consideration of these influences is vital to understanding trends in pesticide concentrations.

Scientific Investigations Report↗
USGS2014

An overview comparing results from two decades of monitoring for pesticides in the Nation’s streams and rivers, 1992-2001 and 2002-2011

This report provides an overview of the U.S. Geological Survey National Water-Quality Assessment program and National Stream Quality Accounting Network findings for pesticide occurrence in U.S. streams and rivers during 2002–11 and compares them to findings for the previous decade (1992–2001). In addition, pesticide stream concentrations were compared to Human Health Benchmarks (HHBs) and chronic Aquatic Life Benchmarks (ALBs). The comparisons between the decades were intended to be simple and descriptive. Trends over time are being evaluated separately in a series of studies involving rigorous trend analysis. During both decades, one or more pesticides or pesticide degradates were detected more than 90 percent of the time in streams across all types of land uses. For individual pesticides during 2002–11, atrazine (and degradate, deethylatrazine), carbaryl, fipronil (and degradates), metolachlor, prometon, and simazine were detected in streams more than 50 percent of the time. In contrast, alachlor, chlorpyrifos, cyanazine, diazinon, EPTC, Dacthal, and tebuthiuron were detected less frequently in streams during the second decade than during the first decade. During 2002–11, only one stream had an annual mean pesticide concentration that exceeded an HHB. In contrast, 17 percent of agriculture land-use streams and one mixed land-use stream had annual mean pesticide concentrations that exceeded HHBs during 1992–2001. The difference between the first and second decades in terms of percent of streams exceeding HHBs was attributed to regulatory changes. During 2002–11, nearly two-thirds of agriculture land-use streams and nearly one-half of mixed land-use streams exceeded chronic ALBs. For urban land use, 90 percent of the streams exceeded a chronic ALB. Fipronil, metolachlor, malathion, cis-permethrin, and dichlorvos exceeded chronic ALBs for more than 10 percent of the streams. For agriculture and mixed land-use streams, the overall percent of streams that exceeded a chronic ALB was very similar between the decades. For urban land-use streams, the percent of streams exceeding a chronic ALB during 2002–11 nearly doubled that seen during 1992–2001. The reason for this difference was the inclusion of fipronil monitoring during the second decade. Across all land-use streams, the percent of streams exceeding a chronic ALB for fipronil during 2002–11 was greater than all other insecticides during both decades. The percent of streams exceeding a chronic ALB for metolachlor, chlorpyrifos, diazinon, malathion, and carbaryl decreased from the first decade to the second decade. The results of the 2002–11 summary and comparison to 1992–2001 are consistent with the results from more rigorous trend analysis of pesticide stream concentrations for individual streams in various regions of the U.S.

Scientific Investigations Report↗
USGS2014

Water quality in Indiana: trends in concentrations of selected nutrients, metals, and ions in streams, 2000-10

Water quality in Indiana streams generally improved during the 2000–10 study period, based on trends in selected nutrients, metals, and ions. This study combined water-quality data from the Indiana Fixed Station Monitoring Program (FSMP) with streamflow data from nearby U.S. Geological Survey streamgages. A parametric time-series model, QWTREND, was used to develop streamflow-adjusted constituent concentrations, to adjust for seasonal variance and serial correlation, and to identify trends independent of streamflow-related variability. This study examined 7,345 water samples from 57 FSMP sites for 11 years. Concentration trends were analyzed for 12 constituents—the nutrients nitrate, organic nitrogen, and phosphorus; suspended solids; the metals copper, iron, lead, and zinc; the ions chloride, and sulfate together with hardness as a measure of the calcium carbonate ion; and dissolved solids. Nutrient concentrations in this study generally were too high relative to standards and criteria. The national recommended criteria for the three ecoregions in Indiana were exceeded by more than one-half of the nitrate and most of the phosphorus concentrations. Copper, lead, zinc, chloride, sulfate, and dissolved solids concentrations were in acceptable ranges relative to standards and criteria in more than 97 percent of samples. The two Lake Michigan Basin sites had the highest concentrations and were in a unique statistical group for 10 of the 12 constituents, with concentrations many times higher than the statewide median and higher than the medians of most other basins. The two Ohio River Basin sites had the lowest concentrations and were in a unique statistical group for 6 of the 12 constituents. Statistically significant trends were identified that included 167 downward trends and 83 upward trends. The Kankakee River Basin had the most significant upward trends while the most significant downward trends were in the Whitewater River Basin, the Lake Michigan Basin, and the Patoka River Basin. For most constituents, a majority of sites had significant downward trends. Two streams in the Lake Michigan Basin have shown substantial decreases in most constituents. The West Fork White River near Indianapolis, Indiana, showed increases in nitrate and phosphorus and the Kankakee River Basin showed increases in copper, zinc, chloride, sulfate, and hardness. Upward trends in nutrients were identified at a few sites, but most nutrient trends were downward. Upward trends in metals corresponded with relatively small concentration increases while downward trends involved considerably larger concentration changes. Downward trends in chloride, sulfate, and suspended solids were observed statewide, but upward trends in hardness were observed in the northern half of Indiana.

Indiana↗
USGS2011

Adjustment of pesticide concentrations for temporal changes in analytical recovery, 1992–2010

Recovery is the proportion of a target analyte that is quantified by an analytical method and is a primary indicator of the analytical bias of a measurement. Recovery is measured by analysis of quality-control (QC) water samples that have known amounts of target analytes added ("spiked" QC samples). For pesticides, recovery is the measured amount of pesticide in the spiked QC sample expressed as a percentage of the amount spiked, ideally 100 percent. Temporal changes in recovery have the potential to adversely affect time-trend analysis of pesticide concentrations by introducing trends in apparent environmental concentrations that are caused by trends in performance of the analytical method rather than by trends in pesticide use or other environmental conditions. This report presents data and models related to the recovery of 44 pesticides and 8 pesticide degradates (hereafter referred to as "pesticides") that were selected for a national analysis of time trends in pesticide concentrations in streams. Water samples were analyzed for these pesticides from 1992 through 2010 by gas chromatography/mass spectrometry. Recovery was measured by analysis of pesticide-spiked QC water samples. Models of recovery, based on robust, locally weighted scatterplot smooths (lowess smooths) of matrix spikes, were developed separately for groundwater and stream-water samples. The models of recovery can be used to adjust concentrations of pesticides measured in groundwater or stream-water samples to 100 percent recovery to compensate for temporal changes in the performance (bias) of the analytical method.

Data Series↗
USGS2011

Sources and preparation of data for assessing trends in concentrations of pesticides in streams of the United States, 1992–2010

This report updates a previously published water-quality dataset of 44 commonly used pesticides and 8 pesticide degradates suitable for a national assessment of trends in pesticide concentrations in streams of the United States. Water-quality samples collected from January 1992 through September 2010 at stream-water sites of the U.S. Geological Survey (USGS) National Water-Quality Assessment (NAWQA) Program and the National Stream Quality Accounting Network (NASQAN) were compiled, reviewed, selected, and prepared for trend analysis. The principal steps in data review for trend analysis were to (1) identify analytical schedule, (2) verify sample-level coding, (3) exclude inappropriate samples or results, (4) review pesticide detections per sample, (5) review high pesticide concentrations, and (6) review the spatial and temporal extent of NAWQA pesticide data and selection of analytical methods for trend analysis. The principal steps in data preparation for trend analysis were to (1) select stream-water sites for trend analysis, (2) round concentrations to a consistent level of precision for the concentration range, (3) identify routine reporting levels used to report nondetections unaffected by matrix interference, (4) reassign the concentration value for routine nondetections to the maximum value of the long-term method detection level (maxLT-MDL), (5) adjust concentrations to compensate for temporal changes in bias of recovery of the gas chromatography/mass spectrometry (GCMS) analytical method, and (6) identify samples considered inappropriate for trend analysis. Samples analyzed at the USGS National Water Quality Laboratory (NWQL) by the GCMS analytical method were the most extensive in time and space and, consequently, were selected for trend analysis. Stream-water sites with 3 or more water years of data with six or more samples per year were selected for pesticide trend analysis. The selection criteria described in the report produced a dataset of 21,988 pesticide samples at 212 stream-water sites. Only 21,144 pesticide samples, however, are considered appropriate for trend analysis.

Data Series↗
USGS2011

USGS library for S-PLUS for Windows -- Release 4.0

Release 4.0 of the U.S. Geological Survey S-PLUS library supercedes release 2.1. It comprises functions, dialogs, and datasets used in the U.S. Geological Survey for the analysis of water-resources data. This version does not contain ESTREND, which was in version 2.1. See Release 2.1 for information and access to that version. This library requires Release 8.1 or later of S-PLUS for Windows. S-PLUS is a commercial statistical and graphical analysis software package produced by TIBCO corporation(http://www.tibco.com/). The USGS library is not supported by TIBCO or its technical support staff.

Open-File Report↗
USGS2011

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↗
USGS2011

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↗
USGS2010

Trends in pesticide concentrations in urban streams in the United States, 1992-2008

Pesticide concentration trends in streams dominated by urban land use were assessed using data from 27 urban streams sampled as part of the U.S. Geological Survey National Water-Quality Assessment Program. The sites were divided into four regions, Northeast, South, Midwest, and West, to examine possible regional patterns. Three partially overlapping 9-year periods (1992-2000, 1996-2004, and 2000-2008) were examined for eight herbicides and one degradation product (simazine, prometon, atrazine, deethylatrazine, metolachlor, trifluralin, pendimethalin, tebuthiuron, and Dacthal), and five insecticides and two degradation products (chlorpyrifos, malathion, diazinon, fipronil, fipronil sulfide, desulfinylfipronil, and carbaryl). The data were analyzed for trends in concentration using a parametric regression model with seasonality, flow-related variability, and trend, called SEAWAVE-Q. The SEAWAVE-Q model also was used to generate estimated daily concentration percentiles for each analysis period to provide a summary of concentration magnitudes. For herbicides, the largest 90th percentiles of estimated concentrations for simazine were in the South, prometon at some sites in all of the regions, atrazine and deethylatrazine in the South and Midwest, metolachlor in the Midwest and a few sites in the South, pendimethalin at scattered sites in all of the regions, and tebuthiuron in the South and a few sites in the Midwest and West. For insecticides, the largest 90th percentiles of estimated concentrations for diazinon and carbaryl were distributed among various sites in all regions (especially during 1996-2004), and fipronil at isolated sites in all of the regions during 2000-2008. Trend analysis results for the herbicides indicated many significant trends, both upward and downward, with varying patterns depending on period, region, and herbicide. Overall, deethylatrazine showed the most consistent pattern of upward trends, especially in the Northeast (2000-2008), South (1996-2004 and 2000-2008), and Midwest (1996-2004 and 2000-2008). Other herbicides showed less consistent upward trends, including simazine in the South (1996-2004), prometon in the Midwest (2000-2008), and atrazine in the South (1996-2004). The most consistent downward trends were for simazine in the Northeast and Midwest (1996-2004), prometon in the Northeast and Midwest (1996-2004) and West (1996-2004 and 2000-2008), and tebuthiuron in the South (1996-2004 and 2000-2008) and West (2000-2008). Strong similarity existed between the trends for atrazine and deethylatrazine during 1996-2004. During 2000-2008, however, there were mixed upward and downward trends in atrazine and predominantly upward trends in deethylatrazine. Ten sites with a downward trend in atrazine were paired with an upward trend in deethylatrazine and for three of these sites (1 in the South and 2 in the Midwest) both opposing trends were significant. Opposing trends showing a decrease in atrazine and an increase in deethylatrazine may indicate that decreases in atrazine from surface runoff are being offset in some cases by increases in deethylatrazine from groundwater for the latter analysis period. Trend results for insecticides indicated widespread significant downward trends for chlorpyrifos (especially 1996-2004), diazinon (1996-2004 and 2000-2008), and malathion (especially 1996-2004); widespread significant upward trends for fipronil and its degradation products (2000-2008); and mostly nonsignificant trends for carbaryl (1996-2004 and 2000-2008). The downward trends for chlorpyrifos and diazinon were consistent with the regulatory phaseout of residential uses of these insecticides and the upward trends for fipronil and its degradation products were consistent with its introduction in 1996 and subsequent increasing use as a possible substitute for chlorpyrifos and diazinon. The downward trends in malathion may be caused by voluntary substitution of pyrethroids or fipronil for malathio

Scientific Investigations Report↗
USGS2009

Trends in concentrations and use of agricultural herbicides for Corn Belt rivers, 1996-2006

Trends in the concentrations and agricultural use of four herbicides (atrazine, acetochlor, metolachlor, and alachlor) were evaluated for major rivers of the Corn Belt for two partially overlapping time periods: 1996-2002 and 2000-2006. Trends were analyzed for 11 sites on the mainstems and selected tributaries in the Ohio, Upper Mississippi, and Missouri River Basins. Concentration trends were determined using a parametric regression model designed for analyzing seasonal variability, flow-related variability, and trends in pesticide concentrations(SEAWAVE-Q).TheSEAWAVE-Qmodel accounts for the effect of changing flow conditions in order to separate changes caused by hydrologic conditions from changes caused by other factors, such as pesticide use. Most of the trends in atrazine and acetochlor concentrations for both time periods were relatively small and nonsignificant, but metolachlor and alachlor were dominated by varying magnitudes of concentration downtrends. Overall, with trends expressed as a percent change per year, trends in herbicide concentrations were consistent with trends in agricultural use; 84 of 88 comparisons for different sites, herbicides, and time periods showed no significant difference between concentration trends and agricultural use trends. Results indicate that decreasing use appears to have been the primary cause for the concentration downtrends during 1996-2006 and that, while there is some evidence that nonuse management factors may have reduced concentrations in some rivers, reliably evaluating the influence of these factors on pesticides in large streams and rivers will require improved, basin-specific information on both management practices and use over time. ?? 2009 American Chemical Society.

Environmental Science & Technology↗
USGS2009

Sources and preparation of data for assessing trends in concentrations of pesticides in streams of the United States, 1992-2006

This report provides a water-quality data set of 44 commonly used pesticides and 8 pesticide degradates suitable for a national assessment of trends in pesticide concentrations in streams of the United States. Water-quality samples collected from January 1992 through August 2006 at stream-water sites of the U.S. Geological Survey National Water-Quality Assessment Program and the National Stream Quality Accounting Network Program were compiled, reviewed, selected, and prepared for trend analysis as described in this report. Samples analyzed at the U.S. Geological Survey National Water Quality Laboratory by a gas chromatography/mass spectrometry analytical method were the most extensive in time and space and were selected for national trend analysis. The selection criteria described in the report produced a trend data set of 16,869 pesticide samples at 201 stream and river sites.

Scientific Investigations Report↗
USGS2009

Trends in pesticide concentrations in corn-belt streams, 1996-2006

Trends in the concentrations of commonly occurring pesticides in the Corn Belt of the United States were assessed, and the performance and application of several statistical methods for trend analysis were evaluated. Trends in the concentrations of 11 pesticides with sufficient data for trend assessment were assessed at up to 31 stream sites for two time periods: 1996–2002 and 2000–2006. Pesticides included in the trend analyses were atrazine, acetochlor, metolachlor, alachlor, cyanazine, EPTC, simazine, metribuzin, prometon, chlorpyrifos, and diazinon. The statistical methods applied and compared were (1) a modified version of the nonparametric seasonal Kendall test (SEAKEN), (2) a modified version of the Regional Kendall test, (3) a parametric regression model with seasonal wave (SEAWAVE), and (4) a version of SEAWAVE with adjustment for streamflow (SEAWAVE-Q). The SEAKEN test is a statistical hypothesis test for detecting monotonic trends in seasonal time-series data such as pesticide concentrations at a particular site. Trends across a region, represented by multiple sites, were evaluated using the regional seasonal Kendall test, which computes a test for an overall trend within a region by computing a score for each season at each site and adding the scores to compute the total for the region. The SEAWAVE model is a parametric regression model specifically designed for analyzing seasonal variability and trends in pesticide concentrations. The SEAWAVE-Q model accounts for the effect of changing flow conditions in order to separate changes caused by hydrologic trends from changes caused by other factors, such as pesticide use. There was broad, general agreement between unadjusted trends (no adjustment for streamflow effects) identified by the SEAKEN and SEAWAVE methods, including the regional seasonal Kendall test. Only about 10 percent of the paired comparisons between SEAKEN and SEAWAVE indicated a difference in the direction of trend, and none of these had differences significant at the 10-percent significance level. This consistency of results supports the validity and robustness of all three approaches as trend analysis tools. The SEAWAVE method is favored, however, because it has less restrictive data requirements, enabling analysis for more site/pesticide combinations, and can incorporate adjustment for streamflow (SEAWAVE-Q) with substantially fewer measurements than the flow-adjustment procedure used with SEAKEN. Analysis of flow-adjusted trends is preferable to analysis of non-adjusted trends for evaluating potential effects of changes in pesticide use or management practices because flow-adjusted trends account for the influence of flow-related variability. Analysis of flow-adjusted trends by SEAWAVE-Q showed that all of the pesticides assessed, except simazine and acetochlor, were dominated by varying degrees of concentration downtrends in one or both analysis periods. Atrazine, metolachlor, alachlor, cyanazine, EPTC, and metribuzin—all major corn herbicides, as well as prometon and chlorpyrifos, showed more prevalent concentration downtrends during 1996–2002 compared to 2000–2006. Diazinon had no clear trends during 1996–2002, but had predominantly downward trends during 2000–2006. Acetochlor trends were mixed during 1996–2002 and slightly upward during 2000–2006, but most of the trends were not statistically significant. Simazine concentrations trended upward at most sites during both 1996–2002 and 2000–2006. Comparison of concentration trends to agricultural-use trends indicated similarity in direction and magnitude for acetochlor, metolachlor, alachlor, cyanazine, EPTC, and metribuzin. Concentration downtrends for atrazine, chlorpyrifos, and diazinon were steeper than agricultural-use downtrends at some sites, indicating the possibility that agricultural management practices may have increasingly reduced transport to streams (particularly atrazine) or, for chlorpyrifos and diazinon, that nonagricultural uses declined substantially. Concentration uptrends for simazine generally were steeper than agricultural-use uptrends, indicating the possibility that nonagricultural uses of this herbicide increased during the study period.

Scientific Investigations Report↗