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Maps showing interpretation, using R-mode factor analysis, of trace-element abundances in heavy-mineral concentrate samples, Delta 1° x 2° quadrangle, Utah

A set of heavy-mineral concentrate data for the Delta 1° x 2° quadrangle, Utah Conterminous U.S. Mineral Assessment Program (CUSMAP) project was compiled from results of analyses of samples collected during the National Uranium Resource Evaluation Program (SURE), as well as results obtained from samples collected more recently by the USGS. Data results, sampling methods, and analytical methods are provided in Abrogast and others, 1993; 1990; 1988a; 1988b). A similar report, discussing results obtained from stream-sediment samples, is presented in Zimbelman (1993a). The Delta 1° x 2° quadrangle, Utah (figure 1) contains a variety of hydrothermal mineral deposit types, including porphyry-, vein-, replacement-, and Carlin-type deposits. These deposit types have been worked for commodities including gold, silver, beryllium, uranium, lead, zinc, copper, manganese, and cadmium (Lindsey, 1977; Morris and Mogensen, 1978; Zimbelman and others, 1990; Zimbelman and others, 1988). Heavy-mineral concentrate and stream-sediment samples derived from these hydrothermally altered rocks typically contain many geochemical anomalies (for example, see Zimbelman 1993b, c, d). Element associations characterizing lithology and hydrothermal mineral deposits can be distinguished using R-mode factor analysis. This tool often is useful in reconnaissance-scale surveys where sample anomalies are often weak. and single-element distributions may not help to delineate targets. R-mode factors analysis can help identify geologic trends and areas most likely to contain the mineral deposits. R-mode factor analysis was performed on a data set of results of analyses for 19 elements in 643 samples and produced a six-factor model. These six factors represent the geochemical contributions to the data set provided by lithologic and mineralization processes, The distribution of samples that contain high scores for mineralization-related factors is widespread in the Delta quadrangle. These sample sites are though to relate to both known prospect and mineralization areas, as well as define new areas that are geochemically favorable to contain altered or mineralized rocks.

Utah

Adjustment of pesticide concentrations for temporal changes in analytical recovery, 1992-2006

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 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 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 examines temporal changes in 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 to 2006 by gas chromatography/mass spectrometry. Recovery was measured by analysis of pesticide-spiked QC water samples. Temporal changes in pesticide recovery were investigated by calculating robust, locally weighted scatterplot smooths (lowess smooths) for the time series of pesticide recoveries in 5,132 laboratory reagent spikes; 1,234 stream-water matrix spikes; and 863 groundwater matrix spikes. A 10-percent smoothing window was selected to show broad, 6- to 12-month time scale changes in recovery for most of the 52 pesticides. Temporal patterns in recovery were similar (in phase) for laboratory reagent spikes and for matrix spikes for most pesticides. In-phase temporal changes among spike types support the hypothesis that temporal change in method performance is the primary cause of temporal change in recovery. Although temporal patterns of recovery were in phase for most pesticides, recovery in matrix spikes was greater than recovery in reagent spikes for nearly every pesticide. Models of recovery based on matrix spikes are deemed more appropriate for adjusting concentrations of pesticides measured in groundwater and stream-water samples than models based on laboratory reagent spikes because (1) matrix spikes are expected to more closely match the matrix of environmental water samples than are reagent spikes and (2) method performance is often matrix dependent, as was shown by higher recovery in matrix spikes for most of the pesticides. Models of recovery, based on 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.

Scientific Investigations Report

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

Bacteria holding times for fecal coliform by mFC agar method and total coliform and Escherichia coli by Colilert®-18 Quanti-Tray® method

Bacteria holding-time experiments of up to 62 h were performed on five surface-water samples from four urban stream sites in the vicinity of Atlanta, GA, USA that had relatively high densities of coliform bacteria ( Escherichia coli densities were all well above the US Environmental Protection Agency criterion of 126 colonies (100 ml)  − 1 for recreational waters). Holding-time experiments were done for fecal coliform using the membrane filtration modified fecal coliform (mFC) agar method and for total coliform and E. coli using the Colilert ® -18 Quanti-Tray ® method. The precisions of these analytical methods were quantified. Precisions determined for fecal coliform indicated that the upper bound of the ideal range of counts could reasonably be extended upward and would improve precision. For the Colilert ® -18 method, analytical precisions were similar to the theoretical precisions for this method. Fecal and total coliform densities did not change significantly with holding times up to about 27 h. Limited information indicated that fecal coliform densities might be stable for holding times of up to 62 h, whereas total coliform densities might not be stable for holding times greater than about 27 h. E. coli densities were stable for holding times of up to 18 h—a shorter period than indicated from a previous studies. These results should be applicable to non-regulatory monitoring sampling designs for similar urban surface-water sample types.

Environmental Monitoring and Assessment

U.S. Geological Survey Trace Elements and related reports through 1953

This report combines and brings up-to-date the information previously given in Trace Elements Investigations Report 325, "Numerical list of U.S. Geological Survey Trace Elements Reports to April 30, 1953," and Trace Elements Investigations Report 301, "Topical index and bibliography of U.S. Geological Survey Trace Elements and related reports." Part I is a numerical list of U.S. Geological Survey Trace Elements Investigations and Memorandum reports. It supersedes TEI-325. This part lists not only reports (followed by a date) that have been transmitted to the U.S. Atomic Energy Commission, but also reports in preparation (followed by an asterisk) for which tentative titles were available on December 31, 1953. Reports that have been published are indicated by the abbreviation of the medium of publication. (See also part II.) Part II is a reference guide to Trace Elements and related reports that are available to the public; this part supersedes Part 2 of the TEI-301 (published as Geological survey Circular 281). These reports are grouped according to the type of publication or release. Abstracts published in Nuclear Science Abstracts are not included in Part II, although certain TEI and TEM reports, the abstracts of which have been published in NSA, are so indicated in Part I. Publications in process on December 31, 1953, are designated by an asterisk. Part III is a finding list of states, areas, and subjects. It is based on information derived mostly from the titles of reports and, where titles are of a general nature, from a cursory review of the reports. This list is not a complete index of the information given in Trace Elements and related reports, but is designed to find subjects of major interest. Because of the numerous entries for Colorado and Utah, information has been listed by counties and, where possible, by subject under these states. Other states have county listings only if a county is included in the title of a report; otherwise, areas may be listed separately under the state. Major subjects are listed separately in the index and also where appropriate under states. Analytical methods and subjects related to analytical research are listed under Analytical Methods and Research, but not separately throughout the index. Most mineralogic studies are included under the heading Mineralogy, but are not necessarily listed according to location. Part IV is a finding list of authors. The words “with” and “and” are used to indicate seniority of authorship. For example, a listing of Jones and Brown indicates that Jones is the senior author. A listing of Jones with Brown indicates that Brown is the senior author. In both parts III and IV all Trace Elements reports are listed, as well as other related reports that have not been issued as Trace Elements reports. The following standard abbreviations have been used: TEI, Trace Elements Investigations report; TEM, Trace Elements Memorandum report; P, Professional Paper; B, Bulletin; C, Circular; J, Journal; OF, open file; TIS, Technical Information Service release; NSA, Nuclear Science Abstracts; QM, Quadrangle Map Series; and OM, Oil and Gas map or Mineral Investigations map or report.

Trace Elements Investigations

U.S. Geological Survey Trace Elements and related reports through 1954

This report supersedes TEI-400, "U.S. Geological Survey Trace Elements and related reports through 1953." Part I is a numerical list of U.S. Geological Survey Trace Elements Investigations and Memorandum reports. This part lists not only reports (followed by a date) that have been transmitted to the U.S> Atomic Energy Commission, but also reports in preparation (followed by an asterisk) for which tentative titles were available on December 31, 1954. If a report, or portion of a report, has been published, the fact is indicated by the abbreviation of the medium of publication. (See also Part II.) Part II is a reference guide to Trace Elements and related reports that are available to the public (this part supersedes Part I of Bulletin 1019-B). These reports are grouped according to the type of publication or release. If a report, or portion of the report, has been published in more than one form, appropriate cross-references are given to indicate the other forms of publication. Abstracts published in Nuclear Science Abstracts are not included in Part II; however, if the abstract of a Trace Elements report has been published in NSA, the fact is indicated in Part I. Publications in process on December 31, 1954, are designated by an asterisk. Part III is a finding list of states, areas, and subjects and supersedes Part II of Bulletin 1019-B. It is based on information derived mostly from the titles of reports and, where titles are of general nature, from a cursory review of the reports. This list is not a complete index of the information given in Trace Elements and related reports, but is designed to find subjects of major interest, Because of the numerous entries for Colorado and Utah, information has been listed by counties and, where possible, by subject under these states. Other states have county listings only if a county is included in the title of a report; otherwise, area may be listed separately under the state. Major subjects are listed separately in the index and also, where appropriate under states. Analytical methods and subjects related to analytical research are listed under Analytical Methods and Research, but not separately throughout the index. Most mineralogic studies are included under the heading Mineralogy, but are not necessarily listed according to location. Part IV is an author index. The words “with” and “and” are used to indicate seniority of authorship. For example, a listing of Smith and Brown indicated that Smith is the senior author. A listing of Smith with Brown indicates that Brown is the senior author. In both parts III and IV all Trace Elements reports are listed, as well as other related reports that have not been issued as Trace Elements reports. The following abbreviations have been used: TEI, Trace Elements Investigations report; TEM, Trace Elements Memorandum report; OF, open file; TIS, Technical Information Service release; C, Circular; B, Bulletin; P, Professional Paper; MC, Maps and Charts; J, Journal; and NSA, Nuclear Science Abstracts.

Trace Elements Investigations

San Francisco Estuary chlorophyll sensor and sample analysis intercomparison

This report presents an assessment of chlorophyll collection methods and anonymous results of field and laboratory comparisons in 2018 - 2019 by agencies in the San Francisco Estuary (SFE). The methods assessment and comparison exercises, with funding provided by the Delta Regional Monitoring Program and Bay Nutrient Management Strategy and in-kind contributions from participating agencies, are a first step to facilitate future comparisons and syntheses of data and inform best science practices in the region. In situ sonde comparison exercises found general agreement between two models of Yellow Springs Instrument (YSI) sensors, but the newer sensor (EXO v2 - total algae) measured higher chlorophyll fluorescence (fCHL) relative to the older YSI sensor (6-series 6025). Results may be attributed to the use of a two-point calibration and the fluorescence response of algal cultures in sensor development by the manufacturer. The laboratory comparison included participation by 12 distinct field - laboratory pairs (or groups), with one group analyzing filters using two analytical methods. Filters were collected in triplicate across three sampling events in 2018, and all sample results were pooled together. Results of statistical analyses indicated that nominal filter pore size, the grinding method associated with pigment extraction, and analytical methods do not introduce variability to the chlorophyll-a measurement (Chl-a). When Chl-a results were assessed by sample event, however, significant differences between nominal pore size and analytical methods existed; these differences could be attributed to the small sample size per event. Consistent reporting units and high-concentration calibration standards for field sensors among data collection agencies would improve the consistency and comparability of data collected in the SFE. More routine split sampling events, longer term sensor comparison exercises, and further processing and analytical comparisons that control for individual filterers may also enhance comparability in the region.

California

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

Antibiotic, pharmaceutical, and wastewater-compound data for Michigan, 1998-2005

Beginning in the late 1990's, the U.S. Geological Survey began to develop analytical methods to detect, at concentrations less than 1 microgram per liter (ug/L), emerging water contaminants such as pharmaceuticals, personal-care chemicals, and a variety of other chemicals associated with various human and animal sources. During 1998-2005, the U.S. Geological Survey analyzed the following Michigan water samples: 41 samples for antibiotic compounds, 28 samples for pharmaceutical compounds, 46 unfiltered samples for wastewater compounds (dissolved and suspended compounds), and 113 filtered samples for wastewater compounds (dissolved constituents only). The purpose of this report is to summarize the status of emerging contaminants in Michigan waters based on data from several different project-specific sample-collection efforts in Michigan during an 8-year period. During the course of the 8-year sampling effort, antibiotics were determined at 20 surface-water sites and 2 groundwater sites, pharmaceuticals were determined at 11 surface-water sites, wastewater compounds in unfiltered water were determined at 31 surface-water sites, and wastewater compounds in filtered water were determined at 40 surface-water and 4 groundwater sites. Some sites were visited only once, but others were visited multiple times. A variety of quality-assurance samples also were collected. This report describes the analytical methods used, describes the variations in analytical methods and reporting levels during the 8-year period, and summarizes all data using current (2009) reporting criteria. Very few chemicals were detected at concentrations greater than current laboratory reporting levels, which currently vary from a low of 0.005 ug/L for some antibiotics to 5 ug/L for some wastewater compounds. Nevertheless, 10 of 51 chemicals in the antibiotics analysis, 9 of 14 chemicals in the pharmaceuticals analysis, 34 of 67 chemicals in the unfiltered-wastewater analysis, and 56 of 62 chemicals in the filtered-wastewater analysis were detected. Antibiotics were detected at 7 of 20 tested surface-water sites, but none were detected in 2 groundwater samples. Pharmaceuticals were detected at 7 of 11 surface-water sites. Wastewater compounds were detected at 25 of 31 sites for which unfiltered water samples were analyzed and at least once at all 40 surface-water sites and all 4 groundwater sites for which filtered water samples were analyzed. Overall, the chemicals detected most frequently in Michigan waters were similar to those reported frequently in other studies nationwide. Patterns of chemical detections were site specific and appear to be related to local sources, overall land use, and hydrologic conditions at the time of sampling. Field-blank results provide important information for the design of future sampling programs in Michigan and demonstrate the need for careful field-study design. Field-replicate results indicated substantial confidence regarding the presence or absence of the many chemicals tested. Overall, data reported herein indicate that a wide array of antibiotic, pharmaceutical, and organic wastewater compounds occur in Michigan waters. Patterns of occurrence, with respect to hydrologic, land use, and source variables, generally appear to be similar for Michigan as for other sampled waters across the United States. The data reported herein can serve as a basis for future studies in Michigan.

Michigan

Occurrence of organic wastewater compounds in drinking water, wastewater effluent, and the Big Sioux River in or near Sioux Falls, South Dakota, 2001-2004

The U.S. Geological Survey (USGS) in cooperation with the city of Sioux Falls conducted several rounds of sampling to determine the occurrence of organic wastewater compounds (OWCs) in the city of Sioux Falls drinking water and waste-water effluent, and the Big Sioux River in or near Sioux Falls during August 2001 through May 2004. Water samples were collected during both base-flow and storm-runoff conditions. Water samples were collected at 8 sites, which included 4 sites upstream from the wastewater treatment plant (WWTP) discharge, 2 sites downstream from the WWTP discharge, 1 finished drinking-water site, and 1 WWTP effluent (WWE) site. A total of 125 different OWCs were analyzed for in this study using five different analytical methods. Analyses for OWCs were performed at USGS laboratories that are developing and/or refining small-concentration (less than 1 microgram per liter (ug/L)) analytical methods. The OWCs were classified into six compound classes: human pharmaceutical compounds (HPCs); human and veterinary antibiotic compounds (HVACs); major agricultural herbicides (MAHs); household, industrial,and minor agricultural compounds (HIACs); polyaromatic hydrocarbons (PAHs); and sterol compounds (SCs). Some of the compounds in the HPC, MAH, HIAC, and PAH classes are suspected of being endocrine-disrupting compounds (EDCs). Of the 125 different OWCs analyzed for in this study, 81 OWCs had one or more detections in environmental samples reported by the laboratories, and of those 81 OWCs, 63 had acceptable analytical method performance, were detected at concentrations greater than the study reporting levels, and were included in analyses and discussion related to occurrence of OWCs in drinking water, wastewater effluent, and the Big Sioux River. OWCs in all compound classes were detected in water samples from sampling sites in the Sioux Falls area. For the five sampling periods when samples were collected from the Sioux Falls finished drinking water, only one OWC was detected at a concentration greater than the study reporting level (metolachlor; 0.0040 ug/L). During base-flow conditions, Big Sioux River sites upstream from the WWTP discharge had OWC contributions that primarily were from nonpoint animal or crop agriculture sources or had OWC concentrations that were minimal. The influence of the WWTP discharge on OWCs at downstream river sites during base-flow conditions ranged from minimal influence to substantial influence depending on the sampling period. During runoff conditions, OWCs at sites upstream from the WWTP discharge probably were primarily contributed by nonpoint animal and/or crop agriculture sources and possibly by stormwater runoff from nearby roads. OWCs at sites downstream from the WWTP discharge probably were contributed by sources other than the WWTP effluent discharge, such as stormwater runoff from urban and/or agriculture areas and/or resuspension of OWCs adsorbed to sediment deposited in the Big Sioux River. OWC loads generally were substantially smaller for upstream sites than downstream sites during both base-flow and runoff conditions.discharge had OWC contributions that primarily were from nonpoint animal or crop agriculture sources or had OWC concentrations that were minimal. The influence of the WWTP discharge on OWCs at downstream river sites during base-flow conditions ranged from minimal influence to substantial influence depending on the sampling period. During runoff conditions, OWCs at sites upstream from the WWTP discharge probably were primarily contributed by nonpoint animal and/or crop agriculture sources and possibly by stormwater runoff from nearby roads. OWCs at sites downstream from the WWTP discharge probably were contributed by sources other than the WWTP effluent discharge, such as stormwater runoff from urban and/or agriculture areas and/or resuspension of OWCs adsorbed to sediment deposited in the Big Sioux River. OWC loads generally were substantially smaller for

South Dakota

Comparability of suspended-sediment concentration and total suspended solids data

Two laboratory analytical methods — suspended-sediment concentration (SSC) and total suspended solids (TSS) — are predominantly used to quantify concentrations of suspended solid-phase material in surface waters of the United States. The analytical methods differ. SSC data are produced by measuring the dry weight of all the sediment from a known volume of a water-sediment mixture. TSS data are produced by several methods, most of which entail measuring the dry weight of sediment from a known volume of a subsample of the original. An evaluation of 3,235 paired SSC and TSS data, of which 860 SSC values include percentages of sand-size material, shows bias in the relation between SSC and TSS —SSC values tend to increase at a greater rate than their corresponding paired TSS values. As sand-size material in samples exceeds about a quarter of the sediment dry weight, SSC values tend to exceed their corresponding paired TSS values. TSS analyses of three sets of quality-control samples (35 samples) showed unexpectedly small sediment recoveries and relatively large variances in the TSS data. Two quality-control data sets (18 samples) that were analyzed for SSC showed both slightly deficient sediment recoveries, and variances that are characteristic of most other quality-control data compiled as part of the U.S. Geological Survey’s National Sediment Laboratory Quality Assurance Program. The method for determining TSS, which was originally designed for analyses of wastewater samples, is shown to be fundamentally unreliable for the analysis of natural-water samples. In contrast, the method for determining SSC produces relatively reliable results for samples of natural water, regardless of the amount or percentage of sand-size material in the samples. SSC and TSS data collected from natural water are not comparable and should not be used interchangeably. The accuracy and comparability of suspended solid-phase concentrations of the Nation’s natural waters would be greatly enhanced if all these data were produced by the SSC analytical method.

Water-Resources Investigations Report

Pesticide data for selected Wyoming streams, 1976-78

In 1976, the U.S. Geological Survey, in cooperation with the Wyoming Department of Agriculture, started a monitoring program to determine pesticide concentrations in Wyoming streams. This program was incorporated into the water-quality data-collection system already in operation. Samples were collected at 20 sites for analysis of various insecticides, herbicides, polychlorinated biphenyls, and polychlorinated napthalenes.\ The results through 1978 revealed small concentrations of pesticides in water and bottom-material samples were DDE (39 percent of the concentrations equal to or greater than the minimum reported concentrations of the analytical methods), DDD (20 percent), dieldrin (21 percent), and polychlorinated biphenyls (29 percent). The herbicides most commonly found in water samples were 2,4-D (29 percent of the concentrations equal to or greater than the minimum reported concentrations of the analytical method) and picloram (23 percent). Most concentrations were significantly less than concentrations thought to be harmful to freshwater aquatic life based on available toxicity data. However for some pesticides, U.S. Environmental Protection Agency water-quality criteria for freshwater aquatic life are based on bioaccumulation factors that result in criteria concentrations less than the minimum reported concentrations of the analytical methods. It is not known if certain pesticides were present at concentrations less than the minimum reported concentrations that exceeded these criteria.

Wyoming

The importance of quality control in validating concentrationsof contaminants of emerging concern in source and treateddrinking water samples

A national-scale survey of 247 contaminants of emerging concern (CECs), including organic and inorganic chemical compounds, andmicrobial contaminants, was conducted in source and treated drinkingwater samples from 25 treatment plants across the United States.Multiplemethodswere used to determine these CECs, including six analytical methods tomeasure 174 pharmaceuticals, personal care products, and pesticides. A three-component quality assurance/quality control (QA/QC) programwas designed for the subset of 174 CECswhich allowed us to assess and compare performances of themethods used. The three components included: 1) a common field QA/ QC protocol and sample design, 2) individual investigator-developed method-specific QA/QC protocols, and 3) a suite of 46method comparison analytes thatwere determined in two or more analytical methods. Overallmethod performance for the 174 organic chemical CECs was assessed by comparing spiked recoveries in reagent, source, and treated water over a two-year period. In addition to the 247 CECs reported in the larger drinking water study, another 48 pharmaceutical compoundsmeasured did not consistentlymeet predetermined quality standards. Methodologies that did not seem suitable for these analytes are overviewed. The need to exclude analytes based on method performance demonstrates the importance of additional QA/QC protocols.

Science of the Total Environment

Approach to an assessment of volatile organic compounds in the nation's ground water and drinking-water supply wells

The National Water-Quality Assessment (NAWQA) Program of the U.S. Geological Survey (USGS) developed an approach for a national assessment of the occurrence, status, and distribution of volatile organic compounds (VOCs) in samples of ground water from aquifer studies and in samples from drinking-water supply wells, specifically domestic and public wells. Data on VOCs in samples from aquifers and from domestic and public wells had three sources: (1) NAWQA sampling of ground water in aquifer studies and of shallow ground water in areas of agricultural or urban land use from 1993-2002, (2) retrospective data from other Federal, State, and local agencies that sampled ground water in aquifer studies from 1985-1997, and (3) sampling of ground water from public wells used as a source of drinking water from 1999-2000 (source-water survey). Data for assessing VOCs in ground water came from the NAWQA sampling of aquifers and from retrospective data (1 and 2). Domestic wells were the most commonly sampled well type in these aquifer studies. Data for assessing VOCs in domestic well samples came from the NAWQA sampling of aquifers and shallow ground water and from retrospective data (1 and 2). Data for assessing VOCs in public well samples came from NAWQA sampling of aquifers and shallow ground water and from the source-water survey (1, 2, and 3). Fifty-five VOCs were included in the national assessment. All ground-water samples were collected using consistent, prescribed field protocols and were analyzed using approved analytical methods. All ground-water collection activities and laboratory procedures included the collection of various quality-control samples in order to ensure the quality of the data. Comparisons of detection frequencies and detected concentrations among individual VOCs, groups of VOCs, aquifer studies, and data sets were performed using two assessment levels: (1) an assessment level of 0.2 microgram per liter (?g/L), and (2) an assessment level of 0.02 ?g/L. Selection of the 0.2-?g/L assessment level was based on historical laboratory reporting levels of VOCs used by the USGS National Water-Quality Laboratory (NWQL) prior to April 1996, and selection of the 0.02-?g/L assessment level was based on a new, low-level analytical method developed by the NWQL and used since April 1996. Relational analyses using multivariate logistic regression were performed on VOC data from aquifers, domestic wells, and public wells to better understand the natural and anthropogenic factors that control or influence the occurrence of VOCs. Ancillary data used in the relational analyses represent a variety of anthropogenic and hydrogeologic controls on the occurrence of VOCs. For aquifers, relational analyses were performed only on NAWQA data analyzed using the new low-level analytical method for 10 frequently detected VOCs. For domestic wells, relational analyses were performed at assessment levels of 0.2 ?g/L and 0.02 ?g/L for 6 and 10 frequently detected VOCs at these levels. For public wells, relational analyses were performed at an assessment level of 0.2 ?g/L for nine frequently detected VOCs.

Open-File Report

Detecting sulfamethoxazole and carbamazepine in groundwater: Is ELISA a reliable screening tool?

In recent years, numerous studies have reported the prevalence of organic micropollutants in natural waters. There is an increasing interest in assessing the occurrence and transport of these contaminants in groundwater because a large number of people in the United States rely on groundwater for their drinking water. However, commonly used mass-spectrometry-based analytical methods are expensive and time-consuming. The enzyme-linked immunosorbent assay (ELISA) method offers an inexpensive analytical alternative that provides semi-quantitative results in a relatively quick timeframe. We investigated the use of ELISA for two commonly detected micropollutants, sulfamethoxazole (SMX) and carbamazepine (CBZ), in groundwater collected as part of two different studies, one in Minnesota and the other in Iowa. The ELISA results were compared with two mass-spectrometry-based methods: (1) direct aqueous injection-high performance liquid chromatography/tandem mass spectrometry (HPLC) and (2) online solid-phase extraction with liquid chromatography/electrospray ionization-mass spectrometry (SPE LC). Differences in SMX and CBZ observations between ELISA and both HPLC and SPE LC were analyzed using the Paired Prentice-Wilcoxon test. Estimates of bias and limits of agreement between paired observations also were calculated. The SMX determinations by ELISA yielded results that were 30 and 14% greater than HPLC and SPE LC, respectively. The CBZ determinations by ELISA yielded results that were 25 and 9% greater than HPLC and SPE LC, respectively. The ELISA determinations were in presence-absence agreement with HPLC for 83% of samples for SMX and CBZ; and with SPE LC for 76 and 80% of samples for SMX and CBZ, respectively. Results indicate that ELISA for SMX and CBZ is a reliable and cost effective screening-tool alternative to more commonly used mass spectrometry-based analytical methods.

Environmental Pollution

Performance of Traditional and Molecular Methods for Detecting Biological Agents in Drinking Water

To reduce the impact from a possible bioterrorist attack on drinking-water supplies, analytical methods are needed to rapidly detect the presence of biological agents in water. To this end, 13 drinking-water samples were collected at 9 water-treatment plants in Ohio to assess the performance of a molecular method in comparison to traditional analytical methods that take longer to perform. Two 100-liter samples were collected at each site during each sampling event; one was seeded in the laboratory with six biological agents - Bacillus anthracis (B. anthracis), Burkholderia cepacia (as a surrogate for Bu. pseudomallei), Francisella tularensis (F. tularensis), Salmonella Typhi (S. Typhi), Vibrio cholerae (V. cholerae), and Cryptospordium parvum (C. parvum). The seeded and unseeded samples were processed by ultrafiltration and analyzed by use of quantiative polymerase chain reaction (qPCR), a molecular method, and culture methods for bacterial agents or the immunomagnetic separation/fluorescent antibody (IMS/FA) method for C. parvum as traditional methods. Six replicate seeded samples were also processed and analyzed. For traditional methods, recoveries were highly variable between samples and even between some replicate samples, ranging from below detection to greater than 100 percent. Recoveries were significantly related to water pH, specific conductance, and dissolved organic carbon (DOC) for all bacteria combined by culture methods, but none of the water-quality characteristics tested were related to recoveries of C. parvum by IMS/FA. Recoveries were not determined by qPCR because of problems in quantifying organisms by qPCR in the composite seed. Instead, qPCR results were reported as detected, not detected (no qPCR signal), or +/- detected (Cycle Threshold or 'Ct' values were greater than 40). Several sample results by qPCR were omitted from the dataset because of possible problems with qPCR reagents, primers, and probes. For the remaining 14 qPCR results (including some replicate samples), F. tularensis and V. cholerae were detected in all samples after ultrafiltration, B. anthracis was detected in 13 and +/- detected in 1 sample, and C. parvum was detected in 9 and +/- detected in 4 samples. Bu. cepacia was detected in nine samples, +/- detected in two samples, and not detected in three samples (for two out of three samples not detected, a different strain was used). The qPCR assay for V. cholerae provided two false positive - but late - signals in one unseeded sample. Numbers found by qPCR after ultrafiltration were significantly or nearly significantly related to those found by traditional methods for B. anthracis, F. tularensis, and V. cholerae but not for Bu. cepacia and C. parvum. A qPCR assay for S. Typhi was not available. The qPCR method can be used to rapidly detect B. anthracis, F. tularensis, and V. cholerae with some certainty in drinking-water samples, but additional work would be needed to optimize and test qPCR for Bu. cepacia and C. parvum and establish relations to traditional methods. The specificity for the V. cholerae assay needs to be further investigated. Evidence is provided that ultrafiltration and qPCR are promising methods to rapidly detect biological agents in the Nation's drinking-water supplies and thus reduce the impact and consequences from intentional bioterrorist events. To our knowledge, this is the first study to compare the use of traditional and qPCR methods to detect biological agents in large-volume drinking-water samples.

Scientific Investigations Report

Adapting standardized trout monitoring to a changing climate for the upper Yellowstone River, Montana, USA

Objective Long‐term standardized monitoring programs are fundamental to assessing how fish populations respond to anthropogenic stressors. Standardized monitoring programs may need to adopt new methods to adapt to rapid environmental changes that are associated with a changing climate. In the upper Yellowstone River, Montana, biologists have used a standardized, mark–recapture monitoring protocol to annually estimate the abundance of trout since 1978 to assess population status and trends. However, within the past two decades, climate change has caused changes in discharge timing that have prevented standardized monitoring from occurring annually. Methods We investigated the feasibility of using two analytical methods, N‐mixture models and mean capture probability, for estimating the abundance of three trout species in the upper Yellowstone River using the historical long‐term data set; these methods allow abundance to be estimated when a mark–recapture estimate cannot be obtained due to hydrologic conditions. Result When compared with abundance estimates from mark–recapture methods, N‐mixture models most often resulted in negatively biased abundance estimates, whereas mean capture probability analyses resulted in positively biased abundance estimates. Additionally, N‐mixture models produced negatively biased estimates when tested against true abundance values from simulated data sets. The bias in the N‐mixture model estimates was caused by poor model fit and variation in capture probability. The bias in the mean capture probability estimates was caused by heterogeneity in capture probability, likely caused by variable environmental conditions, which were not accounted for in the models. Conclusion N‐mixture models and mean capture probability are not viable alternatives for estimating abundance in the upper Yellowstone River. Thus, exploring additional adaptations to sampling methodologies and analytical approaches, including models that require individually marked fish, will be valuable for this system. Climate change will undoubtedly necessitate changes to standardized sampling methods throughout the world; thus, developing alternative sampling and analytical methods will be important for maintaining the utility of long‐term data sets.

Montana

Evaluating the reliability of environmental concentration data to characterize exposure in environmental risk assessments

Environmental risk assessments often rely on measured concentrations in environmental matrices to characterize exposure of the population of interest—typically, humans, aquatic biota, or other wildlife. Yet, there is limited guidance available on how to report and evaluate exposure datasets for reliability and relevance, despite their importance to regulatory decision-making. This paper is the second of a four-paper series detailing the outcomes of a Society of Environmental Toxicology and Chemistry Technical Workshop that has developed Criteria for Reporting and Evaluating Exposure Datasets (CREED). It presents specific criteria to systematically evaluate the reliability of environmental exposure datasets. These criteria can help risk assessors understand and characterize uncertainties when existing data are used in various types of assessments and can serve as guidance on best practice for the reporting of data for data generators (to maximize utility of their datasets). Although most reliability criteria are universal, some practices may need to be evaluated considering the purpose of the assessment. Reliability refers to the inherent quality of the dataset and evaluation criteria address the identification of analytes, study sites, environmental matrices, sampling dates, sample collection methods, analytical method performance, data handling or aggregation, treatment of censored data, and generation of summary statistics. Each criterion is evaluated as “fully met,” “partly met,” “not met or inappropriate,” “not reported,” or “not applicable” for the dataset being reviewed. The evaluation concludes with a scheme for scoring the dataset as reliable with or without restrictions, not reliable, or not assignable, and is demonstrated with three case studies representing both organic and inorganic constituents, and different study designs and assessment purposes. Reliability evaluation can be used in conjunction with relevance evaluation (assessed separately) to determine the extent to which environmental monitoring datasets are “fit for purpose,” that is, suitable for use in various types of assessments. Integr Environ Assess Manag 2024;00:1–23. © 2024 Society of Environmental Toxicology & Chemistry (SETAC). This article has been contributed to by U.S. Government employees and their work is in the public domain in the USA.

Integrated Environmental Assessment and Management