Jeffrey D. Martin

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.

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). The SEAWAVE-Q model 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.

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. Qualitycontrol 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.

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

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Corrigendum to “Pesticide Toxicity Index—A tool for assessing potential toxicity of pesticide mixtures to freshwater aquatic organisms” [Sci. Total Environ. 476–477 (2014) 144–157]

https://doi.org/10.1016/j.scitotenv.2013.12.088 Refers to: L.H. Nowell, J.E. Norman, P.W. Moran, J.D. Martin, W.W. Stone. Pesticide Toxicity Index—A tool for assessing potential toxicity of pesticide mixtures to freshwater aquatic organisms. Science of the Total Environment, Volume 476–477, 1 April 2014, Pages 144–157. The authors regret that in the above published article, an error appeared in one sentence of the text and is corrected below. In Section

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 pesticidegrade 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 sourcesolution 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. None of the 13 VOCs and 16 WICs included in this study were quantified in the VPBW collected and analyzed at the NWQL. This finding indicates that the VPBW was “contaminant free” when it was shipped from the laboratory to each of the field offices, although some compounds were present in some of the samples at concentrations less than minimum detection levels based on evidence-of-presence data. Toluene, mand p-xylene, benzene, and carbon disulfide were each quantified in an FCS field-blank analysis, but not in the associated groundwater sample. The native-water rinse of the sampling equipment conducted just before collection of the groundwater sample likely reduced low-level contamination with respect to these compounds. VOCs had lower detection frequencies in source-solution blanks and field blanks collected during the FCS than in the historical dataset collected by the NAWQA Program during 1996–2008. The detection frequency of toluene in field blanks was reduced about an order of magnitude from about 38 percent in the historical NAWQA dataset to 3.1 percent in the FCS dataset. Other VOCs quantified in 5 percent or more of the field blanks in the NAWQA dataset, but not quantified in the FCS field-blank analyses, were ethylbenzene, o-xylene, styrene, 1,2,4-trimethylbenzene, chloroform, dichloromethane, acetone, 2-butanone, and tetrahydrofuran. The lower detection frequencies of most VOCs for the FCS, compared to historical NAWQA data, can most likely be attributed to the use of fresh supplies and rigorous adherence to the protocols for cleaning equipment and collecting samples. Design and Evaluation of a Field Study on the Contamination of Selected Volatile Organic Compounds and Wastewater-Indicator Compounds in Blanks and Groundwater Samples By Susan A. Thiros, David A. Bender, David K. Mueller, Donna L. Rose, Lisa D. Olsen, Jeffrey D. Martin, Bruce Bernard, and John S. Zogorski 2 Design and Evaluation of a Field Study on the Contamination of Selected VOCs and WICs in Groundwater Samples Chloroform, a disinfection by-product that is commonly present in tap water used to clean sampling equipment, was not quantified and had no evidence of presence in the FCS field-blank analyses. It is probable that the relatively high detection frequency of chloroform in historical NAWQA field blanks (about 20 percent) is the result of inadequate rinsing with sufficient volumes of VPBW following cleaning. The WIC phenol had a high detection frequency in source-solution and field blanks (70 and 64 percent, respectively) collected by the NAWQA Program during 2002–08, compared to a detection frequency of about 3 percent in the FCS source-solution and field blanks. The detection frequency of benzophenone and N,N-diethyl-metatoluamide (DEET) in field blanks also was substantially less in the FCS dataset (no detections) compared to historical NAWQA data (about 29 and 36 percent, respectively). Evidence of presence of benzophenone, caffeine, camphor, DEET, and methyl salicylate in FCS source-solution blanks, field-purged source-solution blanks, and field blanks could be attributed to products containing these compounds being used by sampling personnel. The lower detection frequencies of selected compounds in the FCS field blanks, compared to historical NAWQA data, indicate that careful attention to field protocols will result in higher-quality field blanks. Extrinsic contamination introduced to source-solution blanks and field blanks can make it more difficult to understand the quality of groundwater-sample data and can cause detections of compounds to be questioned. Following the prescribed field procedures will minimize the potential for introduction of VOCs and WICs to blanks and groundwater samples. Introduction A field blank is a quality-control (QC) sample collected in the field in the same manner as a groundwater sample, except for the native-water rinsing, and is used to identify possible contamination not from the groundwater (the first use of selected terms listed in the Glossary are in boldface type). Members of the U.S. Geological Survey (USGS) Office of Water Quality’s Field Quality Control Work Group for Organics designed the Field Contamination Study (FCS) to determine the field processes that tend to result in clean field blanks and to identify sources of contamination from selected volatile organic compounds (VOCs) and wastewater-indicator compounds (WICs) to the field blanks that hinder their utility in interpreting the quality of corresponding groundwater samples. Source-solution (organic-free) water is used to collect source-solution blanks and field blanks, and is presumed to be free of contaminants of interest when it leaves the USGS National Water Quality Laboratory (NWQL) as documented with a certificate of analyses. Historically, some source-solution water, source-solution blanks, and field blanks have become contaminated during shipment to or from USGS Water Science Centers (WSCs), in storage, in transit to sampling sites, during sample collection, or a combination of these steps. The FCS focused on the quality of freshly purged source-solution (blank) water and the quality of source-solution blanks and field blanks collected in the field. The study evaluated the occurrence of selected VOCs and WICs that have been detected historically in NAWQA source-solution blanks, field blanks, and trip blanks, in a series of diagnostic blanks collected during a carefully controlled experiment. Objective of the Field Contamination Study The primary objective of the FCS was to determine the potential source(s) of contamination for selected VOCs and WICs in source-solution and field blanks collected in the field. The study attempted to determine how blank water that is certified to not have concentrations of VOCs and WICs greater than reporting levels can contain some of these compounds following its collection as source-solution and field blanks. Extrinsic contamination, which was the focus of the FCS, is contamination that originates from a process or source that is external to the medium being sampled. Extrinsic contamination of a blank or sample can be caused by the following: 1. contaminant sources within the sampling environment, such as airborne emissions, aerosols, dust, or particulate input; 2. sample-collection equipment, such as pumps and sample tubing; 3. sample-processing equipment and supplies, such as filtration devices, bottles, chemical preservatives, and blank water that can become contaminated through improper storage; 4. sample-cleaning processes and supplies, such as rinse water and cleaning solutions; 5. factors related to sample transport, such as the field vehicle and transportation used during commercial shipment; 6. exposure to contaminants during storage, such as in a cooler or office/laboratory refrigerator; and 7. exposure to contaminants introduced by sampling personnel, such as exposure to food and drinks, personal-care products, and compounds used in (or adhering to) the disposable gloves used during sampling. A recent review (2008) (David Bender, U.S. Geological Survey, written commun., 2010) of field quality-control data collected during 1996–2008 by the USGS National WaterQuality Assessment (NAWQA) Program indicated that some VOCs were detected more frequently in source-solution and field blanks than in groundwater samples. VOCs are rarely Introduction 3 identified during laboratory analysis of the nitrogen-purged volatile pesticide-grade blank water (VP