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Julia E. Norman

Publications and source records attributed to Julia E. Norman.

12 recordsLinked to original sources

Daily stream samples reveal highly complex pesticide occurrence and potential toxicity to aquatic life

Transient, acutely toxic concentrations of pesticides in streams can go undetected by fixed-interval sampling programs. Here we compare temporal patterns in occurrence of current-use pesticides in daily composite samples to those in weekly composite and weekly discrete samples of surface water from 14 small stream sites. Samples were collected over 10–14 weeks at 7 stream sites in each of the Midwestern and Southeastern United States. Samples were analyzed for over 200 pesticides and degradates by direct aqueous injection liquid chromatography with tandem mass spectrometry. Nearly 2 and 3 times as many unique pesticides were detected in daily samples as in weekly composite and weekly discrete samples, respectively. Based on exceedances of acute-invertebrate benchmarks (AIB) and(or) a Pesticide Toxicity Index (PTI) >1, potential acute-invertebrate toxicity was predicted at 11 of 14 sites from the results for daily composite samples, but was predicted for only 3 sites from weekly composites and for no sites from weekly discrete samples. Insecticides were responsible for most of the potential invertebrate toxicity, occurred transiently, and frequently were missed by the weekly discrete and composite samples. The number of days with benthic-invertebrate PTI ≥0.1 in daily composite samples was inversely related to Ephemeroptera, Plecoptera, and Trichoptera (EPT) richness at the sites. The results of the study indicate that short-term, potentially toxic peaks in pesticides frequently are missed by weekly discrete sampling, and that such peaks may contribute to degradation of invertebrate community condition in small streams. Weekly composite samples underestimated maximum concentrations and potential acute-invertebrate toxicity, but to a lesser degree than weekly discrete samples, and provided a reasonable approximation of the 90th percentile total concentrations of herbicides, insecticides, and fungicides, suggesting that weekly composite sampling may be a compromise between assessment needs and cost.

Science of the Total Environment

Mixed-chemical exposure and predicted effects potential in wadeable southeastern USA streams

Complex chemical mixtures have been widely reported in larger streams but relatively little work has been done to characterize them and assess their potential effects in headwaterstreams. In 2014, the United States Geological Survey (USGS) sampled 54 Piedmont streams over ten weeks and measured 475 unique organic compounds using five analytical methods. Maximum and median exposure conditions were evaluated in relation to watershed characteristics and for potential biological effects using multiple lines of evidence. Results demonstrate that mixed-contaminant exposures are ubiquitous and varied in sampled headwater streams. Approximately 56% (264) of the 475 compounds were detected at least once across all sites. Cumulative maximum concentrations ranged 1,922–162,346 ng L −1 per site. Chemical occurrence significantly correlated to urban land use but was not related to presence/absence of wastewater treatment facility discharges. Designed bioactive chemicals represent about 2/3rd of chemicals detected, notably pharmaceuticals and pesticides, qualitative evidence for possible adverse biological effects. Comparative Toxicogenomics Database chemical-gene associations applied to maximum exposure conditions indicate >12,000 and 2,900 potential gene targets were predicted at least once across all sites for fish and invertebrates, respectively. Analysis of cumulative exposure-activity ratios provided additional evidence that, at a minimum, transient exposures with high probability of molecular effects to vertebrates were common. Finally, cumulative detections and concentrations correlated inversely with invertebrate metrics from in-stream surveys. The results demonstrate widespread instream exposure to extensive contaminant mixtures and compelling multiple lines of evidence for adverse effects on aquatic communities.

Science of the Total Environment

Complex mixtures of dissolved pesticides show potential aquatic toxicity in a synoptic study of Midwestern U.S. streams

Aquatic organisms in streams are exposed to pesticide mixtures that vary in composition over time in response to changes in flow conditions, pesticide inputs to the stream, and pesticide fate and degradation within the stream. To characterize mixtures of dissolved-phase pesticides and degradates in Midwestern streams, a synoptic study was conducted at 100 streams during May–August 2013. In weekly water samples, 94 pesticides and 89 degradates were detected, with a median of 25 compounds detected per sample and 54 detected per site. In a screening-level assessment using aquatic-life benchmarks and the Pesticide Toxicity Index (PTI), potential effects on fish were unlikely in most streams. For invertebrates, potential chronic toxicity was predicted in 53% of streams, punctuated in 12% of streams by acutely toxic exposures. For aquatic plants, acute but likely reversible effects on biomass were predicted in 75% of streams, with potential longer-term effects on plant communities in 9% of streams. Relatively few pesticides in water—atrazine, acetochlor, metolachlor, imidacloprid, fipronil, organophosphate insecticides, and carbendazim—were predicted to be major contributors to potential toxicity. Agricultural streams had the highest potential for effects on plants, especially in May–June, corresponding to high spring-flush herbicide concentrations. Urban streams had higher detection frequencies and concentrations of insecticides and most fungicides than in agricultural streams, and higher potential for invertebrate toxicity, which peaked during July–August. Toxicity-screening predictions for invertebrates were supported by quantile regressions showing significant associations for the Benthic Invertebrate-PTI and imidacloprid concentrations with invertebrate community metrics for MSQA streams, and by mesocosm toxicity testing with imidacloprid showing effects on invertebrate communities at environmentally relevant concentrations. This study documents the most complex pesticide mixtures yet reported in discrete water samples in the U.S. and, using multiple lines of evidence, predicts that pesticides were potentially toxic to nontarget aquatic life in about half of the sampled streams.

Illinois, Iowa, Kansas, Kentucky, Michigan, Minnes

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

Development and application of freshwater sediment-toxicity benchmarks for currently used pesticides

Sediment-toxicity benchmarks are needed to interpret the biological significance of currently used pesticides detected in whole sediments. Two types of freshwater sediment benchmarks for pesticides were developed using spiked-sediment bioassay (SSB) data from the literature. These benchmarks can be used to interpret sediment-toxicity data or to assess the potential toxicity of pesticides in whole sediment. The Likely Effect Benchmark (LEB) defines a pesticide concentration in whole sediment above which there is a high probability of adverse effects on benthic invertebrates, and the Threshold Effect Benchmark (TEB) defines a concentration below which adverse effects are unlikely. For compounds without available SSBs, benchmarks were estimated using equilibrium partitioning (EqP). When a sediment sample contains a pesticide mixture, benchmark quotients can be summed for all detected pesticides to produce an indicator of potential toxicity for that mixture. Benchmarks were developed for 48 pesticide compounds using SSB data and 81 compounds using the EqP approach. In an example application, data for pesticides measured in sediment from 197 streams across the United States were evaluated using these benchmarks, and compared to measured toxicity from whole-sediment toxicity tests conducted with the amphipod Hyalella azteca (28-d exposures) and the midge Chironomus dilutus (10-d exposures). Amphipod survival, weight, and biomass were significantly and inversely related to summed benchmark quotients, whereas midge survival, weight, and biomass showed no relationship to benchmarks. Samples with LEB exceedances were rare (n = 3), but all were toxic to amphipods (i.e., significantly different from control). Significant toxicity to amphipods was observed for 72% of samples exceeding one or more TEBs, compared to 18% of samples below all TEBs. Factors affecting toxicity below TEBs may include the presence of contaminants other than pesticides, physical/chemical characteristics of sediment, and uncertainty in TEB values. Additional evaluations of benchmarks in relation to sediment chemistry and toxicity are ongoing.

Science of the Total Environment

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

Prioritizing pesticide compounds for analytical methods development

The U.S. Geological Survey (USGS) has a periodic need to re-evaluate pesticide compounds in terms of priorities for inclusion in monitoring and studies and, thus, must also assess the current analytical capabilities for pesticide detection. To meet this need, a strategy has been developed to prioritize pesticides and degradates for analytical methods development. Screening procedures were developed to separately prioritize pesticide compounds in water and sediment. The procedures evaluate pesticide compounds in existing USGS analytical methods for water and sediment and compounds for which recent agricultural-use information was available. Measured occurrence (detection frequency and concentrations) in water and sediment, predicted concentrations in water and predicted likelihood of occurrence in sediment, potential toxicity to aquatic life or humans, and priorities of other agencies or organizations, regulatory or otherwise, were considered. Several existing strategies for prioritizing chemicals for various purposes were reviewed, including those that identify and prioritize persistent, bioaccumulative, and toxic compounds, and those that determine candidates for future regulation of drinking-water contaminants. The systematic procedures developed and used in this study rely on concepts common to many previously established strategies. The evaluation of pesticide compounds resulted in the classification of compounds into three groups: Tier 1 for high priority compounds, Tier 2 for moderate priority compounds, and Tier 3 for low priority compounds. For water, a total of 247 pesticide compounds were classified as Tier 1 and, thus, are high priority for inclusion in analytical methods for monitoring and studies. Of these, about three-quarters are included in some USGS analytical method; however, many of these compounds are included on research methods that are expensive and for which there are few data on environmental samples. The remaining quarter of Tier 1 compounds are high priority as new analytes. The objective for analytical methods development is to design an integrated analytical strategy that includes as many of the Tier 1 pesticide compounds as possible in a relatively few, cost-effective methods. More than 60 percent of the Tier 1 compounds are high priority because they are anticipated to be present at concentrations approaching levels that could be of concern to human health or aquatic life in surface water or groundwater. An additional 17 percent of Tier 1 compounds were frequently detected in monitoring studies, but either were not measured at levels potentially relevant to humans or aquatic organisms, or do not have benchmarks available with which to compare concentrations. The remaining 21 percent are pesticide degradates that were included because their parent pesticides were in Tier 1. Tier 1 pesticide compounds for water span all major pesticide use groups and a diverse range of chemical classes, with herbicides and their degradates composing half of compounds. Many of the high priority pesticide compounds also are in several national regulatory programs for water, including those that are regulated in drinking water by the U.S. Environmental Protection Agency under the Safe Drinking Water Act and those that are on the latest Contaminant Candidate List. For sediment, a total of 175 pesticide compounds were classified as Tier 1 and, thus, are high priority for inclusion in analytical methods available for monitoring and studies. More than 60 percent of these compounds are included in some USGS analytical method; however, some are spread across several research methods that are expensive to perform, and monitoring data are not extensive for many compounds. The remaining Tier 1 compounds for sediment are high priority as new analytes. The objective for analytical methods development for sediment is to enhance an existing analytical method that currently includes nearly half of the pesticide compounds in Tier 1 by adding as many additional Tier 1 compounds as are analytically compatible. About 35 percent of the Tier 1 compounds for sediment are high priority on the basis of measured occurrence. A total of 74 compounds, or 42 percent, are high priority on the basis of predicted likelihood of occurrence according to physical-chemical properties, and either have potential toxicity to aquatic life, high pesticide useage, or both. The remaining 22 percent of Tier 1 pesticide compounds were either degradates of Tier 1 parent compounds or included for other reasons. As with water, the Tier 1 pesticide compounds for sediment are distributed across the major pesticide-use groups; insecticides and their degradates are the largest fraction, making up 45 percent of Tier 1. In contrast to water, organochlorines, at 17 percent, are the largest chemical class for Tier 1 in sediment, which is to be expected because there is continued widespread detection in sediments of persistent organochlorine pesticides and their degradates at concentrations high enough for potential effects on aquatic life. Compared to water, there are fewer available benchmarks with which to compare contaminant concentrations in sediment, but a total of 19 Tier 1 compounds have at least one sediment benchmark or screening value for aquatic organisms. Of the 175 compounds in Tier 1, 77 percent have high aquatic-life toxicity, as defined for this process. This evaluation of pesticides and degradates resulted in two lists of compounds that are priorities for USGS analytical methods development, one for water and one for sediment. These lists will be used as the basis for redesigning and enhancing USGS analytical capabilities for pesticides in order to capture as many high-priority pesticide compounds as possible using an economically feasible approach.

Scientific Investigations Report

Quality of Source Water from Public-Supply Wells in the United States, 1993-2007

More than one-third of the Nation's population receives their drinking water from public water systems that use groundwater as their source. The U.S. Geological Survey (USGS) sampled untreated source water from 932 public-supply wells, hereafter referred to as public wells, as part of multiple groundwater assessments conducted across the Nation during 1993-2007. The objectives of this study were to evaluate (1) contaminant occurrence in source water from public wells and the potential significance of contaminant concentrations to human health, (2) national and regional distributions of groundwater quality, and (3) the occurrence and characteristics of contaminant mixtures. Treated finished water was not sampled. The 932 public wells are widely distributed nationally and include wells in selected parts of 41 states and withdraw water from parts of 30 regionally extensive aquifers used for public water supply. These wells are distributed among 629 unique public water systems-less than 1 percent of all groundwater-supplied public water systems in the United States-but the wells were randomly selected within the sampled hydrogeologic settings to represent typical aquifer conditions. Samples from the 629 systems represent source water used by one-quarter of the U.S. population served by groundwater-supplied public water systems, or about 9 percent of the entire U.S. population in 2008. One groundwater sample was collected prior to treatment or blending from each of the 932 public wells and analyzed for as many as six water-quality properties and 215 contaminants. Consistent with the terminology used in the Safe Drinking Water Act (SDWA), all constituents analyzed in water samples in this study are referred to as 'contaminants'. More contaminant groups were assessed in this study than in any previous national study of public wells and included major ions, nutrients, radionuclides, trace elements, pesticide compounds, volatile organic compounds (VOCs), and fecal-indicator microorganisms. Contaminant mixtures were assessed in subsets of samples in which most contaminants were analyzed. Contaminant concentrations were compared to human-health benchmarks-regulatory U.S. Environmental Protection Agency (USEPA) Maximum Contaminant Levels (MCLs) for contaminants regulated in drinking water under the SDWA or non-regulatory USGS Health-Based Screening Levels (HBSLs) for unregulated contaminants, when available. Nearly three-quarters of the contaminants assessed in this study are unregulated in drinking water, and the USEPA uses USGS data on the occurrence of unregulated contaminants in water resources to fulfill part of the SDWA requirements for determining whether specific contaminants should be regulated in drinking water in the future. More than one in five (22 percent) source-water samples from public wells contained one or more naturally occurring or man-made contaminants at concentrations greater than human-health benchmarks, and 80 percent of samples contained one or more contaminants at concentrations greater than one-tenth of benchmarks. Most individual contaminant detections, however, were less than one-tenth of human-health benchmarks. Public wells yielding water with contaminant concentrations greater than benchmarks, as well as those with concentrations greater than one-tenth of benchmarks, were distributed throughout the United States and included wells that withdraw water from all principal aquifer rock types included in this study. Ten contaminants individually were detected at concentrations greater than human-health benchmarks in at least 1 percent of source-water samples and collectively accounted for most concentrations greater than benchmarks. Seven of these 10 contaminants occur naturally, including three radionuclides (radon, radium, and gross alpha-particle radioactivity) and four trace elements (arsenic, manganese, strontium, and boron); three of these 10 contaminants (dieldrin, nitrate, and perchl

Scientific Investigations Report

Health-based screening levels to evaluate U.S. Geological Survey ground water quality data

Federal and state drinking‐water standards and guidelines do not exist for many contaminants analyzed by the U.S. Geological Survey's National Water‐Quality Assessment Program, limiting the ability to evaluate the potential human‐health relevance of water‐quality findings. Health‐based screening levels (HBSLs) were developed collaboratively to supplement existing drinking‐water standards and guidelines as part of a six‐year, multi‐agency pilot study. The pilot study focused on ground water samples collected prior to treatment or blending in areas of New Jersey where groundwater is the principal source of drinking water. This article describes how HBSLs were developed and demonstrates the use of HBSLs as a tool for evaluating water‐quality data in a human‐health context. HBSLs were calculated using standard U.S. Environmental Protection Agency (USEPA) methodologies and toxicity information. New HBSLs were calculated for 12 of 32 contaminants without existing USEPA drinking‐water standards or guidelines, increasing the number of unregulated contaminants (those without maximum contaminant levels (MCLs)) with human‐health benchmarks. Concentrations of 70 of the 78 detected contaminants with human‐health benchmarks were less than MCLs or HBSLs, including all 12 contaminants with new HBSLs, suggesting that most contaminant concentrations were not of potential human‐health concern. HBSLs were applied to a state‐scale groundwater data set in this study, but HBSLs also may be applied to regional and national evaluations of water‐quality data. HBSLs fulfill a critical need for federal, state, and local agencies, water utilities, and others who seek tools for evaluating the occurrence of contaminants without drinking‐water standards or guidelines.

Risk Analysis

Health-Based Screening Levels and their Application to Water-Quality Data

To supplement existing Federal drinking-water standards and guidelines, thereby providing a basis for a more comprehensive evaluation of contaminant-occurrence data in a human-health context, USGS began a collaborative project in 1998 with USEPA, the New Jersey Department of Environmental Protection, and the Oregon Health & Science University to calculate non-enforceable health-based screening levels. Screening levels were calculated for contaminants that do not have Maximum Contaminant Level values using a consensus approach that entailed (1) standard USEPA Office of Water methodologies (equations) for establishing Lifetime Health Advisory (LHA) and Risk-Specific Dose (RSD) values for the protection of human health, and (2) existing USEPA human-health toxicity information.

Fact Sheet

Application of health-based screening levels to ground-water quality data in a state-scale pilot effort

A state-scale pilot effort was conducted to evaluate a Health-Based Screening Level (HBSL) approach developed for communicating findings from the U.S. Geological Survey (USGS) National Water-Quality Assessment Program in a human-health context. Many aquifers sampled by USGS are used as drinking-water sources, and water-quality conditions historically have been assessed by comparing measured contaminant concentrations to established drinking-water standards and guidelines. Because drinking-water standards and guidelines do not exist for many analyzed contaminants, HBSL values were developed collaboratively by the USGS, U.S. Environmental Protection Agency (USEPA), New Jersey Department of Environmental Protection, and Oregon Health & Science University, using USEPA toxicity values and USEPA Office of Water methodologies. The main objective of this report is to demonstrate the use of HBSL approach as a tool for communicating water-quality data in a human-health context by conducting a retrospective analysis of ground-water quality data from New Jersey. Another important objective is to provide guidance on the use and interpretation of HBSL values and other human-health benchmarks in the analyses of water-quality data in a human-health context. Ground-water samples collected during 1996-98 from 30 public-supply, 82 domestic, and 108 monitoring wells were analyzed for 97 pesticides and 85 volatile organic compounds (VOCs). The occurrence of individual pesticides and VOCs was evaluated in a human-health context by calculating Benchmark Quotients (BQs), defined as ratios of measured concentrations of regulated compounds (that is, compounds with Federal or state drinking-water standards) to Maximum Contaminant Level (MCL) values and ratios of measured concentrations of unregulated compounds to HBSL values. Contaminants were identified as being of potential human-health concern if maximum detected concentrations were within a factor of 10 of the associated MCL or HBSL (that is, maximum BQ value (BQmax) greater than or equal to 0.1) in any well type (public supply, domestic, monitoring). Most (57 of 77) pesticides and VOCs with human-health benchmarks were detected at concentrations well below these levels (BQmax less than 0.1) for all three well types; however, BQmax values ranged from 0.1 to 3,000 for 6 pesticides and 14 VOCs. Of these 20 contaminants, one pesticide (dieldrin) and three VOCs (1,2-dibromoethane, tetrachloroethylene, and trichloroethylene) both (1) were measured at concentrations that met or exceeded MCL or HBSL values, and (2) were detected in more than 10 percent of samples collected from raw ground water used as sources of drinking water (public-supply and (or) domestic wells) and, therefore, are particularly relevant to human health. The occurrence of multiple pesticides and VOCs in individual wells also was evaluated in a human-health context because at least 53 different contaminants were detected in each of the three well types. To assess the relative human-health importance of the occurrence of multiple contaminants in different wells, the BQ values for all contaminants in a given well were summed. The median ratio of the maximum BQ to the sum of all BQ values for each well ranged from 0.83 to 0.93 for all well types, indicating that the maximum BQ makes up the majority of the sum for most wells. Maximum and summed BQ values were statistically greater for individual public-supply wells than for individual domestic and monitoring wells. The HBSL approach is an effective tool for placing water-quality data in a human-health context. For 79 of the 182 compounds analyzed in this study, no USEPA drinking-water standards or guidelines exist, but new HBSL values were calculated for 39 of these 79 compounds. The new HBSL values increased the number of detected pesticides and VOCs with human-health benchmarks from 65 to 77 (of 97 detected compounds), thereby expanding the basis for interpreting contaminant-occu

Scientific Investigations Report