Geology topics

Mark W. Sandstrom

Publications and source records attributed to Mark W. Sandstrom.

At least 19 recordsLinked to original sources

USGS2022

New-generation pesticides are prevalent in California's Central Coast streams

Pesticides are widely recognized as important biological stressors in streams, especially in heavily developed urban and agricultural areas like the Central California Coast region. We assessed occurrence and potential toxicity of pesticides in small streams in the region using two analytical methods: a broad-spectrum (223 compounds) method in use since 2012 and a newly developed method for 30 additional new-generation fungicides and insecticides. At least one pesticide compound was identified in 83 of the 85 streams sampled. About one-half (48%) of the 253 pesticides measured were detected at least once and 27 were detected in 10% or more of samples. Three of the top 4, and 6 of the top 10 most frequently detected compounds (chlorantraniliprole, dinotefuran, boscalid, thiamethoxam, clothianidin and the fluopicolide degradate 2,6-dichlorobenzamide) were analyzed by the new method. Pesticide mixtures were common, with two or more pesticide compounds detected in 81% of samples and 10 or more in 32% of samples. The pesticide count at a site was relatively consistent over the 6-week study. Four sites with mixed land-use in the lower basin (<5 km from the sampling site) tended to have the highest pesticide counts and the highest concentrations. Potential toxicity (assessed by comparison to benchmarks) to invertebrates was much more common than potential toxicity to fish or plants and was associated with a wide array of insecticides. The common occurrence of new-generation pesticides highlights the need to continuously update analytical methods to keep pace with changing pesticide use for a fuller assessment of pesticide occurrence and effects on the environment.

California↗

USGS2022

Ecological consequences of neonicotinoid mixtures in streams

Neonicotinoid mixtures are common in streams worldwide, but corresponding ecological responses are poorly understood. We combined experimental and observational studies to narrow this knowledge gap. The mesocosm experiment determined that concentrations of the neonicotinoids imidacloprid and clothianidin (range of exposures, 0 to 11.9 μg/liter) above the hazard concentration for 5% of species (0.017 and 0.010 μg/liter, respectively) caused a loss in taxa abundance and richness, disrupted adult emergence, and altered trophodynamics, while mixtures of the two neonicotinoids caused dose-dependent synergistic effects. In 85 Coastal California streams, neonicotinoids were commonly detected [59% of samples ( n = 340), 72% of streams], frequently occurred as mixtures (56% of streams), and potential toxicity was dominated by imidacloprid (maximum = 1.92 μg/liter) and clothianidin (maximum = 2.51 μg/liter). Ecological responses in the field were consistent with the synergistic effects observed in the mesocosm experiment, indicating that neonicotinoid mixtures pose greater than expected risks to stream health.

Science Advances↗

USGS2021

Food, beverage, and feedstock processing facility wastewater: A unique and underappreciated source of contaminants to U.S. streams

Process wastewaters from food, beverage, and feedstock facilities, although regulated, are an under-investigated environmental contaminant source. Food process wastewaters (FPWWs) from 23 facilities in 17 U.S. states were sampled and documented for a plethora of chemical and microbial contaminants. Of the 576 analyzed organics, 184 (32%) were detected at least once, with concentrations as large as 143 μg L –1 (6:2 fluorotelomer sulfonic acid), and as many as 47 were detected in a single FPWW sample. Cumulative per/polyfluoroalkyl substance concentrations up to 185 μg L –1 and large pesticide transformation product concentrations (e.g., methomyl oxime, 40 μg L –1 ; clothianidin TMG, 2.02 μg L –1 ) were observed. Despite 48% of FPWW undergoing disinfection treatment prior to discharge, bacteria resistant to third-generation antibiotics were found in each facility type, and multiple bacterial groups were detected in all samples, including total coliforms. The exposure–activity ratios and toxicity quotients exceeded 1.0 in 13 and 22% of samples, respectively, indicating potential biological effects and toxicity to vertebrates and invertebrates associated with the discharge of FPWW. Organic contaminant profiles of FPWW differed from previously reported contaminant profiles of municipal effluents and urban storm water, indicating that FPWW is another important source of chemical and microbial contaminant mixtures discharged into receiving surface waters.

Alabama, Arkansas, California, Idaho, Illinois, Io↗

USGS2021

Inclusion of pesticide transformation products is key to estimating pesticide exposures and effects in small U.S. streams

Improved analytical methods can quantify hundreds of pesticide transformation products (TPs), but understanding of TP occurrence and potential toxicity in aquatic ecosystems remains limited. We quantified 108 parent pesticides and 116 TPs in more than 3 700 samples from 442 small streams in mostly urban basins across five major regions of the United States. TPs were detected nearly as frequently as parents (90 and 95% of streams, respectively); 102 TPs were detected at least once and 28 were detected in >20% samples in at least one region—TPs of 9 herbicides, 2 fungicides (chlorothalonil and thiophanate-methyl), and 1 insecticide (fipronil) were the most frequently detected. TPs occurred commonly during baseflow conditions, indicating chronic environmental TP exposures to aquatic organisms and the likely importance of groundwater as a TP source. Hazard quotients based on acute aquatic-life benchmarks for invertebrates and nonvascular plants and vertebrate-centric molecular endpoints (sublethal effects) quantify the range of the potential contribution of TPs to environmental risk and highlight several TP exposure–response data gaps. A precautionary approach using equimolar substitution of parent benchmarks or endpoints for missing TP benchmarks indicates that potential aquatic effects of pesticide TPs could be underestimated by an order of magnitude or more.

Environmental Science and Technology↗

USGS2021

Comparison of detection limits estimated using single- and multi-concentration spike-based and blank-based procedures

Spike- and blank-based procedures were applied to estimate the detection limits (DLs) for example analytes from inorganic and organic methods for water samples to compare with the U.S. Environmental Protection Agency's (EPA) Method Detection Limit (MDL) procedures (revisions 1.11 and 2.0). The multi-concentration spike-based procedures ASTM Within-laboratory Critical Level (DQCALC) and EPA's Lowest Concentration Minimum Reporting Level were compared in one application, with DQCALC further applied to many methods. The blank-based DLs, MDL b99 (99th percentile) or MDL bY (= mean blank concentration + s × t ), estimated using large numbers (>100) of blank samples often provide DLs that better approach or achieve the desired ≤1% false positive risk level compared to spike-based DLs. For primarily organic methods that do not provide many uncensored blank results, spike-based DQCALC or MDL rev. 2.0 are needed to simulate the blank distribution and estimate the DL. DQCALC is especially useful for estimating DLs for multi-analyte methods having very different analyte response characteristics. Time series plots of DLs estimated using different procedures reveal that DLs are dependent on the applied procedure, should not be expected to be static over time, and seem best viewed as falling over a range versus being a single value. Use of both blank- and spike-based DL procedures help inform this DL range. Data reporting conventions that censor data at a threshold and report “less than” that threshold concentration as the reporting level have unknown and potentially high false negative risk. The U.S. Geological Survey National Water Quality Laboratory's Laboratory Reporting Level (LRL) convention (applied primarily to organic methods) attempts to simultaneously minimize both the false positive and false negative risk when <LRL is reported and data between DL and the higher LRL are allowed to be reported.

Talanta↗

USGS2020

Quality of pesticide data for groundwater analyzed for the National Water-Quality Assessment Project, 2013–18

The National Water-Quality Assessment (NAWQA) Project of the U.S. Geological Survey (USGS) submitted nearly 1,900 samples collected from groundwater sites across the United States in 2013–18 for analysis of 225 pesticide compounds (pesticides and pesticide degradates, hereafter referred to as “pesticides”) by USGS National Water Quality Laboratory schedule 2437 (S2437). For the associated NAWQA study of pesticide occurrence and concentration in groundwater, and for other studies using pesticide results determined by S2437, it is necessary to assess the ability of reported results to meet data-quality requirements that will allow study objectives to be achieved. This assessment of the quality of S2437 results reported in 2013–18 examined data from field and laboratory quality-control samples, along with third-party performance assessment samples, to estimate bias and variability and to identify their potential sources, with an emphasis on implications for the interpretation of pesticide data for groundwater. Results indicate that measurements produced by the S2437 method for most pesticides have bias and variability that would be considered acceptable for many interpretative studies, which could therefore use the results without qualification or censoring. However, the reported data for a subset of pesticides have the potential for unacceptable contamination bias, high or low recovery bias, or high variability as a consequence of method performance and (or) nonlaboratory factors that could preclude their use for certain common objectives or could necessitate adjustment or qualification to meet those objectives. Based on data for laboratory blanks, censoring of some detections for a subset of pesticides reported by the laboratory in environmental samples might be necessary or desirable to avoid an unacceptably high likelihood of a false-positive result caused by laboratory contamination. The 90-percent upper confidence limit for the 95th percentile of laboratory blank concentration equals or exceeds the minimum reported groundwater concentration in at least 1 water year for 28 pesticides. During at least 1 water year, this upper confidence limit exceeds the maximum laboratory detection limit for 17 pesticides and exceeds the maximum laboratory reporting limit for 3 pesticides (ametryn, atrazine, and diazinon). The level of contamination indicated by this upper confidence limit should not substantially affect the suitability of reported environmental concentrations for any compound for comparison with corresponding human-health benchmarks. Despite being subjected to the same laboratory processes as laboratory blanks, field blanks indicated little evidence of contamination bias. This observation could largely be the consequence of data-reporting practices, which utilize detections in laboratory blanks to censor results in associated field samples (including blanks and environmental samples) when relative concentrations indicate that a result could have a substantial contribution from laboratory contamination. Laboratory censoring appears likely to reduce the risk of false-positive results in environmental samples below the level that laboratory blank results alone would imply. Whereas data available for third-party blind blank samples analyzed in 2018 indicate that only propoxur had any false-positive results, data for pesticides that were not spiked into blind spike samples analyzed in 2013–18 indicate that the false-positive rates for 31 pesticides exceeded 1 percent when considering only detections reported at concentrations greater than the maximum detection limit. Although about half of these pesticides lack substantial supporting evidence of contamination bias based on laboratory blank or field blank detections, indicating that spiking issues or degradation of parent compounds within the spiked samples might be a contributing factor to some false-positive results, these results indicate the need to closely examine detections reported for some pesticides in environmental samples analyzed during a similar period for possible contributions from contamination bias. Data for blind spike samples that were spiked at concentrations above the maximum reporting limit indicate that false-negative rates for eight pesticides exceed 10 percent; substantial low bias could affect results reported for these pesticides in environmental samples analyzed during a similar period. Data for laboratory reagent spikes, which measure recovery of pesticides in blank water, show little evidence for unacceptable recovery bias for S2437 pesticides. However, field matrix spikes, which measure recovery of pesticides in environmental matrices, indicate that degradation and (or) matrix effects could result in moderate to substantial low bias for groundwater results for several pesticides. Low bias could cause some reported concentrations to be categorized as being below a benchmark when the actual concentration in groundwater is greater than the benchmark. Occurrence and concentrations in groundwater could be substantially underrepresented for six pesticides with benchmarks (1H-1,2,4-triazole, asulam, bifenthrin, cis-permethrin, fenbutatin oxide, and naled) that have median recoveries between zero and 50 percent in field matrix spikes. Two compounds (didealkylatrazine and 2-hydroxy-6-ethylamino-4-amino-s-triazine) have median recoveries near or greater than 150 percent in field matrix spikes, indicating a substantial high bias. Plots of data for all spike types show clear changes in the typical recovery with time for some pesticides, which would require further examination for evaluation of temporal trends in environmental concentrations. Data for laboratory reagent spikes indicate that nearly all S2437 pesticides have acceptable variability resulting from random measurement error. Only two compounds (fenbutatin oxide and naled) have F-pseudosigma values greater than 30 percent for recovery, which implies the potential for relatively high variability in reported concentrations and could affect comparison of concentrations to benchmarks and determination of whether concentrations for samples collected at separate locations or times are truly different with a specified level of confidence. Data for third-party blind spike samples show relatively high variability for a greater number of pesticides, although these results likely reflect the influence of degradation and (or) differences in the magnitude and variability of concentrations used for blind spikes relative to laboratory reagent spikes. Detailed analysis of variability using field replicate data is possible for only 12 pesticides on S2437; low variability in analyte detection and concentration is indicated for most of these pesticides in groundwater.

Scientific Investigations Report↗

USGS2020

Determination of low concentrations of acetochlor in water by automated solid-phase extraction and gas chromatography with mass-selective detection

A sensitive and reliable gas chromatographic/mass spectrometric (GC/MS) method for determining acetochlor in environmental water samples was developed. The method involves automated extraction of the herbicide from a filtered 1 L water sample through a C 18 solid-phase extraction column, elution from the column with hexane-isopropyl alcohol (3 + 1), and concentration of the extract with nitrogen gas. The herbicide is quantitated by capillary/column GC/MS with selected-ion monitoring of 3 characteristic ions. The single-operator method detection limit for reagent water samples is 0.0015 μg/L Mean recoveries ranged from about 92 to 115% for 3 water matrixes fortified at 0.05 and 0.5 μg\L. Average single-operator precision, over the course of 1 week, was better than 5%.

Journal of AOAC International↗

USGS2020

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↗

USGS2020

Pesticides and their degradates in groundwater reflect past use and current management strategies, Long Island, New York, USA

Long Island, New York, has a mix of urban/suburban to agricultural/horticultural land use and nearly 3 million residents that rely on a sole-source aquifer for drinking water. The analysis of shallow groundwater (<40 m below land surface) collected from 54 monitoring wells across Long Island detected 53 pesticides or pesticide degradates. Maximum concentrations for individual pesticides or pesticide degradates ranged from 3 to 368,000 ng/L. The highest concentrations and most frequent pesticide detections occurred in samples collected from the pesticide management (PM) network, set in an agricultural/horticultural area in eastern Long Island with coordinated pesticide management by state and local agencies. The other two networks (Suffolk and Nassau/Queens) were set in suburban and urban areas, respectively, and had less frequent detections and lower pesticide concentrations than the PM network. Pesticide detections and concentration patterns (herbicide, insecticide, or fungicide) differed among the three networks revealing broad differences in land use. The predominance of fungicides metalaxyl, 1 H -1,2,4-triazole (propiconazole/myclobutanil degradate), and 4-hydroxychlorothalonil (HCTL, chlorothalonil degradate) in samples from the PM network reflects their intensive use in agricultural settings. Total fungicide concentrations in the PM network ranged from <10 to >300,000 ng/L. The widespread detection of imidacloprid and triazine herbicides, simazine and atrazine, reveal a mixture of current and past use pesticides across the Long Island region. Low concentrations (<200 ng/L) of the triazines in the Suffolk and Nassau/Queens networks may reflect a change in land use and application. Acetanilide herbicides and aldicarb have been discontinued for 20 and 40 years, respectively, yet the concentrations of their degradates were among the highest observed in this study. Acetanilide (total concentrations up to 10,000 ng/L) and aldicarb degradates (up to 270 ng/L) are present in the PM network at much lower concentrations than previous Long Island studies and reflect changes in agricultural practices and pesticide management.

New York↗

USGS2020

Common insecticide disrupts aquatic communities: A mesocosm-to-field ecological risk assessment of fipronil and its degradates in U.S. streams

Insecticides in streams are increasingly a global concern, yet information on safe concentrations for aquatic ecosystems is sparse. In a 30-day mesocosm experiment exposing native benthic aquatic invertebrates to the common insecticide fipronil and four degradates, fipronil compounds caused altered emergence and trophic cascades. Effect concentrations eliciting a 50% response (EC 50 ) were developed for fipronil and its sulfide, sulfone, and desulfinyl degradates; taxa were insensitive to fipronil amide. Hazard concentrations for 5% of affected species derived from up to 15 mesocosm EC 50 values were used to convert fipronil compound concentrations in field samples to the sum of toxic units (∑TU Fipronils ). Mean ∑TU Fipronils exceeded 1 (indicating toxicity) in 16% of streams sampled from five regional studies. The Species at Risk invertebrate metric was negatively associated with ∑TU Fipronils in four of five regions sampled. This ecological risk assessment indicates that low concentrations of fipronil compounds degrade stream communities in multiple regions of the United States.

Science Advances↗

USGS2019

Use of set blanks in reporting pesticide results at the U.S. Geological Survey National Water Quality Laboratory, 2001-15

Executive Summary Background .—Pesticide results from the U.S. Geological Survey (USGS) National Water Quality Laboratory (NWQL) are used for water-quality assessments by many agencies and organizations. The USGS is committed to providing data of the highest possible quality to the consumers of its data. A cooperator’s inquiries about specific pesticide detections in water revealed potential laboratory contamination issues for some results. Consequently, the USGS conducted an extensive evaluation of potential low-level contamination related to processing or analysis of water-quality samples at NWQL for 21 pesticide compounds of interest to the cooperator. This is the most comprehensive study of NWQL pesticide quality-control (QC) results to date. Purpose and scope .—The purpose of this study was to document protocols used by the NWQL to censor pesticide results and to determine the effects of laboratory contamination—as determined from detections in laboratory set blanks—on pesticide detections in groundwater and surface-water samples. More than 30,000 pesticide results from 113 selected batches of samples (2 percent or less of total batches) analyzed by the NWQL during the 15 years from 2001 to 2015 were reviewed. All laboratory results from the selected batches, including results from environmental (surface water and groundwater) and QC (set-blank, blind-blank, and blind-spike) samples, were evaluated. The study includes results for 21 pesticide compounds analyzed in groundwater and surface-water samples collected across the United States. Eleven pesticide compounds were analyzed by a gas chromatography/mass spectrometry method and 10 compounds by a liquid chromatography/mass spectrometry method. Objectives and methods .—The objectives of this study were to (1) determine the characteristics of laboratory contamination over time, (2) compare distributions of pesticide results in set blanks with distributions in environmental samples, (3) evaluate the potential for false-positive and false-negative reporting of results, and (4) evaluate the effects of reevaluating historical pesticide results using 2017 compound identification protocols on detections of pesticides in groundwater and surface-water samples. The 113 instrument batches selected for this study contained detections of one or more of the 21 pesticide compounds in set blanks or were among those batches with the highest pesticide detection frequencies in set blanks. As a result, the dataset for this study was targeted toward pesticides and batches with laboratory contamination. The objectives were addressed by statistically comparing environmental and set-blank results; computing moving averages of set-blank detection frequencies to identify periods of episodic contamination; and using summary statistics, tabular summaries, and graphical approaches, such as time-series plots and cumulative distribution functions. Results .— Objective 1 : Laboratory contamination, as determined by pesticide detections in set blanks, was found in 13 percent of set-blank results from the 113 targeted batches included in this study (as compared to 6 percent of set-blank results from all 7,620 batches analyzed during the study period). It is estimated that 92 percent of the laboratory contamination during the study period was episodic, meaning that it occurred during discrete periods of time. All 21 of the targeted pesticide compounds had periods of episodic contamination, with most episodes ranging in duration from about 1 to 8 months. The remaining 8 percent of laboratory contamination was random or from a known source (deterministic). Objective 2 : For some compounds, graphs of cumulative distribution functions of the entire distributions of set-blank and environmental samples overlap, suggesting that there is no difference in the distributions of the two types of samples. However, time-series graphs show that detections in set blanks often occur at different times (sometimes separated by years) than detections in environmental samples, indicating clear differences in those distributions, and indicating the importance of evaluating the timing of detections in all sample types. For most compounds detected in set-blank and environmental samples, detection frequencies were significantly greater in set blanks than in groundwater or surface-water samples ( p <0.05). There are several explanations for this finding, including that the 113 batches of samples chosen for this study targeted batches with detections in set blanks or that detections in set-blank samples were historically determined with less stringent identification criteria than for environmental samples (groundwater and surface-water samples). Objective 3 : The false-positive and false-negative rates from blind samples submitted during the study period by the USGS Quality Systems Branch generally were less than 1 and 5 percent, respectively, for the 21 pesticides. The only compound with a false-positive rate greater than 1 percent was flumetsulam (2.6 percent), indicating that there is a higher likelihood of flumetsulam being reported as a detection when it is not present in an environmental sample compared with the reporting of other compounds. Objective 4 : Altogether, for data in targeted batches, NWQL would have reported 0.1 percent of results from groundwater samples and 1.4 percent of results from surface-water samples differently if 2017 identification protocols were applied to historical pesticide results. In most of these cases, detections observed in historical results would change to nondetections. The small percentages of changes that would occur if historical data were reevaluated indicate that historical protocols used by the NWQL to identify detections in environmental samples were robust and produced results that are predominantly consistent with current [2017] practices. Conclusions .—The NWQL produces high-quality pesticide results at environmentally relevant concentrations. NWQL identification protocols and censoring practices are largely effective at minimizing the reporting of false-positive and false-negative results. Laboratory contamination, when it occurred, tended to occur in episodes; thus, evaluating the timing and magnitude of detections in set blanks relative to detections in environmental samples was determined to be an important consideration for analysis of environmental results. Because NWQL censoring practices do not address all types and occurrences of laboratory contamination, options for additional censoring practices are provided for data users with more specific or stringent data-quality objectives. The methods used to analyze the 21 compounds for this report can similarly be applied to all 173 pesticide compounds that were analyzed by the NWQL during the same time period. This study also has helped to identify potential improvements in reporting USGS data, such as conducting more frequent review of set-blank datasets.

Scientific Investigations Report↗

USGS2018

Data analysis considerations for pesticides determined by National Water Quality Laboratory schedule 2437

In 2013, the U.S. Geological Survey National Water Quality Laboratory (NWQL) made a new method available for the analysis of pesticides in filtered water samples: laboratory schedule 2437. Schedule 2437 is an improvement on previous analytical methods because it determines the concentrations of 225 fungicides, herbicides, insecticides, and associated degradates in one method at similar or lower concentrations than previously available methods. Additionally, the pesticides included in schedule 2437 were strategically identified in a prioritization analysis that assessed likelihood of occurrence, prevalence of use, and potential toxicity. When the NWQL reports pesticide concentrations for analytes in schedule 2437, the laboratory also provides supplemental information useful to data users for assessing method performance and understanding data quality. That supplemental information is discussed in this report, along with an initial analysis of analytical recovery of pesticides in water-quality samples analyzed by schedule 2437 during 2013–2015. A total of 523 field matrix spike samples and their paired environmental samples and 277 laboratory reagent spike samples were analyzed for this report (1,323 samples total). These samples were collected in the field as part of the U.S. Geological Survey National Water-Quality Assessment groundwater and surface-water studies and as part of the NWQL quality-control program. This report reviews how pesticide samples are processed by the NWQL, addresses how to obtain all the data necessary to interpret pesticide concentrations, explains the circumstances that result in a reporting level change or the occurrence of a raised reporting level, and describes the calculation and assessment of recovery. This report also discusses reasons why a data user might choose to exclude data in an interpretive analysis and outlines the approach used to identify the potential for decreased data quality in the assessment of method recovery. The information provided in this report is essential to understanding pesticide data determined by schedule 2437 and should be reviewed before interpretation of these data.

Scientific Investigations Report↗

USGS2018

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↗

USGS2017

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

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

Scientific Investigations Report↗

USGS2017

Complex mixtures of Pesticides in Midwest U.S. streams indicated by POCIS time-integrating samplers

The Midwest United States is an intensely agricultural region where pesticides in streams pose risks to aquatic biota, but temporal variability in pesticide concentrations makes characterization of their exposure to organisms challenging. To compensate for the effects of temporal variability, we deployed polar organic chemical integrative samplers (POCIS) in 100 small streams across the Midwest for about 5 weeks during summer 2013 and analyzed the extracts for 227 pesticide compounds. Analysis of water samples collected weekly for pesticides during POCIS deployment allowed for comparison of POCIS results with periodic water-sampling results. The median number of pesticides detected in POCIS extracts was 62, and 141 compounds were detected at least once, indicating a high level of pesticide contamination of streams in the region. Sixty-five of the 141 compounds detected were pesticide degradates. Mean water concentrations estimated using published POCIS sampling rates strongly correlated with means of weekly water samples collected concurrently, however, the POCIS-estimated concentrations generally were lower than the measured water concentrations. Summed herbicide concentrations (units of ng/POCIS) were greater at agricultural sites than at urban sites but summed concentrations of insecticides and fungicides were greater at urban sites. Consistent with these differences, summed concentrations of herbicides correlate to percent cultivated crops in the watersheds and summed concentrations of insecticides and fungicides correlate to percent urban land use. With the exception of malathion concentrations at nine sites, POCIS-estimated water concentrations of pesticides were lower than aquatic-life benchmarks. The POCIS provide an alternative approach to traditional water sampling for characterizing chronic exposure to pesticides in streams across the Midwest region.

Environmental Pollution↗

USGS2016

Determination of heat purgeable and ambient purgeable volatile organic compounds in water by gas chromatography/mass spectrometry

Two new analytical methods have been developed by the U.S. Geological Survey (USGS) National Water Quality Laboratory (NWQL) that allow the determination of 37 heat purgeable volatile organic compounds (VOCs) (USGS Method O-4437-16 [NWQL Laboratory Schedule (LS) 4437]) and 49 ambient purgeable VOCs (USGS Method O-4436-16 [NWQL LS 4436]) in unfiltered water. This report documents the procedures and initial performance of both methods. The compounds chosen for inclusion in the methods were determined as having high priority by the USGS National Water-Quality Assessment (NAWQA) Program. Both methods use a purge-and-trap technique with gas chromatography/mass spectrometry. The compounds are extracted from the sample by bubbling helium through a 25-milliliter sample. For the polar and less volatile compounds, the sample is heated at 60 degrees Celsius, whereas the less polar and more volatile compounds are purged using a separate analytical procedure at ambient temperature. The compounds are trapped on a sorbent trap, desorbed into a gas chromatograph/mass spectrometer for separation, and then identified and quantified. Sample preservation is recommended for both methods by adding a 1:1 solution of hydrochloric acid (HCl [1:1]) to water samples to adjust the pH to 2. Analysis within 14 days from sampling is recommended. The heat purgeable method (USGS Method O-4437-16) operates with the mass spectrometer in the simultaneous full scan/selected ion monitoring mode. This method supersedes USGS Method O-4024-03 (NWQL LS 4024). Method detection limits (MDLs) for fumigant compounds 1,2-dibromoethane, 1,2-dichloropropane, 1,2,3-trichloropropane, chloropicrin, and 1,2-dibromo-3-chloropropane range from 0.002 to 0.010 microgram per liter (µg/L). The MDLs for all remaining heat purgeable VOCs range from 0.006 µg/L for tert -butyl methyl ether to 3 µg/L for alpha -terpineol. Calculated holding times indicate that 36 of the 37 heat purgeable VOCs are stable for a minimum of 14 days preserved with HCl (1:1) to pH 2, and many are stable longer. Acrolein was retained in the method validation and initial method implementation and subsequently deleted because of instability and inconsistent performance. 2-Chloromethyl oxirane, methyl oxirane, and oxirane were tested using this method, but the compounds degraded quickly with the HCl (1:1) used for microbial preservation. The ambient purgeable method, USGS Method O-4436-16, operates with the mass spectrometer in the full scan mode. This method is a modification of USGS Method O-4127-96 (NWQL LS 2020). Several compounds were retained from Method O-4127-96 and will continue to be determined in Method O-4436-16. Eleven high priority compounds were added. MDLs for the high priority compounds range from 0.007 µg/L for 2,2-dichloro-1,1,1-trifluoroethane to 0.04 µg/L for 1,2,3,4-tetrahydronaphthalene and 1,3-butadiene. Historical MDLs for the compounds retained from Method O-4127-96 range from 0.009 µg/L for trans -1,2-dichloroethene to 0.1 µg/L for bromomethane. The calculated holding times for the compounds indicate the majority of the compounds are stable for a minimum of 14 days, or longer, at pH 2 with HCl (1:1) preservation. Four semivolatile compounds, 1,2-dimethylnaphthalene, 1,6-dimethylnaphthalene, 2,6-di- tert -butyl phenol, and 2-chloronapthalene, were tested and deleted from the method due to poor performance. Benzyl chloride was tested and deleted due to instability.

Techniques and Methods↗

USGS2016

Determination of pesticides and pesticide degradates in filtered water by direct aqueous-injection liquid chromatography-tandem mass spectrometry

A liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed for determination of 229 pesticides compounds (113 pesticides and 116 pesticide degradates) in filtered water samples from stream and groundwater sites. The pesticides represent a broad range of chemical classes and were selected based on criteria such as current-use intensity, probability of occurrence in streams and groundwater, and toxicity to humans or aquatic organisms. More than half of the analytes are pesticide degradates. The method involves direct injection of a 100-microliter (μL) sample onto the LC-MS/MS without any sample preparation other than filtration. Samples are analyzed with two injections, one in electrospray ionization (ESI) positive mode and one in ESI negative mode, using dynamic multiple reaction monitoring (MRM) conditions, with two MRM transitions for each analyte. The LC-MS/MS instrument parameters were optimized for highest sensitivity for the most analytes. This report describes the analytical method and presents characteristics of the method validation including bias and variability, detection levels, and holding-time studies. Mean recoveries of most analytes (223 of 229) were within data-quality objectives of 100±30 percent at spike concentrations above method detection levels (MDLs) in all four matrices. The calculated MDLs ranged from 1 to 103 nanograms per liter (ng/L) for 182 analytes analyzed in the ESI positive mode, and from 2 to 106 ng/L for 42 analytes analyzed in the ESI negative mode. Five analytes had MDLs between 100 and 250 ng/L. The stability studies in reagent water demonstrated that the largest number of the pesticide compounds (227 of 229) were stable after 14 days of storage at 4 degrees Celsius, so these were selected as the practical holding time and storage temperature for routine sample processing. The use of antimicrobial reagent citric acid to adjust the sample pH to about 4 also resulted in lower recoveries of some analytes, so it should not be used as a routine sample preservative.

Techniques and Methods↗

USGS2015

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

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

Techniques and Methods↗