Geology topics

Kathryn Kuivila

Publications and source records attributed to Kathryn Kuivila.

At least 37 records · Page 2Linked to original sources

USGS2013

Occurrence and persistence of fungicides in bed sediments and suspended solids from three targeted use areas in the United States

To document the environmental occurrence and persistence of fungicides, a robust and sensitive analytical method was used to measure 34 fungicides and an additional 57 current-use pesticides in bed sediments and suspended solids collected from areas of intense fungicide use within three geographic areas across the United States. Sampling sites were selected near or within agricultural research farms using prophylactic fungicides at rates and types typical of their geographic location. At least two fungicides were detected in 55% of the bed and 83% of the suspended solid samples and were detected in conjunction with herbicides and insecticides. Six fungicides were detected in all samples including pyraclostrobin (75%), boscalid (53%), chlorothalonil (41%) and zoxamide (22%). Pyraclostrobin, a strobilurin fungicide, used frequently in the United States on a variety of crops, was detected more frequently than p,p′ -DDE, the primary degradate of p,p′ -DDT, which is typically one of the most frequently occurring pesticides in sediments collected within highly agricultural areas. Maximum fungicide concentrations in bed sediments and suspended solids were 198 and 56.7 μg/kg dry weight, respectively. There is limited information on the occurrence, fate, and persistence of many fungicides in sediment and the environmental impacts are largely unknown. The results of this study indicate the importance of documenting the persistence of fungicides in the environment and the need for a better understanding of off-site transport mechanisms, particularly in areas where crops are grown that require frequent treatments to prevent fungal diseases.

Science of the Total Environment↗

USGS2013

Occurrence of fungicides and other pesticides in surface water, groundwater, and sediment from three targeted-use areas in the United States, 2009

Surface-water, groundwater, and suspended- and bedsediment samples were collected in three targeted-use areas in the United States where potatoes were grown during 2009 and analyzed for an extensive suite of fungicides and other pesticides by gas chromatograph/mass spectrometry and liquid chromatography with tandem mass spectrometry. Fungicides were detected in all environmental matrices sampled during the study. The most frequently detected fungicides were azoxystrobin, boscalid, chlorothalonil, and pyraclostrobin. Other pesticides that were detected frequently included amino phosphonic acid (AMPA), atrazine, metolaclor, and the organochlorine insecticide p,p’-DDT and its degradates p,p’-DDD and p,p’-DDE. A greater number of pesticides were detected in surface water relative to the other environmental matrices sampled, and at least one pesticide was detected in 62 of the 63 surfacewater samples. The greatest numbers of pesticides and the maximum observed concentrations for most pesticides were measured in surface-water samples from Idaho. In eight surface- water samples (six from Idaho and two from Wisconsin), concentrations of bifenthrin, metolachlor, or malathion exceeded U.S. Environmental Protection Agency freshwater aquatic-life benchmarks for chronic toxicity to invertebrates. Thirteen pesticides, including seven fungicides, were detected in groundwater samples. Shallow groundwater samples collected beneath recently harvested potato fields contained more pesticides and had higher concentrations of pesticides than samples collected from other groundwater sources sampled during the study. Generally, pesticide concentrations were lower in groundwater samples than in surfacewater or sediment samples, with the exception of the fungicide boscalid, which was found to have its highest concentration in a shallow groundwater sample collected in Wisconsin. Thirteen pesticides, including four fungicides, were detected in suspended-sediment samples. The most frequently detected compounds were the fungicides boscalid, pyraclostrobin, and zoxamide, and the degradates p,p’-DDD and p,p’-DDE. Twenty pesticides, including six fungicides, were detected in bed-sediment samples. The most frequently detected compounds were pyraclostrobin, p,p’-DDT, p,p’-DDD, and p,p’-DDE.

Idaho, Maine, Wisconsin↗

USGS2012

Contaminants in stream sediments from seven United States metropolitan areas: part I: distribution in relation to urbanization

Organic contaminants and trace elements were measured in bed sediments collected from streams in seven metropolitan study areas across the United States to assess concentrations in relation to urbanization. Polycyclic aromatic hydrocarbons, polychlorinated biphenyls, organochlorine pesticides, the pyrethroid insecticide bifenthrin, and several trace elements were significantly related to urbanization across study areas. Most contaminants (except bifenthrin, chromium, nickel) were significantly related to the total organic carbon (TOC) content of the sediments. Regression models explained 45–80 % of the variability in individual contaminant concentrations using degree of urbanization, sediment-TOC, and study-area indicator variables (which represent the combined influence of unknown factors, such as chemical use or release, that are not captured by available explanatory variables). The significance of one or more study-area indicator variables in all models indicates marked differences in contaminant levels among some study areas, even after accounting for the nationally modeled effects of urbanization and sediment-TOC. Mean probable effect concentration quotients (PECQs) were significantly related to urbanization. Trace elements were the major contributors to mean PECQs at undeveloped sites, whereas organic contaminants, especially bifenthrin, were the major contributors at highly urban sites. Pyrethroids, where detected, accounted for the largest share of the mean PECQ. Part 2 of this series (Kemble et al. 2012) evaluates sediment toxicity to amphipods and midge in relation to sediment chemistry.

Archives of Environmental Contamination and Toxico↗

USGS2012

Contaminants in stream sediments from seven United States metropolitan areas: part II—sediment toxicity to the amphipod Hyalella azteca and the midge Chironomus dilutus

Relationships between sediment toxicity and sediment chemistry were evaluated for 98 samples collected from seven metropolitan study areas across the United States. Sediment-toxicity tests were conducted with the amphipod Hyalella azteca (28 day exposures) and with the midge Chironomus dilutus (10 day exposures). Overall, 33 % of the samples were toxic to amphipods and 12 % of the samples were toxic to midge based on comparisons with reference conditions within each study area. Significant correlations were observed between toxicity end points and sediment concentrations of trace elements, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), or organochlorine (OC) pesticides; however, these correlations were typically weak, and contaminant concentrations were usually below sediment-toxicity thresholds. Concentrations of the pyrethroid bifenthrin exceeded an estimated threshold of 0.49 ng/g (at 1 % total organic carbon) in 14 % of the samples. Of the samples that exceeded this bifenthrin toxicity threshold, 79 % were toxic to amphipods compared with 25 % toxicity for the samples below this threshold. Application of mean probable effect concentration quotients (PECQs) based on measures of groups of contaminants (trace elements, total PAHs, total PCBs,OCpesticides, and pyrethroid pesticides [bifenthrin in particular]) improved the correct classification of samples as toxic or not toxic to amphipods compared with measures of individual groups of contaminants. Sediments are a repository for many contaminants released into surface waters. Because of this, organisms inhabiting sediments may be exposed to a wide range of contaminants (United States Environmental Protection Agency (USEPA) United States Environmental Protection Agency 2000; American Society for Testing and Materials [ASTM] American Society for Testing and Materials International 2012). Contaminants of potential concern in sediments typically include trace elements (metals), organochlorine (OC) pesticides, polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs; Ingersoll et al. 2001). In 2000, the USEPA began to restrict the use of organophosphate pesticides, such as diazinon and chlorpyrifos (Spurlock and Lee 2008). These restrictions have led to increased use of pyrethroid pesticides, which have widespread applications in both agricultural and urban environments (Kuivila et al. 2012). Pyrethroids are hydrophobic compounds that have been observed to accumulate in sediments (Laskowski 2002). Toxicity of pyrethroids in field-collected sediment from small urban streams (Weston et al. 2005; Holmes et al. 2008; Ding et al. 2010; Domagalski et al. 2010) or with pyrethroids spiked into sediment (Amweg et al. 2006; Hintzen et al. 2009) have been evaluated primarily in 10 day lethality tests conducted with the amphipod Hyalella azteca . However, the sublethal effects in long-term exposures to pyrethroids in sediment have not been evaluated, and the distribution of pyrethroids sediments has not typically been evaluated in wadeable streams (Gilliom et al. 2006). This article is the second in a series that describe the results of a study of the distribution and toxicity of pyrethroids and other co-occurring trace elements and organic contaminants (PCBs, PAHs, OC pesticides) in stream sediments from 7 metropolitan areas across the United States (Moran et al. 2012). The study evaluated 98 sediment samples collected from streams ranging from undeveloped to highly urban and differs from previous studies by sampling larger wadeable streams and avoiding point sources (such as storm drains) and other inflows (Gilliom et al. 2006). Part 1 of the series characterizes sediment contaminants in relation to urbanization and other factors in the 7 metropolitan study areas (Nowell et al. 2012). Part 2 (this article) evaluates relationships between sediment chemistry and sediment toxicity in 28 day whole-sediment exposures conducted with the amphipod H. azteca and in 10 day whole-sediment exposure conducted with the midge Chironomus dilutus (USEPA United States Environmental Protection Agency 2000; ASTM American Society for Testing and Materials International 2012). Toxicity end points evaluated in the amphipod and midge exposures included the effects of these field-collected sediments on survival, weight, or biomass of the test organisms.

Georgia;Massachusetts;Texas;Colorado;Wisconsin;Uta↗

USGS2012

Occurrence and potential sources of pyrethroid insecticides in stream sediments from seven U.S. metropolitan areas

A nationally consistent approach was used to assess the occurrence and potential sources of pyrethroid insecticides in stream bed sediments from seven metropolitan areas across the United States. One or more pyrethroids were detected in almost half of the samples, with bifenthrin detected the most frequently (41%) and in each metropolitan area. Cyhalothrin, cypermethrin, permethrin, and resmethrin were detected much less frequently. Pyrethroid concentrations and Hyalella azteca mortality in 28-d tests were lower than in most urban stream studies. Log-transformed total pyrethroid toxic units (TUs) were significantly correlated with survival and bifenthrin was likely responsible for the majority of the observed toxicity. Sampling sites spanned a wide range of urbanization and log-transformed total pyrethroid concentrations were significantly correlated with urban land use. Dallas/Fort Worth had the highest pyrethroid detection frequency (89%), the greatest number of pyrethroids (4), and some of the highest concentrations. Salt Lake City had a similar percentage of detections but only bifenthrin was detected and at lower concentrations. The variation in pyrethroid concentrations among metropolitan areas suggests regional differences in pyrethroid use and transport processes. This study shows that pyrethroids commonly occur in urban stream sediments and may be contributing to sediment toxicity across the country.

Alabama;Connecticut;Georgia;Massachusetts;New Hamp↗

USGS2012

Pyrethroid insecticides in bed sediments from urban and agricultural streams across the United States

Pyrethroid insecticides are hydrophobic compounds that partition to streambed sediments and have been shown to cause toxicity to non-target organisms; their occurrence is well documented in parts of California, but there have been limited studies in other urban and agricultural areas across the United States. To broaden geographic understanding of pyrethroid distributions, bed sediment samples were collected and analyzed from 36 streams in 25 states, with about 2/3 of the sites in urban areas and 1/3 in agricultural areas. At least one pyrethroid (of the 14 included in the analysis) was detected in 78% of samples. Seven pyrethroids were detected in one or more samples. Bifenthrin was the most frequently detected (58% of samples), followed by permethrin (31%), resmethrin (17%), and cyfluthrin (14%). The other three detected pyrethroids (cyhalothrin, cypermethrin and delta/tralomethrin) were found in two or fewer of the samples. Concentrations ranged from 0.3 to 180 ng g -1 dry weight. The number of pyrethroids detected were higher in the urban samples than in the agricultural samples, but the highest concentrations of individual pyrethroids were split between urban and agricultural sites. The pyrethroids detected in the agricultural areas generally followed use patterns. Predicted toxicity was greater for urban areas and attributed to bifenthrin, cyfluthrin and cypermethrin, while in agricultural areas the toxicity was mainly attributed to bifenthrin.

Journal of Environmental Monitoring↗

USGS2012

Occurrence of pesticides in water and sediment collected from amphibian habitats located throughout the United States, 2009-10

Water and bed-sediment samples were collected by the U.S. Geological Survey (USGS) in 2009 and 2010 from 11 sites within California and 18 sites total in Colorado, Georgia, Idaho, Louisiana, Maine, and Oregon, and were analyzed for a suite of pesticides by the USGS. Water samples and bed-sediment samples were collected from perennial or seasonal ponds located in amphibian habitats in conjunction with research conducted by the USGS Amphibian Research and Monitoring Initiative and the USGS Toxic Substances Hydrology Program. Sites selected for this study in three of the states (California, Colorado, and Orgeon) have no direct pesticide application and are considered undeveloped and remote. Sites selected in Georgia, Idaho, Louisiana, and Maine were in close proximity to either agricultural or suburban areas. Water and sediment samples were collected once in 2009 during amphibian breeding seasons. In 2010, water samples were collected twice. The first sampling event coincided with the beginning of the frog breeding season for the species of interest, and the second event occurred 10-12 weeks later when pesticides were being applied to the surrounding areas. Additionally, water was collected during each sampling event to measure dissolved organic carbon, nutrients, and the fungus, Batrachochytrium dendrobatidis , which has been linked to amphibian declines worldwide. Bed-sediment samples were collected once during the beginning of the frog breeding season, when the amphibians are thought to be most at risk to pesticides. Results of this study are reported for the following two geographic scales: (1) for a national scale, by using data from the 29 sites that were sampled from seven states, and (2) for California, by using data from the 11 sampled sites in that state. Water samples were analyzed for 96 pesticides by using gas chromatography/mass spectrometry. A total of 24 pesticides were detected in one or more of the 54 water samples, including 7 fungicides, 10 herbicides, 4 insecticides, 1 synergist, and 2 pesticide degradates. On a national scale, aminomethylphosphonic acid (AMPA), the primary degradate of the herbicide glyphosate, which is the active ingredient in Roundup®, was the most frequently detected pesticide in water (16 of 54 samples) followed by glyphosate (8 of 54 samples). The maximum number of pesticides observed at a single site was nine compounds in a water sample from a site in Louisiana. The maximum concentration of a pesticide or degradate observed in water was 2,880 nanograms per liter of clomazone (a herbicide) at a site in Louisiana. In California, a total of eight pesticides were detected among all of the low and high elevation sites; AMPA was the most frequently detected pesticide, but glyphosate was detected at the highest concentrations (1.1 micrograms per liter). Bed-sediment samples were analyzed for 94 pesticides by using accelerated solvent extraction, gel permeation chromatography for sulfur removal, and carbon/alumina stacked solid-phase extraction cartridges to remove interfering sediment matrices. In bed sediment, 22 pesticides were detected in one or more of the samples, including 9 fungicides, 3 pyrethroid insecticides, p,p' -dichlorodiphenyltrichloroethane ( p,p' -DDT) and its major degradates, as well as several herbicides. Pyraclostrobin, a strobilurin fungicide, and bifenthrin, a pyrethroid insecticide, were detected most frequently. Maximum pesticide concentrations ranged from less than their respective method detection limits to 1,380 micrograms per kilogram (tebuconazole in California). The number of pesticides detected in samples from each site ranged from zero to six compounds. The sites with the greatest number of pesticides were in Maine and Oregon with six pesticides detected in one sample from each state, followed by Georgia with four pesticides in one sample. For California, a total of 10 pesticides were detected among all sites, and 4 pesticides were detected at both low and high elevation sites; tebuconazole and pyraclostrobin were the two most frequently detected pesticides in California. For the other six selected states, the most frequently detected pesticides in bed sediment were pyraclostrobin (detected in 17 of 42 samples), bifenthrin (detected in 14 of 42 samples), and tebuconazole (detected in 10 of 42 samples). The fungus, Batrachochytrium dendrobatidis (Bd), was detected in water samples in sites from four of the seven states during 2009 and 2010, and the number of zoospore equivalents per liter of water in samples where Bd was detected ranged from 1.6 to 343. Bd was not detected in water samples from sites in Georgia, Louisiana, and Oregon.

Data Series↗

USGS2012

Understanding pesticides in California's Delta

The Sacramento-San Joaquin River Delta (Delta) is the hub of California’s water system and also an important habitat for imperiled fish and wildlife. Aquatic organisms are exposed to mixtures of pesticides that flow through the maze of Delta water channels from sources including agricultural, landscape, and urban pest-control applications. While we do not know all of the effects pesticides have on the ecosystem, there is evidence that they cause some damage to organisms in the Delta. Decades of USGS research have provided a good understanding of when, where, and how pesticides enter the Delta. However, pesticide use is continually changing. New field studies and methods are needed so that scientists can analyze which pesticides are present in the Delta, and at what concentrations, enabling them to estimate exposure and ultimate effects on organisms. Continuing research will provide resource managers and stakeholders with crucial information to manage the Delta wisely.

California↗

USGS2012

Contaminants in stream sediments from seven U.S. metropolitan areas: Data summary of a National Pilot Study

This report presents data collected as a part of a synoptic survey of stream sediment contaminants, associated watershed characteristics and invertebrate responses in laboratory sediment toxicity tests from 98 streams (sites) in seven metropolitan study areas across the continental United States. The report presents methods, data, and sediment-quality guidelines, including the derivation of a new sediment pyrethroid probable effects concentration, for the purposes of relating measured contaminants to land use and toxicity evaluation. The study evaluated sites that ranged in their degree of relative urbanization within the study areas of Atlanta, Boston, Dallas-Fort Worth, Denver, Milwaukee-Green Bay, Salt Lake City, and Seattle-Tacoma. In all, 108 chemical analytes quantified in the study are presented, by class and number of individual compounds, as follows: polyaromatic hydrocarbons (PAHs) (28), organochlorine pesticides (OCs) (18), polychlorinated biphenyls (Aroclors) (3), pyrethroid insecticides (14), fipronil compounds (4), priority trace and other major elements (41). The potential of these sediments to cause toxicity to sediment-dwelling invertebrates was evaluated using two standard sediment toxicity tests: a 28-day growth and survival toxicity test with the amphipod Hyalella azteca, and a 10-day growth and survival toxicity test with the midge Chironomus dilutus. Further, approximately 95 relevant watershed and reach-level characteristics were generated and are presented to aid in interpretation and explanation of contaminant and toxicity patterns. Interpretation of the findings of this study, including the relationships with urbanization and other factors, the relationship between sediment toxicity and sediment chemistry in the seven study areas, and the sources and occurrence of pyrethroid insecticides, are discussed in detail in a forthcoming series of journal articles.

Boston;Atlanta;Milwaukee;Green Bay;Dallas;Fort Wor↗

USGS2012

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↗

USGS2010

Accumulation of current-use and organochlorine pesticides in crab embyros from northern California, USA

Invertebrates have long been used as resident sentinels for assessing ecosystem health and productivity. The shore crabs, Hemigrapsus oregonensis and Pachygrapsus crassipes, are abundant in estuaries and beaches throughout northern California, USA and have been used as indicators of habitat conditions in several salt marshes. The overall objectives of the present study were to conduct a lab-based study to test the accumulation of current-use pesticides, validate the analytical method and to analyze field-collected crabs for a suite of 74 current-use and legacy pesticides. A simple laboratory uptake study was designed to determine if embryos could bioconcentrate the herbicide molinate over a 7-d period. At the end of the experiment, embryos were removed from the crabs and analyzed by gas chromatography/mass spectrometry. Although relatively hydrophilic (log K(OW) of 2.9), molinate did accumulate with an estimated bioconcentration factor (log BCF) of approximately 2.5. Following method validation, embryos were collected from two different Northern California salt marshes and analyzed. In field-collected embryos 18 current-use and eight organochlorine pesticides were detected including synthetic pyrethroids and organophosphate insecticides, as well as DDT and its degradates. Lipid-normalized concentrations of the pesticides detected in the field-collected crab embryos ranged from 0.1 to 4 ppm. Pesticide concentrations and profiles in crab embryos were site specific and could be correlated to differences in land-use practices. These preliminary results indicate that embryos are an effective sink for organic contaminants in the environment and have the potential to be good indicators of ecosystem health, especially when contaminant body burden analyses are paired with reproductive impairment assays.

California↗

USGS2009

Collection of pyrethroids in water and sediment matrices: Development and validation of a standard operating procedure

Loss of pyrethroid insecticides onto surfaces during sample collection can confound the interpretation of analytical and toxicity test results. Sample collection devices, container materials, and water matrix composition have a significant influence on the association of pyrethroids to container walls, which can be as high as 50 percent. Any sample collection method involving transfer through multiple containers or pieces of equipment increases the potential for pyrethroid loss. This loose 'surface-association' with container walls can be reversed through agitation. When sampling water matrices with pumps or autosamplers, no pyrethroids were lost as long as the water was moving continuously through the system. When collecting water matrices in containers, the material with the least amount of pyrethroid sorption is as follows: glass less than (<) plastic less than (<) Teflon. Additionally, pyrethroids were easier to re-suspend from the glass container walls. Since the amount of surface-association is proportional to the ratio of volume-to-contact-area of the sample, taking larger-volume field samples (greater than 3 liters) reduced pyrethroid losses to less than 10 percent. The amount of surface-association cannot be predicted easily because of the dependence on water matrix composition; samples with higher dissolved organic carbon or suspended-sediment concentrations were observed to have lower percent loss. Sediment samples were not affected by glass-container sorption (the only containers tested). Standardized sample-collection protocols are critical to yield accurate pyrethroid concentrations for assessment of potential effects, and have been summarized in an accompanying standard operating procedure.

Scientific Investigations Report↗

USGS2009

Methods of analysis: Determination of pyrethroid insecticides in water and sediment using gas chromatography/mass spectrometry

A method for the determination of 14 pyrethroid insecticides in environmental water and sediment samples is described. The method was developed by the U.S. Geological Survey in response to increasing concern over the effects of pyrethroids on aquatic organisms. The pyrethroids included in this method are ones that are applied to many agricultural and urban areas. Filtered water samples are extracted for pyrethroids using solid-phase extraction (SPE) with no additional cleanup steps. Sediment and soil samples are extracted using a microwave-assisted extraction system, and the pyrethroids of interest are separated from co-extracted matrix interferences by passing the extracts through stacked graphitized carbon and alumina SPE cartridges, along with the use of high-performance liquid chromatography and gel-permeation chromatography (HPLC/GPC). Quantification of the pyrethroids from the extracted water and sediment samples is done using gas chromatography with mass spectrometry (GC/MS) or gas chromatography with tandem mass spectrometry (GC/MS/MS). Recoveries in test water samples fortified at 10 ng/L ranged from 83 to 107 percent, and recoveries in test sediment samples fortified at 10 ug/kg ranged from 82 to 101 percent; relative standard deviations ranged from 5 to 9 percent in the water samples and 3 to 9 percent in the sediment samples. Method detection limits (MDLs), calculated using U.S. Environmental Protection Agency procedures (40 CFR 136, Appendix B), in water ranged from 2.0 to 6.0 ng/L using GC/MS and 0.5 to 1.0 ng/L using GC/MS/MS. For sediment, the MDLs ranged from 1.0 to 2.6 ug/kg dry weight using GC/MS and 0.2 to 0.5 ug/kg dry weight using GC/MS/MS. The matrix-spike recoveries for each compound, when averaged for 12 environmental water samples, ranged from 84 to 96 percent, and when averaged for 27 environmental sediment samples, ranged from 88 to 100 percent.

Techniques and Methods↗

USGS2008

Effects of the herbicide diuron on cordgrass (Spartina foliosa) reflectance and photosynthetic parameters

Early indicators of salt marsh plant stress are needed to detect stress before it is manifested as changes in biomass and coverage. We explored a variety of leaf-level spectral reflectance and fluorescence variables as indicators of stress in response to the herbicide diuron. Diuron, a Photosystem II inhibitor, is heavily used in areas adjacent to estuaries, but its ecological effects are just beginning to be recognized. In a greenhouse experiment, we exposed Spartina foliosa , the native cordgrass in California salt marshes, to two levels of diuron. After plant exposure to diuron for 28 days, all spectral reflectance indices and virtually all fluorescence parameters indicated reduced pigment and photosynthetic function, verified as reduced CO 2 assimilation. Diuron exposure was not evident, however, in plant morphometry, indicating that reflectance and fluorescence were effective indicators of sub-lethal diuron exposure. Several indices (spectral reflectance index ARI and fluorescence parameters EQY, Fo, and maximum rETR) were sensitive to diuron concentration. In field trials, most of the indices as well as biomass, % cover, and canopy height varied predictably and significantly across a pesticide gradient. In the field, ARI and Fo regressed most significantly and strongly with pesticide levels. The responses of ARI and Fo in both the laboratory and the field make these indices promising as sensitive, rapid, non-destructive indicators of responses of S. foliosa to herbicides in the field. These techniques are employed in remote sensing and could potentially provide a link between landscapes of stressed vegetation and the causative stressor(s), which is crucial for effective regulation of pollution.

Estuaries and Coasts↗

USGS2008

Pesticides in Water and Suspended Sediment of the Alamo and New Rivers, Imperial Valley/Salton Sea Basin, California, 2006-2007

Water and suspended-sediment samples were collected at eight sites on the Alamo and New Rivers in the Imperial Valley/Salton Sea Basin of California and analyzed for both current-use and organochlorine pesticides by the U.S. Geological Survey. Samples were collected in the fall of 2006 and spring of 2007, corresponding to the seasons of greatest pesticide use in the basin. Large-volume water samples (up to 650 liters) were collected at each site and processed using a flow-through centrifuge to isolate suspended sediments. One-liter water samples were collected from the effluent of the centrifuge for the analysis of dissolved pesticides. Additional samples were collected for analysis of dissolved organic carbon and for suspended-sediment concentrations. Water samples were analyzed for a suite of 61 current-use and organochlorine pesticides using gas chromatography/mass spectrometry. A total of 25 pesticides were detected in the water samples, with seven pesticides detected in more than half of the samples. Dissolved concentrations of pesticides observed in this study ranged from below their respective method detection limits to 8,940 nanograms per liter (EPTC). The most frequently detected compounds in the water samples were chlorpyrifos, DCPA, EPTC, and trifluralin, which were observed in more than 75 percent of the samples. The maximum concentrations of most pesticides were detected in samples from the Alamo River. Maximum dissolved concentrations of carbofuran, chlorpyrifos, diazinon, and malathion exceeded aquatic life benchmarks established by the U.S. Environmental Protection Agency for these pesticides. Suspended sediments were analyzed for 87 current-use and organochlorine pesticides using microwave-assisted extraction, gel permeation chromatography for sulfur removal, and either carbon/alumina stacked solid-phase extraction cartridges or deactivated Florisil for removal of matrix interferences. Twenty current-use pesticides were detected in the suspended-sediment samples, including pyrethroid insecticides and fungicides. Fourteen legacy organochlorine pesticides also were detected in the suspended-sediment samples. Greater numbers of current-use and organochlorine pesticides were observed in the Alamo River samples in comparison with the New River samples. Maximum concentrations of current-use pesticides in suspended-sediment samples ranged from below their method detection limits to 174 micrograms per kilogram (pendimethalin). Most organochlorine pesticides were detected at or below their method detection limits, with the exception of p,p'-DDE, which had a maximum concentration of 54.2 micrograms per kilogram. The most frequently detected current-use pesticides in the suspended-sediment samples were chlorpyrifos, permethrin, tetraconazole, and trifluralin, which were observed in more than 83 percent of the samples. The organochlorine degradates p,p'-DDD and p,p'-DDE were detected in all suspended-sediment samples.

Data Series↗

USGS2008

Occurrence of chlorothalonil, its transformation products, and selected other pesticides in Texas and Oklahoma streams, 2003-2004

The primary purpose of the study described in this report was to determine if the fungicide chlorothalonil (2,4,5,6-tetrachloroisophthalonitrile), three of its transformation products, or selected other pesticides are transported to surface water after use on peanuts or other crops in Texas and Oklahoma. The results summarized here are part of a larger study that includes data from sites in Alabama, Florida, and Georgia. Chlorothalonil is classified as a probable carcinogen, and the 4-hydroxy of chlorothalonil transformation product is more soluble, more stable, and, for some species, more toxic than its parent compound. In 2003, water samples were collected from three surface-water sites in Texas and two surface-water sites in Oklahoma; in 2004, samples were collected from the two Oklahoma sites. Chlorothalonil was not detected in any of the 20 samples analyzed. The 4-hydroxy of chlorothalonil transformation product was detected in three samples collected in 2004, with a maximum concentration of 0.018 microgram per liter (?g/L); the other two transformation products (diamide chlorothalonil and 1-amide-4-hydroxy chlorothalonil) were not detected in any sample. In addition, 19 samples were analyzed for as many as 109 other pesticides and transformation products. Atrazine was detected in 13 samples and had a maximum concentration of 0.122 ?g/L. Deethylatrazine was detected in 10 samples and had a maximum concentration of 0.04 ?g/L. Metolachlor was detected in eight samples and had a maximum concentration of 0.019 ?g/L. Fifteen other pesticides or pesticide transformation products also were detected. In general, concentrations of pesticides were less than concentrations that are commonly observed in Midwestern streams. The results indicate that the use of chlorothalonil on peanut crops has not resulted in substantial contamination of the studied streams in Texas and Oklahoma.

Texas, Oklahoma↗

USGS2008

Understanding the occurrence and transport of current-use pesticides in the San Francisco estuary watershed

The occurrence and potential effects of current-use pesticides are of concern in the San Francisco Estuary watershed but our understanding of the spatial and temporal distribution of contamination is limited. This paper summarizes almost two decades of historical data and uses it to describe our current knowledge of the processes controlling the occurrence of current-use pesticides in the watershed. Monitoring studies analyze fewer than half of the pesticides applied in the watershed and most of our knowledge is about inputs of dissolved pesticides in the upper watershed. The four major seasonal patterns of riverine inputs of pesticides to the estuary can be identified by usage and transport mechanism. Dormant spray insecticides applied to orchards and herbicides applied to a variety of crops are transported by rainfall during the winter. Alfalfa pesticides are detected following rainfall and irrigation return flow in the spring, and rice pesticides are detected following release of rice field water in the summer. Irrigation return flows transport a variety of herbicides during the summer. In addition, pesticides applied on Delta islands can cause elevated pesticide concentrations in localized areas. Although not as well characterized, urban creeks appear to have their own patterns of insecticide concentrations causing toxicity throughout most of the year. Current-use pesticides have also been detected on suspended and bed sediments throughout the watershed but limited data make it difficult to determine occurrence patterns. Data gaps include the lack of analysis of many pesticides (or degradates), changing pesticide use, limited information on pesticide transport within the Delta, and an incomplete understanding of the transport and persistence of sediment-associated pesticides. Future monitoring programs should be designed to address these data gaps.

California↗

USGS2007

Input, flux, and persistence of six select pesticides in San Francisco Bay

Temporal patterns of pesticide inputs to San Francisco Bay were identified and correlated with timing of application and transport mechanism. Fluxes were calculated from measured concentrations and estimated flow. Persistence of the pesticides under typical riverine or estuarine conditions were estimated from laboratory experiments. Simazine was detected most frequently and had the highest flux into the Bay, which could be explained by its continuous use and long half-life. In comparison, diazinon was detected at lower concentrations and had a lower flux which corresponded to its lower use and shorter half-life. The order-of-magnitude lower fluxes of carbofuran and methidathion corresponded to their lower use and expected hydrolysis. Molinate was detected at the highest concentration but its flux was lower than expected, considering its very high use and persistence in the laboratory experiments. Additional loss of molinate is likely to occur from volatilization and photodegradation on the rice fields. Although thiobencarb had the second highest use, it had the lowest flux of the six pesticides, which can be attributed to its loss via hydrolysis, photodegradation, volatilization, and sorption to sediments. Fluxes into San Francisco Bay were equal to or greater than those reported for other estuaries, except for the Gulf of Mexico.

California↗