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Rice pesticide concentrations in the Colusa Basin Drain and the Sacramento River, California, 1990-1993

The pesticides molinate, thiobencarb, and carbofuran are applied to rice ( Oryza sativa L.) fields in the Sacramento Valley, California, each year during April through June. These pesticides are of concern because of their adverse effects on water quality and their potential adverse effects on aquatic life. Therefore, the California Regional Water Quality Control Board (CRWQCB) mandated the holding of irrigation-return water in rice fields to increase pesticide degradation and dissipation before the water is released to the Sacramento River. The CRWQCB also established performance goals to maintain drinking water quality for the city of Sacramento and to protect the habitat for aquatic life. The objectives of this study were to determine the effects of increased irrigation-return water holding times on rice pesticide concentrations and loads in the Colusa Basin Drain and the Sacramento River. Dissolved pesticide concentrations were measured in water samples collected in May through July during 1990–1993 at the Colusa Basin Drain at Road 99E near Knights Landing (Colosa Basin Drain) and at the Sacramento River at Sacramento. Pesticide concentrations and loads at both sites showed a decrease from 1990–1992 and an increase in 1993. This trend cannot be explained by the yearly holding time regulations but can be explained by the amount of yearly emergency releases. The yearly changes in pesticide concentration detected demonstrate that continued monitoring and management of pesticides is necessary to maintain water quality.

California

Results from the Big Spring basin water quality monitoring and demonstration projects, Iowa, USA

Agricultural practices, hydrology, and water quality of the 267-km2 Big Spring groundwater drainage basin in Clayton County, Iowa, have been monitored since 1981. Land use is agricultural; nitrate-nitrogen (-N) and herbicides are the resulting contaminants in groundwater and surface water. Ordovician Galena Group carbonate rocks comprise the main aquifer in the basin. Recharge to this karstic aquifer is by infiltration, augmented by sinkhole-captured runoff. Groundwater is discharged at Big Spring, where quantity and quality of the discharge are monitored. Monitoring has shown a threefold increase in groundwater nitrate-N concentrations from the 1960s to the early 1980s. The nitrate-N discharged from the basin typically is equivalent to over one-third of the nitrogen fertilizer applied, with larger losses during wetter years. Atrazine is present in groundwater all year; however, contaminant concentrations in the groundwater respond directly to recharge events, and unique chemical signatures of infiltration versus runoff recharge are detectable in the discharge from Big Spring. Education and demonstration efforts have reduced nitrogen fertilizer application rates by one-third since 1981. Relating declines in nitrate and pesticide concentrations to inputs of nitrogen fertilizer and pesticides at Big Spring is problematic. Annual recharge has varied five-fold during monitoring, overshadowing any water-quality improvements resulting from incrementally decreased inputs. ?? Springer-Verlag 2001.

Hydrogeology Journal

Uptake, metabolism, and elimination of fungicides from coated wheat seeds in Japanese quail (Coturnix japonica)

Pesticides coated to the seed surface potentially pose an ecological risk to granivorous birds that consume incompletely buried or spilled seeds. To assess the toxicokinetics of seeds treated with current-use fungicides, Japanese quail (Coturnix japonica) were orally dosed with commercially coated wheat seeds. Quail were exposed to metalaxyl, tebuconazole, and fludioxonil at either a low (0.07, 0.03, and 0.03 mg/kg body weight) or high dose (0.2, 0.09, and 0.1 mg/kg body weight). Fungicides were rapidly absorbed and distributed to tissues. Tebuconazole was metabolized into t-butylhydroxy-tebuconazole. All compounds were eliminated to below detection limits within 24 h. The high detection frequencies observed in fecal samples potentially offers a noninvasive matrix to monitor pesticide exposure. Summing total body burden across plasma, tissue, and fecal samples, less than 9% of the administered dose was identified as the parent fungicide, demonstrating the importance to monitor both active ingredients and their metabolites in biological samples.

Journal of Agricultural and Food Chemistry

Introduction to the U.S. Geological Survey National Water-Quality Assessment (NAWQA) of ground-water quality trends and comparison to other national programs

Assessment of temporal trends in national ground-water quality networks are rarely published in scientific journals. This is partly due to the fact that long-term data from these types of networks are uncommon and because many national monitoring networks are not driven by hypotheses that can be easily incorporated into scientific research. The U.S. Geological Survey (USGS) National Water-Quality Assessment Program (NAWQA) since 1991 has to date (2006) concentrated on occurrence of contaminants because sufficient data for trend analysis is only just becoming available. This paper introduces the first set of trend assessments from NAWQA and provides an assessment of the success of the program. On a national scale, nitrate concentrations in ground water have generally increased from 1988 to 2004, but trends in pesticide concentrations are less apparent. Regionally, the studies showed high nitrate concentrations and frequent pesticide detections are linked to agricultural use of fertilizers and pesticides. Most of these areas showed increases in nitrate concentration within the last decade, and these increases are associated with oxic-geochemical conditions and well-drained soils. The current NAWQA plan for collecting data to define trends needs to be constantly reevaluated to determine if the approach fulfills the expected outcome. To assist this evaluation, a comparison of NAWQA to other national ground-water quality programs was undertaken. The design and spatial extent of each national program depend on many factors, including current and long-term budgets, purpose of the program, size of the country, and diversity of aquifer types. Comparison of NAWQA to nine other national programs shows a great diversity in program designs, but indicates that different approaches can achieve similar and equally important goals. Copyright ?? 2008 by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America. All rights reserved.

Conference Paper

The Amphibian Research and Monitoring Initiative (ARMI): 5-year report

The Amphibian Research and Monitoring Initiative (ARMI) is an innovative, multidisciplinary program that began in 2000 in response to a congressional directive for the Department of the Interior to address the issue of amphibian declines in the United States. ARMI’s formulation was cross-disciplinary, integrating U.S. Geological Survey scientists from Biology, Water, and Geography to develop a course of action (Corn and others, 2005a). The result has been an effective program with diverse, yet complementary, expertise. ARMI’s approach to research and monitoring is multiscale. Detailed investigations focus on a few species at selected local sites throughout the country; monitoring addresses a larger number of species over broader areas (typically, National Parks and National Wildlife Refuges); and inventories to document species occurrence are conducted more extensively across the landscape. Where monitoring is conducted, the emphasis is on an ability to draw statistically defensible conclusions about the status of amphibians. To achieve this objective, ARMI has instituted a monitoring response variable that has nationwide applicability. At research sites, ARMI focuses on studying species/environment interactions, determining causes of observed declines, and developing new techniques to sample populations and analyze data. Results from activities at all scales are provided to scientists, land managers, and policymakers, as appropriate. The ARMI program and the scientists involved contribute significantly to understanding amphibian declines at local, regional, national, and international levels. Within National Parks and National Wildlife Refuges, findings help land managers make decisions applicable to amphibian conservation. For example, the National Park Service (NPS) selected amphibians as a vital sign for several of their monitoring networks, and ARMI scientists provide information and assistance in developing monitoring methods for this NPS effort. At the national level, ARMI has had major exposure at a variety of meetings, including a dedicated symposium at the 2004 joint meetings of the Herpetologists’ League, the American Society of Ichthyologists and Herpetologists, and the Society for the Study of Amphibians and Reptiles. Several principal investigators have brought international exposure to ARMI through venues such as the World Congress of Herpetology in South Africa in 2005 (invited presentation by Dr. Gary Fellers), the Global Amphibian Summit, sponsored by the International Union for Conservation of Nature (IUCN) and Wildlife Conservation International, in Washington, D.C., 2005 (invited participation by Dr. P.S. Corn), and a special issue of the international herpetological journal Alytes focused on ARMI in 2004 (edited by Dr. C.K. Dodd, Jr.). ARMI research and monitoring efforts have addressed at least 7 of the 21 Threatened and Endangered Species listed by the U.S. Fish and Wildlife Service (California red-legged frog [Rana draytonii], Chiricahua leopard frog [R. chiricahuensis], arroyo toad [Bufo californicus], dusky gopher frog [Rana sevosa], mountain yellow-legged frog [R. muscosa], flatwoods salamander [Ambystoma cingulatum], and the golden coqui [Eleutherodactylus jasperi]), and 9 additional species of concern recognized by the IUCN. ARMI investigations have addressed time-sensitive research, such as emerging infectious diseases and effects on amphibians related to natural disasters like wildfire, hurricanes, and debris flows, and the effects of more constant, environmental change, like urban expansion, road development, and the use of pesticides. Over the last 5 years, ARMI has partnered with an extensive list of government, academic, and private entities. These partnerships have been fruitful and have assisted ARMI in developing new field protocols and analytic tools, in using and refining emerging technologies to improve accuracy and efficiency of data handling, in conducting amphibian disease, malformation, and environmental effects research, and in implementing a network of monitoring and research sites. Accomplishments from these endeavors include more than 40 publications on amphibian status and trends, nearly 100 publications on amphibian ecology and causes of declines, and over 30 methodological publications. Several databases have emerged as a result of ARMI and its partnerships; one, a digital atlas of ranges for all U.S. amphibian species, was used by the IUCN to display amphibian distribution maps in the Global Amphibian Assessment Project. Given the scope of ARMI and the panoply of projects, findings have had implications for policy. Investigations that demonstrate amphibian declines or illuminate causes of declines provide valuable information about habitat management, environmental effects, mechanisms for the spread of disease, and human/amphibian interfaces. This information has been made available to land managers, scientists, educators, Congress and other policymakers, and the public. The support afforded ARMI by Congress has been influential in the program’s development and success. The value of ARMI’s efforts will continue to increase as we are able to extend our studies spatially and temporally to answer critical questions with more confidence. We are using ARMI’s resources efficiently and continuing to develop innovative mechanisms for leveraging resources for maximum effectiveness during challenging financial times. This report is a 5-year retrospective of the structure, methodology, progress, and contributions to the broader scientific community that have resulted from this national USGS program. We evaluate ARMI’s success to date, with regard to the challenges faced by the program and the strengths that have emerged. We chart objectives for the next 5 years that build on current accomplishments, highlight areas meriting further research, and direct efforts to overcome existing weaknesses.

Scientific Investigations Report

The effect of residential development on ground-water quality near Detroit, Michigan

Two water-quality studies were done on the outskirts of the Detroit metropolitan area to determine how recent residential development has affected ground-water quality. Pairs of monitor and domestic wells were sampled in areas where residential land use overlies glacial outwash deposits. Young, shallow waters had significantly higher median concentrations of nitrate, chloride, and dissolved solids than older, deeper waters. Analysis of chloride/bromide ratios indicates that elevated salinities are due to human activities rather than natural factors, such as upward migration of brine. Trace concentrations of volatile organic compounds were detected in samples from 97 percent of the monitor wells. Pesticides were detected infrequently even though they are routinely applied to lawns and roadways in the study area. The greatest influence on ground-water quality appears to be from septic-system effluent (domestic sewage, household solvents, water-softener backwash) and infiltration of stormwater runoff from paved surfaces (road salt, fuel residue). No health-related drinking-water standards were exceeded in samples from domestic wells. However, the effects of human activities are apparent in 76 percent of young waters, and at depths far below 25 feet, which is the current minimum well-depth requirement.Two water-quality studies were done on the outskirts of the Detroit metropolitan area to determine how recent residential development has affected ground-water quality. Pairs of monitor and domestic wells were sampled in areas where residential land use overlies glacial outwash deposits. Young, shallow waters had significantly higher median concentrations of nitrate, chloride, and dissolved solids than older, deeper waters. Analysis of chloride/bromide ratios indicates that elevated salinities are due to human activities rather than natural factors, such as upward migration of brine. Trace concentrations of volatile organic compounds were detected in samples from 97 percent of the monitor wells. Pesticides were detected infrequently even though they are routinely applied to lawns and roadways in the study area. The greatest influence on ground-water quality appears to be from septic-system effluent (domestic sewage, household solvents, water-softener backwash) and infiltration of stormwater runoff from paved surfaces (road salt, fuel residue). No health-related drinking-water standards were exceeded in samples from domestic wells. However, the effects of human activities are apparent in 76 percent of young waters, and at depths far below 25 feet, which is the current minimum well-depth requirement.

Michigan

Pesticides, polycyclic aromatic hydrocarbons, and polychlorinated biphenyls in transport in two Atlantic coastal plain tributaries and loadings to Chesapeake Bay

Concentrations of current-use pesticides, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and organochlorine (OC) insecticides were determined above the reach of tide in the Chesterville Branch and Nanticoke River on the eastern shore of Chesapeake Bay during base-flow and storm-flow hydrologic regimes to evaluate mass transport to Chesapeake Bay. The two rivers monitored showed relatively high concentrations of atrazine, simazine, alachlor, and metolachlor in comparison to previously investigated western shore tributaries, and reflected the predominant agricultural land use in the eastern shore watersheds. The four current use pesticides showed the greatest seasonal contribution to annual loadings to tidal waters of Chesapeake Bay from the two rivers, and the relative order of annual loadings for the other contaminant classes was PAHs > PCBs > OC insecticides. Annual loadings normalized to the landscape areas of selected Chesapeake Bay watersheds showed correlations to identifiable source areas, with the highest pesticide yields (g/km2/yr) occurring in eastern shore agricultural landscapes, and the highest PAH yields derived from urban regions.

Journal of Environmental Science and Health - Part

Use of pharmaceuticals and pesticides to constrain nutrient sources in coastal groundwater of northwestern Long Island, New York, USA

In developed, non-agricultural, unsewered areas, septic systems and fertilizer application to lawns and gardens represent two major sources of nitrogen to coastal groundwater, in addition to atmospheric input. This study was designed to distinguish between these two possible nitrogen sources by analyzing groundwater samples for pharmaceutical residuals, because fertilizers do not contain any of these pharmaceuticals, but domestic wastewater commonly does. In addition, several herbicides and insecticides used in lawn treatment were analyzed as indicators of nitrogen delivery to groundwater from fertilizers. Groundwater samples were taken through piezometres at shoreline sites in unsewered areas surrounding Northport Harbor and in sewered areas adjacent to Manhasset Bay (hereafter referred to as "Northport" and "Manhasset", respectively), both in northwestern Long Island, USA. Excessive nitrogen loading has led to reduced dissolved oxygen concentrations in Long Island Sound, and the groundwater contribution to the nitrogen budget is poorly constrained. The frequent detection of the anticonvulsant compound carbamazepine in groundwater samples of the Northport Harbor area (unsewered), together with the fact that few pesticides associated with lawn applications were detected, suggests that wastewater input and atmospheric input are the likely sources of nitrogen in the Northport groundwater. High concentrations of nitrogen were also detected in the Manhasset (sewered) groundwater. The low detection frequency and concentration of carbamazepine, however, suggest that the sewer system effectively intercepts nitrogen from wastewater there. The likely sources of nitrogen in the Manhasset groundwater are atmospheric deposition and lawn fertilizers, as this area is densely populated.

New York

Prediction of pesticide toxicity in Midwest streams

The occurrence of pesticide mixtures is common in stream waters of the United States, and the impact of multiple compounds on aquatic organisms is not well understood. Watershed Regressions for Pesticides (WARP) models were developed to predict Pesticide Toxicity Index (PTI) values in unmonitored streams in the Midwest and are referred to as WARP-PTI models. The PTI is a tool for assessing the relative toxicity of pesticide mixtures to fish, benthic invertebrates, and cladocera in stream water. One hundred stream sites in the Midwest were sampled weekly in May through August 2013, and the highest calculated PTI for each site was used as the WARP-PTI model response variable. Watershed characteristics that represent pesticide sources and transport were used as the WARP-PTI model explanatory variables. Three WARP-PTI models—fish, benthic invertebrates, and cladocera—were developed that include watershed characteristics describing toxicity-weighted agricultural use intensity, land use, agricultural management practices, soil properties, precipitation, and hydrologic properties. The models explained between 41 and 48% of the variability in the measured PTI values. WARP-PTI model evaluation with independent data showed reasonable performance with no clear bias. The models were applied to streams in the Midwest to demonstrate extrapolation for a regional assessment to indicate vulnerable streams and to guide more intensive monitoring.

Midwest

Effects of stormwater infiltration on quality of groundwater beneath retention and detention basins

Infiltration of storm water through detention and retention basins may increase the risk of groundwater contamination, especially in areas where the soil is sandy and the water table shallow, and contaminants may not have a chance to degrade or sorb onto soil particles before reaching the saturated zone. Groundwater from 16 monitoring wells installed in basins in southern New Jersey was compared to the quality of shallow groundwater from 30 wells in areas of new-urban land use. Basin groundwater contained much lower levels of dissolved oxygen, which affected concentrations of major ions. Patterns of volatile organic compound and pesticide occurrence in basin groundwater reflected the land use in the drainage areas served by the basins, and differed from patterns in background samples, exhibiting a greater occurrence of petroleum hydrocarbons and certain pesticides. Dilution effects and volatilization likely decrease the concentration and detection frequency of certain compounds commonly found in background groundwater. High recharge rates in storm water basins may cause loading factors to be substantial even when constituent concentrations in infiltrating storm water are relatively low.

New Jersey

Use of field-applied quality control samples to monitor performance of a Goulden large-sample extractor/GC-MS method for pesticides in water

Since 1985, the Goulden large-sample extractor (GLSE) has been used to isolate a broad array of trace-organic contaminants from large volumes of water. In this study, field-applied quality control measures, including matrix and surrogate spikes and blanks, were used to monitor method performance from GLSE extraction through GC-MS analysis. The method was applied to the determination of multiple classes of pesticides isolated from 4- to 112-L filtered surface-water samples. Average recoveries of six surrogate compounds ranged from 84 ?? 18% for [2H10]diazinon to 15 ?? 13% for 4,4'-[2H8]DDT, the low recoveries for which were largely a result of unmonitored breakdown of this surrogate by the GC injection system. Field-matrix-spike samples were prepared by fortifying 10-L, 35-L, and 110-L filtered surface-water samples with 68 pesticides to amended concentrations of 11- to 50-ng/L each. Recoveries ranged from not detected to greater than 100%. Variability in pesticide recoveries from triplicate 10-L water samples collected at one site averaged 5.7% relative standard deviation and did not exceed 19%.Since 1985, the Goulden large-sample extractor (GLSE) has been used to isolate a broad array of trace-organic contaminants from large volumes of water. In this study, field-applied quality control measures, including matrix and surrogate spikes and blanks, were used to monitor method performance from GLSE extraction through GC-MS analysis. The method was applied to the determination of multiple classes of pesticides isolated from 4- to 112-L filtered surface-water samples. Average recoveries of six surrogate compounds ranged from 84 ?? 18% for [2H10]diazinon to 15 ?? 13% for 4,4???-[2H8]DDT, the low recoveries for which were largely a result of unmonitored breakdown of this surrogate by the GC injection system. Field-matrix-spike samples were prepared by fortifying 10-L, 35-L, and 110-L filtered surface-water samples with 68 pesticides to amended concentrations of 11- to 50-ng/L each. Recoveries ranged from not detected to greater than 100%. Variability in pesticide recoveries from triplicate 10-L water samples collected at one site averaged 5.7% relative standard deviation and did not exceed 19%.

International Journal of Environmental Analytical

An adaptive management implementation framework for evaluating supplemental sea lamprey (Petromyzon marinus) controls in the Laurentian Great Lakes

Invasive sea lamprey ( Petromyzon marinus ) populations in the Laurentian Great Lakes Basin have been suppressed for over 60 years primarily by migration barriers and lamprey-specific pesticides. Improving control outcomes by supplementing barriers and pesticides with additional control strategies has been a long-standing objective of managers and stakeholders, but progress towards this objective has been limited. We developed an adaptive management implementation framework and applied it to this objective. The framework consists of a set of adaptive management implementation goals (develop effective monitoring practices, develop effective participatory process, and conduct management experiments), a set of aspirational targets hypothesized to be related to Sea Lamprey Control Program adaptive capacity (multi-level political and social organization, creation of safe-to-fail decision making arenas, and effective use of multi-criteria decision analysis), and a feedback loop linking adaptive capacity and progress towards adaptive management implementation goals. Progress towards improving sea lamprey control outcomes by integrating supplemental control strategy into the Sea Lamprey Control Program may be possible through adaptive management implementation.

Great Lakes

Changes in shallow groundwater quality beneath recently urbanized areas in the Memphis, Tennessee area

Memphis, the largest city in the state of Tennessee, and its surrounding suburbs depend on a confined aquifer, the Memphis aquifer, for drinking water. Concern over the potential for downward movement of water from an overlying shallow aquifer to the underlying Memphis aquifer provided impetus for monitoring groundwater quality within the shallow aquifer. The occurrence of volatile organic compounds (VOCs), nitrate, and pesticides in samples from the shallow well network indicate a widespread affect on water quality from the overlying urban land use. Total pesticide concentration was generally higher in more recently recharged groundwater indicating that as the proportion of recent water increases, the occurrence of pesticides related to the current urban land use also increases. Groundwater samples with nitrate concentrations greater than 1.5 mg/l and detectable concentrations of the pesticides atrazine and simazine also had higher concentrations of chloroform, a VOC primarily associated with urban land use, than in other samples. The age of the water from these wells indicates that these concentrations are most likely not representative of past agricultural use, but of more recent urban use of these chemicals. Given that the median age of water represented by the shallow well network was 21 years, a lag time likely exists between changes in land use and the occurrence of constituents related to urbanization in shallow groundwater.

Journal of the American Water Resources Associatio

Residues of organochlorine insecticides, polychlorinated biphenyls, and heavy metals in biota from Apalachicola River, Florida, 1978

Seventy-seven composite samples composed of largemouth bass ( Micropterus salmoides ), channel catfish ( Ictaluras punctatus ), threadfin shad ( Dorosoma petenense ), Asiatic clam ( Corbicula fluminea ), burrowing mayfly ( Hexagenia sp.), water snake ( Natrix spp.), and little green heron ( Butorides virescens ) were collected from upper and lower reaches of the Apalachicola River, Florida, in 1978 for residue analysis of organochlorine insecticides, PCBs (polychlorinated biphenyls), and metals. Compared with data from the National Pesticide Monitoring Program and criteria recommended for the protection of aquatic life, residue concentrations were moderately high in the Apalachicola River. Biota from the upper river generally had higher organic and lower metal residues than those from the lower river. Highest residues in the biota were total DDT, total PCBs, and toxaphene. Although individual mean concentrations were below 2 μg/g and total organic contaminant residues never exceeded 5 μg/g, residue concentrations of DDT, PCBs, and toxaphene (particularly from the upper river) exceeded recommended permissible levels for the protection of aquatic life. Metal residues were generally below 1 μg/g. Exceptions were arsenic residues in threadfin shad (1.07 μg/g) and Asiatic clams (1.75 μg/g), and selenium in eggs of channel catfish (1.39 μg/g). The residues observed in the biota, particularly from the upper station, indicated moderate contamination of the Apalachicola River system at the time samples were collected.

Journal of the Association of Official Analytical

Nitrate and herbicide loading in two groundwater basins of Illinois' sinkhole plain

This investigation was designed to estimate the mass loading of nitrate (NO3-) and herbicides in spring water discharging from groundwater basins in an agriculturally dominated, mantled karst terrain. The loading was normalized to land use and NO3- and herbicide losses were compared to estimated losses in other agricultural areas of the Midwestern USA. Our study area consisted of two large karst springs that drain two adjoining groundwater basins (total area of 37.7 km2) in southwestern Illinois' sinkhole plain, USA. The springs and stream that they form were monitored for almost 2 years. Nitrate-nitrogen (NO3-N) concentrations at three monitoring sites were almost always above the background concentration (1.9 mg/l). NO3-N concentrations at the two springs ranged from 1.08 to 6.08 with a median concentration of 3.61 mg/l. Atrazine and alachlor concentrations ranged from <0.01 to 34 ??g/l and <0.01 to 0.98 ??g/l, respectively, with median concentrations of 0.48 and 0.12 ??g/l, respectively. Approximately 100,000 kg/yr of NO3-N, 39 kg/yr of atrazine, and 2.8 kg/yr of alachlor were discharged from the two springs. Slightly more than half of the discharged NO3- came from background sources and most of the remainder probably came from fertilizer. This represents a 21-31% loss of fertilizer N from the groundwater basins. The pesticide losses were 3.8-5.8% of the applied atrazine, and 0.05-0.08% of the applied alachlor. The loss of atrazine adsorbed to the suspended solid fraction was about 2 kg/yr, only about 5% of the total mass of atrazine discharged from the springs. ?? 2004 Elsevier B.V. All rights reserved.

Journal of Hydrology

Considerations involved with the use of semipermeable membrane devices for monitoring environmental contaminants

Semipermeable membrane devices (SPMDs) are used with increasing frequency, and throughout the world as samplers of organic contaminants. The devices can be used to detect a variety of lipophilic chemicals in water, sediment/soil, and air. SPMDs are designed to sample nonpolar, hydrophobic chemicals. The maximum concentration factor achievable for a particular chemical is proportional to its octanol–water partition coefficient. Techniques used for cleanup of SPMD extracts for targeted analytes and for general screening by full-scan mass spectrometry do not differ greatly from techniques used for extracts of other matrices. However, SPMD extracts contain potential interferences that are specific to the membrane–lipid matrix. Procedures have been developed or modified to alleviate these potential interferences. The SPMD approach has been demonstrated to be applicable to sequestering and analyzing a wide array of environmental contaminants including organochlorine pesticides, polychlorinated biphenyls, polycyclic aromatic hydrocarbons, polychlorinated dioxins and dibenzofurans, selected organophosphate pesticides and pyrethroid insecticides, and other nonpolar organic chemicals. We present herein an overview of effective procedural steps for analyzing exposed SPMDs for trace to ultra-trace levels of contaminants sequestered from environmental matrices.

Journal of Chromatography A

Assessing the potential effects of fungicides on nontarget gut fungi (trichomycetes) and their associated larval black fly hosts

Fungicides are moderately hydrophobic and have been detected in water and sediment, particularly in agricultural watersheds, but typically are not included in routine water quality monitoring efforts. This is despite their widespread use and frequent application to combat fungal pathogens. Although the efficacy of these compounds on fungal pathogens is well documented, little is known about their effects on nontarget fungi. This pilot study, a field survey in southwestern Idaho from April to December 2010 on four streams with varying pesticide inputs (two agricultural and two reference sites), was conducted to assess nontarget impact of fungicides on gut fungi, or trichomycetes. Tissues of larval black flies (Diptera: Simuliidae), hosts of gut fungi, were analyzed for pesticide accumulation. Fungicides were detected in hosts from streams within agricultural watersheds but were not detected in hosts from reference streams. Gut fungi from agricultural sites exhibited decreased percent infestation, density and sporulation within the gut, and black fly tissues had elevated pesticide concentrations. Differences observed between the sites demonstrate a potential effect on this symbiotic system. Future research is needed to parse out the details of the complex biotic and abiotic relationships; however, these preliminary results indicate that impacts to nontarget organisms could have far-reaching consequences within aquatic ecosystems.

Journal of the American Water Resources Associatio

Temporal trends in concentrations of DBCP and nitrate in groundwater in the eastern San Joaquin Valley, California, USA

Temporal monitoring of the pesticide 1,2-dibromo-3-chloropropane (DBCP) and nitrate and indicators of mean groundwater age were used to evaluate the transport and fate of agricultural chemicals in groundwater and to predict the long-term effects in the regional aquifer system in the eastern San Joaquin Valley, California. Twenty monitoring wells were installed on a transect along an approximate groundwater flow path. Concentrations of DBCP and nitrate in the wells were compared to concentrations in regional areal monitoring networks. DBCP persists at concentrations above the US Environmental Protection Agency's maximum contaminant level (MCL) at depths of nearly 40 m below the water table, more than 25 years after it was banned. Nitrate concentrations above the MCL reached depths of more than 20 m below the water table. Because of the intensive pumping and irrigation recharge, vertical flow paths are dominant. High concentrations (above MCLs) in the shallow part of the regional aquifer system will likely move deeper in the system, affecting both domestic and public-supply wells. The large fraction of old water (unaffected by agricultural chemicals) in deep monitoring wells suggests that it could take decades for concentrations to reach MCLs in deep, long-screened public-supply wells, however. ?? Springer-Verlag 2007.

Hydrogeology Journal