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.

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.

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.

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, MDLb99 (99th percentile) or MDLbY (= 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 

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.

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, 1H-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.

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 (EC50) 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 EC50 values were used to convert fipronil compound concentrations in field samples to the sum of toxic units (∑TUFipronils). Mean ∑TUFipronils exceeded 1 (indicating toxicity) in 16% of streams sampled from five regional studies. The Species at Risk invertebrate metric was negatively associated with ∑TUFipronils 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.

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.

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.

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.

Device and method of optically orienting biaxial crystals for sample preparation.

An optical instrument we refer to as the "biaxial orientation device" has been developed for finding the optical plane, acute bisectrix, and obtuse bisectrix in biaxial crystals by means of optically aligning conoscopically formed melatopes and measuring the angular coordinates of the melatopes, where the angular values allow for determination of the optical plane containing the optical axes using a vector algebra approach. After determination of the optical plane, the instrument allows for the sample to be aligned in the acute bisectrix or obtuse bisectrix orientations and to be transferred to a simple mechanical component for subsequent grinding and polishing, while preserving the orientation of the polished faces relative to the optical plane, acute bisectrix, and obtuse bisectrix during the grinding and polishing process. Biaxial crystalline material samples prepared in the manner are suitable for accurate spectroscopic absorption measurements in the acute bisectrix and obtuse bisectrix directions as well as perpendicular to the optical plane.

Persistence and potential effects of complex organic contaminant mixtures in wastewater-impacted streams.

Natural and synthetic organic contaminants in municipal wastewater treatment plant (WWTP) effluents can cause ecosystem impacts, raising concerns about their persistence in receiving streams. In this study, Lagrangian sampling, in which the same approximate parcel of water is tracked as it moves downstream, was conducted at Boulder Creek, Colorado and Fourmile Creek, Iowa to determine in-stream transport and attenuation of organic contaminants discharged from two secondary WWTPs. Similar stream reaches were evaluated, and samples were collected at multiple sites during summer and spring hydrologic conditions. Travel times to the most downstream (7.4 km) site in Boulder Creek were 6.2 h during the summer and 9.3 h during the spring, and to the Fourmile Creek 8.4 km downstream site times were 18 and 8.8 h, respectively. Discharge was measured at each site, and integrated composite samples were collected and analyzed for >200 organic contaminants including metal complexing agents, nonionic surfactant degradates, personal care products, pharmaceuticals, steroidal hormones, and pesticides. The highest concentration (>100 µg L(-1)) compounds detected in both WWTP effluents were ethylenediaminetetraacetic acid and 4-nonylphenolethoxycarboxylate oligomers, both of which persisted for at least 7 km downstream from the WWTPs. Concentrations of pharmaceuticals were lower (<1 µg L(-1)), and several compounds, including carbamazepine and sulfamethoxazole, were detected throughout the study reaches. After accounting for in-stream dilution, a complex mixture of contaminants showed little attenuation and was persistent in the receiving streams at concentrations with potential ecosystem implications.

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.

Chemical contaminants in water and sediment near fish nesting sites in the Potomac River basin: determining potential exposures to smallmouth bass (Micropterus dolomieu).

The Potomac River basin is an area where a high prevalence of abnormalities such as testicular oocytes (TO), skin lesions, and mortality has been observed in smallmouth bass (SMB, Micropterus dolomieu). Previous research documented a variety of chemicals in regional streams, implicating chemical exposure as one plausible explanation for these biological effects. Six stream sites in the Potomac basin (and one out-of-basin reference site) were sampled to provide an assessment of chemicals in these streams. Potential early life-stage exposure to chemicals detected was assessed by collecting samples in and around SMB nesting areas. Target chemicals included those known to be associated with important agricultural and municipal wastewater sources in the Potomac basin. The prevalence and severity of TO in SMB were also measured to determine potential relations between chemistry and biological effects. A total of 39 chemicals were detected at least once in the discrete-water samples, with atrazine, caffeine, deethylatrazine, simazine, and iso-chlorotetracycline being most frequently detected. Of the most frequently detected chemicals, only caffeine was detected in water from the reference site. No biogenic hormones/sterols were detected in the discrete-water samples. In contrast, 100 chemicals (including six biogenic hormones/sterols) were found in a least one passive-water sample, with 25 being detected at all such samples. In addition, 46 chemicals (including seven biogenic hormones/sterols) were found in the bed-sediment samples, with caffeine, cholesterol, indole, para-cresol, and sitosterol detected in all such samples. The number of herbicides detected in discrete-water samples per site had a significant positive relation to TO(rank) (a nonparametric indicator of TO), with significant positive relations between TO(rank) and atrazine concentrations in discrete-water samples and to total hormone/sterol concentration in bed-sediment samples. Such significant correlations do not necessarily imply causation, as these chemical compositions and concentrations likely do not adequately reflect total SMB exposure history, particularly during critical life stages.

Simulation of branched serial first-order decay of atrazine and metabolites in adapted and nonadapted soils.

In the present study a branched serial first-order decay (BSFOD) model is presented and used to derive transformation rates describing the decay of a common herbicide, atrazine, and its metabolites observed in unsaturated soils adapted to previous atrazine applications and in soils with no history of atrazine applications. Calibration of BSFOD models for soils throughout the country can reduce the uncertainty, relative to that of traditional models, in predicting the fate and transport of pesticides and their metabolites and thus support improved agricultural management schemes for reducing threats to the environment. Results from application of the BSFOD model to better understand the degradation of atrazine supports two previously reported conclusions: atrazine (6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4-diamine) and its primary metabolites are less persistent in adapted soils than in nonadapted soils; and hydroxyatrazine was the dominant primary metabolite in most of the soils tested. In addition, a method to simulate BSFOD in a one-dimensional solute-transport unsaturated zone model is also presented.

Comparative study of transport processes of nitrogen, phosphorus, and herbicides to streams in five agricultural basins, USA.

Agricultural chemical transport to surface water and the linkage to other hydrological compartments, principally ground water, was investigated at five watersheds in semiarid to humid climatic settings. Chemical transport was affected by storm water runoff, soil drainage, irrigation, and how streams were linked to shallow ground water systems. Irrigation practices and timing of chemical use greatly affected nutrient and pesticide transport in the semiarid basins. Irrigation with imported water tended to increase ground water and chemical transport, whereas the use of locally pumped irrigation water may eliminate connections between streams and ground water, resulting in lower annual loads. Drainage pathways in humid environments are important because the loads may be transported in tile drains, or through varying combinations of ground water discharge, and overland flow. In most cases, overland flow contributed the greatest loads, but a significant portion of the annual load of nitrate and some pesticide degradates can be transported under base-flow conditions. The highest basin yields for nitrate were measured in a semiarid irrigated system that used imported water and in a stream dominated by tile drainage in a humid environment. Pesticide loads, as a percent of actual use (LAPU), showed the effects of climate and geohydrologic conditions. The LAPU values in the semiarid study basin in Washington were generally low because most of the load was transported in ground water discharge to the stream. When herbicides are applied during the rainy season in a semiarid setting, such as simazine in the California basin, LAPU values are similar to those in the Midwest basins.

Pesticide fate and transport throughout unsaturated zones in five agricultural settings, USA.

Pesticide transport through the unsaturated zone is a function of chemical and soil characteristics, application, and water recharge rate. The fate and transport of 82 pesticides and degradates were investigated at five different agricultural sites. Atrazine and metolachlor, as well as several of the degradates of atrazine, metolachlor, acetochlor, and alachlor, were frequently detected in soil water during the 2004 growing season, and degradates were generally more abundant than parent compounds. Metolachlor and atrazine were applied at a Nebraska site the same year as sampling, and focused recharge coupled with the short time since application resulted in their movement in the unsaturated zone 9 m below the surface. At other sites where the herbicides were applied 1 to 2 yr before sampling, only degradates were found in soil water. Transformations of herbicides were evident with depth and during the 4-mo sampling time and reflected the faster degradation of metolachlor oxanilic acid and persistence of metolachor ethanesulfonic acid. The fraction of metolachlor ethanesulfonic acid relative to metolachlor and metolachlor oxanilic acid increased from 0.3 to >0.9 at a site in Maryland where the unsaturated zone was 5 m deep and from 0.3 to 0.5 at the shallowest depth. The flux of pesticide degradates from the deepest sites to the shallow ground water was greatest (3.0-4.9 micromol m(-2) yr(-1)) where upland recharge or focused flow moved the most water through the unsaturated zone. Flux estimates based on estimated recharge rates and measured concentrations were in agreement with fluxes estimated using an unsaturated-zone computer model (LEACHM).

Occurrence and fate of pesticides in four contrasting agricultural settings in the United States.

Occurrence and fate of 45 pesticides and 40 pesticide degradates were investigated in four contrasting agricultural settings--in Maryland, Nebraska, California, and Washington. Primary crops included corn at all sites, soybeans in Maryland, orchards in California and Washington, and vineyards in Washington. Pesticides and pesticide degradates detected in water samples from all four areas were predominantly from two classes of herbicides--triazines and chloroacetanilides; insecticides and fungicides were not present in the shallow ground water. In most samples, pesticide degradates greatly exceeded the concentrations of parent pesticide. In samples from Nebraska, the parent pesticide atrazine [6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4-diamine] was about the same concentration as the degradate, but in samples from Maryland and California atrazine concentrations were substantially smaller than its degradate. Simazine [6-chloro-N,N'-diethyl-1,3,5-triazine-2,4-diamine], the second most detected triazine, was detected in ground water from Maryland, California, and Washington. Metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide] rarely was detected without its degradates, and when they were detected in the same sample metolachlor always had smaller concentrations. The Root-Zone Water-Quality Model was used to examine the occurrence and fate of metolachlor at the Maryland site. Simulations accurately predicted which metolachlor degradate would be predominant in the unsaturated zone. In analyses of relations among redox indicators and pesticide variance, apparent age, concentrations of dissolved oxygen, and excess nitrogen gas (from denitrification) were important indicators of the presence and concentration of pesticides in these ground water systems.

Variations in pesticide leaching related to land use, pesticide properties, and unsaturated zone thickness.

Pesticide leaching through variably thick soils beneath agricultural fields in Morgan Creek, Maryland was simulated for water years 1995 to 2004 using LEACHM (Leaching Estimation and Chemistry Model). Fifteen individual models were constructed to simulate five depths and three crop rotations with associated pesticide applications. Unsaturated zone thickness averaged 4.7 m but reached a maximum of 18.7 m. Average annual recharge to ground water decreased from 15.9 to 11.1 cm as the unsaturated zone increased in thickness from 1 to 10 m. These point estimates of recharge are at the lower end of previously published values, which used methods that integrate over larger areas capturing focused recharge in the numerous detention ponds in the watershed. The total amount of applied and leached masses for five parent pesticide compounds and seven metabolites were estimated for the 32-km2 Morgan Creek watershed by associating each hectare to the closest one-dimensional model analog of model depth and crop rotation scenario as determined from land-use surveys. LEACHM parameters were set such that branched, serial, first-order decay of pesticides and metabolites was realistically simulated. Leaching is predicted to be greatest for shallow soils and for persistent compounds with low sorptivity. Based on simulation results, percent parent compounds leached within the watershed can be described by a regression model of the form e(-depth) (a ln t1/2-b ln K OC) where t1/2 is the degradation half-life in aerobic soils, K OC is the organic carbon normalized sorption coefficient, and a and b are fitted coefficients (R2 = 0.86, p value = 7 x 10(-9)).

Chemical loading into surface water along a hydrological, biogeochemical, and land use gradient: a holistic watershed approach.

Identifying the sources and impacts of organic and inorganic contaminants at the watershed scale is a complex challenge because of the multitude of processes occurring in time and space. Investigation of geochemical transformations requires a systematic evaluation of hydrologic, landscape, and anthropogenic factors. The 1160 km2 Boulder Creek Watershed in the Colorado Front Range encompasses a gradient of geology, ecotypes, climate, and urbanization. Streamflow originates primarily as snowmelt and shows substantial annual variation. Water samples were collected along a 70-km transect during spring-runoff and base-flow conditions, and analyzed for major elements, trace elements, bulk organics, organic wastewater contaminants (OWCs), and pesticides. Major-element and trace-element concentrations were low in the headwaters, increased through the urban corridor, and had a step increase downstream from the first major wastewater treatment plant (WWTP). Boron, gadolinium, and lithium were useful inorganic tracers of anthropogenic inputs. Effluent from the WWTP accounted for as much as 75% of the flow in Boulder Creek and was the largest chemical input. Under both hydrological conditions, OWCs and pesticides were detected in Boulder Creek downstream from the WWTP outfall as well as in the headwater region, and loads of anthropogenic-derived contaminants increased as basin population density increased. This report documents a suite of potential endocrine-disrupting chemicals in a reach of stream with native fish populations showing indication of endocrine disruption.