James L. Orlando

Occurrence of boscalid and other selected fungicides in surface water and groundwater in three targeted use areas in the United States.

To provide an assessment of the occurrence of fungicides in water resources, the US Geological Survey used a newly developed analytical method to measure 33 fungicides and an additional 57 current-use pesticides in water samples from streams, ponds, and shallow groundwater in areas of intense fungicide use within three geographic areas across the United States. Sampling sites were selected near or within farms using prophylactic fungicides at rates and types typical of their geographic location. At least one fungicide was detected in 75% of the surface waters and 58% of the groundwater wells sampled. Twelve fungicides were detected including boscalid (72%), azoxystrobin (51%), pyraclostrobin (40%), chlorothalonil (38%) and pyrimethanil (28%). Boscalid, a carboxamide fungicide registered for use in the US in 2003, was detected more frequently than atrazine and metolachlor, two herbicides that are typically the most frequently occurring pesticides in many large-scale water quality studies. Fungicide concentrations ranged from less than the method detection limit to approximately 2000 ngL(-1). Currently, limited toxicological data for non-target species exists and the environmental impacts are largely unknown. The results of this study indicate the importance of including fungicides in pesticide monitoring programs, particularly in areas where crops are grown that require frequent treatments to prevent fungal diseases.

Environmental fate of fungicides and other current-use pesticides in a central California estuary

The current study documents the fate of current-use pesticides in an agriculturally-dominated central California coastal estuary by focusing on the occurrence in water, sediment and tissue of resident aquatic organisms. Three fungicides (azoxystrobin, boscalid, and pyraclostrobin), one herbicide (propyzamide) and two organophosphate insecticides (chlorpyrifos and diazinon) were detected frequently. Dissolved pesticide concentrations in the estuary corresponded to the timing of application while bed sediment pesticide concentrations correlated with the distance from potential sources. Fungicides and insecticides were detected frequently in fish and invertebrates collected near the mouth of the estuary and the contaminant profiles differed from the sediment and water collected. This is the first study to document the occurrence of many current-use pesticides, including fungicides, in tissue. Limited information is available on the uptake, accumulation and effects of current-use pesticides on non-target organisms. Additional data are needed to understand the impacts of pesticides, especially in small agriculturally-dominated estuaries.

Expanded Target-Chemical Analysis Reveals Extensive Mixed-Organic-Contaminant Exposure in U.S. Streams

Surface water from 38 streams nationwide was assessed using 14 target-organic methods (719 compounds). Designed-bioactive anthropogenic contaminants (biocides, pharmaceuticals) comprised 57% of 406 organics detected at least once. The 10 most-frequently detected anthropogenic-organics included eight pesticides (desulfinylfipronil, AMPA, chlorpyrifos, dieldrin, metolachlor, atrazine, CIAT, glyphosate) and two pharmaceuticals (caffeine, metformin) with detection frequencies ranging 66-84% of all sites. Detected contaminant concentrations varied from less than 1 ng L-1 to greater than 10 μg L-1, with 77 and 278 having median detected concentrations greater than 100 ng L-1 and 10 ng L-1, respectively. Cumulative detections and concentrations ranged 4-161 compounds (median 70) and 8.5-102 847 ng L-1, respectively, and correlated significantly with wastewater discharge, watershed development, and toxic release inventory metrics. Log10 concentrations of widely monitored HHCB, triclosan, and carbamazepine explained 71-82% of the variability in the total number of compounds detected (linear regression; p-values: < 0.001-0.012), providing a statistical inference tool for unmonitored contaminants. Due to multiple modes of action, high bioactivity, biorecalcitrance, and direct environment application (pesticides), designed-bioactive organics (median 41 per site at μg L-1 cumulative concentrations) in developed watersheds present aquatic health concerns, given their acknowledged potential for sublethal effects to sensitive species and lifecycle stages at low ng L-1.

Genotoxicity in native fish associated with agricultural runoff events

The primary objective of the present study was to test whether agricultural chemical runoff was associated with in-stream genotoxicity in native fish. Using Sacramento sucker (Catostomus occidentalis), we combined field-caging experiments in an agriculturally dominated watershed with controlled laboratory exposures to field-collected water samples, and we coupled genotoxicity biomarker measurements in fish with bacterial mutagenicity analysis of water samples. We selected DNA strand breakage as a genotoxicity biomarker and Ames Salmonella mutagenicity tests as a second, supporting indicator of genotoxicity. Data from experiments conducted during rainfall runoff events following winter application of pesticides in 2000 and 2001 indicated that DNA strand breaks were significantly elevated in fish exposed to San Joaquin River (CA, USA) water (38.8, 28.4, and 53.6% DNA strand breakage in year 2000 field, year 2000 lab, and year 2001 field exposures, respectively) compared with a nearby reference site (15.4, 8.7, and 12.6% DNA strand breakage in year 2000 field, year 2000 lab, and year 2001 field exposures, respectively). Time-course measurements in field experiments supported a linkage between induction of DNA strand breakage and the timing of agricultural runoff. San Joaquin River water also caused significant reversion mutation in two Ames Salmonella tester strains. Salmonella mutagenicity corroborated in-stream effects, further strengthening a causal relationship between runoff events and genotoxicity. Potentially responsible agents are discussed in the context of timing of runoff events in the field, concordance between laboratory and field exposures, pesticide application patterns in the drainage, and analytical chemistry data.

Stream macroinvertebrate response models for bioassessment metrics: addressing the issue of spatial scale

We developed independent predictive disturbance models for a full regional data set and four individual ecoregions (Full Region vs. Individual Ecoregion models) to evaluate effects of spatial scale on the assessment of human landscape modification, on predicted response of stream biota, and the effect of other possible confounding factors, such as watershed size and elevation, on model performance. We selected macroinvertebrate sampling sites for model development (n = 591) and validation (n = 467) that met strict screening criteria from four proximal ecoregions in the northeastern U.S.: North Central Appalachians, Ridge and Valley, Northeastern Highlands, and Northern Piedmont. Models were developed using boosted regression tree (BRT) techniques for four macroinvertebrate metrics; results were compared among ecoregions and metrics. Comparing within a region but across the four macroinvertebrate metrics, the average richness of tolerant taxa (RichTOL) had the highest R2 for BRT models. Across the four metrics, final BRT models had between four and seven explanatory variables and always included a variable related to urbanization (e.g., population density, percent urban, or percent manmade channels), and either a measure of hydrologic runoff (e.g., minimum April, average December, or maximum monthly runoff) and(or) a natural landscape factor (e.g., riparian slope, precipitation, and elevation), or a measure of riparian disturbance. Contrary to our expectations, Full Region models explained nearly as much variance in the macroinvertebrate data as Individual Ecoregion models, and taking into account watershed size or elevation did not appear to improve model performance. As a result, it may be advantageous for bioassessment programs to develop large regional models as a preliminary assessment of overall disturbance conditions as long as the range in natural landscape variability is not excessive.

Prediction of fish and sediment mercury in streams using landscape variables and historical mining.

Widespread mercury (Hg) contamination of aquatic systems in the Sierra Nevada of California, U.S., is associated with historical use to enhance gold (Au) recovery by amalgamation. In areas affected by historical Au mining operations, including the western slope of the Sierra Nevada and downstream areas in northern California, such as San Francisco Bay and the Sacramento River-San Joaquin River Delta, microbial conversion of Hg to methylmercury (MeHg) leads to bioaccumulation of MeHg in food webs, and increased risks to humans and wildlife. This study focused on developing a predictive model for THg in stream fish tissue based on geospatial data, including land use/land cover data, and the distribution of legacy Au mines. Data on total mercury (THg) and MeHg concentrations in fish tissue and streambed sediment collected during 1980-2012 from stream sites in the Sierra Nevada, California were combined with geospatial data to estimate fish THg concentrations across the landscape. THg concentrations of five fish species (Brown Trout, Rainbow Trout, Sacramento Pikeminnow, Sacramento Sucker, and Smallmouth Bass) within stream sections were predicted using multi-model inference based on Akaike Information Criteria, using geospatial data for mining history and landscape characteristics as well as fish species and length (r(2)=0.61, p<0.001). Including THg concentrations in streambed sediment did not improve the models fit, however including MeHg concentrations in streambed sediment, organic content (loss on ignition), and sediment grain size resulted in an improved fit (r(2)=0.63, p<0.001). These models can be used to estimate THg concentrations in stream fish based on landscape variables in the Sierra Nevada in areas where direct measurements of THg concentration in fish are unavailable.

Recent Rates of Carbon Accumulation in Montane Fens of Yosemite National Park, California, U.S.A.

Abstract Little is known about recent rates of carbon storage in montane peatlands, particularly in the western United States. Here we report on recent rates of carbon accumulation (past 50 to 100 years) in montane groundwater-fed peatlands (fens) of Yosemite National Park in central California, U.S.A. Peat cores were collected at three sites ranging in elevation from 2070 to 2500 m. Core sections were analyzed for bulk density, % organic carbon, and 210Pb activities for dating purposes. Organic carbon densities ranged from 0.026 to 0.065 g C cm-3. Mean vertical accretion rates estimated using 210Pb over the 50-year period from ∼1960 to 2011 and the 100-year period from ∼1910 to 2011 were 0.28 (standard deviation = ±0.09) and 0.18 (±-0.04) cm yr-1, respectively. Mean carbon accumulation rates over the 50- and 100-year periods were 95.4 (±25.4) and 74.7 (±17.2) g C m-2 yr-1, respectively. Such rates are similar to recent rates of carbon accumulation in rich fens in western Canada, but more studies are needed to definitively establish both the similarities and differences in peat formation between boreal and temperate montane fens.

Dissolved pesticide concentrations in the lower Sacramento River and its source waters, California, 2016

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Understanding pesticides in California's Delta

• 400 pesticides applied for total of 10 million pounds each year. 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.