Acute toxicity of Headline® fungicide to Blanchard's cricket frogs (Acris blanchardi).

Previous laboratory studies have suggested that pyraclostrobin-containing fungicide formulations are toxic to amphibians at environmentally relevant concentrations. However, it is unknown if all pyraclostrobin formulations have similar toxicity and if toxicity occurs in different amphibian species. We investigated the acute toxicity of two formulations, Headline(®) fungicide and Headline AMP(®) fungicide, to Blanchard's cricket frogs (Acris blanchardi) based on a direct overspray scenario. In addition, we examined body residues of fungicide active ingredients in A. blanchardi following direct exposure to Headline AMP fungicide. Headline fungicide and Headline AMP fungicide had similar toxicity to A. blanchardi with calculated median lethal doses of 2.1 and 1.7 µg pyraclostrobin/cm(2), respectively, which are similar to the suggested maximum label rate in North American corn (2.2 and 1.52 µg pyraclostrobin/cm(2), respectively). Tissue concentrations of pyraclostrobin were lower than predicted based on full uptake of a direct dose, and did not drop during the first 24 h after exposure. Headline fungicides at corn application rates are acutely toxic to cricket frogs, but acute toxicity in the field will depend on worst-case exposure.

Field studies of pollutant removal from nursery and greenhouse runoff by constructed wetlands.

Plant nursery runoff commonly contains pesticides and nutrients that often threaten aquatic ecosystems. Constructed wetlands could be a tool to remove pesticides and nutrients from nursery runoff but have not been extensively studied in this setting. Two field-scale constructed wetlands (one subsurface-flow constructed wetland [SFCW] and one free-surface constructed wetland [FSCW]) were implemented and monitored for water quality improvement. The SFCW demonstrated significant mass reduction of 78% or greater for nitrate, orthophosphate, total nitrogen, total phosphorus, and total suspended solids. The SFCW also demonstrated significant mass reduction of 79% or greater for 10 of the 12 pesticide compounds detected in over half of the collected samples. The FSCW demonstrated significant mass reduction of 46% or greater for all nonpesticide analytes except total nitrogen. Loading rate and actual storage volume compared with inflow volume likely affected performance. Reduced size and increased loading rate of the FSCW likely reduced its ability to effectively reduce pesticides. Results from this study indicate that constructed wetlands are likely an effective tool for nursery runoff management. When designing and implementing constructed wetlands, it is important for practitioners to consider the tradeoff between system size (additional cost and land otherwise dedicated to production) and performance.

Development of Helisoma trivolvis pond snails as biological samplers for biomonitoring of current-use pesticides.

Nontarget aquatic organisms residing in wetlands are commonly exposed to current-use pesticides through spray drift and runoff. However, it is frequently challenging to measure exposure because of rapid dissipation of pesticides from water and reduced bioavailability. The authors' hypothesis is that freshwater snails can serve as bioindicators of pesticide exposure based on their capacity to passively accumulate tissue residues. Helisoma trivolvis snails were evaluated as biomonitors of pesticide exposure using a fungicide formulation that contains pyraclostrobin and metconazole and is frequently applied to crops surrounding depressional wetlands. Exposure-response studies indicate that H. trivolvis are tolerant of pyraclostrobin and metconazole at concentrations >10 times those lethal to many aquatic species, with a median lethal concentration based on pyraclostrobin of 441 µg/L (95% confidence interval of 359-555 µg/L). Bioconcentration factors ranged from 137 mL/g to 211 mL/g and from 39 mL/g to 59 mL/g for pyraclostrobin and metconazole, respectively. Elimination studies suggested one-compartmental elimination and snail tissue half-lives (t50 ) of approximately 15 h and 5 h for pyraclostrobin and metconazole, respectively. Modeling derived toxicokinetic parameters in the context of an environmentally relevant pulsed exposure suggests that residues can be measured in snails long after water concentrations fall below detection limits. With high fungicide tolerance, rapid accumulation, and slow elimination, H. trivolvis may be viable for biomonitoring of pyraclostrobin and should be investigated for other pesticides. Environ Toxicol Chem 2016;35:2320-2329. © 2016 SETAC.

Calibration of nylon organic chemical integrative samplers and sentinel samplers for quantitative measurement of pulsed aquatic exposures.

Environmental exposures often occur through short, pulsed events; therefore, the ability to accurately measure these toxicologically-relevant concentrations is important. Three different integrative passive sampler configurations were evaluated under different flow and pulsed exposure conditions for the measurement of current-use pesticides (n=19), polyaromatic hydrocarbons (n=10), and personal care products (n=5) spanning a broad range of hydrophobicities (log Kow 1.5-7.6). Two modified POCIS-style samplers were investigated using macroporous nylon mesh membranes (35µm pores) and two different sorbent materials (i.e. Oasis HLB and Dowex Optipore L-493). A recently developed design, the Sentinel Sampler (ABS Materials), utilizing Osorb media enclosed within stainless steel mesh (145µm pores), was also investigated. Relatively high sampling rates (Rs) were achieved for all sampler configurations during the short eight-day exposure (4300-27mL/d). Under flow conditions, median Rs were approximately 5-10 times higher for POCIS-style samplers and 27 times higher for Sentinel Samplers, as compared to static conditions. The ability of samplers to rapidly measure hydrophobic contaminants may be a trade off with increased flow dependence. Analyte accumulation was integrative under pulsed and continuous exposures for POCIS-style samplers with mean difference between treatments of 11% and 33%; however, accumulation into Sentinel Samplers was more variable. Collectively, results show that reducing membrane limitations allows for rapid, integrative accumulation of a broad range of analytes even under pulsed exposures. As such, these sampler designs may be suitable for monitoring environmental substances that have short aquatic half-lives.

Characterization of performance reference compound kinetics and analyte sampling rate corrections under three flow regimes using nylon organic chemical integrative samplers.

Performance reference compounds (PRCs) can be spiked into passive samplers prior to deployment. If the dissipation kinetics of PRCs from the sampler corresponds to analyte accumulation kinetics, then PRCs can be used to estimate in-situ sampling rates, which may vary depending on environmental conditions. Under controlled laboratory conditions, the effectiveness of PRC corrections on prediction accuracy of water concentrations were evaluated using nylon organic chemical integrative samplers (NOCIS). Results from PRC calibrations suggest that PRC elimination occurs faster under higher flow conditions; however, minimal differences were observed for PRC elimination between fast flow (9.3cm/s) and slow flow (5.0cm/s) conditions. Moreover, minimal differences were observed for PRC elimination from Dowex Optipore L-493; therefore, PRC corrections did not improve results for NOCIS configurations containing Dowex Optipore L-493. Regardless, results suggest that PRC corrections were beneficial for NOCIS configurations containing Oasis HLB; however, due to differences in flow dependencies of analyte sampling rates and PRC elimination rates across the investigated flow regimes, the use of multiple PRC corrections was necessary. As such, a "Best-Fit PRC" approach was utilized for Oasis HLB corrections using caffeine-(13)C3, DIA-d5, or no correction based on the relative flow dependencies of analytes and these PRCs. Although PRC corrections reduced the variability when in-situ conditions differed from laboratory calibrations (e.g. static versus moderate flow), applying PRC corrections under similar flow conditions increases variability in estimated values.

Comparisons of discrete and integrative sampling accuracy in estimating pulsed aquatic exposures.

Most current-use pesticides have short half-lives in the water column and thus the most relevant exposure scenarios for many aquatic organisms are pulsed exposures. Quantifying exposure using discrete water samples may not be accurate as few studies are able to sample frequently enough to accurately determine time-weighted average (TWA) concentrations of short aquatic exposures. Integrative sampling methods that continuously sample freely dissolved contaminants over time intervals (such as integrative passive samplers) have been demonstrated to be a promising measurement technique. We conducted several modeling scenarios to test the assumption that integrative methods may require many less samples for accurate estimation of peak 96-h TWA concentrations. We compared the accuracies of discrete point samples and integrative samples while varying sampling frequencies and a range of contaminant water half-lives (t50 = 0.5, 2, and 8 d). Differences the predictive accuracy of discrete point samples and integrative samples were greatest at low sampling frequencies. For example, when the half-life was 0.5 d, discrete point samples required 7 sampling events to ensure median values > 50% and no sampling events reporting highly inaccurate results (defined as < 10% of the true 96-h TWA). Across all water half-lives investigated, integrative sampling only required two samples to prevent highly inaccurate results and measurements resulting in median values > 50% of the true concentration. Regardless, the need for integrative sampling diminished as water half-life increased. For an 8-d water half-life, two discrete samples produced accurate estimates and median values greater than those obtained for two integrative samples. Overall, integrative methods are the more accurate method for monitoring contaminants with short water half-lives due to reduced frequency of extreme values, especially with uncertainties around the timing of pulsed events. However, the acceptability of discrete sampling methods for providing accurate concentration measurements increases with increasing aquatic half-lives.

Simultaneous extraction and cleanup of high-lipid organs from white sturgeon (Acipenser transmontanus) for multiple legacy and emerging organic contaminants using QuEChERS sample preparation.

The objective of this research was to utilize the QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) method to extract a broad range of persistent organic pollutants from sturgeon organs (liver and gonad) as indicators of exposure. The analyte list was prioritized to include carcinogenic polyaromatic hydrocarbons (PAHs), the most commonly occurring polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs), persistent bioaccumulative and toxic chemicals (PBTs), and emergent contaminants of concern (ECCs) as indicators of human sewage exposure. White sturgeon (Acipenser transmontanus) were selected for this study to support a larger ecotoxicological study to monitor contaminants as an assessment of fish health. Organ tissues contained high lipid content with percentages of 15% and 34% for liver and gonad, respectively. Overall recoveries from fortified sturgeon tissues were high, 71-98% for PAHs, 60-107% for PBDEs and PCBs, 86-107% for PBT chemicals, and 88-107% for ECCs with the exception of octinoxate (28%) from liver tissues. Analyte recovery trends decreased as analyte lipophilicity and molecular weight increased. These recoveries demonstrate that extraction using QuEChERS can be used for screening of the most common bioaccumulating organic compounds in high lipid fish tissue using a single extraction and analysis.

Land use effects on pesticides in sediments of prairie pothole wetlands in North and South Dakota.

Prairie potholes are the dominant wetland type in the intensively cultivated northern Great Plains of North America, and thus have the potential to receive pesticide runoff and drift. We examined the presence of pesticides in sediments of 151 wetlands split among the three dominant land use types, Conservation Reserve Program (CRP), cropland, and native prairie, in North and South Dakota in 2011. Herbicides (glyphosate and atrazine) and fungicides were detected regularly, with no insecticide detections. Glyphosate was the most detected pesticide, occurring in 61% of all wetlands, with atrazine in only 8% of wetlands. Pyraclostrobin was one of five fungicides detected, but the only one of significance, being detected in 31% of wetlands. Glyphosate was the only pesticide that differed by land use, with concentrations in cropland over four-times that in either native prairie or CRP, which were equal in concentration and frequency of detection. Despite examining several landscape variables, such as wetland proximity to specific crop types, watershed size, and others, land use was the best variable explaining pesticide concentrations in potholes. CRP ameliorated glyphosate in wetlands at concentrations comparable to native prairie and thereby provides another ecosystem service from this expansive program.

Acute toxicity of pyraclostrobin and trifloxystrobin to Hyalella azteca.

Fungicide application rates on row crop agriculture have increased across the United States, and subsequently, contamination of adjacent wetlands can occur through spray drift or field runoff. To investigate fungicide toxicity, Hyalella azteca amphipods were exposed to 2 fungicide formulations, Headline and Stratego, and their active strobilurin ingredients, pyraclostrobin and trifloxystrobin. Water-only exposures resulted in similar median lethal concentration (LC50; 20-25 µg/L) values for formulations and strobilurin ingredients, suggesting that toxicity is due to strobilurin ingredients. These values were below concentrations that could occur following spray drift over embedded cropland wetlands. When fungicides were added to overlying water of sediment-water microcosms, toxicity was reduced by 500% for Headline and 160% for Stratego, compared with water-only exposures, based on the total amount of fungicide added to the systems. In addition, when fungicides were added to sediment prior to the addition of water, the reduction in toxicity was even greater, with no toxicity occurring at environmentally relevant levels. Differences in toxicity among exposure groups were explained by dissipation from water as toxicity values based on measured water concentrations were within 20% between all systems. The present study reinforces previous studies that Headline and Stratego are toxic to nontarget aquatic organisms. However, the presence of sediment is likely to ameliorate some toxicity of fungicide formulations, especially if spraying occurs prior to wetland inundation.