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For pesticide registrations in the USA under the Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA), as implemented by the United States Environmental Protection Agency, drinking water risk assessments for groundwater sources are based on standard scenario modeling concentration estimates. The conceptual model for the drinking water protection goals is defined in terms of (1) a rural well in or near a relatively high pesticide use area, a shallow well (4-10 m); (2) long-term, single-station weather data; (3) soils characterized as highly leachable; (4) upper-end or surrogate, worst-case environmental fate parameters; and (5) maximum, annual use rates repeated every year. To date, monitoring data have not been quantitatively incorporated into FIFRA drinking water risk assessment; even though considerable, US national-scale temporal and spatial data for some chemistries exists. Investigations into drinking water monitoring data development have historically focused on single-source efforts that may not represent wide geographies and/or time periods, whereas Safe Drinking Water Act groundwater monitoring data are focused on a community-level scale rather than an individual, shallow, rural well. In the current case study, US national-scale, rural well data for the herbicide atrazine was collected, quality controlled, and combined into a single database from mixed sources (termed the atrazine rural well database) to (1) characterize differences between exposure estimates from standard EPA modeling approaches for specific characterization, (2) evaluate monitoring data toward direct use in US drinking water risk assessments to compliment or supersede standard modeling approaches to define risk, and (3) evaluate monitoring trends a function of time relative to label changes implemented as part of the registration review process. Of the 75,665 drinking water samples collected from groundwater, atrazine was only detected in 3185, a 4% detection rate., (© 2022. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

Given the limited data available for estuarine/marine fish species and potential risk of being exposed to the herbicide atrazine, additional toxicity data regarding sensitive life-stages are needed. As such, this work sought to characterize: 1) the acute larval toxicity, and 2) early life-stage toxicity of technical atrazine in the model marine species sheepshead minnow (Cyprinodon variegatus). Atrazine was observed to be slightly to moderately toxic towards C. variegatus under acute conditions (as per U.S. EPA 2017 criteria). After 96 h exposure, mortality rates of 5%, 15%, 35%, and 90% were observed among fish exposed to atrazine at 4.6, 7.6, 13, and 22 mg a.i./L, respectively. Sub-lethal effects were observed among surviving fish exposed to > 3.2 mg a.i/L. The 96 h LC50 was 13 mg a.i./L and the NOEC was 3.2 mg a.i./L. In the 33 d early-life stage test, mean embryo survival rates in 0.15, 0.30, 0.57, 1.1, and 2.2 mg a.i./L treatments ranged from 71% to 79% and were not different from survival in the control (78%). Following 28 d post-hatch exposure (Day 33), mean larval survival ranged from 98% to 100% in all treatments and the control. Larval length and wet weight were the most sensitive indicators of the toxicity of atrazine to early life-stage sheepshead minnow. The NOEC for growth was 1.1 mg a.i./L and the LOEC was 2.2 mg a.i./L. Based on these, the MATC for atrazine to sheepshead minnow embryos and larvae was estimated to be 1.6 mg a.i./L. These results were consistent with previous investigations in sheepshead minnow and other marine fish species. Based on the results, atrazine would not be expected to pose unacceptable risks for sheepshead minnow early life-stages at environmentally relevant concentrations., (Copyright © 2021 The Authors. Published by Elsevier Inc. All rights reserved.)

Short-term reproduction assays were conducted with fathead minnow (Pimephales promelas) and Japanese medaka (Oryzias latipes) to evaluate responses from atrazine exposure at environmentally relevant concentrations and above. Breeding groups of fish with multiple males and females were exposed to atrazine under flow-through conditions. Fathead minnows were exposed to mean measured concentrations of 1.0, 10, 26, 52, and 105 μg atrazine/L for 28 days. Medaka were exposed to mean measured concentrations of 9.4, 48, 74, 97, and 244 μg atrazine/L for 28 or 29 days. Fish were evaluated for survival, fecundity, fertility, total length, wet weight, secondary sex characteristics, gonadosomatic index (GSI) (P. promelas only), plasma or hepatic vitellogenin (VTG), and histopathology of gonads. General observations of health and behaviour were also conducted. There were no statistically significant effects (i.e., p < 0.05) of atrazine on survival, size, reproduction, behaviour, GSI, VTG, or secondary sex characteristics in either species at any exposure level. In fathead minnows, there were no histopathological findings associated with atrazine exposure in male fish, but there was an increased proportion of Stage 4.0 ovaries accompanied by an increase in proportion of Grade 3 post-ovulatory follicles in females of the 105 μg/L treatment group. Without a concomitant increase in oocyte atresia, neither of these findings are considered adverse for the health of the fish. In medaka, there were no significant effects of atrazine exposure on histopathology in either sex. These data support current weight-of-evidence assessments that atrazine does not cause direct adverse effects on fish reproduction at environmentally realistic concentrations., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The acute toxicity of herbicides to algae is commonly assessed under conditions (e.g., light intensity, water temperature, concentration of nutrients, pH) prescribed by standard test protocols. However, the observed toxicity may vary with changes in one or more of these parameters. This study examined variation in toxicity of the herbicide atrazine to a representative green algal species Raphidocelis subcapitata (formerly Pseudokirchneriella subcapitata) with changes in light intensity, water temperature, concentrations of nutrients or combinations of these three parameters. Conditions were chosen that could be representative of the intensive corn growing Midwestern region of the United States of America where atrazine is used extensively. Varying light intensity (4-58µmol/m(2)s) resulted in no observable trend in 96-h EC50 values for growth rate. EC50 values for PSII yield generally increased with decreasing light intensity but not significantly in all cases. The 96-h EC50 values for growth rate decreased with decreases in temperature (20-5°C) from standard conditions (25°C), but EC50 values for PSII yield at lower temperatures were not significantly different from standard conditions. Finally, there was no clear trend in 96-h EC50 values for both endpoints with increases in nitrogen (4.1-20mg/L) and phosphorus (0.24-1.2mg/L). The 96-h EC50 values for both endpoints under combinations of conditions mimicking aquatic systems in the Midwestern U.S. were not significantly different from EC50 values generated under standard test conditions. This combination of decreased light intensity and temperature and increased nutrients relative to standard conditions does not appear to significantly affect the observed toxicity of atrazine to R. subcapitata. For atrazine specifically, and for perhaps other herbicides, this means current laboratory protocols are useful for extrapolating to effects on algae under realistic environmental conditions., (Copyright © 2016 Elsevier Inc. All rights reserved.)

Embryonic growth of the yellow-spotted salamander (Ambystoma maculatum) is enhanced by the presence of the green alga Oophila amblystomatis, in the egg capsule. To further assess potential impacts of herbicides on this relationship, A. maculatum egg masses were exposed to atrazine (0-338 μg/L) until hatching (up to 66 days). Exposure to atrazine reduced PSII yield of the symbiotic algae in a concentration-dependent manner, but did not significantly affect visible algal growth or any metrics associated with salamander development. Algal cells were also cultured in the laboratory for toxicity testing. In the 96-h growth inhibition test (0-680 μg/L), ECx values were generally greater than those reported for standard algal test species. Complete recovery of growth rates occurred within 96-h of transferring cells to untreated media. Overall, development of A. maculatum embryos was not affected by exposure to atrazine at concentrations and durations exceeding those found in the environment., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Lotic systems in agriculturally intensive watersheds can experience short-term pulsed exposures of pesticides as a result of runoff associated with rainfall events following field applications. Of special interest are herbicides that could potentially impair communities of primary producers, such as those associated with periphyton. Therefore, this study examined agroecosystem-derived lotic periphyton to assess (1) variation in community sensitivity to, and ability to recover from, acute (48h) exposure to the photosystem II (PSII)-inhibiting herbicide atrazine across sites and time, and (2) attempt to determine the variables (e.g., community structure, hydrology, water quality measures) that were predictive for observed differences in sensitivity and recovery. Periphyton were sampled from six streams in the Midwestern U.S. on four different dates in 2012 (April to August). Field-derived periphyton were exposed in the laboratory to concentrations of atrazine ranging from 10 to 320μg/L for 48h, followed by untreated media for evaluation of recovery for 48h. Effective quantum yield of PSII was measured after 24h and 48h exposure and 24h and 48h after replacement of media. Inhibition of PSII EC50 values ranged from 53 to >320µg/L. The majority of periphyton samples (16 out of 22) exposed to atrazine up to 320µg/L recovered completely by 48h after replacement of media. Percent inhibition of effective quantum yield of PSII in periphyton (6 of 22 samples) exposed to 320µg/L atrazine that were significantly lower than controls after 48h ranged from 2% to 24%. No distinct spatial or temporal trends in sensitivity and recovery potential were observed over the course of the study. Conditional inference forest analysis and variation partitioning were used to investigate potential associations between periphyton sensitivity to and ability to recover from exposure to atrazine. Although certain environmental variables (i.e., proximity of high flow/velocity events and dissolved solutes) were significantly associated with sensitivity to atrazine, recovery was not significantly associated with any variables, which is predicted by the rapid reversible binding at PSII. Consistent and rapid recovery of effective quantum yield of PSII across sites and sampling dates indicates that acute exposure to atrazine is unlikely to adversely affect function of these communities in their current state in intensive agroecosystems., (Copyright © 2015 Elsevier Inc. All rights reserved.)

Light intensity can have a profound influence on the degree of phytotoxicity experienced by plants exposed to photosystem II (PSII) inhibiting herbicides. This relationship was evaluated in the submerged aquatic macrophyte Elodea canadensis exposed to three different concentrations of atrazine (510, 1000 and 2000 μg a.i./L) plus an untreated control at three different light intensities (0, 500 and 6000 lx) under static-renewal conditions for 14 days. Under 500 lx light intensity, control plants demonstrated a rapid increase in shoot length but minimal increase in dry shoot weight, suggesting limited photosynthesis. Based on shoot-length and biomass, growth was not affected by any atrazine exposure relative to controls under dark conditions (0 lx). Under low-light conditions at 500 lx, exposures to 510, 1000 and 2000 μg a.i./L atrazine significantly decreased net shoot lengths by 34%, 38% and 35%, respectively, relative to corresponding (500 lx) controls. However, atrazine exposure under this light condition did not significantly decrease biomass (dry shoot weight). Compared to 6000 lx, only approximately 8% of photosynthetically active radiation (PAR) was measured under 500 lx intensity, indicating that minimal PAR was available for photosynthesis. Under optimal light conditions (6000 lx), net shoot lengths significantly decreased in the treated atrazine groups by 48%, 51% and 68%, and net dry shoot weights (biomass) were significantly decreased by 79%, 81% and 91%, respectively, relative to corresponding (6000 lx) controls. These data show that under low light conditions, atrazine-induced effects on dry shoot weight (biomass) are dependent on available PAR and active photosynthesis., (Copyright © 2011 Elsevier Inc. All rights reserved.)

The toxicity and hazard of a mixture of selective serotonin reuptake inhibitors (SSRIs), including fluoxetine, fluvoxamine, and sertraline, to zooplankton communities were evaluated using 120,00l outdoor microcosms. Acute (day 4) and chronic (day 35) zooplankton abundance and species richness were assessed for Rotifera, Cladocera, and Copepoda. For acute SSRI exposures, rotifers were the most sensitive zooplankton taxa to changes in abundance (predicted no effect concentration (PNEC)=19 nM); however, no effects in zooplankton species richness were observed for this treatment period. A decrease in Copepoda abundance and species richness was observed following chronic exposures of SSRIs (PNEC=9.1 nM). A 99th-centile predicted environmental concentration (PEC=0.51 nM) yielded HQs at least two orders of magnitude below 1. Therefore, mixtures of SSRIs do not appear to present a hazard to zooplankton communities at environmentally relevant concentrations.

The toxicity of SSRIs to algae/phytoplankton was investigated using the US EPA ECOSAR, acute single-species growth inhibition assays, species sensitivity distributions (SSDs), and an outdoor microcosm mixture experiment. Worst-case ECOSAR estimates of SSRI toxicity to algae ranged from 0.73 to 13.08 mg/L. Sertraline was the most toxic SSRI tested in single-species growth inhibition assays followed by fluoxetine and fluvoxamine with worst-case 96-h IC10s of 4.6, 31.3, and 1662 microg/L, respectively. HC5s of 2.4, 3.6, and 1100 microg/L were estimated, respectively, for sertraline, fluoxetine, and fluvoxamine toxicity to algae-using SSDs. Microcosm phytoplankton structural endpoints were more sensitive than functional endpoints in the short term. However, in the long term, structural endpoints were resilient and functional endpoints remained impacted even after a period of recovery. The worst-case EC10 determined from the outdoor microcosm mixture toxicity to phytoplankton communities was 15.2 nM. Although SSRIs are toxic to algae, hazard quotients using worst-case PECs represent a margin of safety of 20 to phytoplankton. Although SSRIs do not appear to pose a hazard to primary production, this assessment is not protective of higher aquatic organisms and further research into the chronic toxicity to low levels of SSRIs to higher-level aquatic species is recommended.

The practicality of a probabilistic ecological hazard assessment (PEHA) methodology using intraspecies endpoint sensitivity distributions (IESDs) and chemical toxicity distributions (CTDs) was evaluated on data sets of pharmaceutical toxicity to aquatic macrophytes. A PEHA does not use an exposure distribution but rather uses a point estimate, which is useful for applications with sufficient effects data but lacking in comprehensive exposure data or when a criterion concentration is desired. The probability of finding an effect measure or potency value below a threshold can be calculated from the effects distribution. PEHA analyses using CTDs for both EC(10) and EC(25)Lemna gibba toxicity values indicated a <1% probability of encountering an antibiotic with toxicity below 1 microg/L. IESDs for microcosm mixture studies with eight pharmaceuticals (8PM) and four tetracyclines showed that the probability was nearly 20% for Myriophyllum sibiricum and 13% for L. gibba (8PM data). Hazard quotients calculated from the 1% and 5% distribution thresholds indicated potential risk only in certain cases.

The impact of a mixture of oxytetracycline, chlortetracycline, tetracycline and doxycycline on Myriophyllum sibiricum and Lemna gibba was investigated using fifteen 12,000-L microcosms (k=5, n=3). Significant concentration-response relationships were only found for M. sibiricum, where dry mass was 69, 47, 30, and 7% of controls at respective treatment concentrations of 0.080, 0.218, 0.668, and 2.289 micromol/L. Somatic endpoints were strongly and negatively correlated with percent light transmission, except plant length, which was positively correlated. Treated microcosms experienced a reduction in the percent of surface irradiance penetrating the water column as high as 99.8% at a depth of 70 cm, relative to controls. Position relative to the water column was likely responsible for the differential effects observed between floating (L. gibba) and submerged (M. sibiricum) species of macrophytes. A hazard quotient assessment of the lowest EC10 value indicated significant risk, exceeding the critical HQ value, but not the lowest EC25 value.

A mixture of four tetracyclines; oxytetracycline (OTC), chlortetracycline (CTC), tetracycline (TC), and doxycycline (DC) was applied in fifteen 12000l outdoor microcosms at four treatment levels plus controls each with three replicates (n = 3). The dissipation times of parent compounds were monitored and half-lives (DT50) of 1-4 days, depending on treatment level were recorded. This is in accordance with half-lives from previous findings in bench-top experiments. Parent compound DT50, were determined using HPLC-UV. Furthermore, the samples were analyzed for ten different tetracycline products using LC/MS/MS. Two products were found for chlortetracycline; 4-epi-anh-chlortetracyline and the iso-chlortetracycline. Iso-forms were only found for CTC and only at the highest treatment (300 microg l(-1)). The half-lives, trajectories, and relative amounts of the products were analogous for all four tetracyclines. DT50 for products were less than 1.2 days. Formation of 4-epi-anh-tetracyclines, occurred at neutral to weak alkaline conditions.

Tylosin is a macrolide antibiotic commonly used for therapeutic treatment and prophylaxis in livestock. As part of a larger ecotoxicological study, the potential phytotoxic effects of tylosin on the rooted macrophyte Myriophyllum spicatum and the floating macrophyte Lemna gibba were assessed under semi-field conditions using 15 12 000-L microcosms. Concentrations of 0, 10, 30, 300 microg/L (n = 3), and 600, 1000, and 3000 microg/L (n = 1) were evaluated as part of separate ANOVA and regression analyses over an exposure period of 35 days. Fate of tylosin was monitored over time in the highest three treatments, where dissipation followed pseudo-first order kinetics with associated half-lives ranging from 9 to 10 days. For both M. spicatum and L. gibba, tylosin was found to cause no biologically significant changes to any endpoint assessed compared to controls at a Type I error rate of 0.1. However, subsequent power analyses revealed that there was generally insufficient power to declare that there were no significant differences at a Type II error rate of 0.2. Conclusions concerning biologically significant impacts were therefore further assessed based on other statistical criteria including comparisons of percent differences between replicated treatments and controls, minimum significant and minimum detectable differences, and coefficients of variation. Based on these criteria, at an ecological effect size of >20% change, tylosin was concluded to elicit no biologically or ecologically significant toxicity to M. spicatum or L. gibba. A hazard quotient assessment indicated that tylosin poses little risk to either species of macrophyte, with an HQ value calculated to be nearly three orders of magnitude below 1 (0.002).

Pharmaceuticals have been detected in surface waters of the US and Europe, originating largely from two sources, sewage effluent and agricultural runoff. These compounds often occur as mixtures leading to potential combined effects. In order to investigate the effects of a realistic pharmaceutical mixture on an ecosystem, a study utilizing 15 of 12,000 L aquatic microcosms treated with eight common pharmaceuticals (atorvastatin, acetaminophen, caffeine, sulfamethoxazole, carbamazepine, levofloxacin, sertraline, and trimethoprim) at total (summed) molar concentrations of 0, 0.044, 0.608, 2.664, and 24.538 micromol/L (n = 3) was conducted. Phytotoxicity was assessed on a variety of somatic and pigment endpoints in rooted (Myriophyllum sibiricum) and floating (Lemna gibba) macrophytes over a 35-day period. EC10, EC25 and EC50 values were calculated for each endpoint exhibiting a concentration-dependent response. Generally, M. sibiricum and L. gibba displayed similar sensitivity to the pharmaceutical mixture, with phytotoxic injury evident in both species, which was concentration dependent. Through single compound 7-day daily static renewal toxicity tests with L. gibba, the sulfonamide antibiotic sulfamethoxazole, the fluoroquinolone antibiotic levofloxacin and the blood lipid regulator atorvastatin were found to be the only compounds to elicit phytotoxic effects in the concentration range utilized (0-1000 microg/L). Atorvastatin concentration was highly correlated to decreased pigment content in L. gibba, likely inhibiting the known target enzyme HMGR, the rate-limiting enzyme in isoprenoid biosynthesis. Hazard quotients were calculated for both microcosm and laboratory studies; the highest HQ values were 0.235 (L. gibba) and 0.051 (L. gibba), which are below the threshold value of 1 for chronic risks. The microcosm data suggest that at an ecological effect size of >20%, biologically significant risks are low for L. gibba and M. sibiricum exposed to similar mixtures of pharmaceutical compounds. For M. sibiricum and L. gibba, respective minimum differences of 5 and 1%, were detectable, however, these effect sizes are not considered ecologically significant.