Characterizing the exposure of streams in southern Ontario to agricultural pesticides.

Aquatic communities can be exposed to pesticides transported from land. Characterizing this exposure is key to predicting potential toxic effects. In this study, samples of streamwater from 21 sites were used to characterize pesticide exposure to aquatic communities. Sites were in agricultural areas of southwestern Ontario, Canada and were sampled monthly from 2012 to 2019 from April to November. Samples were analyzed for a suite of hundreds of pesticides and pesticide degradation products and other water quality indicators (e.g., nutrients). Frequently detected pesticides included herbicides (2,4-D; bentazon; MCPP; metolachlor) and neonicotinoid insecticides (NNIs) (clothianidin; thiamethoxam) which were detected in >50% of samples collected between 2015 and 2019. Non-metric multidimensional scaling (NMDS) was used to explore connections between pesticide concentrations and upstream land use and crop type. Detectable concentrations of the NNI clothianidin and many herbicides were related to corn, soybean, and grain/cereal crops while concentrations of the NNI imidacloprid, insecticide flonicamid, and fungicide boscalid were related to greenhouse/nursery land use. Potential toxicity to aquatic communities was assessed by comparing pesticide concentrations to Pesticide Toxicity Index (PTI) values. Few samples exceeded levels where acute (1% of samples) or chronic toxicity (10.5%) would be expected. The diamide insecticide chlorantraniliprole was detected in several streamwater samples at levels that may cause toxicity to aquatic invertebrates, highlighting the need for continued toxicity research into this pesticide class. The number of pesticides detected was positively correlated with nutrient and total suspended solids levels, underscoring the multiple stressors aquatic communities are exposed to in these habitats.

Comparative evaluation of four biosolids formulations on the effects of triclosan on plant-arbuscular mycorrhizal fungal interactions in three crop species.

Triclosan (TCS) is an antimicrobial ingredient found in personal care products that include soaps, shampoos, and other sanitation goods. TCS is moderately hydrophobic and has been shown to be resistant to wastewater treatment and thus accumulates in biosolids. Biosolids are commonly applied to agricultural land but little is known about the risk that TCS in biosolids poses to soil fungal communities following land application. The purpose of this study was to characterize the effects of TCS on the symbiotic colonization of roots in three field crops (soybean, corn, and spring wheat) by arbuscular mycorrhizal fungi (AMF) in soils amended with four different types of biosolids (liquid, dewatered, composted, alkaline and hydrolyzed). Crops were grown to maturity in pot-exposure systems under controlled temperature settings. Biosolids treatments were spiked with concentrations of TCS typically found in amended fields. Analysis of AMF colonization by hyphae, and the production of arbuscules and vesicles indicated no significant TCS concentration-dependent effects in the three plant species for any of the biosolids formulations. The data indicate that TCS present in municipal biosolids applied to agricultural lands likely poses minimal risks to AMF or its establishment of a symbiotic relationship in the three species tested.

Evaluating the effects of triclosan on 3 field crops grown in 4 formulations of biosolids.

A growing body of evidence suggests that amending soil with biosolids can be an integral component of sustainable agriculture. Despite strong evidence supporting its beneficial use in agriculture, there are concerns that chemicals, such as pharmaceuticals and personal care products, could present a risk to terrestrial ecosystems and human health. Triclosan is one of the most commonly detected compounds in biosolids. To date, laboratory studies indicate that triclosan likely poses a de minimis risk to field crops; however, these studies were either conducted under unrealistic exposure conditions or only assessed 1 or 2 formulations of biosolids. The purpose of the present study was to characterize the effects of triclosan on field crops in soils amended with 4 different formulations of biosolids (liquid, dewatered, compost, and alkaline-hydrolyzed), containing both background and spiked triclosan concentrations, following best management practices used in the province of Ontario. Three crop species (corn, soybean, and spring wheat) were evaluated using several plant growth endpoints (e.g., root wet mass, shoot length, shoot wet/dry mass) in 70-d to 90-d potted soil tests. The results indicated no adverse impact of triclosan on any crop-biosolids combination. Conversely, amending soil with biosolids either enhanced or had no negative effect, on the growth of plants. Results of the present study suggest little risk of triclosan to crops in agricultural fields amended with biosolids. Environ Toxicol Chem 2017;36:1896-1908. © 2016 SETAC.

Aquatic hazard assessment of MON 0818, a commercial mixture of alkylamine ethoxylates commonly used in glyphosate-containing herbicide formulations. Part 2: Roles of sediment, temperature, and capacity for recovery following a pulsed exposure.

A series of toxicity tests with MON 0818, a commercial surfactant mixture of polyoxyethylene tallow amines, were performed: 1) in the presence of sediment for benthic invertebrates and fish: 2) to examine the recovery capacity of Daphnia magna and 4 primary producers after a pulsed (24-h) exposure; and 3) to examine the potential effect of increased water temperature on toxicity of MON 0818 to 2 cold-water fishes. In the presence of sediment, no acute (24-h) mortality was observed for 3 of the 5 species up to 10 mg L-1 . The median effective concentrations for the other 2 species were significantly greater than for water only tests. The EC50 at 15 °C for Salvelinus alpinus was statistically lower than that at 10 °C. Latent effects of a 24-h exposure (1 mg L-1 ) were observed for Rhabdocelis subcapitata and Chlorella vulgaris, as indicated by delayed growth during recovery phase; however, both cultures were able to recover, as indicated by a lack of changes in maximum absolute growth rates. No significant effects of a 24-h exposure to MON 0818 were observed for Oophila sp. (1.5 mg L-1 ) or Lemna minor (100 mg L-1 ). Latent mortality after a 24-h exposure to 5 mg L-1 was observed during the recovery phase for D. magna; however, reproduction endpoints on surviving individuals were not altered. The results indicate that quick dissipation of MON 0818 in the presence of sediment can reduce the effects on exposed organisms, and that full recovery from 24-h exposures to concentrations of MON 0818 equal to, or greater than, those expected in the environment is possible. Environ Toxicol Chem 2017;36:512-521. © 2016 SETAC.

Aquatic hazard assessment of MON 0818, a commercial mixture of alkylamine ethoxylates commonly used in glyphosate-containing herbicide formulations. Part 1: Species sensitivity distribution from laboratory acute exposures.

The sensitivity of 15 aquatic species, including primary producers, benthic invertebrates, cladocerans, mollusks, and fish, to MON 0818, a commercial surfactant mixture of polyoxyethylene tallow amines, was evaluated in standard acute (48-96-h) laboratory tests. In addition, the potential for chronic toxicity (8 d) was evaluated with Ceriodaphnia dubia. Exposure concentrations were confirmed. No significant effects on any endpoint were observed in the chronic test. A tier-1 hazard assessment was conducted by comparing species sensitivity distributions based on the generated data, as well as literature data, with 4 exposure scenarios. This assessment showed moderate levels of hazard (43.1% of the species exposed at or above median effective concentration levels), for a chosen worst-case scenario-unintentional direct over-spray of a 15-cm-deep body of water with the maximum label application rate for the studied formulations (Roundup Original, Vision Forestry Herbicide; 12 L formulation ha-1 , equivalent to 4.27 kg acid equivalent [a.e.] ha-1 ). The hazard decreased to impairment of 20.9% of species under the maximum application rate for more typical uses (6 L formulation ha-1 , 2.14 kg a.e. ha-1 ), and down to 6.9% for a more frequently employed application rate (2.5 L formulation ha-1 , 0.89 kg a.e. ha-1 ). Finally, the percentage (3.8%) was less than the hazardous concentration for 5% of the species based on concentrations of MON 0818 calculated from maximum measured concentrations of glyphosate in the environment. Environ Toxicol Chem 2017;36:501-511. © 2016 SETAC.

Influence of light, nutrients, and temperature on the toxicity of atrazine to the algal species Raphidocelis subcapitata: Implications for the risk assessment of herbicides.

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.

Dissipation of a commercial mixture of polyoxyethylene amine surfactants in aquatic outdoor microcosms: Effect of water depth and sediment organic carbon.

This study optimized existing analytical approaches and characterized the effect of sediment total organic carbon (0.05-2.05% TOC), and water depth (15, 30, and 90cm) on the fate of MON 0818, a commercial mixture of polyoxyethylene amine surfactants (POEAs), in outdoor microcosms. Mixtures of POEAs are commonly used as adjuvants in commercial herbicide formulations containing glyphosate. Until recently, analytical methods sensitive enough to monitor environmental concentrations of POEAs in aquatic systems were not available. After optimizing recently developed analytical methods, we found that the combined use of accelerated solvent extraction (ASE) and liquid chromatography-tandem mass spectrometry provided a reliable approach for determining the concentration of sediment-adsorbed POEAs. The surfactant showed strong affinity for sediment materials, with low maximum recoveries by ASE of 52%. Under microcosm conditions, water depth or sediment characteristics did not significantly affect the water-column half-life of POEA, which ranged from 3.2 to 5.3h. Binding of POEAs to suspended solids was observed, which dissipated via one- or two-phase exponential decay; when two-phase decay occurred, fast phase half-life values ranged from 0.71 to 1.3h and slow-phase values ranged from 18 to 44h. Concentrations of POEA increased in sediment shortly after application and decreased over the study period with a half-life of 5.8 to 71d. The concentrations of POEAs in the sediment of the shallow (15cm) ponds dissipated following a two-phase exponential decay model with an initial fast-phase half-life of 1.1 to 8.9d and a slower second-phase half-life of 21d. Our results suggest that aquatic organisms are unlikely to be exposed to POEAs in aqueous phase for periods of more than a few hours following an over-water application, and that sediment is a significant sink for POEAs in aquatic systems.

Toxicity of biosolids-derived triclosan and triclocarban to six crop species.

Biosolids are an important source of nutrients and organic matter, which are necessary for the productive cultivation of crop plants. Biosolids have been found to contain the personal care products triclosan and triclocarban at high concentrations relative to other pharmaceuticals and personal care products. The present study investigates whether exposure of 6 plant species (radish, carrot, soybean, lettuce, spring wheat, and corn) to triclosan or triclocarban derived from biosolids has an adverse effect on seed emergence and/or plant growth parameters. Plants were grown in soil amended with biosolids at a realistic agronomic rate. Biosolids were spiked with triclosan or triclocarban to produce increasing environmentally relevant exposures. The concentration of triclosan and triclocarban in biosolids-amended soil declined by up to 97% and 57%, respectively, over the course of the experiments. Amendment with biosolids had a positive effect on the majority of growth parameters in radish, carrot, soybean, lettuce, and wheat plants. No consistent triclosan- or triclocarban-dependent trends in seed emergence and plant growth parameters were observed in 5 of 6 plant species. A significant negative trend in shoot mass was observed for lettuce plants exposed to increasing concentrations of triclocarban (p<0.001). If best management practices are followed for biosolids amendment, triclosan and triclocarban pose a negligible risk to seed emergence and growth of crop plants.

Bioaccumulation of triclosan and triclocarban in plants grown in soils amended with municipal dewatered biosolids.

Biosolids generally contain the microbiocidal agents triclosan (TCS) and triclocarban (TCC) that are persistent during wastewater treatment and sorp to organic material. The present study investigated the concentration of TCS in tissues of radish, carrot, and soybean grown in potted soil amended with biosolids. Highest mean concentrations of TCS in radish, carrot, and soybean root tissue midway through the life cycle were 24.8 ng/g, 49.8 ng/g, and 48.1 ng/g dry weight, respectively; by the conclusion of the test, however, concentrations had declined to 2.1 ng/g, 5.5 ng/g, and 8.4 ng/g dry weight, respectively. Highest mean concentrations of TCS in radish and carrot shoot tissue were 33.7 and 18.3 ng/g dry weight at days 19 and 45, respectively, but had declined to 13.7 ng/g and 5.5 ng/g dry weight at days 34 and 69, respectively. Concentration of TCS in all samples of soybean seeds was below method detection limit (i.e., 2.8 ng/g dry wt). The present study also examined the concentration of TCS and TCC in edible portions of green pepper, carrot, cucumber, tomato, radish, and lettuce plants grown in a field amended with biosolids. Triclosan was detected only in cucumber and radish up to 5.2 ng/g dry weight. Triclocarban was detected in carrot, green pepper, tomato, and cucumber up to 5.7 ng/g dry weight. On the basis of the present study and other studies, we estimate that vegetable consumption represents less than 0.5% of the acceptable daily intake of TCS and TCC. These results demonstrate that, if best management practices for land application of biosolids in Ontario are followed, the concentration of TCS and TCC in edible portions of plants represents a negligible exposure pathway to humans.

Synergy in microcosms with environmentally realistic concentrations of prochloraz and esfenvalerate.

Laboratory experiments have shown that azole fungicides enhance the toxic effect of pyrethroid insecticides towards the aquatic crustacean Daphnia magna. Due to their sorptive properties the pesticides may, however, be less bioavailable in natural environments, possibly rendering them less toxic to aquatic organisms. In the present study, the synergistic potential of azoles on pyrethroids in natural environments was assessed by treating 18 outdoor aquatic microcosms with concentrations of the pyrethroid esfenvalerate at 0.167, 0.333, or 0.833µg/L either alone or in combination with 90µg/L of the azole prochloraz. Pesticide concentrations and the zooplankton and phytoplankton communities were assessed prior to pesticide application and at days 0, 1, 2, 4, 7, 14, 21, and 28 after pesticide application. DT(50)-values for disappearance of the pesticides from the water of 4.7 days and 30h were observed for prochloraz and esfenvalerate, respectively. The monitored communities showed larger decreases in abundance of cladoceran, copepods, and chironomids in treatments with esfenvalerate in combination with prochloraz compared to treatments with esfenvalerate alone. No systematic effects were observed in populations of Ostracoda. Adverse effects on populations of cladocerans and copepods occurred between day 2 and day 7 and, though copepods in general were less sensitive than cladocerans to both esfenvalerate alone and in combination with prochloraz, the potentiation factors for the two taxa were similar. Thus, comparison of EC(20)-values estimated on the basis of concentration-response curves for days 2, 4, and 7 showed that prochloraz enhanced the toxicity of esfenvalerate four to sixfold for copepods and three to sevenfold for cladocerans. Rotifers were not significantly affected by any of the treatments, though there was a tendency of a population increase when cladoceran and copepod populations decreased. In all invertebrate populations that showed response to the pesticide treatments, indications of stabilisation or the beginning of recovery occurred between day 7 and day 14 and full recovery was observed in some of the less affected populations of cladocerans, copepods, and chironomids after 28 days. The occurrence of the synergistic interactions between prochloraz and esfenvalerate in the microcosms and at environmentally realistic concentrations implies that the synergistic interactions may also take place in invertebrate communities in natural ponds and ditches being exposed to azoles and pyrethroids via for example runoff or drift. The question of how to deal with synergy between chemicals in the environment from a regulatory perspective is briefly discussed.

Effects of monensin on zooplankton communities in aquatic microcosms.

The effects of monensin, an antibiotic widely used in the poultry and beef industry, were evaluated on zooplankton community structure and population dynamics. Monensin was added to 12 000 L aquatic microcosms as a single treatment at concentrations ranging from 0.5 to 500 microg/L, and they were evaluated over a 50 day period. Changes in the zooplankton assemblage were evaluated by principal response curves (PRC), while changes in abundance and species richness were evaluated by analysis of variance (ANOVA). Monensin did not significantly affect community structure. However, significant changes within specific taxonomic groups were observed with decreases in the abundance of Rotifera and Copepoda nauplii and in the richness of Rotifera and Cladocera. Concentration-dependent increases in Ostracoda abundance were also observed. Changes in chlorophyll-a concentrations within the microcosms over the course of the study indicated that the changes in zooplankton populations were the indirect result of the effects of monensin on the algal community. Monensin concentrations measured in surface waters were 40 times lower than the determined no-observable effect concentration (NOEC) of 50 microg/L and do not likely present a risk to zooplankton.

Herbicidal effects of statin pharmaceuticals in Lemna gibba.

Statin pharmaceuticals, heavily prescribed in the treatment of hypercholesterolemia, are competitive inhibitors of 3-hydroxy-3-methylglutaryl coenzyme-A reductase (HMGR). In plants, these compounds also inhibit HMGR, which regulates cytosolic isoprenoid biosynthesis in the mevalonic acid (MVA) pathway. Phytotoxicity was evaluated in the higher aquatic plant Lemna gibba exposed to atorvastatin and lovastatin for 7-days by measuring the concentrations of sterols and ubiquinone; products downstream in the MVA pathway. The efficiency of the parallel and unaffected methylerythritol phosphate pathway (MEP) was also evaluated by measuring the end product, plastoquinone. Statin treatment caused an accumulation of plastoquinone, and unexpectedly, ubiquinone, an artifact likely due to metabolite sharing from the plastidial MEP pathway. Statins were, however, highly phytotoxic to L. gibba and HPLC-UV analysis of plant extracts showed significantly decreased concentrations of both stigmasterol and beta-sitosterol, which are critical components of plant membranes and regulate morphogenesis and development. EC10 values for atorvastatin and lovastatin were as small as 26.1 and 32.8 microg/L, respectively. However, hazard quotients indicated that statins present little risk to the model higher aquatic plant Lemna gibba at environmentally relevant concentrations, even though pathway-specific endpoints were 2-3 times more sensitive than traditional gross morphological endpoints typically used in risk assessment.

An exposure assessment for selected pharmaceuticals within a watershed in Southern Ontario.

Recent studies from a number of countries have shown that measurable concentrations of both human and veterinary pharmaceuticals can be found in a variety of environmental matrices such as surface and ground water, soils, and sediments. Few data are available that characterize the sources, exposure and effects of pharmaceuticals in the environment and there is clearly a need to define these parameters within a Canadian context. We present in this paper the first report in southern Ontario, Canada on the geographic and temporal distribution of pharmaceuticals detected within seven tributaries receiving primarily agricultural inputs in a typical watershed. Of the 28 pharmaceuticals surveyed, 14 were detected in the streams sampled (n=125). Temporal trends in concentration for five frequently detected pharmaceuticals show pulses occurring between May and November of 2003 at similar but varying times over the seasons, depending on the pharmaceuticals, flow rate, and precipitation. Fluctuations in concentration of ions indicative of agricultural run off, such as nitrate and phosphate, were not found to be useful predictors of changes in pharmaceutical concentration (P>0.4), however a significant correlation between dissolved organic carbon and monensin and carbamazepine concentrations were observed (P<0.013). Exposure profiles illustrating concentration distributions for three of the more prevalent pharmaceuticals detected, including lincomycin, monensin and carbamazepine, showed a log normal distribution, useful for calculating centiles of environmental concentrations. While distributions of estimated total potency of pharmaceuticals detected in the surface waters suggested small risks of environmental effects of mixtures to daphnia, green algae, Lemna gibba, and fish, the significance of non-target effects and impacts due to chronic low level exposures to chemical mixtures remains unclear.

Determination of pharmaceuticals in environmental waters by liquid chromatography/electrospray ionization/tandem mass spectrometry.

A high-performance liquid chromatography/electrospray ionization/tandem mass spectrometry (LC/MS-MS) method was developed, validated and used to characterize pharmaceutical inputs in the Grand River watershed, Ontario, Canada. Twenty-seven antibiotics and neutral pharmaceuticals were extracted from aqueous environmental samples in a single step using 13C6-labeled sulfamethazine phenyl as a method surrogate and analyzed by LC/MS-MS. Method detection limits were in the range of 20-1,400 ng/L for the compounds of interest with recoveries from 51 to 130%. Using this method, pharmaceutical profiles in tributaries flowing into the Grand River were investigated using samples collected from seven agricultural sites and one urban site. Quality control data collected during the 5-month field study period showed good method performance. Concentrations of pharmaceuticals in source water with heavy agricultural input and surface waters downstream with urban inputs were determined to examine the effect of agricultural and urban inputs to surface water quality. Only human prescription drugs were found from urban site samples taken at both high-flow (spring and fall) and low-flow (summer) events in 2003, indicating minimal agricultural input. We also found for the first time the presence of the ionophore monensin in the environment as well as the occurrence of the human prescription drug carbamazepine in surface waters receiving primarily agricultural inputs. Possible causes and analytical solutions for some poor recoveries are discussed with respect to extraction pH, total organic carbon and metal ions in the water samples. The ability to extract 27 pharmaceuticals in a single solid-phase extraction step from diverse environmental matrices such as agricultural tile drain, tributary and surface water samples, followed by a single LC/MS-MS analysis, enabled the effective delivery of quality data.

Comparative persistence of pesticides on selected cultivars of specialty vegetables.

The behavior and dissipation of several pesticides on selected cultivars of specialty vegetable crops were compared to determine appropriate preharvest intervals for compliance with maximum residue limits. To reduce application variability, a tank mix of pesticides was applied for each trial. Residues of eight pesticides applied to bok choi, Chinese broccoli, and fuzzy squash were similar for the two leafy vegetables; residues were higher than on squash because of the latter's larger mass-to-surface area ratio. Whereas residues of five of the nine pesticides applied to cabbage, Chinese cabbage, and bok choi did not differ significantly from 3 to 14 days after application, residues of cypermethrin and three fungicides were significantly higher on Chinese cabbage and bok choi. The residue deposits of the pesticides were about 50% lower on Chinese cabbage and 90% lower on cabbage than on bok choi. Dissipation of residues on different cultivars of lettuce and cabbage were compared after application of nine pesticides. With the exception of captan, residues on head lettuce were lower than on the other lettuces on day 1; cultivar differences were not significant for most of the nine applied pesticides on days 3 and 8. Generally, residues of the nine individual pesticides on storage cabbage, savoy cabbage, Chinese cabbage, and tah tsai did not differ significantly from day 1 to day 7 after application. Residue concentrations were generally significantly higher on bok choi than on the other cultivars. Residue deposits generally correlated with the rate of application; residues of captan, however, were about 50% of the predicted value. Significant differences in deposit and dissipation were observed among cultivars and pesticides, with dramatic initial decreases for diazinon and parathion. Because of their higher exposed surface area-to-mass ratios, leafier crops had higher residue concentrations than head varieties. Residues on lettuce cultivars were higher than on the cabbages. The results clearly indicate that structure significantly affects residue deposit and dissipation, and pesticide recommendations cannot always be extended to specialty crops without an investigation of the changes in preharvest intervals to prevent violations of the maximum residue limits.