Treating Agricultural Runoff with a Mobile Carbon Filtration Unit.

Several classes of pesticides have been shown to impair water quality in California, including organophosphates, pyrethroids and neonicotinoids. Vegetative treatment systems (VTS) can reduce pesticide loads and associated toxicity in agricultural runoff, but many water-soluble pesticides such as neonicotinoids are not effectively treated by VTS, and VTS installation is not always an option for growers required to remove non-crop vegetation for food safety concerns. Recent studies have shown that biochar filtration can be used to remove soluble contaminants, especially when coupled with other VTS components. We evaluated a mobile carbon filter system consisting of a trailer-mounted tank containing approximately 600L (~ 180 kg) of biochar. Input water from a 437-hectare agricultural drainage was pre-filtered and treated with biochar during two multi-week study periods. Laboratory toxicity tests and chemical and nutrient analyses were conducted on input and output water. Pesticide concentrations were initially reduced by greater than 99%. Treatment efficacy declined linearly and was expected to remain at least 50% effective for up to 34 weeks. Toxicity was assessed with Ceriodaphnia dubia, Hyalella azteca and Chironomus dilutus. Significant input toxicity was reduced to non-toxic levels in 6 of 16 samples. Some input concentrations of the neonicotinoid imidacloprid and the pyrethroid cypermethrin exceeded organism-specific toxicity thresholds and benchmarks, but the overall causes of toxicity were complex mixtures of agricultural chemicals. Nutrients were not reduced by the biochar. Results demonstrate the utility of biochar in treating agricultural runoff and provide measures of the longevity of biochar under field conditions.

Effectiveness of a Constructed Wetland with Carbon Filtration in Reducing Pesticides Associated with Agricultural Runoff.

The Salinas Valley in Monterey County, California, USA, is a highly productive agricultural region. Irrigation runoff containing pesticides at concentrations toxic to aquatic organisms poses a threat to aquatic ecosystems within local watersheds. This study monitored the effectiveness of a constructed wetland treatment system with a granulated activated carbon (GAC) filter installation at reducing pesticide concentrations and associated toxicity to Ceriodaphnia dubia, Hyalella azteca, and Chironomus dilutus. The wetland was supplied with water pumped from an impaired agricultural and urban drainage. Across five monitoring trials, the integrated system's average pesticide concentration reduction was 52%. The wetland channel and GAC filtration components individually provided significant treatment, and within each, pesticide solubility had a significant effect on changes in pesticide concentrations. The integrated treatment system also reduced nitrate by 61%, phosphate by 73%, and turbidity by 90%. Input water was significantly toxic to C. dubia and H. azteca in the first trial. Toxicity to C. dubia persisted throughout the system, whereas toxicity to H. azteca was removed by the channel, but there was residual toxicity post-GAC. The final trial had significant input toxicity to H. azteca and C. dilutus. The channel reduced toxicity to H. azteca and removed toxicity to C. dilutus. GAC filtration reduced H. azteca toxicity to an insignificant level. There was no input toxicity in the other three trials. The results demonstrate that a wetland treatment system coupled with GAC filtration can reduce pesticide concentrations, nutrients, suspended particles, and aquatic toxicity associated with agricultural runoff.

Acute and Chronic Effects of Clothianidin, Thiamethoxam and Methomyl on Chironomus dilutus.

Organism tolerance thresholds for emerging contaminants are vital to the development of water quality criteria. Acute (96-h) and chronic (10-day) effects thresholds for neonicotinoid pesticides clothianidin and thiamethoxam, and the carbamate pesticide methomyl were developed for the midge Chironomus dilutus to support criteria development using the UC Davis Method. Median lethal concentrations (LC50s) were calculated for acute and chronic exposures, and the 25% inhibition concentrations (IC25) were calculated for the chronic exposures based on confirmed chemical concentrations. Clothianidin effect concentrations were 4.89 µg/L, 2.11 µg/L and 1.15 µg/L for 96-h LC50, 10-day LC50 and 10-day IC25, respectively. Similarly, thiamethoxam concentrations were 56.4 µg/L, 32.3 µg/L and 19.6 µg/L, and methomyl concentrations were 244 µg/L, 266 µg/L and 92.1 µg/L. Neonicotinoid effect concentrations compared favorably to previously published 96-h and 14-day LC50 concentrations, and methomyl effect concentrations were within the acute survival range reported for Chironomus species and other organisms.

Comparison of the Relative Efficacies of Granulated Activated Carbon and Biochar to Reduce Chlorpyrifos and Imidacloprid Loading and Toxicity Using Laboratory Bench Scale Experiments.

Pesticide loads and associated toxicity can be significantly reduced using integrated vegetated treatment systems, which remove moderately soluble and hydrophobic pesticides, but need a sorbent material to remove more soluble pesticides. Neonicotinoids such as imidacloprid are widely used insecticides, acutely toxic, and have been linked to a range of ecological effects. Laboratory experiments were conducted to test the sorptive capacity of granulated activated carbon and biochar for removing imidacloprid and the organophosphate insecticide chlorpyrifos in a scaled-down treatment system. Simulated irrigation water spiked with individual pesticides was treated with a bench-top system designed to mimic a 600 L carbon installation receiving 108,000 L of flow per day for sixteen days. Biochar reduced insecticides to less than detectable and non-toxic levels. Granulated activated carbon similarly reduced chlorpyrifos, but allowed increasing concentrations of imidacloprid to break through. Both media treated environmentally relevant concentrations, and would be effective if used under conditions with reduced particle loads.

Carbon Treatment as a Method to Remove Imidacloprid from Agriculture Runoff.

Use of neonicotinoid pesticides is increasing worldwide and there is growing evidence of surface water contamination from this class of insecticide. Due to their high solubility, traditional mitigation practices may be less effective at reducing neonicotinoid concentrations in agricultural runoff. In the current study, laboratory experiments were conducted to determine if granulated activated carbon (GAC) reduces concentrations of the neonicotinoid imidacloprid in water under simulated flow conditions. Imidacloprid was pumped through columns packed with GAC using flow rates scaled to mimic previously reported field studies. Treatments were tested at two different flow rates and samples were collected after 200 and 2500 mL of treated water were pumped through the column. Chemical analysis of the post-column effluent showed the GAC removed all detectable imidacloprid from solution at both flow rates and at both sample times. These results demonstrate the efficacy of GAC for treating neonicotinoids and the results are discussed in the context of incorporating this treatment into integrated vegetated treatment systems for mitigating pesticides in agricultural runoff. Future studies are being designed to evaluate this technology in full scale field trials.

The Effects of the Landguard™ A900 Enzyme on the Macroinvertebrate Community in the Salinas River, California, United States of America.

Agricultural use of organophosphate pesticides are responsible for surface water toxicity in California and has led to a number of impaired water body listings under section 303(d) of the Clean Water Act. Integrated passive-treatment systems can reduce pesticide loading in row crop runoff, but they are only partially effective for the more soluble organophosphates. The Landguard™ enzyme has been effectively proven as an on-farm management practice for the removal of chlorpyrifos and diazinon in furrow runoff, but it has not been used in larger-scale treatment because of concerns regarding the potential impact on in-stream macroinvertebrates after chronic use. A first-order agricultural creek was treated with the Landguard enzyme for 30 days approximately 450 m upstream of its intersection with the Salinas River. Toxicity and pesticide chemistry were measured in the creek during treatment as well as in the river both upstream and downstream of the creek input before and after treatment. Benthic macroinvertebrates were also surveyed in the river before and after enzyme treatment. Low concentrations of organophosphate pesticides were detected in the creek, but Landguard removed detected concentrations of chlorpyrifos. Toxicity detected in the creek was likely caused by pyrethroid pesticides, and no toxicity was detected in river samples. There were no differences in habitat or macroinvertebrate assemblages between upstream and downstream samples or between pre- and post-treatment samples. These results indicate that chronic treatment of the creek with Landguard enzyme had no impact on macroinvertebrate community structure in the river.

Impacts of pesticides in a Central California estuary.

Recent and past studies have documented the prevalence of pyrethroid and organophosphate pesticides in urban and agricultural watersheds in California. While toxic concentrations of these pesticides have been found in freshwater systems, there has been little research into their impacts in marine receiving waters. Our study investigated pesticide impacts in the Santa Maria River estuary, which provides critical habitat to numerous aquatic, terrestrial, and avian species on the central California coast. Runoff from irrigated agriculture constitutes a significant portion of Santa Maria River flow during most of the year, and a number of studies have documented pesticide occurrence and biological impacts in this watershed. Our study extended into the Santa Maria watershed coastal zone and measured pesticide concentrations throughout the estuary, including the water column and sediments. Biological effects were measured at the organism and community levels. Results of this study suggest the Santa Maria River estuary is impacted by current-use pesticides. The majority of water samples were highly toxic to invertebrates (Ceriodaphnia dubia and Hyalella azteca), and chemistry evidence suggests toxicity was associated with the organophosphate pesticide chlorpyrifos, pyrethroid pesticides, or mixtures of both classes of pesticides. A high percentage of sediment samples were also toxic in this estuary, and sediment toxicity occurred when mixtures of chlorpyrifos and pyrethroid pesticides exceeded established toxicity thresholds. Based on a Relative Benthic Index, Santa Maria estuary stations where benthic macroinvertebrate communities were assessed were degraded. Impacts in the Santa Maria River estuary were likely due to the proximity of this system to Orcutt Creek, the tributary which accounts for most of the flow to the lower Santa Maria River. Water and sediment samples from Orcutt Creek were highly toxic to invertebrates due to mixtures of the same pesticides measured in the estuary. This study suggests that the same pyrethroid and organophosphate pesticides that have been shown to cause water and sediment toxicity in urban and agriculture water bodies throughout California, have the potential to affect estuarine habitats. The results establish baseline data in the Santa Maria River estuary to allow evaluation of ecosystem improvement as management initiatives to reduce pesticide runoff are implemented in this watershed.

Hypersalinity toxicity thresholds for nine California ocean plan toxicity test protocols.

Currently, several desalination facilities have been proposed to operate or are actually operating in California. These facilities' use of reverse osmosis (RO) may discharge hypersaline reject brine into the marine environment. The risks, if any, this brine would pose to coastal receiving waters are unknown. To test the toxicity of hypersaline brine in the absence of any additional toxic constituents, we prepared brine and tested it with the seven toxicity test organisms listed in the 2009 California Ocean Plan. The most sensitive protocols were the marine larval development tests, whereas the most tolerant to increased salinities were the euryhaline topsmelt, mysid shrimp, and giant kelp tests. Reject brines from the Monterey Bay Aquarium's RO desalination facility were also tested with three species. The effects of the aquarium's brine effluent on topsmelt, mussels, and giant kelp were consistent with those observed in the salinity tolerance experiments. This information will be used by regulators to establish receiving water limitations for hypersaline discharges.

An Integrated Vegetated Treatment System for Mitigating Imidacloprid and Permethrin in Agricultural Irrigation Runoff.

Pyrethroid and neonicotinoid pesticides control an array of insect pests in leafy greens, but there are concerns about the off-site movement and potential water quality impacts of these chemicals. Effective on-farm management practices can eliminate aquatic toxicity and pesticides in runoff. This project evaluated an integrated vegetated treatment system (VTS), including the use of polyacrylamide (PAM), for minimizing the toxicity of imidacloprid and permethrin pesticides in runoff. The VTS incorporated a sediment trap to remove coarse particles, a grass-lined ditch with compost swales to remove suspended sediment and insecticides, and granulated activated carbon (GAC) or biochar to remove residual insecticides. Runoff was sampled throughout the VTS and analyzed for pesticide concentrations, and aquatic toxicity using the midge Chironomus dilutus and the amphipod Hyalella azteca. In simulated runoff experiments, the VTS reduced suspended sediment load by 88%, and imidacloprid and permethrin load by 97% and 99%, respectively. In runoff events from a conventionally grown lettuce field, suspended sediment load was reduced by 98%, and insecticide load by 99%. Toxicity was significantly reduced in approximately half of the simulated runoff events, and most of the lettuce runoff events. Integrated vegetated treatment systems that include components for treating soluble and hydrophobic pesticides are vital tools for reducing pesticide load and occurrence of pesticide-related toxicity.

Evaluation of methods to determine causes of sediment toxicity in San Diego Bay, California, USA.

Regulation of waterbodies impaired due to sediment toxicity may require development of Total Maximum Daily Load (TMDL) allocations to reduce chemicals of concern. A key step in this process is the identification of chemicals responsible for toxicity, and sediment toxicity identification evaluation procedures (TIEs) are the primary tools used to accomplish this. Several sites in San Diego Bay (CA, USA) are listed as impaired due to sediment toxicity associated with organic chemicals and metals, and due to degraded benthic macroinvertebrate communities. Sediment was collected from one of these sites, at the confluence of Switzer Creek in San Diego Harbor. The sediment was subjected to selected whole-sediment TIE treatments to evaluate the efficacy of these procedures for identifying the causes of toxicity at Switzer Creek. Toxicity was assessed using the estuarine amphipod Eohaustorius estuarius. The results indicated that toxicity of San Diego Bay sediment was likely partly due to mixtures of pyrethroid pesticides. These experiments showed that the effectiveness of the individual TIE procedures varied by treatment. Variability was mainly due to inconsistency between results of samples subjected to various Phase II TIE procedures, including chemical analyses of samples subjected to high-pressure liquid chromatography and direct analyses of acetone extractions of carbonaceous resin. The procedures require further refinement to ensure maximum sorption and complete elution and detection of sorbed chemicals. Despite these inconsistencies, the results indicate the utility of these procedures for identifying chemicals of concern in this system.

An evaluation of temporal and spatial trends of pyrethroid concentrations in California surface waters.

Pyrethroid insecticides are frequently detected in urban surface waters at levels that are deleterious to sensitive aquatic species. The California Department of Pesticide Regulation (CDPR) Surface Water Protection Program collected 717 water and 191 sediment samples from 2009 to 2018 throughout California, providing a large dataset to conduct spatial and temporal trend analysis of pyrethroid concentrations. The pyrethroid bifenthrin accounted for 72% of average sample concentrations, and a strong relationship between whole water bifenthrin concentrations and the observed toxicity to the test species Hyallela azteca was established. To help mitigate runoff concentrations, CDPR adopted regulations in 2012 intended to limit the mass of pyrethroids applied to structures by professional pest control operators. A statistical analysis of CDPR statewide monitoring data collected at storm drain outfall and receiving water sites was conducted to determine if any significant trends in pyrethroid concentrations exist. Nonparametric statistical analysis of monitoring data revealed significant regional differences. In Northern California, decreasing trends in bifenthrin and cypermethrin concentrations may be counterbalanced by a potential switch to deltamethrin-containing products. Conversely, the few observed trends in concentrations at Southern California monitoring stations could be a result of regional hydrological and pest pressure differences. To evaluate the effects of structural applications on pyrethroid concentrations in urban runoff, CDPR conducted field trials using a tracer pyrethroid that was applied in accordance with the regulations. Detectable levels in runoff were observed, with an estimated 0.004-0.005% mass transport offsite per storm. Using field-derived sediment, the observed half-lives (514 days+) highlight the potential for contaminant laden sediment to serve as a long-term source of pyrethroids within waterways. Both chemistry and observed toxicity data identify storm water runoff as a primary transport mechanism. However, the presence of pyrethroids in dry-weather runoff suggests that significant loading can occur under various hydrologic conditions.

Size-specific responses of the amphipod Eohaustorius estuarius to clay in sediment toxicity testing.

A number of lines of evidence suggest that the amphipod Eohaustorius estuarius has variable tolerance to clay in sediments. In the current study, two laboratory dose-response experiments were conducted with kaolin clay to evaluate whether clay effects varied with amphipod size. The results indicated that smaller amphipods (< 0.9 mg dry wt.) were significantly more tolerant of clay than larger individuals up to 2.9 mg dry wt. Average survival in clay/sand mixtures with > 70% clay was 88%, 71%, and 52% for small (0.6-1.2 mg), medium (1.4-1.9 mg), and large (1.8-2.9 mg) amphipods, respectively. Standard 96-h reference toxicant tests with cadmium chloride (CdCl2) were conducted to determine whether there were size-specific differences in response to this metal reference toxicant. The CdCl2 median lethal concentrations (LC50s) for small, medium, and large amphipods were 6.78, 5.13, and 4.63 mg/L, respectively. Responses of all three size classes to cadmium were within historic confidence intervals for this reference metal, and were not significantly different from one another based on overlapping confidence intervals. Additional experiments with high clay reference site sediments from San Francisco Bay were conducted to confirm the size-related response with field sediments, but were only partially conclusive. Overall results suggest that the use of smaller amphipods in routine monitoring of high clay sediments will reduce the influence of this factor on test results.

Water Quality Impairments Due to Aquatic Life Pesticide Toxicity: Prevention and Mitigation in California, USA.

The management of pesticides to protect water quality remains a significant global challenge. Historically, despite regulatory frameworks intended to prevent, minimize, and manage off-site movement of pesticides, multiple generations of pesticide active ingredients have created a seemingly unending cycle of pesticide water pollution in both agricultural and urban watersheds. In California, the most populous and most agricultural US state, pesticide and water quality regulators realized in the 1990s that working independently of each other was not an effective approach to address pesticide water pollution. Over the years, these California agencies have developed a joint vision and have continued to develop a unified approach that has the potential to minimize pesticide risks to aquatic life through a combination of prevention, monitoring, and management actions, while maintaining pesticide availability for effective pest control. Key elements of the current California pesticide/water quality effort include: 1) pesticide and toxicity monitoring, coupled with watershed modeling, to maximize information obtained from monitoring; 2) predictive fate and exposure modeling to identify potential risks to aquatic life for new pesticide products when used as allowed by the label or to identify effective mitigation measures; and 3) management approaches tailored to the different pesticide uses, discharge sources, physical environments, and regulatory environments that exist for agricultural runoff, urban runoff, and municipal wastewater. Lessons from this effort may inform pesticide management elsewhere in the world as well as other chemical regulatory programs, such as the recently reformed US Toxic Substances Control Act and California's Safer Consumer Products regulatory program. Environ Toxicol Chem 2020;39:953-966. © 2020 SETAC.

Applications of carboxylesterase activity in environmental monitoring and toxicity identification evaluations (TIEs).

This review has examined a number of issues surrounding the use of carboxylesterase activity in environmental monitoring. It is clear that carboxylesterases are important enzymes that deserve increased study. This class of enzymes appears to have promise for employment in environmental monitoring with a number of organisms and testing scenarios, and it is appropriate for inclusion in standard monitoring assays. Given the ease of most activity assays, it is logical to report carboxylesterase activity levels as well as other esterases (e.g., acetylcholinesterase). Although it is still unclear as to whether acetylcholinesterase or carboxylesterase is the most "appropriate" biomarker, there are sufficient data to suggest that at the very least further studies should be performed with carboxylesterases. Most likely, data will show that it is optimal to measure activity for both enzymes whenever possible. Acetylcholinesterase has the distinct advantage of a clear biological function, whereas the endogenous role of carboxylesterases is still unclear. However, a combination of activity measurements for the two enzyme systems will provide a much more detailed picture of organism health and insecticide exposure. The main outstanding issues are the choice of substrate for activity assays and which tissues/organisms are most appropriate for monitoring studies. Substrate choice is very important, because carboxylesterase activity consists of multiple isozymes that most likely fluctuate on an organism- and tissue-specific basis. It is therefore difficult to compare work in one organism with a specific substrate with work performed in a different organism with a different substrate. An attempt should therefore be made to standardize the method. The most logical choice is PNPA (p-nitrophenyl acetate), as this substrate is commercially available, requires inexpensive optics for assay measurements, and has been used extensively in the literature. However, none of these beneficial properties indicates that the substrate is an appropriate surrogate for a specific compound, e.g., pyrethroid-hydrolyzing activity. It will most likely be necessary to have more specific surrogate substrates for use in assays that require information on the ability to detoxify/hydrolyze specific environmental contaminants. The use of carboxylesterase activity in TIE protocols appears to have excellent promise, but there are further technical issues that should be addressed to increase the utility of the method. The main concerns include the large amount of nonspecific protein added to the testing system, which can lead to undesirable side effects including nonspecific reductions in observed toxicity, decrease in dissolved oxygen content, and organism growth. It is probable that these issues can be resolved with further assay development. The ideal solution would be to have a commercial recombinant carboxylesterase that possessed elevated pyrethroid-hydrolysis activity and which was readily available, homogeneous, and inexpensive. The availability of such an enzyme would address nearly all the current method shortcomings. Such a preparation would be extremely useful for the aquatic toxicology community. Further work should focus on screening available esterases for stability, cost, and activity on pyrethroids, with specific focus on esterases capable of distinguishing type I from type II pyrethroids. It would also be beneficial to identify esterases that are not sensitive to OP insecticides. Many esterases and lipases are available as sets to test chemical reactions for green chemistry, enabling large-scale screening. Other potential approaches to increase the utility of the enzyme include derivatization with polyethylene glycol (PEG) or cyanuric acid chloride to increase stability and reduce microbial degradation. It is also possible that the enzyme could be formulated in a sol gel preparation to increase stability. It is likely that the use of carboxylesterase addition will increase for applications in sediment TIEs. Carboxylesterases are an interesting and useful enzyme family that deserves further study for applications in environmental monitoring as well as to increase our understanding of the fundamental biological role(s) of these enzymes. There are, of course, other enzymes that show high esterase activity on pyrethroids but are not technically carboxylesterases in the alpha/beta-hydrolase fold protein family. These enzymes should also be examined for use in TIE protocols and "esterase" arrays as well as for general applications in environmental monitoring. One can envision the creation of a standardized screen of enzymes with esterase activity to (1) identify environmental contaminants, (2) estimate the potential toxic effects of new compounds on a range of organisms, and (3) monitor organism exposure to agrochemicals (and potentially other contaminants). This approach would provide a multibiomarker integrative assessment of esterase-inhibiting potential of a compound or mixture. In conclusion, much is still unknown about this enzyme family, indicating that this area is still wide open to researchers interested in the applications of carboxylesterase activity as well as basic biological questions into the nature of enzyme activity and the endogenous role of the enzyme.

Comparison of methods for evaluating acute and chronic toxicity in marine sediments.

Sublethal test methods are being used with increasing frequency to measure sediment toxicity, but little is known about the relative sensitivity of these tests compared to the more commonly used acute tests. The present study was conducted to compare the sensitivity of several acute and sublethal methods and to investigate their correlations with sediment chemistry and benthic community condition. Six sublethal methods (amphipod: Leptocheirus plumulosus survival, growth, and reproduction; polychaete: Neanthes arenaceodentata survival and growth; benthic copepod: Amphiascus tenuiremis life cycle; seed clam: Mercenaria mercenaria growth; oyster: Crassostrea virginica lysosome destabilization; and sediment-water interface testing with mussel embryos, Mytilus galloprovincialis) and two acute methods (amphipod survival with Eohaustorius estuarius and L. plumulosus) were used to test split sediment samples from stations in California. The test with Amphiascus proved to be the most sensitive sublethal test and the most sensitive overall, identifying 90% of the stations as toxic. The Leptocheirus 10-d test was the most sensitive of the acute tests, identifying 60% of the stations as toxic. In general, the sublethal tests were not more sensitive to sediments than the acute tests, with the sublethal tests finding an average of 35% of the stations to be toxic while the acute found 44%. Of the sublethal tests, only the Amphiascus endpoints and Neanthes growth significantly (p

Extracts from benthic anatoxin-producing Phormidium are toxic to 3 macroinvertebrate taxa at environmentally relevant concentrations.

Toxin-producing cyanobacteria are increasing in rivers and streams globally, leading to growing concerns over their potential impacts on aquatic ecosystems. The present study was designed to culture field-collected Phormidium in the laboratory, identify individual species, conduct chemical analyses to identify cyanotoxins, and conduct toxicity tests to investigate the potential for this genera to impact stream health. Freshwater toxicity tests were conducted with standard US Environmental Protection Agency invertebrate test protocols with culture water used to grow 3 Phormidium strains isolated from the Russian River (CA, USA). Enzyme linked immunosorbent assays were used to measure total anatoxin concentrations. Culture waters from the 3 Phormidium strains were highly toxic to Ceriodaphnia dubia, Hyalella azteca, and Chironomus dilutus. The C. dubia 7-d survival median lethal concentrations were 0.71, 0.49, and 0.56 µg/L anatoxin for Phormidum strains 1, 2, and 3, respectively. The 7-d reproduction inhibitory concentrations, 25% were 0.55, 0.32, and 0.30 µg/L anatoxin for strains 1, 2, and 3, respectively. Chironomus dilutus survival was reduced at concentrations <2 µg/L anatoxin by all 3 strains, and the H. azteca 96-h lethal concentrations, 25% were 2.82, 1.26, and 5.30 µg/L for strains 1, 2, and 3, respectively. Additional liquid chromatography-mass spectrometry analyses demonstrated that the likely anatoxin variant in these cultures was dihydro-anatoxin-a. The results suggest that anatoxins produced by Phormidium have the potential to impact stream macroinvertebrates. Environ Toxicol Chem 2018;37:2851-2859. © 2018 SETAC.

Changing patterns in water toxicity associated with current use pesticides in three California agriculture regions.

Regulation of agriculture irrigation water discharges in California, USA, is assessed and controlled by its 9 Regional Water Quality Control Boards under the jurisdiction of the California State Water Resources Control Board. Each Regional Water Board has developed programs to control pesticides in runoff as part of the waste discharge requirements implemented through each region's Irrigated Lands Regulatory Program. The present study assessed how pesticide use patterns differ in the Imperial (Imperial County) and the Salinas and Santa Maria (Monterey County) valleys, which host 3 of California's prime agriculture areas. Surface-water toxicity associated with current use pesticides was monitored at several sites in these areas in 2014 and 2015, and results were linked to changes in pesticide use patterns in these areas. Pesticide use patterns appeared to coincide with differences in the way agriculture programs were implemented by the 2 respective Regional Water Quality Control Boards, and these programs differed in the 2 Water Board Regions. Different pesticide use patterns affected the occurrence of pesticides in agriculture runoff, and this influenced toxicity test results. Greater detection frequency and higher concentrations of the organophosphate pesticide chlorpyrifos were detected in agriculture runoff in Imperial County compared to Monterey County, likely due to more rigorous monitoring requirements for growers using this pesticide in Monterey County. Monterey County agriculture runoff contained toxic concentrations of pyrethroid and neonicotinoid pesticides, which impacted amphipods (Hyalella azteca) and midge larvae (Chironomus dilutus) in toxicity tests. Study results illustrate how monitoring strategies need to evolve as regulatory actions affect change in pesticide use and demonstrate the importance of using toxicity test indicator species appropriate for the suite of contaminants in runoff in order to accurately assess environmental risk. Integr Environ Assess Manag 2018;14:270-281. © 2017 SETAC.

Causes of water toxicity to Hyalella azteca in the New River, California, USA.

The New River (CA, USA) was created in 1905 to 1907 when the Colorado River washed out diversionary works and flowed into the Salton Basin, creating the Salton Sea. Approximately 70% of the river's current flow is agricultural wastewater from the Imperial Valley. The river is contaminated with pesticides, industrial organic chemicals, metals, nutrients, bacteria, and silt. Monitoring for the State of California Surface Water Ambient Monitoring Program has indicated persistent water column toxicity to the epibenthic amphipod Hyalella azteca. Four toxicity identification evaluations (TIEs), along with chemical analyses, were performed, and the results indicated multiple and varying causes of toxicity. The first two TIEs characterized the causes of toxicity as a combination of metals and organics, but only the second sample contained enough total copper to contribute to toxicity. The third TIE used an emerging method for characterizing and identifying toxicity caused by pyrethroid pesticides. This TIE characterized organics as the cause of toxicity, and a carboxylesterase enzyme treatment further identified the cause of toxicity as pyrethroids. The final TIE used the enzyme and Phase II procedures to identify cypermethrin as the cause of toxicity. The TIE results demonstrate the evolving causes of toxicity in the New River and should assist regulators with implementing the total maximum daily load process for pesticides, particularly pyrethroids. Further research will determine if pyrethroids and other New River contaminants are having an impact on the Salton Sea.

Vegetated Treatment Systems for Removing Contaminants Associated with Surface Water Toxicity in Agriculture and Urban Runoff.

Urban stormwater and agriculture irrigation runoff contain a complex mixture of contaminants that are often toxic to adjacent receiving waters. Runoff may be treated with simple systems designed to promote sorption of contaminants to vegetation and soils and promote infiltration. Two example systems are described: a bioswale treatment system for urban stormwater treatment, and a vegetated drainage ditch for treating agriculture irrigation runoff. Both have similar attributes that reduce contaminant loading in runoff: vegetation that results in sorption of the contaminants to the soil and plant surfaces, and water infiltration. These systems may also include the integration of granulated activated carbon as a polishing step to remove residual contaminants. Implementation of these systems in agriculture and urban watersheds requires system monitoring to verify treatment efficacy. This includes chemical monitoring for specific contaminants responsible for toxicity. The current paper emphasizes monitoring of current use pesticides since these are responsible for surface water toxicity to aquatic invertebrates.

An integrated vegetated ditch system reduces chlorpyrifos loading in agricultural runoff.

Agricultural runoff containing toxic concentrations of the organophosphate pesticide chlorpyrifos has led to impaired water body listings and total maximum daily load restrictions in California's central coast watersheds. Chlorpyrifos use is now tightly regulated by the Central Coast Regional Water Quality Control Board. This study evaluated treatments designed to reduce chlorpyrifos in agricultural runoff. Initial trials evaluated the efficacy of 3 different drainage ditch installations individually: compost filters, granulated activated carbon (GAC) filters, and native grasses in a vegetated ditch. Treatments were compared to bare ditch controls, and experiments were conducted with simulated runoff spiked with chlorpyrifos at a 1.9 L/s flow rate. Chlorpyrifos concentrations and toxicity to Ceriodaphnia dubia were measured at the input and output of the system. Input concentrations of chlorpyrifos ranged from 858 ng/L to 2840 ng/L. Carbon filters and vegetation provided the greatest load reduction of chlorpyrifos (99% and 90%, respectively). Toxicity was completely removed in only one of the carbon filter trials. A second set of trials evaluated an integrated approach combining all 3 treatments. Three trials were conducted each at 3.2 L/s and 6.3 L/s flow rates at input concentrations ranging from 282 ng/L to 973 ng/L. Chlorpyrifos loadings were reduced by an average of 98% at the low flow rate and 94% at the high flow rate. Final chlorpyrifos concentrations ranged from nondetect (<50 ng/L) to 82 ng/L. Toxicity to C. dubia was eliminated in 3 of 6 integrated trials. Modeling of the ditch and its components informed design alterations that are intended to eventually remove up to 100% of pesticides and sediment. Future work includes investigating the adsorption capacity of GAC, costs associated with GAC disposal, and real-world field trials to further reduce model uncertainties and confirm design optimization. Trials with more water-soluble pesticides such as neonicotinoids are also recommended. Integr Environ Assess Manag 2017;13:423-430. © 2016 SETAC.