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.

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.

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.

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.

Bioswales reduce contaminants associated with toxicity in urban storm water.

Contamination and toxicity associated with urban storm water runoff are a growing concern because of the potential impacts on receiving systems. California water regulators are mandating implementation of green infrastructure as part of new urban development projects to treat storm water and increase infiltration. Parking lot bioswales are low impact development practices that promote filtering of runoff through plants and soil. Studies have demonstrated that bioswales reduce concentrations of suspended sediments, metals, and hydrocarbons. There have been no published studies evaluating how well these structures treat current-use pesticides, and studies have largely ignored whether bioswales reduce toxicity in surface water. Three storms were monitored at 3 commercial and residential sites, and reductions of contaminants and associated toxicity were quantified. Toxicity testing showed that the majority of untreated storm water samples were toxic to amphipods (Hyalella azteca) and midges (Chironomus dilutus), and toxicity was reduced by the bioswales. No samples were toxic to daphnids (Ceriodaphnia dubia) or fish (Pimephales promelas). Contaminants were significantly reduced by the bioswales, including suspended solids (81% reduction), metals (81% reduction), hydrocarbons (82% reduction), and pyrethroid pesticides (74% reduction). The single exception was the phenypyrazole pesticide fipronil, which showed inconsistent treatment. The results demonstrate these systems effectively treat contaminated storm water associated with surface water toxicity but suggest that modifications of their construction may be required to treat some contaminant classes. Environ Toxicol Chem 2016;35:3124-3134. © 2016 SETAC.

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.

Temporal and spatial trends in sediment contaminants associated with toxicity in California watersheds.

California's Stream Pollution Trends program (SPoT) assesses long-term water quality trends, using 100 base-of-the-watershed sampling sites. Annual statewide sediment surveys from 2008 to 2012 identified consistent levels of statewide toxicity (19%), using the freshwater amphipod Hyalella azteca. Significant contaminant trends included a decrease in PCBs, stable concentrations of metals and PAHs, and a statewide increase in detections and concentrations of pyrethroid pesticides. The pyrethroid pesticide bifenthrin was detected in 69% of samples (n = 410). Detection of toxicity increased in a subset of samples tested at a more environmentally relevant test temperature (15 °C), and the magnitude of toxicity was much greater, indicating pyrethroid pesticides as a probable cause. Pyrethroid toxicity thresholds (LC50) were exceeded in 83% of samples with high toxicity. Principal components analysis related pyrethroids, metals and total organic carbon to urban land use.

Monitoring the aquatic toxicity of mosquito vector control spray pesticides to freshwater receiving waters.

Pesticides are applied to state and local waterways in California to control insects such as mosquitoes, which are known to serve as a vector for West Nile Virus infection of humans. The California State Water Resources Control Board adopted a National Pollutant Discharge Elimination System General Permit to address the discharge to waters of the United States of pesticides resulting from adult and larval mosquito control. Because pesticides used in spray activities have the potential to cause toxicity to nontarget organisms in receiving waters, the current study was designed to determine whether toxicity testing provides additional, useful environmental risk information beyond chemical analysis in monitoring spray pesticide applications. Monitoring included a combination of aquatic toxicity tests and chemical analyses of receiving waters from agricultural, urban, and wetland habitats. The active ingredients monitored included the organophosphate pesticides malathion and naled, the pyrethroid pesticides etofenprox, permethrin, and sumithrin, pyrethrins, and piperonyl butoxide (PBO). Approximately 15% of the postapplication water samples were significantly toxic. Toxicity of half of these samples was attributed to the naled breakdown product dichlorvos. Toxicity of 2 other water samples likely occurred when PBO synergized the effects of pyrethroid pesticides that were likely present in the receiving system. Four of 43 postapplication sediment samples were significantly more toxic than their corresponding pre-application samples, but none of the observed toxicity was attributed to the application events. These results indicate that many of the spray pesticides used for adult mosquito control do not pose significant acute toxicity risk to invertebrates in receiving systems. In the case of naled in water, analysis of only the active ingredient underestimated potential impacts to the receiving system, because toxicity was attributed to the breakdown product, dichlorvos. Toxicity testing can provide useful risk information about unidentified, unmeasured toxicants or mixtures of toxicants. In this case, toxicity testing provided information that could lead to the inclusion of dichlorvos monitoring as a permit requirement.

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.

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

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

Pyrethroid and organophosphate pesticide-associated toxicity in two coastal watersheds (California, USA).

Portions of the Santa Maria River and Oso Flaco Creek watersheds in central California, USA, are listed as impaired under section 303(d) of the Clean Water Act and require development of total maximum daily load (TMDL) allocations. These listings are for general pesticide contamination, but are largely based on historic monitoring of sediment and fish tissue samples that showed contamination by organochlorine pesticides. Recent studies have shown that toxicity in these watersheds is caused by organophosphate pesticides (water and sediment) and pyrethroid pesticides (sediment). The present study was designed to provide information on the temporal and spatial variability of toxicity associated with these pesticides to better inform the TMDL process. Ten stations were sampled in four study areas, one with urban influences, and the remaining in agriculture production areas. Water toxicity was assessed with the water flea Ceriodaphnia dubia, and sediment toxicity was assessed with the amphipod Hyalella azteca. Stations in the lower Santa Maria River had the highest incidence of toxicity, followed by stations influenced by urban inputs. Toxicity identification evaluations and chemical analysis demonstrated that the majority of the observed water toxicity was attributed to organophosphate pesticides, particularly chlorpyrifos, and that sediment toxicity was caused by mixtures of pyrethroid pesticides. The results demonstrate that both agriculture and urban land uses are contributing toxic concentrations of these pesticides to adjacent watersheds, and regional water quality regulators are now using this information to develop management objectives.