Quantum Yield for the Aqueous Photochemical Degradation of Chlorantraniliprole and Simulation of Its Environmental Fate in a Model California Rice Field.

The photochemical degradation of chlorantraniliprole (3-bromo-N-[4-chloro-2-methyl-6-(methylcarbamoyl)phenyl]-1-(3-chloro-2-pyridine-2-yl)-1H-pyrazole-5-carboxamide; CAP) was characterized under simulated solar light with 2-nitrobenzaldehyde (2NB) actinometry. Overall, aqueous CAP degraded quickly via direct photodegradation with no significant difference observed between high-purity water and filtered rice field water. The 24-h average half-life normalized to summer sunlight using 2NB was 34.5 ± 4.0 h (jCAP,env = 0.020 ± 0.0023 h-1 , n = 3), and the calculated apparent quantum yield in simulated sunlight was 0.0099 ± 0.00060. These new values were used-alongside previously characterized data for air/and soil/water partitioning, degradation in soil, and hydrolysis-in the Pesticides in Flooded Applications Model to simulate CAP dissipation in a model California (USA) rice field. The model estimates an environmental half-life of 26 d in the aqueous phase, but the bulk of applied CAP remains in the benthic zone and degrades, with estimated half-lives of 29 and 92 d in flooded and drained fields, respectively. Environ Toxicol Chem 2020;39:1929-1935. © 2020 SETAC.

Influence of pH and Divalent Metals Relevant to California Rice Fields on the Hydroxide-Mediated Hydrolysis of the Insecticide Chlorantraniliprole.

The hydrolysis of chlorantraniliprole (3-bromo-N-[4-chloro-2-methyl-6-(methylcarbamoyl)phenyl]-1-(3-chloro-2-pyridine-2-yl)-1H-pyrazole-5-carboxamide; CAP) was investigated over the pH range of 6-10, reflective of California rice field conditions, with variable additions of Cu2+, Zn2+, Mn2+, or Ni2+. Dissipation accelerated as pH increased with half-lives ranging from 26.9 to 2.2 days with slight inhibition in rice field water. The addition of divalent metals was not observed to catalyze the hydrolysis of CAP at pH 6, indicating that the insecticide is likely to remain recalcitrant to hydrolysis in neutral or acidic surface waters. However, Mn2+ and Ni2+ were observed to inhibit hydrolysis at pH 8 and 9. Attenuated total reflectance Fourier transform infrared analysis supports the conclusion that divalent metals may withdraw electron density from the amide nitrogen via interaction with the amide oxygen, though additional quantum chemical modeling is necessary to provide further mechanistic insights. Overall, the hydrolysis of CAP in California rice fields and their surrounding surface waters will be dominated by pH and inhibited by dissolved metal species.

Influence of Flooding, Salinization, and Soil Properties on Degradation of Chlorantraniliprole in California Rice Field Soils.

Chlorantraniliprole (3-bromo-N-[4-chloro-2-methyl-6-(methylcarbamoyl)phenyl]-1-(3-chloro-2-pyridine-2-yl)-1H-pyrazole-5-carboxamide; CAP) was granted supplemental registration for use in rice cultivation in California through December, 2018. Previous work investigated the partitioning of CAP in California rice field soils; however, its degradation in soils under conditions relevant to California rice culture has not been investigated. The degradation of CAP in soils from two California rice fields was examined under aerobic and anaerobic conditions with varying salinity via microcosm experiments. Results indicate that soil properties governing bioavailability may have a greater influence on degradation than flooding practices or field salinization over a typical growing season. Differences between native and autoclaved soils (t1/2 = 59.0-100.2 and 78.5-171.7 days) suggest that biological processes were primarily responsible for CAP degradation; however, future work should be done to confirm specific biotic processes as well as to elucidate abiotic processes, such as degradation via manganese oxides and formation of nonextractable residues, which may contribute to its dissipation.

Aqueous Photolysis of Benzobicyclon Hydrolysate.

Benzobicyclon [3-(2-chloro-4-(methylsulfonyl)benzoyl)-2-phenylthiobicyclo[3.2.1]oct-2-en-4-one] is a pro-herbicide used against resistant weeds in California rice fields. Persistence of its active product, benzobicyclon hydrolysate, is of concern. As an acidic herbicide, the neutral species photolyzed faster than the more predominant anionic species ( t1/2 = 1 and 320 h, respectively; natural sunlight), from a >10-fold difference in the quantum yield. Dissolved organic matter in natural waters reduced direct photolysis and increased indirect photolysis compared to high-purity water. Light attenuation appears significant in rice field water and can slow photolysis. These results, used in the pesticides in flooded applications model with other experimental properties, indicate that a floodwater hold time of 20 days could be sufficient for dissipation of the majority of initial aqueous benzobicyclon hydrolysate prior to release. However, soil recalcitrance of both compounds will keep aqueous benzobicyclon hydrolysate levels constant months after benzobicyclon application.

Impact of Simulated California Rice-Growing Conditions on Chlorantraniliprole Partitioning.

Chlorantraniliprole (3-bromo-N-[4-chloro-2-methyl-6-(methylcarbamoyl)phenyl]-1-(3-chloro-2-pyridine-2-yl)-1H-pyrazole-5-carboxamide, CAP; water solubility 1.023 mg·L-1) was recently registered for application on California rice fields. Air- and soil-water partitioning of CAP were investigated under simulated California rice field conditions through calculation of KH and ΔawH and a batch equilibrium method following OECD 106 guidelines, respectively. KH and ΔawH were determined to be 1.69 × 10-16 - 2.81 × 10-15 atm·m3·mol-1 (15-35 °C) and 103.68 kJ·mol-1, respectively. Log(Koc) ranged from 2.59 to 2.96 across all soil and temperature treatments. Log(KF) ranged from 0.61 to 1.14 across all soil, temperature, and salinity treatments. Temperature and salinity increased sorption significantly at 35 °C (P < 0.05) and 0.2 M (P < 0.0001), respectively, while soil properties impacted sorption across all treatments. Overall results, corroborated using the Pesticides in Flooded Applications Model, indicate that volatilization of CAP is not a major route of dissipation and sorption of CAP to California rice field soils is moderately weak and reversible.

Azithromycin sorption and biodegradation in a simulated California river system.

Azithromycin (AZ) is a widely-used macrolide antibiotic that is continually deposited into natural waterways by sewage effluent. Though recognized as an emerging contaminant of concern, little is known about its fate and transport in aquatic systems. American River soils and water were used to determine degradation of AZ in microcosms simulating flooded (anaerobic) and non-flooded (aerobic) California watershed conditions. Under aerobic conditions the degradation rate constant (k=0.0084 ± 0.0039 day-1) and DT50 (82.52 ± 56.54 days) were calculated, as AZ disappearance indicated potential degradation. However, based on concurrent product appearance, less than one percent of the parent degraded over 150 days. Throughout the experiment microbial growth was observed by culturing in tryptic soy broth despite antibiotic addition and soil being autoclaved. Sorption likely contributes to AZ recalcitrance, thus the soil-water partition coefficient (log Kd = 2.18 Lkg-1), Freundlich sorption and desorption coefficients (log Kf = 1.90 ± 0.14 and log Kfd = 2.51 ± 0.30, respectively), and organic-carbon-normalized distribution coefficient (log Koc = 4.25 Lkg-1) were also calculated. Based on these results, AZ degradation in aquatic systems will likely be very limited and transport will fluctuate based on the extent of soil-water saturation or bulk movement of sediment.

Dissipation of the Herbicide Benzobicyclon Hydrolysate in a Model California Rice Field Soil.

The herbicide benzobicyclon (BZB; 3-(2-chloro-4-(methylsulfonyl)benzoyl)-2-phenylthiobicyclo[3.2.1]oct-2-en-4-one) has recently been approved for use on California rice fields by the United States Environmental Protection Agency (U.S. EPA). Hydrolysis of BZB rapidly forms the active compound, benzobicyclon hydrolysate (BH), whose fate is currently not well understood. A model California rice soil was used to determine BH soil dissipation. The pKa and aqueous solubility were also determined, as experimental values are not currently available. Sorption data indicate BH does not bind tightly, or irreversibly, with this soil. Flooding resulted in decreased BH loss, indicating anaerobic microbes are less likely to transform BH compared to aerobic microorganisms. Temperature increased dissipation, while autoclaving decreased BH loss. Overall, dissipation was slow regardless of treatment. Further investigation is needed to elucidate the exact routes of loss in soil, though BH is expected to dissipate slowly in flooded rice field soil.

Comparison of Direct and Indirect Photolysis in Imazosulfuron Photodegradation.

Imazosulfuron, a sulfonylurea herbicide used in rice cultivation, has been shown to undergo photodegradation in water, but neither the photochemical mechanism nor the role of indirect photolysis is known. The purpose of this study was to investigate the underlying processes that operate on imazosulfuron during aqueous photodegradation. Our data indicate that in the presence of oxygen, most photochemical degradation proceeds through a direct singlet-excited state pathway, whereas triplet-excited state imazosulfuron enhanced decay rates under low dissolved oxygen conditions. Oxidation by hydroxyl radical and singlet oxygen were not significant. At dissolved organic matter (DOM) concentrations representative of rice field conditions, fulvic acid solutions exhibited faster degradation than rice field water containing both humic and fulvic acid fractions. Both enhancement, via reaction with triplet-state DOM, and inhibition, via competition for photons, of degradation was observed in DOM solutions.

Aerobic versus Anaerobic Microbial Degradation of Clothianidin under Simulated California Rice Field Conditions.

Microbial degradation of clothianidin was characterized under aerobic and anaerobic California rice field conditions. Rate constants (k) and half-lives (DT50) were determined for aerobic and anaerobic microcosms, and an enrichment experiment was performed at various nutrient conditions and pesticide concentrations. Temperature effects on anaerobic degradation rates were determined at 22 ± 2 and 35 ± 2 °C. Microbial growth was assessed in the presence of various pesticide concentrations, and distinct colonies were isolated and identified. Slow aerobic degradation was observed, but anaerobic degradation occurred rapidly at both 25 and 35 °C. Transformation rates and DT50 values in flooded soil at 35 ± 2 °C (k = -7.16 × 10(-2) ± 3.08 × 10(-3) day(-1), DT50 = 9.7 days) were significantly faster than in 25 ± 2 °C microcosms (k= -2.45 × 10(-2) ± 1.59 × 10(-3) day(-1), DT50 = 28.3 days). At the field scale, biodegradation of clothianidin will vary with extent of oxygenation.

Hydrolytic Activation Kinetics of the Herbicide Benzobicyclon in Simulated Aquatic Systems.

Herbicide resistance is a growing concern for weeds in California rice fields. Benzobicyclon (BZB; 3-(2-chloro-4-(methylsulfonyl)benzoyl)-2-phenylthiobicyclo[3.2.1]oct-2-en-4-one) has proven successful against resistant rice field weeds in Asia. A pro-herbicide, BZB forms the active agent, benzobicyclon hydrolysate (BH), in water; however, the transformation kinetics are not understood for aquatic systems, particularly flooded California rice fields. A quantitative experiment was performed to assess the primary mechanism and kinetics of BZB hydrolysis to BH. Complete conversion to BH was observed for all treatments. Basic conditions (pH 9) enhanced the reaction, with half-lives ranging from 5 to 28 h. Dissolved organic carbon (DOC) hindered transformation, which is consistent with other base-catalyzed hydrolysis reactions. BH was relatively hydrolytically stable, with 18% maximum loss after 5 days. Results indicate BZB is an efficient pro-herbicide under aqueous conditions such as those of a California rice field, although application may be best suited for fields with recirculating tailwater systems.

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.

Photochemical degradation of imazosulfuron under simulated California rice field conditions.

BACKGROUND: The photodegradation of imazosulfuron (IMZ), a potent broad-spectrum herbicide, was investigated under simulated rice field conditions. Previous reports have indicated that it is photolabile, but have failed to report radiation intensity or determine a quantum yield, precluding extrapolation to environmental rates. Therefore, the objective of this investigation was to determine the photolytic rate of IMZ under simulated rice field conditions and how it is influenced by environmental factors such as turbidity, salinity and temperature. RESULTS: IMZ was efficiently photolyzed in all solutions and fitted pseudo-first-order kinetics. Degradation was faster in HPLC-grade water than in field water. Field-relevant variances in temperature, turbidity and salinity did not significantly influence degradation. The experimentally derived quantum yield for direct photolysis (2.94 × 10(3) ) was used to predict the half-life of IMZ in a California rice field (3.6 days). CONCLUSIONS: Aqueous photolysis is predicted to be an important process in the overall degradation of IMZ in the environment, regardless of variances in salinity, organic matter and temperature. Based on the predicted half-life of IMZ in a California rice field (3.6 days), state-mandated holding periods for field water post-IMZ application (30 days) are expected to allow for sufficient clearance of the herbicide (>98%), preventing significant contamination of the environment upon release of tailwater. © 2015 Society of Chemical Industry.

Photodegradation of clothianidin under simulated California rice field conditions.

BACKGROUND: Photodegradation can be a major route of dissipation for pesticides applied to shallow rice field water, leading to diminished persistence and reducing the risk of offsite transport. The objective of this study was to characterize the aqueous-phase photodegradation of clothianidin under simulated California rice field conditions. RESULTS: Photodegradation of clothianidin was characterized in deionized, Sacramento River and rice field water samples. Pseudo-first-order rate constants and DT50 values in rice field water (mean k = 0.0158 min(-1) ; mean DT50 = 18.0 equivalent days) were significantly slower than in deionized water (k = 0.0167 min(-1) ; DT50 = 14.7 equivalent days) and river water (k = 0.0146 min(-1) ; DT50 = 16.6 equivalent days) samples. Quantum yield ϕc values demonstrate that approximately 1 and 0.5% of the light energy absorbed results in photochemical transformation in pure and field water respectively. Concentrations of the photodegradation product thiazolymethylurea in aqueous photolysis samples were determined using liquid chromatography-tandem mass spectrometry and accounted for ≤17% in deionized water and ≤8% in natural water. CONCLUSION: Photodegradation rates of clothianidin in flooded rice fields will be controlled by turbidity and light attenuation. Aqueous-phase photodegradation may reduce the risk of offsite transport of clothianidin from flooded rice fields (via drainage) and mitigate exposure to non-target organisms. © 2015 Society of Chemical Industry.

Relative toxicity of bifenthrin to Hyalella azteca in 10 day versus 28 day exposures.

Many watersheds in the Central Valley region of California are listed as impaired due to pyrethroid-associated sediment toxicity. The Central Valley Regional Water Quality Control Board is developing numeric sediment quality criteria for pyrethroids, beginning with bifenthrin. Criteria are being developed using existing data, along with data from 10 d and 28 d toxicity tests with Hyalella azteca conducted as part of the current study. A single range-finder and 2 definitive tests were conducted for each test duration. Median lethal concentrations (LC50s), as well as LC20s and inhibition concentrations (IC20s) were calculated based on measured whole sediment bifenthrin concentrations and interstitial water concentrations. Sediment LC50s were also corrected for organic C content. Average LC50s were not significantly different in 10 d versus 28 d tests with H. azteca: 9.1 and 9.6 ng/g bifenthrin for 10 d and 28 d tests, respectively. Average LC20 values were also similar with concentrations at 7.1 and 7.0 for 10 d and 28 d tests, respectively. Bifenthrin inhibition concentrations (IC20s) based on amphipod growth were variable, particularly in the 28 d tests, where a clear dose-response relationship was observed in only 1 of the definitive experiments. Average amphipod growth IC20s were 3.9 and 9.0 ng/g for 10 d and 28 d tests, respectively. Amphipod growth calculated as biomass resulted in IC20s of 4.1 and 6.3 ng/g for the 10 d and 28 d tests, respectively. Lack of a clear growth effect in the longer term test may be related to the lack of food adjustment to account for amphipod mortality in whole sediment exposures. The average C-corrected LC50s were 1.03 and 1.09 µg/g OC for the 10 d and 28 d tests, respectively. Interstitial water LC50s were determined as the measured dissolved concentration of bifenthrin relative to interstitial water dissolved organic carbon. The average LC50s for dissolved interstitial water bifenthrin were 4.23 and 4.28 ng/L for the 10 d and 28 d tests, respectively. In addition, a set of 10 d and 28 d tests were conducted at 15 °C to assess the relative toxicity of bifenthrin at a lower temperature than the standard 23 °C test temperature. These results showed that bifenthrin was more toxic at the lower temperature, with LC50s of 5.1 and 3.4 ng/g bifenthrin in 10 d and 28 d tests, respectively. Amphipod growth at 15 °C after a 28 d exposure resulted in the lowest effect concentration of all experiments conducted (IC20 = 0.61 ng/g). This article discusses how bifenthrin dose-response data from 10 d and 28 d exposures inform development of sediment quality criteria for this pesticide for California Central Valley watersheds.

Abiotic partitioning of clothianidin under simulated rice field conditions.

BACKGROUND: Clothianidin is registered for pre- and post-flood application in Californian rice fields for control of the rice seed midge, Cricotopus sylvestris, and the rice water weevil, Lissorhoptrus oryzophilus. The objective was to characterize air-water and soil-water partitioning of clothianidin under simulated Californian rice field conditions. RESULTS: Clothianidin was confirmed to be non-volatile (from water) via the gas purge method, as no loss from the aqueous phase was observed at 22 and 37 °C; an upper-limit KH value was calculated at 2.9 × 10(-11) Pa m(3) mol(-1) (20 °C). Soil-water partitioning was determined by the batch equilibrium method using four soils collected from rice fields in the Sacramento Valley, and sorption affinity (Kd ), sorbent capacity, desorption and organic-carbon-normalized distribution (Koc ) were determined. Values for pH, cation exchange capacity and organic matter content ranged from 4.5 to 6.6, from 5.9 to 37.9 and from 1.25 to 1.97% respectively. The log Koc values (22 and 37 °C) ranged from 2.6 to 2.7, while sorption capacity was low at 22 °C and decreased further at 37 °C. Hysteresis was observed in soils at both temperatures, suggesting that bound residues do not readily desorb. CONCLUSIONS: Soil-water and air-water partitioning will not significantly reduce offsite transport of clothianidin from flooded rice fields via drainage.

Environmental fate and toxicology of chlorothalonil.

Chlorothalonil is a broad spectrum, non systemic, organochlorine pesticide that was first registered in 1966 for turf grasses, and later for several food crops. Chlorthalonil has both a low Henry's law constant and vapor pressure, and hence, volatilization losses are limited. Although, chlorothalonil's water solubility is low, studies have shown it to be highly toxic to aquatic species. Mammalian toxicity (to rats and mice) is moderate, and produces adverse effects such as, tumors, eye irritation and weakness. Although, there is no indication that chlorothalonil is a human carcinogen,there is sufficient evidence from animal studies to classify it as a probable carcinogen.Chlorothalonil has a relatively low water solubility and is stable to hydrolysis.However, hydrolysis under basic conditions may occur and is considered to be a minor dissipation pathway. As a result of its high soil adsorption coefficient this fungicide strongly sorbs to soil and sediment. Therefore, groundwater contamination is minimal. Degradation via direct aqueous or foliar photolysis represents a major dissipation pathway for this molecule, and the photolysis rate is enhanced by natural photosensitizers such as dissolved organic matter or nitrate. In addition to photolysis, transformation by aerobic and anaerobic microbes is also a major degradation pathway. Under anaerobic conditions, hydrolytic dechlorination produces the stable metabolite 4-hydroxy-2,5,6-trichloroisophthalonitrile. Chlorothalonil is more efficiently degraded under neutral pH conditions and in soil containing a low carbon content.

Environmental fate and toxicology of clomazone.

Clomazone, an isoxazolane herbicide, was first registered for use in 1986 for pest grasses and broad leaf weeds. Although the exact mode of action is still unclear, it is well documented that clomazone causes bleaching of foliar structures; the clomazone metabolite 5-ketoclomazone is regarded to cause the bleaching and to be the ultimate plant toxicant. Although clomazone exhibits low mammalian toxicity and is selective towards certain plant species, studies have shown that it does inhibit AChE and catalase activities. In addition, it has been found to be highly toxic to aquatic invertebrates, in particular mysid shrimp.Clomazone has a low Henry's law constant and moderate vapor pressure, and thus may volatilize from dry soils. Photolysis represents a minor dissipationpathway; however, clomazone can be photolytically degraded under both direct and indirect conditions. Clomazone has high water solubility, and it is often assumed to undergo hydrolysis easily; unfortunately, this is not the case. Clomazone is stable over a wide pH range and does not hydrolyze. Clomazone has a weak to moderates oil adsorption coefficient; therefore, its affinity to sorb to soil is minimal, rendering it a potential threat to groundwater supplies.Microbial metabolism is the major degradation pathway, resulting in products such as 5-hydroxyclomazone, hydroxymethylclomazone, 2-chlorobenzyl alcohol and 3'-hydroxyclomazone. Although clomazone has not been shown to degrade viahydrolysis, it nonetheless represents a potential threat to aquatic organisms. With this in mind, caution should be taken when applying clomazone or when draining fields that have detectable clomazone residues.

Use of semipermeable membrane devices (SPMDs) to characterize dissolved hydrocarbon fractions of both dispersed and undispersed oil.

Crude oil contamination remains a problem along coastal California and its impacts on pelagic organisms are of concern. Previous crude and dispersed oil studies showed a decrease in fish toxicity when Corexit 9500 dispersant was applied. However, observed sublethal metabolic effects were similar for both oil conditions, suggesting fish were accumulating similar dissolved hydrocarbons. This study aimed to characterize the bioavailable fraction of the water-accommodated fraction (WAF) and the chemically-enhanced WAF (CEWAF) of Prudhoe Bay Crude Oil (PBCO), using semi-permeable membrane devices (SPMDs) as fish models. Seven accumulated PAHs were identified (naphthalene, 2-methylnaphthalene, 1-methylnapthalene, biphenyl, fluorene, dibenzothiophene and phenanthrene) from 24 h static exposures. Although WAF and CEWAF oil loadings differed by eight-fold, accumulated dissolved concentrations among the seven PAHs differed by some three-fold. Overall, the use of SPMDs in characterizing the dissolved fraction of PBCO, has provided a better understanding of the bioavailability of crude and dispersed oil.