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.

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.

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.