Chronic larval and adult honey bee laboratory testing: Which dietary additive should be considered when a test substance is not solubilized in acetone?

Chronic toxicity tests on adult and larval honey bees (Apis mellifera) can require the use of dietary additives (solvents, emulsifiers, adjuvants and viscosifier agents) when the active ingredient of plant protection products cannot be dissolved or does not remain stable and homogeneous within the test diets. Acetone is the widely used and accepted solvent allowed within the international regulatory guidelines, but it can be ineffective in keeping certain compounds in solution and can cause toxicity to adults and larvae. In this publication, we present an evaluation of alternative additives in adult and larval diets. Six dietary additives including five solvents (ethanol, isopropanol, n-propanol, propylene glycol and triethylene glycol) and a viscosifier agent (xanthan gum) at five concentrations along with a negative control and a solvent control (acetone) were investigated at seven laboratories. The safe levels for bees were determined for each of the additives used in the 10-day chronic adult and 22-day chronic larval tests. In the 10-day chronic adult study, ethanol and isopropanol were found to be safe at concentrations ≤ 5.0 %, while xanthan gum can be reliably used at concentrations ≤ 0.1 %. Greater variability across laboratories was observed for N-propanol, propylene glycol, and triethylene glycol and these agents may cause mortality when added to diets at concentrations above 0.25-0.5 %. The safe levels of additives to larval diet in the 22-day chronic larval test had a greater variability and were generally lower than what were observed for adult diet. Our results do not recommend the inclusion of ethanol or n-propanol into the larval diet, and isopropanol, propylene glycol, and triethylene glycol may cause mortality at concentrations above 0.25-0.5 %. Safe levels for xanthan gum were more variable than what was observed for adults, but it can be used reliably at concentrations ≤ 0.05 %. Our analyses conclude that several additives can be integrated successfully in honey bee laboratory bioassays at levels that cause low mortality to adults and larvae.

Insecticide washoff from concrete surfaces: characterization and prediction.

Pesticide runoff from impervious surfaces is a significant cause of aquatic contamination and ecologic toxicity in urban waterways. Effective mitigation requires better understanding and prediction of off-site transport processes. Presented here is a comprehensive study on pesticide washoff from concrete surfaces, including washoff tests, experimental data analysis, model development, and application. Controlled rainfall experiments were conducted to characterize washoff loads of commercially formulated insecticides with eight different active ingredients. On the basis of the analysis of experimental results, a semimechanistic model was developed to predict pesticide buildup and washoff processes on concrete surfaces. Three pesticide product specific parameters and their time dependences were introduced with empirical functions to simulate the persistence, transferability, and exponential characteristics of the pesticide washoff mechanism. The parameters were incorporated using first-order kinetics and Fick's second law to describe pesticide buildup and washoff processes, respectively. The model was applied to data from 21 data sets collected during 38 rainfall events, with parameters calibrated to pesticide products and environmental conditions. The model satisfactorily captured pesticide mass loads and their temporal variations for pesticides with a wide range of chemical properties (log KOW = 0.6-6.9) under both single and repeated (1-7 times) rainfall events after varying set times (1.5 h∼238 days after application). Results of this study suggested that, in addition to commonly reported physicochemical properties for the active ingredient of a pesticide product, additional parameters determined from washoff experiments are required for risk assessments of pesticide applications on urban impervious surfaces.

Pesticide washoff from concrete surfaces: literature review and a new modeling approach.

Use of pesticides over impervious surfaces like concrete and subsequent washoff and offsite transport significantly contribute to pesticide detection and aquatic toxicity in urban watersheds. This paper presents a comprehensive study on pesticide washoff from concrete surfaces, including reviews of reported experiments and existing models, development of a new model, and its application to controlled experimental conditions. The existing modeling approaches, mainly the exponential function and power-law function, have limitations in explaining pesticide washoff processes characterized from experimental data. Here we develop a mathematical and conceptual framework for pesticide washoff from concrete surfaces. The new modeling approach was designed to characterize pesticide buildup and washoff processes on concrete surfaces, including the time-dependence of the washoff potential after application and the dynamics in pesticide washoff during a runoff event. One benefit is the ability to integrate and quantify multiple processes that influence pesticide washoff over concrete surfaces, including product formulation, aging effects, multiple applications, and rainfall duration and intensity. The model was applied to experimental configurations in two independent studies, and satisfactorily simulated the measured temporal variations of pesticide washoff loads from concrete surfaces for the five selected pyrethroids in 15 runoff events. Results suggested that, with appropriate parameterization and modeling scenarios, the model can be used to predict washoff potentials of pesticide products from concrete surfaces, and support pesticide risk assessments in urban environmental settings.

Factors contributing to the off-target transport of pyrethroid insecticides from urban surfaces.

Pyrethroid insecticides used in urban and suburban contexts have been found in urban creek sediments and associated with toxicity in aquatic bioassays. The objectives of this study were to evaluate the main factors contributing to the off-target transport of pyrethroid insecticides from surfaces typical of residential landscapes. Controlled rainfall simulations over concrete, bare soil, and turf plots treated individually with pyrethroid insecticides in a suspension concentrate, an emulsifiable concentrate, or a granule formulation were conducted at different rainfall intensities and different product set-time intervals. Pyrethroid mass washoff varied by several orders of magnitude between experimental treatments. Suspension concentrate product application to concrete yielded significantly greater washoff than any other treatment; granule product application to turf yielded the least washoff. Fractional losses at 10 L of runoff ranged from 25.9 to 0.011% of pyrethroid mass applied, and 10 L nominal mass losses ranged from 3970 to 0.18 µg. Mass washoff depended principally on formulation and surface type combination and, to a lesser degree, on set-time interval and rainfall intensity. Treatment effects were analyzed by ANOVA on main factors of formulation, surface type, and set time. Factor effects were not purely additive; a significant interaction between formulation and surface type was noted.

Wash off of imidacloprid and fipronil from turf and concrete surfaces using simulated rainfall.

The surface runoff of imidacloprid granular product (GR) from turf surfaces, and imidacloprid emulsifiable concentrate (EC), fipronil suspension concentrate (SC) products and fipronil byproducts from concrete surfaces was investigated during 1h rainfall simulations at 50 mm/h or 25 mm/h with product incubation times of 1.5 h, 1 d, 7 d, and 14 d. About 57.3% of the applied mass of imidacloprid, corresponding to an event mean concentration of 392.0 µg/L, was washed off from the concrete surfaces after 1.5h of incubation. After 1 d, 7 d, and 14 d of incubation on either turf or concrete surfaces, up to 5.9% of the applied mass of pesticide was removed in each of the run-off events. The maximum concentrations of pesticides were observed in the initial fraction of the runoff collected in the first rainfall event. They were 157.8, 3267.8 and 143.3 µg/L for imidacloprid GR, imidacloprid EC and fipronil SC, respectively. Imidacloprid was not persistent on concrete surfaces, with run-off concentrations below detection limits in 7d incubation experiments. The cumulative mass losses of imidacloprid from turf and fipronil from concrete had a linear relation with cumulative surface run-off depth, while cumulative mass losses of imidacloprid from concrete surfaces were better fit by a power function of the cumulative surface run-off depth. The concentrations of fipronil in the runoff from the third rainfall event at 14 d incubation time were still relatively high and ranged from 12.0 to 31.0 µg/L. A toxicity unit approach was also employed to evaluate the potential acute toxicity of fipronil and its byproducts to aquatic organisms.

Formulation effects and the off-target transport of pyrethroid insecticides from urban hard surfaces.

Controlled rainfall experiments utilizing drop-forming rainfall simulators were conducted to study various factors contributing to off-target transport of off-the-shelf formulated pyrethroid insecticides from concrete surfaces. Factors evaluated included active ingredient, product formulation, time between application and rainfall (set time), and rainfall intensity. As much as 60% and as little as 0.8% of pyrethroid applied could be recovered in surface runoff depending primarily on product formulation, and to a lesser extent on product set time. Resulting wash-off profiles during one-hour storm simulations could be categorized based on formulation, with formulations utilizing emulsifying surfactants rather than organic solvents resulting in unique wash-off profiles with overall higher wash-off efficiency. These higher wash-off efficiency profiles were qualitatively replicated by applying formulation-free neat pyrethroid in the presence of independently applied linear alkyl benzene sulfonate (LAS) surfactant, suggesting that the surfactant component of some formulated products may be influential in pyrethroid wash-off from urban hard surfaces.