Nanopesticides or nano plant protection products represent an emerging technological development that, in relation to pesticide use, could offer a range of benefits including increased efficacy, durability, and a reduction in the amounts of active ingredients that need to be used. A number of formulation types have been suggested including emulsions (e.g., nanoemulsions), nanocapsules (e.g., with polymers), and products containing pristine engineered nanoparticles, such as metals, metal oxides, and nanoclays. The increasing interest in the use of nanopesticides raises questions as to how to assess the environmental risk of these materials for regulatory purposes. Here, the current approaches for environmental risk assessment of pesticides are reviewed and the question of whether these approaches are fit for purpose for use on nanopesticides is addressed. Potential adaptations to existing environmental risk assessment tests and procedures for use with nanopesticides are discussed, addressing aspects such as analysis and characterization, environmental fate and exposure assessment, uptake by biota, ecotoxicity, and risk assessment of nanopesticides in aquatic and terrestrial ecosystems. Throughout, the main focus is on assessing whether the presence of the nanoformulation introduces potential differences relative to the conventional active ingredients. The proposed changes in the test methodology, research priorities, and recommendations would facilitate the development of regulatory approaches and a regulatory framework for nanopesticides.
ObjectiveClimate change is likely to affect the nature of pathogens and chemicals in the environment and their fate and transport. Future risks of pathogens and chemicals could therefore be very different from those of today. In this review, we assess the implications of climate change for changes in human exposures to pathogens and chemicals in agricultural systems in the United Kingdom and discuss the subsequent effects on health impacts.Data sourcesIn this review, we used expert input and considered literature on climate change; health effects resulting from exposure to pathogens and chemicals arising from agriculture; inputs of chemicals and pathogens to agricultural systems; and human exposure pathways for pathogens and chemicals in agricultural systems.Data synthesisWe established the current evidence base for health effects of chemicals and pathogens in the agricultural environment; determined the potential implications of climate change on chemical and pathogen inputs in agricultural systems; and explored the effects of climate change on environmental transport and fate of different contaminant types. We combined these data to assess the implications of climate change in terms of indirect human exposure to pathogens and chemicals in agricultural systems. We then developed recommendations on future research and policy changes to manage any adverse increases in risks.ConclusionsOverall, climate change is likely to increase human exposures to agricultural contaminants. The magnitude of the increases will be highly dependent on the contaminant type. Risks from many pathogens and particulate and particle-associated contaminants could increase significantly. These increases in exposure can, however, be managed for the most part through targeted research and policy changes.
Degradation and sorption of six acidic pesticides (2,4-D, dicamba, fluroxypyr, fluazifop-P, metsulfuron-methyl, and flupyrsulfuron-methyl) and four basic pesticides (metribuzin, terbutryn, pirimicarb, and fenpropimorph) were determined in nine temperate soils. Results were submitted to statistical analyses against a wide range of soil and pesticide properties to (i) identify any commonalities in factors influencing rate of degradation and (ii) determine whether there was any link between sorption and degradation processes for the compounds and soils studied. There were some marked differences between the soils in their ability to degrade the different pesticides. The parameters selected to explain variations in degradation rates depended on the soil-pesticide combination. The lack of consistent behavior renders a global approach to prediction of degradation unrealistic. The soil organic carbon content generally had a positive influence on degradation. The relationship between pH and degradation rates depended on the dominant mode of degradation for each pesticide. There were positive relationships between sorption and rate of degradation for metsulfuron-methyl, pirimicarb, and all acidic pesticides considered together (all P < 0.001) and for dicamba and all bases considered together (P < 0.05). No relationship between these processes was observed for the remaining seven individual pesticides.
The ability of soils to adsorb and degrade pesticides strongly influences their environmental fate. This paper examines the adsorption and degradation of a weak acid, a new herbicide mesotrione 12-[4-(methylsulfonyl)-2-nitrobenzoyl]-1,3-cyclohexanedione], in 15 different soils from Europe and the USA. Experiments were conducted to understand the influence of soil properties, covering a wide range of soil textures, soil pH values (4.4 to 7.5), and organic carbon contents (0.6 to 3.35%). Mesotrione adsorption (Kd values ranged from 0.13 to 5.0 L/kg) was primarily related to soil pH, and to a lesser extent by percent organic carbon (%OC). As soil pH rose. mesotrione Kd values got smaller as mesotrione dissociated from the molecular to anionic form. Mesotrione degradation (half-lives ranged from 4.5 to 32 d) was also related to soil pH, getting shorter as soil pH rose. Simple regression of mesotrione adsorption against soil pH and %OC and against degradation provided a close fit to the data. The correlation between mesotrione adsorption and degradation means that Kd and half-life values are only relevant for use in environmental fate assessment if these values are "paired" for the same soil pH and %OC. The implications were as illustrated for leaching, raising important issues about combining pesticide adsorption and degradation behavior in environmental fate assessments.
Simulations of pesticide fate in soils are often based on persistence models developed nearly 30 years ago. These models predict dissipation in the field on a daily basis by correcting laboratory degradation half‐lives for actual soil temperature and moisture content. They have been extensively applied, but to date no attempt has been made to evaluate existing studies in a consistent, quantitative way. This paper reviews 178 studies comparing pesticide soil residues measured in the field with those simulated by persistence models. The simulated percentage of initial pesticide concentration at the time of 50% measured loss was taken as a common criterion for model performance. The models showed an overall tendency to overestimate persistence. Simulated values ranged from 12 to 96% of initial pesticide concentrations with a median of 60%. Simulated soil residues overestimated the target value (50% of initial) by more than a factor of 1.25 in 44% of the cases. An underestimation by more than a factor of 1.25 was found in only 17% of the experiments. Discrepancies between simulated and observed data are attributed to difficulties in characterizing pesticide behavior under outdoor conditions using laboratory studies. These arise because of differences in soil conditions between the laboratory and the field and the spatial and temporal variability of degradation. Other possible causes include losses in the field by processes other than degradation, deviations of degradation from first‐order kinetics, discrepancies between simulated and actual soil temperature and moisture content, and the lack of soil‐specific degradation parameters. Implications for modeling of pesticide behavior within regulatory risk assessments are discussed.
Sensitivity analyses using a one-at-a-time approach were carried out for leaching models which have been widely used for pesticide registration in Europe (PELMO, PRZM, PESTLA and MACRO). Four scenarios were considered for simulation of the leaching of two theoretical pesticides in a sandy loam and a clay loam soil, each with a broad distribution across Europe. Input parameters were varied within bounds reflecting their uncertainty and the influence of these variations on model predictions was investigated for accumulated percolation at 1-m depth and pesticide loading in leachate. Predictions for the base-case scenarios differed between chromatographic models and the preferential flow model MACRO for which large but transient pesticide losses were predicted in the clay loam. Volumes of percolated water predicted by the four models were affected by a small number of input parameters and to a small extent only, suggesting that meteorological variables will be the main drivers of water balance predictions. In contrast to percolation, predictions for pesticide loss were found to be sensitive to a large number of input parameters and to a much greater extent. Parameters which had the largest influence on the prediction of pesticide loss were generally those related to chemical sorption (Freundlich exponent nf and distribution coefficient Kf) and degradation (either degradation rates or DT50, QTEN value). Nevertheless, a significant influence of soil properties (field capacity, bulk density or parameters defining the boundary between flow domains in MACRO) was also noted in at least one scenario for all models. Large sensitivities were reported for all models, especially PELMO and PRZM, and sensitivity was greater where only limited leaching was simulated. Uncertainty should be addressed in risk assessment procedures for crop-protection products.
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