MRL calculations based on both intra- and inter-trial residue variability.

Methods for calculating maximum residue levels or, at least, high percentile values (e.g. 95th percentile) to support the estimation have been developed in recent years. A mathematical equation is proposed that, for a set of supervised pesticide residue trials on a crop, expresses the incidence of residues as a function of residue concentration in the food commodity. Each residue concentration is expressed as a population reflecting its intra-trial variability. The equation is then the sum of these sub-populations to represent the set of trials, a population of sub-populations (POSP). The equation is formulated so that the area under the curve precisely equals the number of trials. Calculation of a residue concentration corresponding to a percentage of the area under the curve produces the required percentile. Results are generally consistent with the current OECD method calculation. The POSP calculation will be a useful tool in estimating maximum residue levels, where the first choice, other matters being acceptable, would be a value between the 95th and 99th percentiles. Replicate data are directly accommodated in the calculation. The POSP calculator can answer such questions as: what percentile corresponds to the highest residue (HR) in the residue data set?

Bioavailability of xenobiotics in the soil environment.

It is often presumed that all chemicals in soil are available to microorganisms, plant roots, and soil fauna via dermal exposure. Subsequent bioaccumulation through the food chain may then result in exposure to higher organisms. Using the presumption of total availability, national governments reduce environmental threshold levels of regulated chemicals by increasing guideline safety margins. However, evidence shows that chemical residues in the soil environment are not always bioavailable. Hence, actual chemical exposure levels of biota are much less than concentrations present in soil would suggest. Because "bioavailability" conveys meaning that combines implications of chemical sol persistency, efficacy, and toxicity, insights on the magnitude of a chemicals soil bioavailability is valuable. however, soil bioavailability of chemicals is a complex topic, and is affected by chemical properties, soil properties, species exposed, climate, and interaction processes. In this review, the state-of-art scientific basis for bioavailability is addressed. Key points covered include: definition, factors affecting bioavailability, equations governing key transport and distributive kinetics, and primary methods for estimating bioavailability. Primary transport mechanisms in living organisms, critical to an understanding of bioavailability, also presage the review. Transport of lipophilic chemicals occurs mainly by passive diffusion for all microorganisms, plants, and soil fauna. Therefore, the distribution of a chemical between organisms and soil (bioavailable proportion) follows partition equilibrium theory. However, a chemical's bioavailability does not always follow partition equilibrium theory because of other interactions with soil, such as soil sorption, hysteretic desorption, effects of surfactants in pore water, formation of "bound residue", etc. Bioassays for estimating chemical bioavailability have been introduced with several targeted endpoints: microbial degradation, uptake by higher plants and soil fauna, and toxicity to organisms. However, there bioassays are often time consuming and laborious. Thus, mild extraction methods have been employed to estimate bioavailability of chemicals. Mild methods include sequential extraction using alcohols, hexane/water, supercritical fluids (carbon dioxide), aqueous hydroxypropyl-beta-cyclodextrin extraction, polymeric TENAX beads extraction, and poly(dimethylsiloxane)-coated solid-phase microextraction. It should be noted that mild extraction methods may predict bioavailability at the moment when measurements are carried out, but not the changes in bioavailability that may occur over time. Simulation models are needed to estimate better bioavailability as a function of exposure time. In the past, models have progressed significantly by addressing each group of organisms separately: microbial degradation, plant uptake via evapotranspiration processes, and uptake of soil fauna in their habitat. This approach has been used primarily because of wide differences in the physiology and behaviors of such disparate organisms. However, improvement of models is badly needed, Particularly to describe uptake processes by plant and animals that impinge on bioavailability. Although models are required to describe all important factors that may affect chemical bioavailability to individual organisms over time (e.g., sorption/desorption to soil/sediment, volatilization, dissolution, aging, "bound residue" formation, biodegradation, etc.), these models should be simplified, when possible, to limit the number of parameters to the practical minimum. Although significant scientific progress has been made in understanding the complexities in specific methodologies dedicated to determining bioavailability, no method has yet emerged to characterized bioavailability across a wide range of chemicals, organisms, and soils/sediments. The primary aim in studying bioavailability is to define options for addressing bioremediation or environmental toxicity (risk assessment), and that is unlikely to change. Because of its importance in estimating research is needed to more comprehensively address the key environmental issue of "bioavailability of chemicals in soil/sediment."

Estimation methods for Maximum Residue Limits for pesticides.

Maximum Residue Limits (MRLs) are standards that represent the maximum residue concentration expected to be found if a pesticide is applied according to good agricultural practice (GAP). MRLs are established only where the residues in food resulting from particular use patterns of the pesticide pass the public health risk assessment. Foodstuffs are monitored for MRL compliance and MRL exceedance can have economic and trade consequences. There is a trade-off when deciding on values for MRLs. The aim is to establish MRLs at levels that are high enough to prevent chance exceedance but not so high that misuse will not be detected. Small data sets typically available for estimating MRLs present problems for establishing consistent values. A review of MRL estimation methods is presented together with an assessment of the various methods.

Developing Global Leaders for Research, Regulation, and Stewardship of Crop Protection Chemistry in the 21st Century.

To provide sufficient food and fiber to the increasing global population, the technologies associated with crop protection are growing ever more sophisticated but, at the same time, societal expectations for the safe use of crop protection chemistry tools are also increasing. The goal of this perspective is to highlight the key issues that face future leaders in crop protection, based on presentations made during a symposium titled "Developing Global Leaders for Research, Regulation and Stewardship of Crop Protection Chemistry in the 21st Century", held in conjunction with the IUPAC 13th International Congress of Pesticide Chemistry in San Francisco, CA, USA, during August 2014. The presentations highlighted the fact that leaders in crop protection must have a good basic scientific training and understand new and evolving technologies, are aware of the needs of both developed and developing countries, and have good communication skills. Concern is expressed over the apparent lack of resources to meet these needs, and ideas are put forward to remedy these deficiencies.

Disposal and degradation of pesticide waste.

Generation of pesticide waste is inevitable during every agricultural operation from storage to use and equipment cleanup. Large-scale pesticide manufacturers can afford sophisticated recovery, treatment, and cleanup techniques. Small-scale pesticide users, for example, single farms or small application businesses, struggle with both past waste problems, including contaminated soils, and disposal of unused product and equipment rinsewater. Many of these problems have arisen as a result of inability to properly handle spills during, equipment loading and rinsewater generated after application. Small-scale facilities also face continued problems of wastewater handling. Old, obsolete pesticide stocks are a vexing problem in numerous developing countries. Pesticide waste is characterized by high concentrations of a diversity of chemicals and associated adjuvants. Dissipation of chemicals at elevated concentrations is much slower than at lower concentrations, in part because of microbial toxicity and mass transfer limitations. High concentrations of pesticides may also move faster to lower soil depths, especially when pore water becomes saturated wish a compound. Thus, if pesticide waste is not properly disposed of, groundwater and surface water contamination become probable. The Waste Management Hierarchy developed as an Australian Code of Practice can serve as a guide for development of a sound waste management plan. In order of desirability, the course of actions include waste avoidance, waste reduction, waste recycling, waste treatment, and waste disposal. Proper management of pesticide stocks, including adequate storage conditions, good inventory practices, and regular turnover of products,. will contribute to waste avoidance and reduction over the long-term. Farmers can also choose to use registered materials that have the lowest recommended application rates or are applied in the least volume of water. Wastewater that is generated during equipment rinsing can be recycled by spraying it onto cropland, thus avoiding a soil contamination problem. If it is not feasible to spray out rinsates, then water treatment becomes necessary. However, for small waste generators, practical technology is still too experimental and not easily implemented on an individual farm or at a small application business. Nevertheless, research has been quite active in application of advanced oxidation processes (UV/ozonation: photoassisted Fenton reaction: photocatalysis using TiO2). Obsolete pesticide stocks in developing countries are being packaged and shipped to developed countries for incineration. Contaminated soil can also be incinerated, but this is not practical nor affordable for small waste generators. Chemical degradation of chlorinated hydrocarbon pesticides may be amenable to dechlorination by alkali polyethylene glycol treatment, but further study is needed to make the technique practical for small waste generators. Contaminated soils may be amenable to cleanup by one of several biological treatment methods, including composting, landfarming, and bioaugmentation/ biostimulation. Composting and landfarming (which may be used in combination with biostimulation) may be the most practical of the biological methods that is immediately ready for implementation by small-scale pesticide waste generators.

Pesticide residues in food--acute dietary exposure.

Consumer risk assessment is a crucial step in the regulatory approval of pesticide use on food crops. Recently, an additional hurdle has been added to the formal consumer risk assessment process with the introduction of short-term intake or exposure assessment and a comparable short-term toxicity reference, the acute reference dose. Exposure to residues during one meal or over one day is important for short-term or acute intake. Exposure in the short term can be substantially higher than average because the consumption of a food on a single occasion can be very large compared with typical long-term or mean consumption and the food may have a much larger residue than average. Furthermore, the residue level in a single unit of a fruit or vegetable may be higher by a factor (defined as the variability factor, which we have shown to be typically x3 for the 97.5th percentile unit) than the average residue in the lot. Available marketplace data and supervised residue trial data are examined in an investigation of the variability of residues in units of fruit and vegetables. A method is described for estimating the 97.5th percentile value from sets of unit residue data. Variability appears to be generally independent of the pesticide, the crop, crop unit size and the residue level. The deposition of pesticide on the individual unit during application is probably the most significant factor. The diets used in the calculations ideally come from individual and household surveys with enough consumers of each specific food to determine large portion sizes. The diets should distinguish the different forms of a food consumed, eg canned, frozen or fresh, because the residue levels associated with the different forms may be quite different. Dietary intakes may be calculated by a deterministic method or a probabilistic method. In the deterministic method the intake is estimated with the assumptions of large portion consumption of a 'high residue' food (high residue in the sense that the pesticide was used at the highest recommended label rate, the crop was harvested at the smallest interval after treatment and the residue in the edible portion was the highest found in any of the supervised trials in line with these use conditions). The deterministic calculation also includes a variability factor for those foods consumed as units (eg apples, carrots) to allow for the elevated residue in some single units which may not be seen in composited samples. In the probabilistic method the distribution of dietary consumption and the distribution of possible residues are combined in repeated probabilistic calculations to yield a distribution of possible residue intakes. Additional information such as percentage commodity treated and combination of residues from multiple commodities may be incorporated into probabilistic calculations. The IUPAC Advisory Committee on Crop Protection Chemistry has made 11 recommendations relating to acute dietary exposure.

A review of the effect of different application rates on pesticide residue levels in supervised residue trials.

Residue trial data reported by the Joint FAO/WHO Meeting on Pesticide Residues (JMPR) have been reviewed to establish whether or not the resulting residues in harvested commodities are proportional to the pesticide application rate used on the crop. Numerous sets of trials were identified where the only parameter varied was application rate or spray concentration. Analysis of this database in terms of application rate, spray concentration, formulation type, preharvest interval, crop, pesticide, residue level and application type confirms that residues scale with application rate (proportionality principle). It is anticipated that use of the proportionality principle by regulators and those interested in evaluating pesticide residue data will improve pesticide risk assessment.