Kenneth D. Racke

Environmental fate of chlorpyrifos.

Chlorpyrifos is an organophosphorus compound that displays broad-spectrum insecticidal activity against a number of important arthropod pests. As a result, it is employed in a wide variety of agricultural and specialty pest control scenarios. Various formulations of chlorpyrifos have been developed to maximize stability and contact with pests and minimize human exposure. From corn agriculture in the United States to termite control in Japan to cotton agriculture in Egypt to citrus horticulture in Spain, chloropyrifos has been successfully employed to combat insect and other arthropod pests threatening the production of food and fiber and maintenance of human health. Due to the nonpolar nature of the chlorpyrifos molecule, it possesses a low water solubility (< 2 ppm) and great tendency to partition from aqueous into organic phases in the environment (log P of 4.7-5.3). It is characterized by an average soil and sediment sorption coefficient (Koc) of 8498 and aquatic bioconcentration factor of 100-5100 in fish. As a result of its high propensity for sorption, its movement through and over the soil profile is limited. It has been found to be relatively immobile vertically in soil and has not proved to be a groundwater contaminant. Surface runoff and erosion mobility are also low, and, in general, less than 0.3% of soil surface application has been observed to move even under the heaviest simulated precipitation conditions. Chlorpyrifos has an intermediate vapor pressure (2 x 10(-5) mm Hg, 25 degrees C), and under some conditions volatility is a significant mechanism of dissipation. This is especially true for plant foliage, from which it is the major means of loss, to some extent from water surfaces, and to a lesser degree from moist soil surfaces. Chlorpyrifos is a degradable compound, and both abiotic and biotic transformation processes effect its degradation within environmental compartments (Fig. 1). In all cases, the major pathway of transformation involves cleavage of the phosphate ester bond to form 3,5,6-trichloro-2-pyridinol (TCP). Hydrolytic transformation, although relatively slow in pure water under ideal conditions (half-lives of 29-74 d at pH 7, 25 degrees C), may be catalyzed under certain environmental conditions. These include alkaline conditions in water (pH > or = 8) and alkaline (pH > or = 7.5) and air-dry conditions in soil, and in some soils hydrolysis may be the major means of dissipation (Fig. 2).(ABSTRACT TRUNCATED AT 400 WORDS)

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.

Foliar Interception and Retention Values after Pesticide Application. A Proposal for Standardized Values for Environmental Risk Assessment (Technical Report)

In performing risk assessments for plant protection products by applicants or regulators in relation to the registration of the products, an important aspect to take into account is the foliar interception and retention of the active substance of the product on the plant. An overview is given of the approaches to this item in several parts of the world. The relevant circumstances and influencing variables, such as growth phase, planting density, and some physicochemical characteristics (e.g., vapor pressure and Henrys coefficient) are dealt with. Finally, a proposal is presented for how to take into account the phenomenon of foliar interception and retention in the initial phase, first tier, of the risk assessment process.

SIGNIFICANCE OF THE LONG RANGE TRANSPORT OF PESTICIDES IN THE ATMOSPHERE

Synopsis:Since the 1960’s there has been a growing body of data regarding the presence of pesticides in the atmosphere. The monitoring results obtained show that traces of pesticides may undergo long range transport and be deposited considerable distances away from the treatment areas, including remote areas such as the Arctic and Antarctic regions. Pesticides have been found in air, rain, cloud water, fog and snow. The appearance and subsequent behaviour of pesticides in the atmosphere are complex processes and the concentrations found depend on several variables such as their volatility, photostability, method of application and extent of use. Whilst volatility of pesticides can be linked to their Henry’s Law constant this is very much a simplification since it is also influenced by the surfaces treated, e.g. soil or leaves, and by the extent to which aerosols are formed during the application. The disappearance of pesticides from the atmosphere is due to hydrolysis, indirect photolysis via OH. radicals and to deposition in rain. Pesticides which are resistant to hydrolysis and photolysis can be transported over great distances, for example, organochlorine insecticides have been detected in the Arctic regions. In general, concentrations in rainwater are, when detected, in the low or sub mg/l range and highest concentrations are found during the time of application. The use of fugacity models has been shown to be a useful approach to predict concentrations in air. Under most conditions the presence of pesticides in air, or rainwater, has no significant effects on non-target systems, including direct and indirect effects. Exceptions to this are damage by auxin-type herbicides to sensitive plants which has resulted on restrictions in their use in certain areas and transient chlorotic spotting thought to be caused by drift of aerosols from application of low rate sulfonyl urea herbicides. For animal species one possible exception has been postulated. This is for persistent organochlorine pesticides in Arctic regions where, due to the very oligotrophic nature of the Arctic ocean, they are more liable to bioaccumulate and be transported in the food web giving enhanced levels in mothers’ milk.

Release of pesticides into the environment and initial concentrations in soil, water, and plants

Considerable information exists as to the initial concentrations of pesticide residues to be expected in soils, plants, and water. Empirical or theoretical models have been developed for incorporating this data into exposure assessments for humans as well as terrestrial and aquatic wildlife. In addition, monitoring data exists for many older products, especially with respect to typical concentrations observed in food commodities for human consumption and in surface and ground waters. Estimated and observed concentrations of pesticides in these matrices have been routinely employed for more than 30 years in assessing the potential impacts of pesticides on a variety of biologically relevant endpoints. The same data will also prove useful for exposure assessments of endocrine active substances. There are some additional research needs, however. First, further research and development is needed to ensure that estimation and monitoring methods for pesticide concentrations in soil, water, and food are applicable and utilized for all important and relevant cultural, agronomic, and environmental conditions. This is especially true with respect to developing countries and tropical climates, which are often disproportionately ignored in favor of developing countries and temperate climates. Second, methodologies for collection of monitoring data and generation of modeled estimates for pesticide residues in soil, water, and food need to be carefully designed with the requirements of higher-tier, probabilistic exposure assessments in view. Although worst-case, point estimates or analyses may be useful for screening-level assessments, advanced assessments targeted at addressing the likelihood of biologically relevant exposures are urgently required by scientists and regulatory authorities for reaching sound risk assessment and risk management decisions.