Toshiyuki Katagi

Photodegradation of Pesticides on Plant and Soil Surfaces

Photodegradation is an abiotic process in the dissipation of pesticides where molecular excitation by absorption of light energy results in various organic reactions, or reactive oxygen species such as OH*, O3, and 1O2 specifically or nonspecifically oxidize the functional groups in a pesticide molecule. In the case of soil photolysis, the heterogeneity of soil together with soil properties varying with meteorological conditions makes photolytic processes difficult to understand. In contrast to solution photolysis, where light is attenuated by solid particles, both absorption and emission profiles of a pesticide are modified through interaction with soil components such as adsorption to clay minerals or solubilization to humic substances. Diffusion of a pesticide molecule results in heterogeneous concentration in soil, and either steric constraint or photoinduced generation of reactive species under the limited mobility sometimes modifies degradation mechanisms. Extensive investigations of meteorological effects on soil moisture and temperature as well as development of an elaborate testing chamber controlling these factors seems to provide better conditions for researchers to examine the photodegradation of pesticides on soil under conditions similar to the real environment. However, the mechanistic analysis of photodegradation has just begun, and there still remain many issues to be clarified. For example, how photoprocesses affect the electronic states of pesticide molecules on soil or how the reactive oxygen species are generated on soil via interaction with clay minerals and humic substances should be investigated in greater detail. From this standpoint, the application of diffuse reflectance spectroscopy and usage or development of various probes to trap intermediate species is highly desired. Furthermore, only limited information is yet available on the reactions of pesticides on soil with atmospheric chemical species. For photodegradation on plants, the importance of an emission spectrum of the light source near its surface was clarified. Most photochemical information comes from photolysis in organic solvents or on glass surfaces and/or plant metabolism studies. Epicuticular waxes may be approximated by long-chain hydrocarbons as a very viscous liquid or solid, but the existing form of pesticide molecules in waxes is still obscure. Either coexistence of formulation agents or steric constraint in the rigid medium would cause a change of molecular excitation, deactivation, and photodegradation mechanisms, which should be further investigated to understand the dissipation profiles of a pesticide in or on crops in the field. A thin-layer system with a coat of epicuticular waxes extracted from leaves or isolated cuticles has been utilized as a model, but its application has been very limited. There appear to be gaps in our knowledge about the surface chemistry and photochemistry of pesticides in both rigid media and plant metabolism. Photodegradation studies, for example, by using these models to eliminate contribution from metabolic conversion as much as possible, should be extensively conducted in conjunction with wax chemistry, with the controlling factors being clarified. As with soil surfaces, the effects of atmospheric oxidants should also be investigated. Based on this knowledge, new methods of kinetic analysis or a device simulating the fate of pesticides on these surfaces could be more rationally developed. Concerning soil photolysis, detailed mechanistic analysis of the mobility and fate of pesticides together with volatilization from soil surfaces has been initiated and its spatial distribution with time has been simulated with reasonable precision on a laboratory scale. Although mechanistic analyses have been conducted on penetration of pesticides through cuticular waxes, its combination with photodegradation to simulate the real environment is awaiting further investigation.

Bioconcentration, Bioaccumulation, and Metabolism of Pesticides in Aquatic Organisms

The ecotoxicological assessment of pesticide effects in the aquatic environment should normally be based on a deep knowledge of not only the concentration of pesticides and metabolites found but also on the influence of key abiotic and biotic processes that effect rates of dissipation. Although the bioconcentration and bioaccumulation potentials of pesticides in aquatic organisms are conveniently estimated from their hydrophobicity (represented by log K(ow), it is still indispensable to factor in the effects of key abiotic and biotic processes on such pesticides to gain a more precise understanding of how they may have in the natural environment. Relying only on pesticide hydrophobicity may produce an erroneous environmental impact assessment. Several factors affect rates of pesticide dissipation and accumulation in the aquatic environment. Such factors include the amount and type of sediment present in the water and type of diet available to water-dwelling organisms. The particular physiological behavior profiles of aquatic organisms in water, such as capacity for uptake, metabolism, and elimination, are also compelling factors, as is the chemistry of the water. When evaluating pesticide uptake and bioconcentration processes, it is important to know the amount and nature of bottom sediments present and the propensity that the stuffed aquatic organisms have to absorb and process xenobiotics. Extremely hydrophobic pesticides such as the organochlorines and pyrethroids are susceptible to adsorb strongly to dissolved organic matter associated with bottom sediment. Such absorption reduces the bioavailable fraction of pesticide dissolved in the water column and reduces the probable ecotoxicological impact on aquatic organisms living the water. In contrast, sediment dweller may suffer from higher levels of direct exposure to a pesticide, unless it is rapidly degraded in sediment. Metabolism is important to bioconcentration and bioaccumulation processes, as is detoxification and bioactivation. Hydrophobic pesticides that are expected to be highly stored in tissues would not be bioconcentrated if susceptible to biotic transformation by aquatic organisms to more rapidly metabolized to hydrophilic entities are generally less toxic. By analogy, pesticides that are metabolized to similar entities by aquatic species surely are les ecotoxicologically significant. One feature of fish and other aquatic species that makes them more relevant as targets of environmental studies and of regulation is that they may not only become contaminated by pesticides or other chemicals, but that they constitute and important part of the human diet. In this chapter, we provide an overview of the enzymes that are capable of metabolizing or otherwise assisting in the removal of xenobiotics from aquatic species. Many studies have been performed on the enzymes that are responsible for metabolizing xenobiotics. In addition to the use of conventional biochemical methods, such studies on enzymes are increasingly being conducted using immunochemical methods and amino acid or gene sequences analysis. Such studies have been performed in algae, in some aquatic macrophytes, and in bivalva, but less information is available for other aquatic species such as crustacea, annelids, aquatic insecta, and other species. Although their catabolizing activity is often lower than in mammals, oxidases, especially cytochrome P450 enzymes, play a central role in transforming pesticides in aquatic organisms. Primary metabolites, formed from such initial enzymatic action, are further conjugated with natural components such as carbohydrates, and this aids removal form the organisms. The pesticides that are susceptible to abiotic hydrolysis are generally also biotically degraded by various esterases to from hydrophilic conjugates. Reductive transformation is the main metabolic pathway for organochlorine pesticides, but less information on reductive enzymology processes is available. The information on aquatic species, other than fish, that pertains to bioconcentration factors, metabolism, and elimination is rather limited in the literature. The kinds of basic information that is unavailable but is needed on important aquatic species includes biochemistry, physiology, position in food web, habitat, life cycle, etc. such information is very important to obtaining improved ecotoxicology risk assessments for many pesticides and other chemicals. More research attention on the behavior of pesticides in, and affect on many standard aquatic test species (e.g., daphnids, chironomids, oligochaetes and some bivalves) would particularly be welcome. In addition to improving ecotoxicology risk assessments on target species, such information would also assist in better delineating affects on species at higher trophic levels that are predaceous on the target species. There is also need for designing and employing more realistic approaches to measure bioconcentration and bioaccumulation, and ecotoxicology effects of pesticides in natural environment. The currently employed steady-state laboratory exposure studies are insufficient to deal with the complexity of parameters that control the contrasts to the abiotic processes of pesticide investigated under the strictly controlled conditions, each process is significantly affected in the natural environment not only by the site-specific chemistry of water and sediment but also by climate. From this viewpoint, ecotoxicological assessment should be conducted, together with the detailed analyses of abiotic processes, when higher-tier mesocosm studies are performed. Moreover, in-depth investigation is needed to better understand the relationship between pesticide residues in organisms and associated ecotoxicological endpoints. The usual exposure assessment is based on apparent (nominal) concentrations fo pesticides, and the residues of pesticides or their metabolites in the organisms are not considered in to the context of ecotoxicological endpoints. Therefore, more metabolic and tissue distribution information for terminal pesticide residues is needed for aquatic species both in laboratory settings and in higher-tier (microcosm, mesocosm) studies.

Surfactant Effects on Environmental Behavior of Pesticides

The potential effects of adjuvants, including surfactants used in pesticide formulation, have been extensively studied for many small organic chemicals, but similar investigation on pesticides is limited in most cases. Solubilizing effects leading to the apparently increased water solubility of a pesticide are commonly known through the preparation of formulations, but fundamental profiles, especially for a specific monodisperse surfactant, are not fully studied. Reduced volatilization of a pesticide from the formulation can be explained by analogy of a very simple organic chemical, but the actual mechanism for the pesticide is still obscure. In contrast, from the point of view of avoiding groundwater contamination with a pesticide, adsorption/desorption profiles in the presence of surfactants and adjuvants have been examined extensively as well as pesticide mobility in the soil column. The basic mechanism in micelle-catalyzed hydrolysis is well known, and theoretical approaches including the PPIE model have succeeded in explaining the observed effects of surfactants, but its application to pesticides is also limited. Photolysis, especially in an aqueous phase, is in the same situation. The dilution effect in the real environment would show these effects on hydrolysis and photolysis to be much less than expected from the laboratory basic studies, but more information is necessary to examine the practical extent of the effects in an early stage of applying a pesticide formulation to crops and soil. Many adjuvants, including surfactants, are biodegradable in the soil environment, and thus their effects on the biodegradation of a pesticide in soil and sediment may be limited, as demonstrated by field trials. Not only from the theoretical but also the practical aspect, the foliar uptake of pesticide in the presence of adjuvants has been investigated extensively and some prediction on the ease of foliar uptake can be realized in relation to the formulation technology. However, effect on root uptake of pesticides is to be further investigated. In an aqueous environment more or less contaminated by various chemicals such as detergents and their degradates, it is necessary to investigate the effect of adjuvants on uptake, bioconcentration, and trophic transfer of pesticides for better understanding of pesticide contamination of aquatic species in the aquatic environment.

Soil Column Leaching of Pesticides

In this review, I address the practical and theoretical aspects of pesticide soil mobility.I also address the methods used to measure mobility, and the factors that influence it, and I summarize the data that have been published on the column leaching of pesticides.Pesticides that enter the unsaturated soil profile are transported downwards by the water flux, and are adsorbed, desorbed, and/or degraded as they pass through the soil. The rate of passage of a pesticide through the soil depends on the properties of the pesticide, the properties of the soil and the prevailing environmental conditions.Because large amounts of many different pesticides are used around the world, they and their degradates may sometimes contaminate groundwater at unacceptable levels.It is for this reason that assessing the transport behavior and soil mobility of pesticides before they are sold into commerce is important and is one indispensable element that regulators use to assess probable pesticide safety. Both elementary soil column leaching and sophisticated outdoor lysimeter studies are performed to measure the leaching potential for pesticides; the latter approach more reliably reflects probable field behavior, but the former is useful to initially profile a pesticide for soil mobility potential.Soil is physically heterogeneous. The structure of soil varies both vertically and laterally, and this variability affects the complex flow of water through the soil profile, making it difficult to predict with accuracy. In addition, macropores exist in soils and further add to the complexity of how water flow occurs. The degree to which soil is tilled, the density of vegetation on the surface, and the type and amounts of organic soil amendments that are added to soil further affect the movement rate of water through soil, the character of soil adsorption sites and the microbial populations that exist in the soil. Parameters that most influence the rate of pesticide mobility in soil are persistence (DT50) of the pesticide, and its sorption/desorption(Koc) characteristics. These parameters may vary for the same pesticide from geographic site-to-site and with soil depth. The interactions that normally occur between pesticides and dissolved organic matter (DOM) or WDC are yet other factors that may complicate pesticide leaching behavior.The soil mobility of pesticides is normally tested both in the laboratory and in the field. Lab studies are initially performed to give researchers a preliminary appraisal of the relative mobility of a pesticide. Later, field lysimeter studies can be performed to provide more natural leaching conditions that emulate the actual field use pattern. Lysimeter studies give the most reliable information on the leaching behavior of a pesticide under field conditions, but these studies are time-consuming and expensive and cannot be performed everywhere. It is for this reason that the laboratory soil column leaching approach is commonly utilized to profile the mobility of a pesticide,and appraise how it behaves in different soils, and relative to other pesticides.Because the soil structure is chemically and physically heterogenous, different pesticide tests may produce variable DT50 and Koc values; therefore, initial pesticide mobility testing is undertaken in homogeneously packed columns that contain two or more soils and are eluted at constant flow rates. Such studies are done in duplicate and utilize a conservative tracer element. By fitting an appropriate mathematical model to the breakthrough curve of the conservative tracer selected,researchers determine key mobility parameters, such as pore water velocity, the column-specific dispersion coefficient, and the contribution of non equilibrium transport processes. Such parameters form the basis for estimating the probable transport and degradation rates that will be characteristic of the tested pesticide. Researchers also examine how a pesticide interacts with soil DOM and WDC, and what contribution from facilitated transport to mobility is made as a result of the effects of pH and ionic strength. Other methods are used to test how pesticides may interact with soil components to change mobility. Spectroscopic approaches are used to analyze the nature of soil pesticide complexes. These may provide insight into the mechanism by which interactions occur. Other studies may be performed to determine the effect of agricultural practices (e.g., tillage) on pesticide leaching under controlled conditions using intact soil cores from the field. When preferential flow is suspected to occur, dye staining is used to examine the contribution of macropores to pesticide transport. These methods and others are addressed in the text of this review.

Environmental Behavior of Synthetic Pyrethroids

New experimental approaches together with recent progress in spectroscopic technologies have given useful information to understand better the environmental fate of synthetic pyrethroids. The successive transformation of intermediate free radicals by using spin-trapping reagents and fluorophores enables their easier detection in aqueous photolysis. Chiral chromatographic analyses have shown stereo-selective metabolism of pyrethroids in soil. The knowledge on relevant enzymes in soil and plant being involved in hydrolysis, oxidation, and glucose conjugation of pyrethroids has been accumulated. Utilization of either iron-porphyrin with an oxidant or isolated leaf cells as model systems can give more information on metabolism of pyrethroids.

Novel Fluorescence Detection of Free Radicals Generated in Photolysis of Fenvalerate

Photoinduced decarboxylation via homolytic cleavage of the ester linkage generating two benzyl radicals being recoupled is known to be a major photolytic pathway of the insecticide fenvalerate in aqueous or organic solvents. A highly sensitive and selective fluorescence spectroscopic method was applied to detect these radicals generated under xenon lamp irradiation in organic solvents and aqueous acetonitrile solutions. The short-lived radicals were efficiently trapped by the nitroxide free radical having a primary amino group, and the resultant diamagnetic adducts were instantaneously derivatized with fluorescamine as a fluorescent probe. The highly fluorescent derivatives were successfully separated and detected by a reversed-phase high-performance liquid chromatography equipped with a fluorescence detector, and their structures were individually identified by liquid chromatography/mass spectrometry.

Metabolism, bioaccumulation, and toxicity of pesticides in aquatic insect larvae

Aquatic insects having a high diversity are good biotic indicators for freshwater quality. Their larvae living in freshwater are sensitive to pesticides, and its impacts has been examined not only through laboratory toxicity studies using water and sediment exposure but also through higher-tier micro-/mesocosm studies and field monitoring. Many sophisticated statistical methods have been applied to assess the impacts of pesticides at levels from species to community, but their body burden has been studied much less, especially in relation to toxicity. We review the uptake, metabolism with relevant detoxifying enzymes, and depuration of pesticides in aquatic insect larvae, which determine their body burden and help to understand the toxicity profiles specific to each chemical class. We also discuss experimental conditions, environmental factors, and species sensitivity in relation to the bioconcentration/-accumulation and toxicity of pesticides.

Uptake, Translocation, and Metabolism of Phenols by Submerged Rooted Macrophyte, Water Milfoil (Myriophyllum elatinoides).

Shoot and root uptakes of (14)C-labeled phenol (1), 4-nitrophenol (2), 4-cyanophenol (3), 4-hydroxybenzamide (4), and 4-hydroxybenzoic acid (5) by Myriophyllum elatinoides were individually examined with water or sediment treatments using the sequestered chamber. Shoot uptake of each (14)C-phenol dissolved in water amounted to 21.0% (1), 14.3% (2), 12.8% (3), 4.2% (4) and 41.7% (5) of the applied radioactivity (AR) after 96 h without significant (14)C translocation from shoot to root (≤0.9% AR), and the major metabolite produced was the glucose conjugate. On the other hand, root uptake of (14)C-phenols from sediment was much slower/smaller (≤6.6% AR), and (14)C transportation from root to shoot was scarcely observed, except for compound 5 (≤1.5% AR). For the water treatment, a kinetic analysis on uptake/metabolism was conducted using the assumed compartment. Good correlation was observed between lipophilicity and shoot uptake rate constants, and the electronic state of the hydroxyl group (σ, σ(-), or EHOMO(OH)) and the transformation rate constant of glucosidation.

Degradation of Flumioxazin in Illuminated Water–Sediment Systems

The aerobic aquatic metabolism of flumioxazin was studied in two water-sediment systems under illumination and in darkness to investigate its degradation profiles. (14)C-Flumioxazin separately labeled at the 1- and 2-positions of the tetrahydrophthalimide moiety or uniformly labeled at the phenyl ring was applied to a overlying water at a rate equivalent to 600 g ai/ha by assuming uniform distribution in the water layer to a depth of 100 cm. Flumioxazin was rapidly degraded at 20 °C in the overlying waters irrespective of irradiation with half-lives of 0.1-0.4 day. Both various modes of liquid chromatography-mass spectrometry (LC-MS) and nuclear magnetic resonance (NMR) spectroscopy analyses showed four major degradates under irradiation. Two of them were formed via successive hydrolysis of the cyclic imide ring, and the others were 2-arizidinone derivatives via photoinduced rearrangement. The presence of sediment under illumination greatly reduced the formation of these degradates and accelerated their degradation. The partitions of flumioxazin and its degradates to the bottom sediment not only reduced their fractions in the water layer subjected to hydrolysis and photolysis but also enhanced their microbial degradation in the sediment. The illuminated water-sediment systems were considered to more adequately represent the behavior of flumioxazin and its degradates in the environment than the corresponding studies of aqueous photolysis and water-sediment in darkness.

Photoinduced oxidation of the insecticide phenothrin on soil surfaces.

Photodegradation profiles of the pyrethroid insecticide phenothrin on a moistened U.S. soil thin layer was investigated by using its predominant component, the 1R-trans-isomer (I), under continuous exposure to light at >290 nm from a xenon arc lamp. Its degradation was moderately accelerated by irradiation with half-lives of 5.7-5.9 days (dark control 21-24 days), mainly via successive oxidation of the 2-methylprop-1-enyl group and ester cleavage followed by mineralization to carbon dioxide. Spectroscopic and cochromatographic analyses showed that the major degradates were the alcohol and ketone derivatives of I formed via photoinduced oxidation of the 2-methylprop-1-enyl group by singlet oxygen. The photoinduced generation of singlet oxygen in/on the soil surface was confirmed by using chemical trapping reactions together with ESR spectroscopy.