Atrazine leaching through surface and subsurface of a tropical Oxisol

The fate of ¹⁴C atrazine was investigated using microcosms and an undisturbed Red-Yellow Latossol (Oxisol) under simulated rainfall conditions of 200 mm water month^?1. Experiments were carried out using microcosm cores, the first with an uncovered surface soil; the second set with uncovered subsurface soil; the third with subsurface soil covered with 3 cm of cow manure and the last with subsurface soil covered with 5 cm of grass straw. Average values for the amount of atrazine leached after 60 days were as follows: surface soil 1.6%; subsurface 47.3%; subsurface plus manure 17.3% and subsurface plus straw 24.8%. In the surface soil, 53% of the ¹⁴C atrazine remained within the upper 1 cm, while in the subsurface microcosms the atrazine was more evenly distributed. The authors report that surface soil was retained atrazine and its metabolites for 60 days. The addition of a straw or manure covering to exposed subsoil helped to retard atrazine leaching.     

An evaluation of the cytochrome P450 inhibition potential of selected pesticides in human hepatic microsomes

The goal of this work was to study the ability of 18 pesticides to inhibit selective model activities for all major xenobiotic-metabolizing enzymes, namely CYP1A1/2, 2A6, 2B6, 2C8, 2C9, 2C19, 2D6, 2E1 and 3A4. Generally organophosphorus insecticides were the most potent and extensive inhibitors, especially towards CYP1A1/2 (IC₅₀ values of chlorpyrifos, fenitrothion and profenofos ～3 μ M), CYP2B6 (IC₅₀ values of chlorpyrifos and fenitrothion 2.5 μ M), CYP2C8 (fenitrothion 4.3 μ M), CYP2C9 (fenitrothion and malathion 4.8 and 2.5 μ M, respectively), CYP2D6 (chlorpyrifos and phenthoate ～ 3 μ M) and CYP3A4 (chlorpyrifos, fenitrothion and phenthoate 3–4 μ M). Otherwise there were quite considerable differences in potency and extent of inhibition between different organophosphates. Pyrethroids were in general very weak or inactive. Deltamethrin and fenvalerate were potent inhibitors of CYP2D6 (IC₅₀ values of ～ 3 μ M) while lambda-cyhalothrin potently inhibited both CYP2D6 and CYP3A4-mediated activities (IC₅₀'s about 3–4 μ M). Some pesticides caused relatively potent inhibitions sporadically (carbendazim, CYP2D6, IC₅₀ = 12 μ M; atrazine, CYP3A4, IC₅₀ = 2.8 μ M; glyphosate, CYP2C9, IC₅₀ = 3.7 μ M; hexaflumuron, IC₅₀ = 6.0 μ M). With the exceptions of alpha-cypermethrin, cypermethrin, isoproturon, carbaryl and abamectin, most pesticides inhibited relatively potently at least one CYP-selective activity, which may have relevance for potential interactions in occupational exposures and for further studies on the CYP-associated metabolism of respective pesticides.     

IMPACT OF FOUR PESTICIDES ON THE GROWTH AND METABOLIC ACTIVITIES OF TWO PHOTOSYNTHETIC ALGAE

The acute toxicity was determined for soil algae Chlorella kesslerei and Anabaena inaequalis, exposed to pesticides lindane, pentachlorophenol (PCP), isoproturon (IPU), and methyl parathion (MP). Toxicity markers included growth inhibition, chlorophyll biosynthesis, and total carbohydrate content, as a function of dose and time. Concentration response functions (EC₅₀) were estimated by probit data transformation and weighted linear regression analyses. Lindane's toxicity to Chlorella increased sharply with time (EC₅₀=7490, 10.3, 0.09 mg L^?1; 24, 48, 72 h), but remained nearly constant through 72 h with Anabaena (8.7?6.7 mg L^?1; 24–72 h). PCP at low concentrations stimulated algal growth and chlorophyll a production, an effect reversed at higher doses. Anabaena was less tolerant of PCP and MP than was Chlorella. The 96-h static EC₅₀ values for Chlorella were: 0.003, 34, 0.05, and 291 mg L^?1 for lindane, PCP, isoproturon, and MP, respectively; for Anabaena, these were 4.2, 0.13, 0.21, and 19 mg L^?1. Carbohydrate production responses were similar to those of cell density (growth) and chlorophyll biosynthesis, with MP having the lowest adverse impact. The overall relative toxicity among the four tested pesticides was: for Chlorella, lindane>IPU?PCP?MP; and for Anabaena, PCP>IPU>lindane>MP. The results confirm that toxicants such as these pesticides may affect individual (though related) species to significantly different degrees.     

Possible alkylation of inorganic Hg(II) by photochemical processes in the environment

Contamination of surface waters by pesticides continues to be the focus of concern for water authorities due to the growing evidence of their deleterious effects on aquatic life. In this context, the present work investigates the occurrence of 16 selected pesticides belonging to the classes of triazines, phenylureas, organophosphates, chloroacetanilides and thiocarbamates in surface waters from the Llobregat River (NE Spain) and some of its tributaries (Anoia and Rubí) and assesses their potential impact on the aquatic organisms by applying a recently developed index, the Short-term Pesticide Risk Index for the Surface Water System (PRISW-1), which takes into account the pesticides concentrations and their overall toxicity against three aquatic organisms (algae, Daphnia, and fish). Chemical analysis, performed by means of a fully automated method based on isotope dilution on-line solid phase extraction-liquid chromatography-electrospray-tandem mass spectrometry (on-line SPE-LC-ESI-MS/MS), revealed diuron and diazinon as the most ubiquitous and abundant compounds with levels up to 818 and 132 ng L⁻¹, respectively. Total pesticide concentrations, which in only 1 out of 66 samples surpassed 500 ng L⁻¹, were higher in the tributaries than in the river but their contribution in terms of mass-loads to the overall pesticide pollution of the Llobregat River was relatively small. Contamination increased downstream of the river and was clearly influenced by rainfall and hence river flow. Application of the PRISW-1 index indicated that, although pesticides levels fulfilled the European Union Environmental Quality Standards (EQS) for surface waters, the existing pesticide contamination poses a low to high ecotoxicological risk for aquatic organisms, that algae and macro-invertebrates are at higher risk than fish, and that the organophosphates diazinon and malathion and the phenylurea diuron are the major contributors to the overall toxicity and therefore the most problematic compounds.     

The use of a lacertid lizard as a model for reptile ecotoxicology studies: part 2--biomarkers of exposure and toxicity among pesticide exposed lizards

As part of a wider study examining the impacts of corn pesticides on lacertid lizards in north-western Portugal, we examined various physiological, biochemical, and histological biomarkers of exposure and effect among field populations of Podarcis bocagei. Biomarkers included body condition index, standard metabolic rate, locomotor performance, parasitization, glutathione oxidative pathways and related enzyme activity, lipid peroxidation and liver and testis histology. Few of the various biomarkers investigated provided statistically significant evidence of toxic effect. However, using a weight of evidence approach, we conclude that pesticides are affecting lizards living in the vicinity of pesticide exposed corn agriculture sites. Lizards from these locations present a profile of animals under metabolic stress with reduced condition indices, increased standard metabolic rate, lower incidence of hepatocyte vacuolation, altered iron metabolism, increased activation of GSH oxidation pathways, and even increased prevalence of hemoparasites.     

Leaching of azoxystrobin and its degradation product R234886 from Danish agricultural field sites

The objective was to estimate leaching of the fungicide azoxystrobin (methyl (αE)-2-[[6-(2-cyanophenoxy)-4-pyrimidinyl]oxy]-α-(methoxymethylene)benzene-acetate) and one of its primary degradation products R234886 ([(E)-2-(2-[6-cyanophenoxy)-pyrimidin-4-yloxyl]-phenyl-3-methoxyacrylic acid], major fraction) at four agricultural research fields (one sandy and three loamy) in Denmark. Water was sampled from tile drains, suction cups and groundwater wells for a minimum period of two years after application of azoxystrobin. Neither azoxystrobin nor R234886 were detected at the sandy site, but did leach through loamy soils. While azoxystrobin was generally only detected during the first couple of months following application, R234886 leached for a longer period of time and at higher concentrations (up to 2.1 μg L⁻¹). Azoxystrobin is classified as very toxic to aquatic organisms and R234886 as very harmful. Our study shows that azoxystrobin and R234886 can leach through loamy soils for a long period of time following application of the pesticide and thereby pose a potential threat to vulnerable aquatic environments and drinking water resources. We thus recommend the inclusion of azoxystrobin and R234886 in pesticide monitoring programmes and further investigation of their long-term ecotoxicological effects.     

Pesticide resistance from historical agricultural chemical exposure in Thamnocephalus platyurus (Crustacea: Anostraca)

Extensive pesticide usage in modern agriculture represents a considerable anthropogenic stressor to freshwater ecosystems throughout the United States. Acute toxicity of three of the most commonly used agricultural pesticides (Methyl Parathion^® 4ec, Tempo^® SC Ultra, Karmex^® DF, and DDT) was determined in two different wild-caught strains of the fairy shrimp Thamnocephalus platyurus. Fairy shrimp collected from playas surrounded by native grasslands were between 200% and 400% more sensitive than fairy shrimp derived from playas in agricultural watersheds for Methyl Parathion^® 4ec, Tempo^® SC Ultra, and Karmex^® DF, likely due to the development of resistance. Additionally, reduced sensitivity to DDT was observed among fairy shrimp from agriculturally-impacted playas as compared to those from native grassland-dominated playas. These data suggest that fairy shrimp inhabiting playas in agricultural regions have developed some degree of resistance to a variety of agrochemicals in response to historical usage.     

Ageing processes and soil microbial community effects on the biodegradation of soil C-2,4-D nonextractable residues

The biodegradation of nonextractable residues (NER) of pesticides in soil is still poorly understood. The aim of this study was to evaluate the influence of NER ageing and fresh soil addition on the microbial communities responsible for their mineralisation. Soil containing either 15 or 90-day-old NER of ¹³C-2,4-D (NER15 and NER90, respectively) was incubated for 90 days with or without fresh soil. The addition of fresh soil had no effect on the mineralisation of NER90 or of SOM, but increased the extent and rate of NER15 mineralisation. The analyses of ¹³C-enriched FAME (fatty acids methyl esters) profiles showed that the fresh soil amendment only influenced the amount and structure of microbial populations responsible for the biodegradation of NER15. By coupling biological and chemical analyses, we gained some insight into the nature and the biodegradability of pesticide NER.     

Combining polar organic chemical integrative samplers (POCIS) with toxicity testing to evaluate pesticide mixture effects on natural phototrophic biofilms

Polar organic chemical integrative samplers (POCIS) are valuable tools in passive sampling methods for monitoring polar organic pesticides in freshwaters. Pesticides extracted from the environment using such methods can be used to toxicity tests. This study evaluated the acute effects of POCIS extracts on natural phototrophic biofilm communities. Our results demonstrate an effect of POCIS pesticide mixtures on chlorophyll a fluorescence, photosynthetic efficiency and community structure. Nevertheless, the range of biofilm responses differs according to origin of the biofilms tested, revealing spatial variations in the sensitivity of natural communities in the studied stream. Combining passive sampler extracts with community-level toxicity tests offers promising perspectives for ecological risk assessment.     

Life cycle toxicity assessment of pesticides used in integrated and organic production of oranges in the Comunidad Valenciana, Spain

The relative impacts of 25 pesticides including acaricides, fungicides, herbicides, insecticides, and post-harvest fungicides, used in the production of oranges in Spain were assessed with current life cycle impact assessment (LCIA) tools. Chemical specific concentrations were combined with pesticide emission data and information on chemical toxicity to assess human toxicity and freshwater ecotoxicity impacts. As a case study, the relative impacts of two orange production systems in the region of Valencia, integrated pest management (IP) and organic production (OP), were assessed. The evaluation of active ingredients showed that on average acaricides have the highest human toxicity impact scores, while for freshwater ecotoxicity insecticides show the highest impact. In both impact categories the lowest impact scores were calculated for herbicides. In the production of 1 kg of orange fruits, where several kinds of pesticides are combined, results show that post-harvest fungicides can contribute more than 95% to the aggregate human toxicity impacts. More than 85% of aquatic ecotoxicity is generated by fungicides applied before harvest. The potential to reduce impacts on freshwater ecosystems is seven orders of magnitude, while impacts on human health can be reduced by two orders of magnitude. Hence, this stresses the importance of a careful pre-selection of active ingredients. In both impact categories, organic production represents the least toxic pest-control method.