Evaluation of soil ecotoxicity tests with functional endpoints for the risk assessment of plant protection products

This paper outlines the state-of-the-art in discussing tests with functional endpoints for the soil compartment for regulatory purposes. In spite of the fact that organic matter decomposition is one of the most important functions in the soil ecosystem, this process has not been the subject of a test requirement for risk assessment of plant protection products until very recently. Since EU Directive 91/414/EEC concerning the placing of plant protection products on the market requires in its Annex III, point 10.6.2 (entitled “Effects on other soil, non-target macro-organisms”), the evaluation of effects on organic matter breakdown, there is an urgent need to fulfil this requirement. The use of functional endpoints in terrestrial model ecosystems is also under discussion in the framework of the notification process for chemicals. Four potential methods (bait-lamina-test, litterbag test, minicontainer test, cotton-strip assay) taken from ecological literature are briefly reviewed and evaluated in this paper using several defined criteria regarding their usefulness for registration purposes. In this context, areas for further research are identified. The insecticide Dimilin (a.i. diflubenzuron) is used as an example to show how such a test improves risk assessment. Therefore, it is strongly recommended that a guidance paper describing the main principles of at least one test method on organic matter decomposition should be written in order to realise the EU requirement.     

A teratological assessment of four trihalomethanes in the rat

Abstract

Four trihalomethanes were administered by gavage to Sprague‐Dawley rats from day 6 to day 15 of gestation. Chloroform (Ch) was administered at levels of 100, 200 and 400 mg/kg and bromoform (Br), bromodichloromethane (BDCM) and chlorodibromomethane (CDBM) were administered at levels of 50, 100 or 200 mg/kg/day. A separate control was used for each compound. Maternal weight gain was depressed in all groups receiving Ch and at the highest dose levels of BDCM and CDBM. Ch administration caused decreased maternal hemoglobin and hematocrit values at all dose levels and also produced increased serum inorganic phosphorus and cholesterol at the highest dose. Liver enlagement was observed at all dose levels of Ch but in no other treatment groups. Evidence of a fetotoxic response was observed with Ch, CDBM and Br but not BDCM. No dose‐related histopathological changes were observed in either mothers or fetuses as a result of treatment. None of the chemicals tested produced any teratogenic effects.     

Application of chemometric analysis based on physicochemical and chromatographic data for the differentiation origin of plant protection products containing chlorpyrifos

The aim of this study was to investigate the similarities and dissimilarities between the pesticide samples in form of emulsifiable concentrates (EC) formulation containing chlorpyrifos as active ingredient coming from different sources (i.e., shops and wholesales) and also belonging to various series. The results obtained by the Headspace Gas Chromatography–Mass Spectrometry method and also some selected physicochemical properties of examined pesticides including pH, density, stability, active ingredient and water content in pesticides tested were compared using two chemometric methods. Applicability of simple cluster analysis and also principal component analysis of obtained data in differentiation of examined plant protection products coming from different sources was confirmed. It would be advantageous in the routine control of originality and also in the detection of counterfeit pesticides, respectively, among commercially available pesticides containing chlorpyrifos as an active ingredient.     

Pesticide residues in products of plant origin in the European Union

The results of a co-ordinated monitoring programme for pesticide residues in the European Union and Norway carried out in 1996 and 1997 are presented. The aim of this programme is to work towards a system, which makes it possible to estimate actual dietary pesticide intake for the population of the European Union. Based on a statistically dérived sampling plan and within the limited number of pesticides/commodities analysed, the most critical pesticides (benomyl group and dithiocarbamates) and commodities (mandarine and lettuce) were identified. In case of detected non-compliances, repeated sampling and, if necessary, enforcement actions are to be taken by national authorities. The programme will be continued in the next years.     

Transformation products of pharmaceuticals in surface waters and wastewater formed during photolysis and advanced oxidation processes - degradation, elucidation of byproducts and assessment of their biological potency

The significance of transformation products of pharmaceuticals resulting from the parent compounds during natural and technical photolytic processes and advanced oxidation processes has only recently started to attract the interest of the scientific community. Even though relevant studies have now started to produce important knowledge, still many gaps exist that hinder the in-depth and broad understanding of the extent of the potential problems stemming from the presence of such compounds in the environment and the applicability of such techniques for wastewater and potable water treatment. The great diversity of pharmaceutical compounds, the variety of processes and conditions applied by the various research groups active in the field, and the endless list of potential biological endpoints that could potentially be explored, coupled with the limitations related to the analytical capabilities presently available, are some of the crucial parameters that characterize this challenging research direction. This review paper tries to highlight some of the most relevant studies performed so far and to summarize the parameters that prevent scientists from reaching comprehensive conclusions in relation to the formation, fate, and effects of transformation products of pharmaceutical compounds during photo-driven and advanced oxidation processes.     

Spatial trends of polybrominated diphenyl ethers in avian species: utilization of stored samples in the Environmental Specimen Bank of Ehime University (es-Bank)

The present study determined concentrations and patterns of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in specimens of open sea, and Japanese coastal and inland avian species, which have been stored in the Environmental Specimen Bank of Ehime University (es-Bank), to examine the spatial trends. PBDEs and PCBs were detected in all the muscle samples analyzed, suggesting that PBDE pollution has spread even to the remote open sea areas, as in the case of PCBs. Japanese coastal and inland birds accumulated higher concentrations of PBDEs than open sea birds. In addition, higher PBDE/PCB concentration ratios were observed in Japanese coastal and inland birds than in open sea birds, indicating the input of PBDEs into the Japanese terrestrial environment. Compositions of PBDEs varied among avian species with a predominance of BDE47 or BDE153. This could be due to differences in their habitat, food habit and/or biotransformation capacity of PBDEs.     

Reproductive toxicity assessment of surface water of the Tai section of the Yangtze River, China by in vitro bioassays coupled with chemical analysis

Reproductive toxicity of organic extracts of the surface water from the Tai section of the Yangtze River was assessed by in vitro cytotoxity assays and selected persistent organic pollutants including PCBs, OCPs and PAHs were quantified by instrumental analysis. Eleven of the US EPA priority PAHs were detected. Individual PAHs were found to range from 0.7 to 20 ng/L. Concentrations of BaP did not exceed the national drinking water source quality standard of China. However, a 286-fold concentrated organic extract induced significant reproductive toxicity in adult male rats. The morphology of cells, MTT assay and LDH release assay were all affected by exposure to the organic extracts of water. The results of the reproductive toxicity indicated that PAHs posed the greatest risk of the chemicals studied. The compounds present in the water could be bioconcentrated and result in adverse effects.     

A comparison of mixture toxicity assessment: examining the chronic toxicity of atrazine, permethrin and chlorothalonil in mixtures to Ceriodaphnia cf. dubia

Pesticides predominantly occur in aquatic ecosystems as mixtures of varying complexity, yet relatively few studies have examined the toxicity of pesticide mixtures. Atrazine, chlorothalonil and permethrin are widely used pesticides that have different modes of action. This study examined the chronic toxicities (7-d reproductive impairment) of these pesticides in binary and ternary mixtures to the freshwater cladoceran Ceriodaphnia cf. dubia. The toxicity of the mixtures was compared to that predicted by the independent action (IA) model for mixtures, as this is the most appropriate model for chemicals with different modes of action. Following this they were compared to the toxicity predicted by the concentration addition (CA) model for mixtures. According to the IA model, the toxicity of the chlorothalonil plus atrazine mixture conformed to antagonism, while that of chlorothalonil and permethrin conformed to synergism. The toxicity of the atrazine and permethrin mixture as well as the ternary mixture conformed to IA implying there was either no interaction between the components of these mixtures and/or in the case of the ternary mixture the interactions cancelled each other out to result in IA. The synergistic and antagonistic mixtures deviated from IA by factors greater than 3 and less than 2.5, respectively. When the toxicity of the mixtures was compared to the predictions of the CA model, the binary mixture of chlorothalonil plus atrazine, permethrin plus atrazine and the ternary mixture all conformed to antagonism, while the binary mixture of chlorothalonil plus permethrin conformed to CA. Using the CA model provided estimates of mixture toxicity that did not markedly underestimate the measured toxicity, unlike the IA model, and therefore the CA model is the most suitable to use in ecological risk assessments of these pesticides.     

Assessing the diurnal variability of pharmaceutical and personal care products in a full-scale activated sludge plant

An intensive sampling campaign has been carried out in a municipal wastewater treatment plant (WWTP) to assess the dynamics of the influent pharmaceutical active compounds (PhAC) and musks. The mass loadings of these compounds in wastewater influents displayed contrasting diurnal variations depending on the compound. The musks and some groups of PhACs tended to follow a similar diurnal trend as compared to macropollutants, while the majority of PhACs followed either the opposite trend or no repeatable trend. The total musk loading to the WWTP was 0.74 ± 0.25 g d⁻¹, whereas the total PhAC mass loading was 84.7 ± 63.8 g d⁻¹. Unlike the PhACs, the musks displayed a high repeatability from one sampling day to the next. The range of PhAC loadings in the influent to WWTPs can vary several orders of magnitude from one day or week to the next, representing a challenge in obtaining data for steady-state modelling purposes.     

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.     

Large-scale risk assessment of polycyclic aromatic hydrocarbons in shoreline sediments from Saudi Arabia: Environmental legacy after twelve years of the Gulf war oil spill

A large-scale assessment of polycyclic aromatic hydrocarbons (PAHs) from the 1991 Gulf War oil spill was performed for 2002-2003 sediment samples (n = 1679) collected from habitats along the shoreline of Saudi Arabia. Benthic sediment toxicity was characterized using the Equilibrium Partitioning Sediment Benchmark Toxic Unit approach for 43 PAHs (ESBTU_FCV,43). Samples were assigned to risk categories according to ESBTU_FCV,43 values: no-risk (≤1), low (>1-≤2), low-medium (>2-≤3), medium (>3-≤5) and high-risk (>5). Sixty seven percent of samples had ESBTU_FCV,43 > 1 indicating potential adverse ecological effects. Sediments from the 0-30 cm layer from tidal flats, and the >30-<60 cm layer from heavily oiled halophytes and mangroves had high frequency of high-risk samples. No-risk samples were characterized by chrysene enrichment and depletion of lighter molecular weight PAHs, while high-risk samples showed little oil weathering and PAH patterns similar to 1993 samples. North of Safaniya sediments were not likely to pose adverse ecological effects contrary to sediments south of Tanaqib. Landscape and geomorphology has played a role on the distribution and persistence in sediments of oil from the Gulf War.     

基于活力和恢复力的典型草原健康评价和群落退化分级研究

根据群落的不同退化演替状况和物种组成情况,随机选取19个位于锡林郭勒高原和呼伦贝尔高原的调查样地,进行典型草原健康评价和群落退化分级研究。结果表明,处在不同退化演替阶段的草原中的群落的优势种类型、活力和恢复力指数均存在很大差异,活力和恢复力指数不存在明显的相关性,这可能是由于活力指数表现的是植物的地上生物量,而恢复力指数表现的是植物的株/丛数,在株/丛数很多的情况下生物量可能很小;草原群落地上总生物量受放牧强度、刈割程度、围封时间、围封前群落状态和区域降水等因素的综合作用,使得各调查样地群落的活力指数差异显著;以中国科学院草原生态系统定位研究站1981年设置的围封的羊草+大针茅草原当时的状态作为参照系统,评价了呼伦贝尔高原和锡林郭勒高原典型草原的健康状况,并对其退化程度进行了量化分级,可为草原管理、植被恢复重建和生态系统健康评价提供参考。     

Iron-catalyzed oxidation of s(IV) species by oxygen in aqueous solution: Influence of pH on the redox cycling of iron

Redox cycling of Fe(II)/Fe(III) during the catalyzed aqueous S(IV) oxidation by dissolved oxygen in the presence of Fe(II) and/or Fe(III) at an initial pH_i of 4.4, often observed in atmospheric waters, was studied in detail. It has been found that the reaction rate is not considerably affected by the oxidation state of iron at the start of the reaction. An equilibrium between Fe(II) and Fe(III) was established a few minutes after the start of the reaction, regardless of the oxidation state of iron at the beginning of the experiment. The prevailing oxidation state of iron in a particular phase of the reaction depends on the concentration of S(IV) in the reaction solution. It has been found that the formation of polymerized hydroxo Fe(III) species is also included in the mechanism of the Fe-catalyzed oxidation of S(IV). The formation of these species was confirmed by the on-line measurement of Fe(II) and Fe_reac. The results also clearly demonstrate that the pH_i of the solution is a major factor, controlling the concentration of Fe(III) ions, the form of S(IV) species, and consequently the reaction rate of S(IV) oxidation by oxygen.