Bound residues of organic compounds in the soil: the significance of pesticide persistence in soil and water: a European regulatory view

The paper discusses key aspects of the European Union (EU) regulatory policy for persistence of agricultural pesticide active substances (a.s.) in soil, which is examined in the context of the EU Authorisations Directive (91/414/EEC). For agricultural pesticide regulation within EU Member States (MS), the Authorisations Directive will gradually replace existing national systems. Discussion is concentrated on this directive, looking in particular at the Uniform Principles therein and the possible ways that these decision-making guidelines could be developed into a regulatory framework. The aim in this process of negotiated development is to identify any questions or data requirements that will be needed for persistent pesticides, over and above those generally required for all compounds. The present European regulatory position on soil non-extractable or bound residues is discussed. Finally, a brief mention of pesticide persistence in water and sediment is made.     

Pesticide persistence and bound residues in soil--regulatory significance

The paper discusses key aspects of the European Union (EU) regulatory policy related to the persistence and bound residues of agricultural pesticide active substances in soil. This is examined in the context of the EU Authorisations Directive (91/414/EEC) which will gradually replace existing national systems of agricultural pesticide regulation within EU Member States. Discussion is concentrated on this directive, looking in particular at the Uniform Principles therein and the possible ways that these decision-making guidelines could be developed into a regulatory framework. The aim in this process of negotiated development is to identify any questions or data requirements that will be needed for persistent pesticides or soil bound residues, over and above those generally required for all compounds. The present EU regulatory position on soil non-extractable or bound residues is examined and possible future improvements to the system are described and discussed.     

Plant protection products: assessing the risk for terrestrial plants

The fundamental data requirements for the authorization of plant protection products and the inclusion of active ingredients in Annex I of Council Directive 91/414/EEC (Council Directive of 15 July 1991 referring to placing plant protection products on the market (91/414/EEC). Official Journal of European Communities L 230, 19 August 1991) are described in the Annexes II and III of this Directive. Definite instructions with regard to preconditions for implementation and methodology (guidelines) concerning investigations with terrestrial plants are deficient. In addition to that, the uniform principles for the registration of plant protection products in the Member States described in Annex VI of the directive do not include any criteria concerning the risk assessment for non-target plants. However, plant protection products often show effects on non-target plants which need to be assessed as a requirement for the authorisation of the product. Hence, the German Federal Environmental Agency has developed a tiered approach to assess the effects of plant protection products on non-terrestrial plants. The risk is assessed using the effect-concentration evaluated in ecotoxicological tests and the environmental concentration predicted by validated exposure models. To protect non-target plants in terrestrial ecosystems assessment factors need to be considered. In the future, the risk for terrestrial plants needs to be addressed, also with regard to the revision of the Annexes of Directive 91/414/EEC.     

A protocol to select high quality datasets of ecotoxicity values for pesticides

The key to any QSAR model is the underlying dataset. In order to construct a reliable dataset to develop a QSAR model for pesticide toxicity, we have derived a protocol to critically evaluate the quality of the underlying data. In developing an appropriate protocol that would enable data to be selected in constructing a QSAR, we concentrated on one toxicity end point, the 96 h LC50 from the acute rainbow trout study. This end point is key in pesticide regulation carried out under 91/414/EEC. The dataset used for this exercise was from the US EPA-OPP database.     

A Protocol to Select High Quality Datasets of Ecotoxicity Values for Pesticides

Abstract

The key to any QSAR model is the underlying dataset. In order to construct a reliable dataset to develop a QSAR model for pesticide toxicity, we have derived a protocol to critically evaluate the quality of the underlying data. In developing an appropriate protocol that would enable data to be selected in constructing a QSAR, we concentrated on one toxicity end point, the 96 h LC50 from the acute rainbow trout study. This end point is key in pesticide regulation carried out under 91/414/EEC. The dataset used for this exercise was from the US EPA-OPP database.     

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.     

Comments on pesticide risk assessment by the revision of Directive EU 91/414

Introduction  

Human health and the environment are major concerns for European Commission policy on the authorisation of plant protection products. The new regulation that revises and replaces the directive 91/414/EC moves towards the adoption of a Persistent Bioaccumulation Toxicity cutoff criterion because current pesticide risk assessment (PRA) is deterministic, based on few standard cases and therefore characterised by uncertainty. This revision could create concerns about sustainability.     

Consumer health risk to pesticide residues in Salvia officinalis L. and its infusions

Salvia officinalis L. is a popular herb widely used in culinary, cosmetic, and medicinal preparations, and also as an ornamental plant. Sage crops are threatened by many diseases, such as gray mold, powdery mildew, and leaf spot, by weeds, and by pests, such as aphids. Use of crop protection products may lead to presence of pesticide residues in this herb. The aim of this work was to study presence of pesticide residues in the herb, S. officinalis L., available on the retail market in Poland, to verify their compliance with the maximum residue levels (MRLs) and to assess the chronic and acute risks associated with consumption of this herb and infusions prepared from contaminated sage plants. Ninety active substances of pesticides were analyzed, including all active substances registered in Poland for protection of the sage. Five active substances were found, one fungicide – boscalid and four insecticides: chlorpyrifos, pp′-DDT, dimethoate (residue levels above MRL) and indoxacarb. The chronic and acute exposure to pesticide residues consumed with sage did not exceed 0.02% of the acceptable daily intake (ADI) and 0.1% of the acute reference dose (ARfD), respectively.     

Investigation of various physicochemical and environmental parameter influence on pesticide sorption to ditch bed substratum by means of experimental design

Diffuse pollution by pesticide applied in rural catchments may contribute to alter water quality. Besides actions relative to the way the substances are introduced into the environment, it is also possible to limit the contamination by interfering on their transfer pathways from fields to the main river network. Especially, interface areas such as buffer strips or small ditches may play a major part in pesticide diffuse pollution decrease. In ditches a great variety of materials may act as sorbents for organic contaminants: grass, leaves, wood debris or sediments. In this study, laboratory experiments were designed to determine sorption characteristics for three herbicides with different physicochemical properties on sediment and leaves in decay commonly found in agricultural ditches. Sorption capacities were assessed for the herbicides isoproturon, diuron and diflufenican.

Experimental design was carried out to investigate the effects of five parameters on herbicide sorption on sediment and dead leaves. These parameters have been chosen according to parallel field experiment needs. Thus, the influence of initial sorbent moisture, herbicide form, i.e. active substance or commercial formulation, water quality (tap or natural ditch water), bromide ions (used as conservative tracers) and solid/liquid ratio have been tested. Within the parameters investigated, pesticide formulation and solid/liquid ratio were the most important parameters affecting pesticide sorption on both ditch materials.     

Steps towards environmental hazard assessment of new chemicals (including a hazard ranking scheme,based upon directive 79/831/EEC)

Directive 79/831/EEC came into force on 18th September 1981, enabling all the Member States of the EEC to classify so-called “new chemicals” with respect to their potential hazard to the environment and to human health on a standardized basis (Directive 79/831/EEC, Annex VII). The authors are of the opinion that the assessment of the “environmental hazard” of new chemicals before they are placed on the market, represents, in the present critical economic /ecological situation, which practically all the Member States have in common, a particular challenge to the scientific community and the competent authorities. The comments aim to achieve the following - to provide a more precise definition of certain key terms and to point out a way of selecting from the bundle of new chemicals those (few) which are potentially hazardous; a way which is clear to the administration, the scientific community, industry and, not least of all, to the individual as taxpayer and consumer.     

Results of the monitoring program of pesticide residues in organic food of plant origin in Lombardy (Italy)

Organic agriculture, with its restrictions on the use of synthetic chemical inputs, seems to offer a low-residue alternative to conventional methods. In Europe, the Council Regulation n. 2092/91/EEC regulates the production and trade of organic products and foodstuffs; national and regional legislation in Italy gives specific guidance on the surveillance of organic agriculture. However, monitoring of specific chemical residues in organic foodstuffs is part of the regular controls on food, aiming to safeguard consumer's health. Monitoring programs are coordinated at the national level by the Ministry of Health and at local level by Regional authorities. In Lombardy, in accordance with the provisions of the General Directorate of Health of the Region and under the supervision of the 15 Local Health Units, a monitoring program of pesticide residues in food of plant origin is undertaken every year. The International Centre for Pesticides and Health Risk Prevention (ICPS), on behalf of the General Directorate of Health of the Region of Lombardy, has been collecting and elaborating the data resulting from the analysis of food samples, carried out by the local laboratories. During the period 2002–2005, a total of 3508 samples food of plant origin were analyzed for pesticide residues, among which were 266 samples of organic farming products. Commodities were classified into groups (citrus fruits, legumes, vegetables, potatoes, processed products, cereals, and fruit other than citrus) and the outcomes of the analyses were reported by year, origin of the sample and presence/absence of pesticide residues. Results showed that the vast majority of organic farming products were in conformity with the relevant legislation and did not contain detectable pesticide residues. A limited amount of samples had residues at concentration below the Maximum Residue Limit (MRL). Only in one sample the residue level was above the MRL, however it did not pose a concern for public health, as demonstrated by the outcomes of dietary risk assessment. Organic fruits and vegetables can be expected to contain fewer agrochemical residues than conventionally grown alternatives. There is a widespread belief that organic agriculture products are safer and healthier than conventional foods. It is difficult to come to conclusions, but what should be made clear to the consumer is that “organic” does not automatically equal “safe”. In the absence of adequate comparative data, additional studies in this area of research are required.     

Results of the monitoring program of pesticide residues in organic food of plant origin in Lombardy (Italy)

Organic agriculture, with its restrictions on the use of synthetic chemical inputs, seems to offer a low-residue alternative to conventional methods. In Europe, the Council Regulation n. 2092/91/EEC regulates the production and trade of organic products and foodstuffs; national and regional legislation in Italy gives specific guidance on the surveillance of organic agriculture. However, monitoring of specific chemical residues in organic foodstuffs is part of the regular controls on food, aiming to safeguard consumer's health. Monitoring programs are coordinated at the national level by the Ministry of Health and at local level by Regional authorities. In Lombardy, in accordance with the provisions of the General Directorate of Health of the Region and under the supervision of the 15 Local Health Units, a monitoring program of pesticide residues in food of plant origin is undertaken every year. The International Centre for Pesticides and Health Risk Prevention (ICPS), on behalf of the General Directorate of Health of the Region of Lombardy, has been collecting and elaborating the data resulting from the analysis of food samples, carried out by the local laboratories. During the period 2002-2005, a total of 3508 samples food of plant origin were analyzed for pesticide residues, among which were 266 samples of organic farming products. Commodities were classified into groups (citrus fruits, legumes, vegetables, potatoes, processed products, cereals, and fruit other than citrus) and the outcomes of the analyses were reported by year, origin of the sample and presence/absence of pesticide residues. Results showed that the vast majority of organic farming products were in conformity with the relevant legislation and did not contain detectable pesticide residues. A limited amount of samples had residues at concentration below the Maximum Residue Limit (MRL). Only in one sample the residue level was above the MRL, however it did not pose a concern for public health, as demonstrated by the outcomes of dietary risk assessment. Organic fruits and vegetables can be expected to contain fewer agrochemical residues than conventionally grown alternatives. There is a widespread belief that organic agriculture products are safer and healthier than conventional foods. It is difficult to come to conclusions, but what should be made clear to the consumer is that "organic" does not automatically equal "safe". In the absence of adequate comparative data, additional studies in this area of research are required.     

Estimation of plant protection product application dates for environmental fate modeling based on phenological stages of crops

According to the EU directive 91/414/EEC potential environmental concentrations of pesticides have to be assessed with environmental fate models. For the calculation of pesticide concentrations it is necessary to provide an application date which has to match the specific Biologische Bundesanstalt, Bundesamt, Chemische Industrie (BBCH) stage at which the pesticide shall be applied. If these application dates are not available for a specific stage, crop and country they must be estimated, which adds an additional uncertainty to the predicted concentrations. In the present study, we therefore evaluate to which extent application dates can be derived from phenological data. For this analysis phenological data, converted to BBCH stages, of two field crops provided by the German Weather Service (DWD) were analyzed. We found a linear correlation between BBCH stages and the respective appearance dates, which can be used for interpolation of appearance dates of specific BBCH stages. Remarkably, when comparing BBCH stages from Germany and the Czech Republic almost identical correlations of appearance dates and BBCH stages were found. In the next step, soil and climate data from Joint Research Centre (JRC) were analyzed together with phenological data in order to evaluate if BBCH stages can be estimated for countries with other climate or soil conditions. This analysis revealed that temperature, global radiation and evaporation were the parameters with the strongest impact. These parameters were used for estimating appearance dates of BBCH stages for other countries. Exemplarily, appearance dates for maize BBCH were calculated for Italy. Estimated and observed appearance dates showed a high concordance (on average six days difference). Finally, the political of impact a variation of a few days on calculated pesticide concentration was analyzed. Exemplarily, the pesticide fate model FOCUS PEARL was used to estimate pesticide groundwater concentrations. When calculating concentrations for application dates varying by ± two weeks, concentrations in groundwater usually varied very little. The highest variation was found for application at BBCH 30 in maize (6.6 % variation over all scenarios). These results showed that the uncertainty included in the estimation of appearance dates of BBCH stages for other countries has a relatively small effect on the results of PEARL and consequentially on the decision of the pesticide risk assessment by changing only the application date.     

Photocatalytic oxidation of pesticide rinsate

Pesticide rinsate has been considered as one of the major threats for the environment. In this study, photocatalysts such as TiO2 and O3 were used to promote the efficiency of direct UV photolysis to prevent such wastewater pollution. Carbofuran (a carbamate pesticide) and mevinphos (an organophosphate pesticide) with a concentration of 100 mg/L were selected as the test pesticide rinsates. Parent pesticide compound, COD, and microtoxicity analysis were employed to investigate the effect of photocatalyst on the degradation efficiency of pesticide in rinsate. It was found that the photocatalytic oxidation process (UV/O3, UV/TiO2) showed much higher COD removal and microtoxicity reduction efficiency for pesticide rinsate than did direct UV photolysis under the imposed conditions, suggesting that photocatalytic oxidation processes such as UV/O3 and UV/TiO2 could be a better alternative to treat pesticide rinsate. In addition, it was noted that increasing the initial pH of mevinphos rinsate to a basic level was required to reach higher COD removal efficiency and positive microtoxicity reduction efficiency while it was not necessary for the treatment of carbofuran rinsate.     

Contents and sources of DDT impurities in dicofol formulations in Turkey

Background, aim, and scope  Dicofol is widely used as a pesticide in agriculture applications. Since dicofol is mainly synthesized from dichlorodiphenyltrichlorethane (DDT), it contains DDT as an impurity. The European Community has forced Prohibition Directive 79/117/EEC to reduce DDT in dicofol formulations. Specifically, DDT content in a dicofol formulation cannot exceed 0.1%. The goal of this project was to determine the DDT content in dicofol formulations used in Turkey. Materials and methods  Samples of all the dicofol formulations in Turkey were collected to quantify DDT and DDT-related compounds. Four replicates were used for each sample. GC/MS/MS was used to analyze p,p′ and o,p′ isomers of DDT, DDD, and DDE. A HPLC was used to determine p,p′-Cl-DDT concentrations. Results  The total DDT content of the formulated dicofol was found between 0.3% and 14.3%. The concentration of p,p′-DDE ranged from 167 to 1,042 mg kg⁻¹ in dicofol samples. p,p′-DDT concentrations were found to be 32 to 183 mg kg⁻¹. The o,p’-DDT level ranged from 2 to 34 mg kg⁻¹ in the dicofol formulations analyzed. Discussion  It was estimated that 617.8 kg of DDT was released from dicofol. The main impurity was identified as p,p-Cl-DDT. Based on these results, dicofol serves as a continuing source of DDT contamination. Conclusions  All DDT concentrations in dicofol samples analyzed were higher than the permitted 0.1% level of Prohibition Directive 79/117/EEC. The reduction of dicofol is critical since it serves as a continual source of DDT contamination. Recommendations and perspectives  DDT has been found in soil, water, and air samples. Dicofol has been identified as a contributor to continued DDT contamination in soil and water. More studies are needed to ascertain the source of DDT in the air.     

A preliminary assessment of consumer's exposure to pesticide residues in fisheries products

The fisheries products in this study comprise fish, bivalve, crustacean and cephalopod collected from different types of markets in Taiwan between the years 2001 and 2003. A total of 91 pesticide residues belonging to four major pesticide groups were tested and analyzed. The test results show that 65.40% of fish, 93.55% of shellfish, 84.92% of crustacean and 98.33% of cephalopod samples contain no detectable residues. There are only two kinds (organochlorine and organophosphate) of totally six pesticides (DDTs, dieldrin, chlorpyrifos, fenitrotion, fenthion and prothion) that have been detected from the fisheries products in this study. For there were pesticides present in the fish products, consumption of fisheries product there was no zero risk. But the exposure of consumer did not exceed the acceptable daily intakes (ADI). For male, there was the highest risk in exposure to dieldrin, which the percentage of ADI was 93.56%. This study also suggests that a yearly monitoring program for organophosphate pesticide residues in fish is necessity.     

Leaching of the organophosphorus nematicide fosthiazate

Fosthiazate is an organophosphorus nematicide which was recently included in Annex I of the Directive 91/414/EEC under the clause that it should be used with special care in soils vulnerable to leaching. Thus, the leaching of fosthiazate was investigated in columns packed with three different soils which represented situations of high (site 2), intermediate (site 1) and low (site 3) leaching potential. The recommended dose of fosthiazate was applied at the surface of the soil columns and fosthiazate fate and transport was investigated for the next two months. Fosthiazate concentrations in the leachate collected from the bottom of the columns packed with soil from site 2 exceeded 0.1 microgl(-1) in most cases. This soil was characterized as acidic, indicating longer fosthiazate persistence, with low organic matter content, indicating weak adsorption, thus representing a situation vulnerable to leaching. In contrast, the lowest concentrations of fosthiazate in the leachate were evident in the columns packed with soil from site 3. This soil was characterized as alkaline, indicating faster degradation, with higher organic matter content, indicating stronger adsorption, thus representing a situation not favoring leaching of fosthiazate. The highest concentration of fosthiazate in the leachate from the columns packed with soil from site 2 was 3.44 microgl(-1) compared to 1.17 and 0.16 microgl(-1), which were the corresponding maximum values measured in columns packed with soil from sites 1 and 3, respectively. The results of the current study further suggest that fosthiazate is mobile in soil and can leach under conducive soil conditions like acidic soils with low organic matter content.     

蜂窝陶瓷载体生物膜技术处理农药废水

以蜂窝陶瓷为载体进行生物挂膜,处理经化学预处理后的某农药厂有机磷和除虫菊酯类混合废水。对处理结果、蜂窝陶瓷载体及其生物挂膜法的特点进行了深入讨论。当废水的COD为1 600～1 700 mg/L,TP(总磷)为70～80mg/L,DMAC(二甲基乙酰胺)为0.8～1.2 mg/L,甲醇为8～12 mg/L,pH为6.8～7.2,水温为27～30℃,流量为0.1 m3/h,水力停留时间为15 h,进水容积负荷约为2.5 kg COD/(m3.d)时,发现15 d就完成生物挂膜,连续运行20 d COD去除率为73%～75%,TP去除率为53%～55%,DMAC去除率为54%～57%,甲醇去除率为91%～93%。与同样条件下的普通活性污泥处理相比,COD去除率提高85%,TP去除率提高83%,DMAC去除率提高119%,甲醇去除率提高27%,排出的剩余活性污泥量减少89%。测得的活性生物膜量为1.8 kg/m2,生物膜的厚度为1.5～2 mm,用偏光显微镜摄取了载体表面生物膜的图像。     

Model approach for estimating potato pesticide bioconcentration factor

We presented a model that estimates the bioconcentration factor (BCF) of pesticides in potatoes supposing that the pesticide in the soil solution is absorbed by the potato by passive diffusion, following Fick's second law. The pesticides in the model are nonionic organic substances, traditionally used in potato crops that degrade in the soil according to a first-order kinetic equation. This presents an expression that relates BCF with the pesticide elimination rate by the potato, with the pesticide accumulation rate within the potato, with the rate of growth of the potato and with the pesticide degradation rate in the soil. BCF was estimated supposing steady state equilibrium of the quotient between the pesticide concentration in the potato and the pesticide concentration in the soil solution. It is suggested that a negative correlation exists between the pesticide BCF and the soil sorption partition coefficient. The model was built based on the work of Trapp et al. [Trapp, S., Cammarano, A., Capri, E., Reichenberg, F., Mayer, P., 2007. Diffusion of PAH in potato and carrot slices and application for a potato model. Environ. Sci. Technol. 41 (9), 3103-3108], in which an expression to calculate the diffusivity of persistent organic substances in potatoes is presented. The model consists in adding to the expression of Trapp et al. [Trapp, S., Cammarano, A., Capri, E., Reichenberg, F., Mayer, P., 2007. Diffusion of PAH in potato and carrot slices and application for a potato model. Environ. Sci. Technol. 41 (9), 3103-3108] the hypothesis that the pesticide degrades in the soil. The value of BCF suggests which pesticides should be monitored in potatoes.