Assessing the ecotoxicity of pesticide transformation products

Once released to the environment, pesticides may be degraded by abiotic and biotic processes. While parent compounds are assessed in detail in many regulatory schemes, the requirements for the assessment of transformation products are less well developed. This study was therefore performed to explore the relationships between the toxicity of transformation products and their parent compounds and to develop a pragmatic approach for use in the risk assessment of transformation products. Data were obtained on the properties and ecotoxicity of transformation products arising from a wide range of pesticides. Generally, transformation products were less toxic to fish, daphnids, and algae than their parent compound. In instances where a product was more toxic, the increase in toxicity could be explained by either (1) the presence of a pesticide toxicophore; (2) the fact that the product is the active part of a propesticide; (3) the product is accumulated to a greater extent than the parent compound; or (4) the product has a more potent mode of action than the parent. On the basis of the findings, an approach has been proposed to estimate the ecotoxicity of transformation products based on chemical structure and data on the toxicity of the parent compound. The assessments can be performed at an early stage in the risk assessment process to identify those substances that require further testing.     

Indicators for the exposure assessment of transformation products of organic micropollutants

Environmental transformation products of organic micropollutants have the potential to be similarly or even more mobile, persistent, ortoxic than their parent compounds. They should, therefore, be included in chemical hazard and risk assessment procedures as well as in the assessment of soil and water quality. To fulfill this requirement most efficiently, screening approaches that select relevant transformation products for detailed assessment are needed. This paper presents two process-based multimedia, multispecies models that allow us to quantitatively estimate the environmental fate of transformation products. The resulting exposure patterns are assessed with two indicators: joint persistence (JP), which describes the temporal extent of environmental exposure to a parent compound and its transformation products, and the predicted relative aquatic concentrations (RAC), which estimate the relative concentrations of parent compounds and their transformation products in surface water bodies. As a case study, JP and RAC are calculated for 16 pesticides and their relevant transformation products. The results for the JP indicator confirm the importance of considering transformation products in the assessment of overall persistence; for example, in the context of PBT assessments. Comparison of RAC results with monitoring data on herbicides and their transformation products shows the suitability of our approach for estimating relative concentrations in surface water, and as a consequence, its usefulness in identifying transformation products for future water quality monitoring programs. Transformation products of triketones and other highly used acidic herbicides are specifically identified as targets.     

Including transformation products into the risk assessment for chemicals: the case of nonylphenol ethoxylate usage in Switzerland

A method for applying the risk assessment approach using ratios of predicted environmental concentrations (PECs) and predicted no-effect concentrations (PNECs) to mixtures of parent compounds and their environmental transformation products is presented. Nonylphenol ethoxylates (NPnEOs) and a selection of their most relevant transformation products are investigated as a case study illustrating the method. The PEC values of NPnEO and its transformation products are calculated with a regional multimedia fate model including the transformation kinetics of the NPnEO degradation cascade. PNEC values are derived from a selection of toxicity data on NPnEO and its transformation products. The toxicity of the emerging mixture of NPnEO and its transformation products is then estimated under the assumption of concentration addition (similar mode of action). On this basis, PEC-to-PNEC ratios for the aquatic environment and the sediment are calculated for the individual components of the mixture and the mixture itself. For this purpose, average release rates of NPnEO and its transformation products from Swiss sewage treatment plants were used. While the PEC values of the individual components do not exceed the corresponding PNEC values, the risk quotient of the mixture in water is greater than 1. In sediment, the mixture does not exceed a risk quotient of 1. A combination of sensitivity and scenario analyses is employed to identify the upper and lower bounds of the results.     

Chronic exposure of the oligochaete Lumbriculus variegatus to polycyclic aromatic compounds (PACs): bioavailability and effects on reproduction

This study aimed to monitor PAC availability to the oligochaete Lumbriculus variegatus during 28 days of exposure to spiked sediments, in order to obtain reliable chronic effect concentrations for reproduction. Sediment toxicity tests were performed using three pairs of PAC isomers: two homocyclic compounds (anthracene and phenanthrene), two azaarenes (acridine and phenanthridine), and the two main transformation products of the azaarenes (acridone and phenanthridone). During the experiment, available PAC concentrations in pore water (estimated using solid phase microextraction) decreased more than total PAC concentrations in the sediment. Relating effect concentrations to PAC concentrations in pore water and in organisms showed that the two homocyclic compounds caused narcotic effects during chronic exposure, but only one of the four tested heterocyclic PACs caused narcotic effects. The transformation product phenanthridone was not toxic at the tested concentrations (up to 4000 micromol/kg dry sediment), whereas EC50 values for the parent compound phenanthridine and the isomer acridone were below the estimated limit for narcosis, suggesting a specific mode of action. These results demonstrated the unpredictable (isomer) specific toxicity of azaarenes and their transformation products, emphasizing the need of chronic toxicity testing to gain insight into the long-term effects of heterocyclic PACs, which have been overlooked in risk assessment.     

Comparative ecotoxicological hazard assessment of beta-blockers and their human metabolites using a mode-of-action-based test battery and a QSAR approach

We analyzed nontarget effects of the beta-blockers propranolol, metoprolol, and atenolol with a screening test battery encompassing nonspecific, receptor-mediated, and reactive modes of toxic action. All beta-blockers were baseline toxicants and showed no specific effects on energy transduction nor endocrine activity in the yeast estrogen and androgen screen, and no reactive toxicity toward proteins and DNA. However, in a phytotoxicity assay based on the inhibition of the photosynthesis efficiency in green algae, all beta-blockers were 10 times more toxic than their modeled baseline toxicity. Baseline- and phytotoxicity effects increased with hydrophobicity. The beta-blockers showed concentration addition in mixture experiments, indicating a mutual specific nontarget effect on algae. Using literature data and quantitative structure-activity relationships (QSAR), we modeled the total toxic potential of mixtures of the beta-blockers and their associated human metabolites for the phytotoxicity endpoint with two scenarios. The realistic scenario (I) assumes that the metabolites lose their specific activity and act as baseline toxicants. In the worst-case scenario (II) the metabolites exhibitthe same specific mode of action as their parent drug. For scenario (II), metabolism hardly affected the overall toxicity of atenolol and metoprolol, whereas propranolol's hazard potential decreased significantly. In scenario (I), metabolism reduced the apparent EC50 of the mixture of parent drug and metabolite even further. The proposed method is a simple approach to initial hazard assessment of pharmaceuticals and can guide higher tier testing. It can be applied to other classes of pollutants, e.g., biocides, as well as to environmental transformation products of pollutants.     

Prioritization of pesticide environmental transformation products in drinking water supplies

Receiving waters within catchments may be exposed to many different transformation products following the application of pesticides. As environmental waters are abstracted for drinking water treatment these compounds may pose a risk to human health. This paper describes a prioritization approach for identifying the most important transformation products in drinking water sources. The approach can be applied to different geographical areas that have suitable pesticide usage data. The risk based approach incorporates data on pesticide usage and toxicity as well as transformation product formation, mobility, and persistence. The application of the approach is illustrated for two geographical areas that have good quality pesticide usage data: Great Britain and California. The transformation products with the highest risk index and a complete experimentally derived data set for Great Britain were 3,5,6-trichloro-2-pyridinol, thifensulfuron acid, and kresoxim-methyl acid and for California were carbendazim, aldicarb sulfoxide, and RP30228.     

Microbial transformation of triadimefon to triadimenol in soils: selective production rates of triadimenol stereoisomers affect exposure and risk

The microbial transformation of triadimefon, an agricultural fungicide of the 1,2,4-triazole class, was followed at a nominal concentration of 50 μg/mL over 4 months under aerobic conditions in three different soil types. Rates and products of transformation were measured, as well as enantiomer fractions of parent and products. The transformation was biotic and enantioselective, and in each soil the S-(+)-enantiomer reacted faster than the R-(-) one. Rates of the first-order reactions were 0.047, 0.057, and 0.107 d(-1) for the three soils. The transformation involves reduction of the prochiral ketone moiety of triadimefon to an alcohol, resulting in triadimenol, which has two chiral centers and four stereoisomers. The abundances of the four product stereoisomers were different from each other, but abundance ratios were similar for all three soil types. Triadimenol is also a fungicide; the commercial product is composed of two diastereomers of unequal amounts (ratio of about 4.3:1), each having two enantiomers of equal amounts. However, the triadimenol formed by soil transformation of triadimefon exhibited no such stereoisomer profile. Instead, different production rates were observed for each of the four triadimenol stereoisomers, resulting in all stereoisomer concentrations being different from each other and very different from concentration/abundance patterns of the commercial standard. This result is important in risk assessment if the toxicity of the environmental transformation product were to be compared to that of the commercial triadimenol. Because triadimenol stereoisomers differ in their toxicities, at least to fungi and rats, the biological activity of the triadimenol formed by microbes or other biota in soils depends on the relative abundances of its four stereoisomers. This is an exposure and risk assessment issue that, in principle, applies to any chiral pesticide and its metabolites.     

Input dynamics and fate in surface water of the herbicide metolachlor and of its highly mobile transformation product metolachlor

A large number of herbicide transformation products has been detected in surface waters and groundwaters of agricultural areas, often even in higher concentrations and more frequently than their parent compounds. However, their input dynamics and fate in surface waters are still rather poorly understood. This study compares the aquatic fate, concentration levels, and dynamics of the transformation product metolachlor ethanesulfonic acid (metolachlor ESA) and its parent compound metolachlor, an often-used corn herbicide. To this end, laboratory photolysis studies were combined with highly temporally resolved concentration measurements and lake mass balance modeling in the study area of Lake Greifensee (Switzerland). It is found that the two compounds show distinctly different concentration dynamics in the lake tributaries. Concentration-discharge relationships for metolachlor ESA in the main tributary showed a high baseflow concentration and increasing discharge dependence during harvest season, whereas baseflow concentrations of metolachlor were negligible and the discharge dependence was restricted to the period immediately following application. From this it was estimated that 70% of the yearly load of metolachlor ESA to the lake was due to groundwater recharge, whereas, for metolachlor, the bigger part of the load, 50-80%, stemmed from event-driven runoff. Lake mass balance modeling showed that the input dynamics of metolachlor and metolachlor ESA are reflected in their concentration dynamics in the lake's epilimnion and that both compounds show a similar fate in the epilimnion of Lake Greifensee during the summer months with half-lives on the order of 100-200 days, attributable to photolysis and another loss process of similar magnitude, potentially biodegradation. The behavior of metolachlor ESA can likely be generalized to other persistent and highly mobile transformation products. In the future, this distinctly different behavior of mobile pesticide transformation products should find a more appropriate reflection in exposure models used in chemical risk assessment and in pesticide risk management.     

Using chemical reactivity to provide insights into environmental transformations of priority organic substances: the Fe⁰-mediated reduction of Acid Blue 129

Sulfonated anthracenedione dyes are medium priority organic compounds targeted for environmental assessment under the Government of Canada's Chemical Management Plan (CMP). Since organic compounds undergo transformations in environmental matrices, understanding these transformations is critical for a proper assessment of their environmental fate. In the current study, we used zero-valent iron (ZVI) to provide insight into reductive transformation processes available to the anthracenedione dye, Acid Blue 129 (AB 129), a dye which is used in the textile industry. At high temperatures, we found that AB 129 was rapidly reduced (within 3 h) after being adsorbed onto the ZVI-surface, whereupon decomposition took place via multiple competitive and consecutive reaction pathways. Reaction products were identified using state-of-the-art accurate mass Liquid Chromatography-Quadrupole Time of Flight-Mass Spectroscopy (LC-QToF-MS). Five transformation products were identified, including a genotoxic (and thus, potentially carcinogenic) end-product, 2,4,6-trimethylaniline. The same products were found at room temperature, demonstrating that the transformation pathways revealed here could plausibly arise from biological and/or environmental reductions of AB 129. Our results demonstrate the importance of identifying reaction product arising from priority substances as part of the environmental risk assessment process.     

Principles for the risk assessment of genetically modified microorganisms and their food products in the European Union

Genetically modified microorganisms (GMMs) are involved in the production of a variety of food and feed. The release and consumption of these products can raise questions about health and environmental safety. Therefore, the European Union has different legislative instruments in place in order to ensure the safety of such products. A key requirement is to conduct a scientific risk assessment as a prerequisite for the product to be placed on the market. This risk assessment is performed by the European Food Safety Authority (EFSA), through its Scientific Panels. The EFSA Panel on Genetically Modified Organisms has published complete and comprehensive guidance for the risk assessment of GMMs and their products for food and/or feed use, in which the strategy and the criteria to conduct the assessment are explained, as well as the scientific data to be provided in applications for regulated products. This Guidance follows the main risk assessment principles developed by various international organisations ( and ). The assessment considers two aspects: the characterisation of the GMM and the possible effects of its modification with respect to safety, and the safety of the product itself. Due to the existing diversity of GMMs and their products, a categorisation is recommended to optimise the assessment and to determine the extent of the required data. The assessment starts with a comprehensive characterisation of the GMM, covering the recipient/parental organism, the donor(s) of the genetic material, the genetic modification, and the final GMM and its phenotype. Evaluation of the composition, potential toxicity and/or allergenicity, nutritional value and environmental impact of the product constitute further cornerstones of the process. The outcome of the assessment is reflected in a scientific opinion which indicates whether the product raises any safety issues. This opinion is taken into account by the different European regulatory authorities prior to a decision regarding authorisation to commercialise the product.     

农产品质量安全风险评估研究进展

农产品质量安全问题不仅关系到消费者的身体健康,也成为我国加入WTO后保护国内产业、扩大农产品出口的巨大障碍。风险评估是解决当前农产品质量安全问题,确立农产品质量安全政策和指南的科学依据,对保护消费者健康和促进国际贸易至关重要。本文分析了影响农产品质量安全的危害因素及来源,并针对农产品化学性污染和生物性污染两种不同危害因素风险评估的4个方面:危害识别、危害描述、暴露评估、风险描述进行研究,总结了我国农产品质量安全风险评估研究现状。     

Quantitative risk assessment of Campylobacter spp. in poultry based meat preparations as one of the factors to support the development of risk-based microbiological criteria in Belgium

The objective of this study was to do an exercise in risk assessment on Campylobacter spp. for poultry based meat preparations in Belgium. This risk assessment was undertaken on the demand of the competent national authorities as one of the supportive factors to define risk-based microbiological criteria. The quantitative risk assessment model follows a retail to table approach and is divided in different modules. The contamination of raw chicken meat products (CMPs) was represented by a normal distribution of the natural logarithm of the concentration of Campylobacter spp. (ln[Camp]) in raw CMPs based on data from surveillance programs in Belgium. To analyse the relative impact of reducing the risk of campylobacteriosis associated with a decrease in the Campylobacter contamination level in these types of food products, the model was run for different means and standard deviations of the normal distribution of the ln[Camp] in raw CMPs. The limitation in data for the local situation in Belgium and on this particular product and more precisely the semi-quantitative nature of concentration of Campylobacter spp. due to presence/absence testing, was identified as an important information gap. Also the knowledge on the dose-response relationship of Campylobacter spp. was limited, and therefore three different approaches of dose-response modelling were compared. Two approaches (1 and 2), derived from the same study, showed that the reduction of the mean of the distribution representing the ln[Camp] in raw CMPs is the best approach to reduce the risk of Campylobacter spp. in CMPs. However, for the simulated exposure and approach 3 it was observed that the reduction of the standard deviation is the most appropriate technique to lower the risk of campylobacteriosis. Since the dose-response models used in approach 1 and 2 are based on limited data and the reduction of the mean corresponds with a complete shift of the contamination level of raw CMPs, demanding high efforts from the poultry industry, it is proposed to lower the standard deviation of the concentration of Campylobacter spp. in raw CMPs. This proposal corresponds with the elimination of the products that are highly contaminated. Simulation showed that eating raw chicken meat products can give rise to exposures that are 10(10) times higher than when the product is heated, indicating that campaigns are important to inform consumers about the necessity of an appropriate heat treatment of these type of food products.     

环境中二苯甲酮类紫外稳定剂的风险评估研究进展

二苯甲酮类紫外稳定剂是一类新型环境污染物,已经在环境中检出,严重威胁了人体健康和生态系统。然而,国内对环境中二苯甲酮类紫外稳定剂风险评估仍显不足。本文从危害识别、危害特征描述、暴露评估和相关政策法规等方面系统介绍了环境中二苯甲酮类紫外稳定剂的来源、危害及残留状况。针对目前环境中二苯甲酮类紫外稳定剂风险评估研究现状,提出了进一步深入开展水产品中二苯甲酮类紫外稳定剂风险评估的建议。     

Photochemical Formation of Brominated Dioxins and Other Products of Concern from Hydroxylated Polybrominated Diphenyl Ethers (OH-PBDEs)

The photochemical conversion of selected hydroxylated polybrominated diphenyl ethers (OH-PBDEs) to dioxins and other products was investigated. OH-PBDEs, which are both transformation products of polybrominated diphenyl ethers and naturally occurring compounds, undergo direct photolysis to yield a number of products that may have a higher toxicity than their parent. The compounds investigated were 6-OH-PBDE 99, 6'-OH-PBDE 100, and 6'-OH-PBDE 118. Of special interest was 6'-OH-PBDE 118, a potential transformation product of PBDE 153 that is capable of photochemically generating 2,3,7,8-tetrabromodibenzo-p-dioxin, the most toxic brominated dioxin congener. Photolysis experiments were conducted at two different pH values to assess the photochemical behavior of both the phenol and phenolate form of the compounds. The percent conversion to dioxin and other photoproducts was determined and the natural product, 6-OH-PBDE 99, was found to have the highest conversion to dioxin (7%). The reaction quantum yields ranged from 0.027 to 0.16 across all photolysis conditions. In addition, it is shown that all three compounds are capable of photochemically generating other compounds of concern, including brominated phenols and a dibenzofuran.     

Quantifying recontamination through factory environments--a review

Recontamination of food products can be the origin of foodborne illnesses and should therefore be included in quantitative microbial risk assessment (MRA) studies. In order to do this, recontamination should be quantified using predictive models. This paper gives an overview of the relevant modelling approaches that are available in the literature to quantify recontamination via factory environment. Different recontamination routes are described: recontamination via air, via processing equipment or via hand contact. Unfortunately, not many available models are directly applicable to the food industry; most models are developed for aquatic or environmental systems. Finally, a general systematic approach is proposed for modelling contamination from surfaces via air, hands or liquid into the product and ranges for the parameters are given.     

Sunscreen claims,risk management and consumer confidence

This essay is a personal reflection on how the concept of risk is impacting on the development of sunscreen products and claims, and whether these developments are jeopardizing consumer confidence. In order to estimate the risk of harm, we need not only to identify a hazard but, as importantly, determine the degree of exposure to the hazard and understand the health of impact of consequent exposure. A practice by many manufacturers is simply to market a product that claims to be protective against a hazard with little, or no, regard to exposure or consequence. The inherent danger with this approach is to undermine trust in product efficacy and in so doing to put at risk consumer confidence in both product and manufacturer. An example of this approach using infrared radiation as the hazard will be discussed.     

Environmental transformations of silver nanoparticles: impact on stability and toxicity

Silver nanoparticles (Ag-NPs) readily transform in the environment, which modifies their properties and alters their transport, fate, and toxicity. It is essential to consider such transformations when assessing the potential environmental impact of Ag-NPs. This review discusses the major transformation processes of Ag-NPs in various aqueous environments, particularly transformations of the metallic Ag cores caused by reactions with (in)organic ligands, and the effects of such transformations on physical and chemical stability and toxicity. Thermodynamic arguments are used to predict what forms of oxidized silver will predominate in various environmental scenarios. Silver binds strongly to sulfur (both organic and inorganic) in natural systems (fresh and sea waters) as well as in wastewater treatment plants, where most Ag-NPs are expected to be concentrated and then released. Sulfidation of Ag-NPs results in a significant decrease in their toxicity due to the lower solubility of silver sulfide, potentially limiting their short-term environmental impact. This review also discusses some of the major unanswered questions about Ag-NPs, which, when answered, will improve predictions about their potential environmental impacts. Research needed to address these questions includes fundamental molecular-level studies of Ag-NPs and their transformation products, particularly Ag(2)S-NPs, in simplified model systems containing common (in)organic ligands, as well as under more realistic environmental conditions using microcosm/mesocosm-type experiments. Toxicology studies of Ag-NP transformation products, including different states of aggregation and sulfidation, are also required. In addition, there is the need to characterize the surface structures, compositions, and morphologies of Ag-NPs and Ag(2)S-NPs to the extent possible because they control properties such as solubility and reactivity.     

药食两用天麻的安全性评价研究进展

天麻是我国的名贵中药材,作为药食同源物质被广泛食用及药用。国家相关部门已经批准,将天麻按照传统既是食品又是中药材的物质进行试点管理。随着天麻药食同源在现代食品领域的广泛应用,有关天麻食品、功能性食品、活性物质、复方制剂等天麻制品的研究开发会越来越多。天麻制品的毒理学研究还不够深入,多为急性、遗传毒性试验,而亚急性、长期毒性试验的数据较少;天麻素、天麻复方制剂的临床安全性评估多为联合用药评价分析,缺乏单独使用的安全性数据。因此,探讨天麻的食用安全性对天麻制品开发具有一定的参考意义。本文概述了天麻制品的毒理学研究、临床安全性评价及环境污染风险评估研究现状,为未来天麻制品的安全性评价研究提供了新方向和思路。     

Hazard identification and exposure assessment for microbial food safety risk assessment

The four cornerstones of microbial food safety risk assessment are hazard identification, exposure assessment, hazard characterization, and risk characterization. These steps represent a systematic process for identifying adverse consequences and their associated probabilities arising from consumption of foods that may be contaminated with microbial pathogens and/or microbial toxins. This paper presents a discussion of the first two steps: hazard identification and exposure assessment, and considerations for different approaches that can be used to analyze the relevant information.     

Microbiological risk assessment for personal care products

Regulatory decisions regarding microbiological safety of cosmetics and personal care products are primarily hazard‐based, where the presence of a potential pathogen determines decision‐making. This contrasts with the Food industry where it is a commonplace to use a risk‐based approach for ensuring microbiological safety. A risk‐based approach allows consideration of the degree of exposure to assess unacceptable health risks. As there can be a number of advantages in using a risk‐based approach to safety, this study explores the Codex Alimentarius (Codex) four‐step Microbiological Risk Assessment (MRA) framework frequently used in the Food industry and examines how it can be applied to the safety assessment of personal care products. The hazard identification and hazard characterization steps (one and two) of the Codex MRA framework consider the main microorganisms of concern. These are addressed by reviewing the current industry guidelines for objectionable organisms and analysing reports of contaminated products notified by government agencies over a recent 5‐year period, together with examples of reported outbreaks. Data related to estimation of exposure (step three) are discussed, and examples of possible calculations and references are included. The fourth step, performed by the risk assessor (risk characterization), is specific to each assessment and brings together the information from the first three steps to assess the risk. Although there are very few documented uses of the MRA approach for personal care products, this study illustrates that it is a practicable and sound approach for producing products that are safe by design. It can be helpful in the context of designing products and processes going to market and with setting of microbiological specifications. Additionally, it can be applied reactively to facilitate decision‐making when contaminated products are released on to the marketplace. Currently, the knowledge available may only allow a qualitative or semi‐quantitative rather than fully quantitative risk assessment, but an added benefit is that the disciplined structuring of available knowledge enables clear identification of gaps to target resources and if appropriate, instigate data generation.