预测沉积物-水微宇宙系统中化学品浓度变化的多介质模型

沉积物-水微宇宙系统是经济合作发展组织(Organisation for Economic Co-Operation and Development,OECD)颁布的化学品测试准则中推荐的试验系统之一,可用来测试化学品对底栖生物的慢性毒性。为了在试验前对化学品的浓度变化进行预测,进而确定试验方法,以摇蚊慢性毒性试验系统为例,采用环境多介质模型的建模方法,构建了一种可通过化学品理化性质和试验系统参数,对化学品在沉积物-水试验系统中浓度变化进行预测的模型。结合试验数据和文献资料,给出了模型中试验系统参数的推荐取值,并使用Matlab软件中的Simulink工具对模型进行编程和求解。以此模型为基础,给出了模型在3个方面的应用,即预测蓄积时间、预测平衡时间以及拟合试验数据。对80种已有或假想化学品的蓄积时间和平衡时间进行了计算,得出的范围分别为1~204 d和1~73 d。此外,适当修改模型结构和模型参数,也可将其应用于其他暴露场景中。但使用模型对化学品浓度进行预测时发现,模型仅对沉积物中化学品浓度的预测结果较为准确,而对水中化学品浓度的预测结果与实测值相差1~2个数量级。模型对浓度的预测精度未来仍需进一步提高。上述研究结果完善了沉积物-水微宇宙系统试验方法。     

Role of surface chemical signals in egg cannibalism and intraguild predation in ladybirds (Coleoptera: Coccinellidae)

Summary. The eggs of some ladybirds are known to be toxic to intraguild ladybird predators. However, this defence is of little value if the eggs are killed before their toxicity becomes apparent. The results presented in this paper indicate that chemicals on the surface of the eggs of two species of ladybirds signal the relative risk of cannibalism and intraguild predation. In Adalia bipunctata and Coccinella septempunctata, 87% of the chemicals are alkanes. Each species of ladybird is less reluctant to eat their own eggs than those of the other species. This asymmetry is to be expected because there is a greater risk to ladybirds from intraguild predation than cannibalism. Similar alkanes to those on the surface of the eggs of A. bipunctata are present in tracks left by larvae and on the elytra of the adults of this species. Those in the larval tracks deter females from ovipositing in patches of prey already being attacked by their larvae and those on the elytra are used in mate recognition. That different context dependent messages could be signalled by similar chemicals is an example of semiochemical parsimony. Received 25 February 2000; accepted 22 May 2000     

Die Umsetzung des EU Weißbuches zur Chemikalienpolitik

Background

Aim and Scope. Implementation of the European Union White Paper on chemicals policy shall provide more safety and more transparency in chemicals use. In the past, when assessing existing commercial substances there was often a lack of information in the fields of application of the chemicals and the exposures arising in those contexts. The White Paper therefore calls for ‘shared responsibility’. Processors and commercial users of substances are to be involved much more closely in the risk evaluation process than has hitherto been the case. They are to provide data on substance applications and exposures, and, to some extent, they are also to carry out exposure assessments and risk assessments themselves. By analysing case studies, the paper highlights the consequences of this approach.

Results and Discussion

Fear has often been voiced that these new tasks will completely overburden small and medium-sized enterprises. It is assumed that many chemicals are no longer available for smallvolume applications, as — for cost reasons — producers do not include these applications in their registration. The wording of the White Paper is not precise enough to be able to appraise the costs that will be associated with the required intensified communication. In this situation, it is essential to analyse prototypical substances and their applications in order to gain an improved understanding of the principle of shared responsibility.

Conclusions

The concrete study of several product chains has shown that the flow of information required between producers and users is very likely feasible within the context of the REACH system. For the producers of chemicals, the intensified communication will presumably make it simpler to procure information in the fields of application and exposures. However, in order to avoid users being overburdened, it will be important that registration requirements and focuses are shaped in a manner doing justice to practical realities. Users will need to undertake community-wide efforts on an industry federation and branch level. In this context, the protection of company know-how also needs to be ensured.

Recommendation and Outlook

In practice, implementation of the principle of shared responsibility can lead to intensified communication among the producers and users of chemicals. This can greatly facilitate exposure assessments and risk assessments. There is a need to develop manageable procedures that can also be implemented by small and medium-sized enterprises. Numerous proposals have been made in this context, and extensive reference material is now available.     

Systemic risks of genetically modified crops: the need for new approaches to risk assessment

Background

European chemicals legislation (registration, evaluation, authorisation and restriction of chemical substances (REACH)) requires a broad assessment of chemicals with respect to, inter alia, their health-relevant properties. Due to the extreme number of substances to be assessed and the limited current toxicological knowledge on their respective properties, REACH implicitly requires a paradigm change: away from knowledge generated mainly from costly animal experiments towards the use of mechanistic findings. Moreover, effect mechanisms at the biochemical or cellular level are essential when conclusions shall be drawn about "new" endpoints and mixtures of xenobiotics. This study (funded by the German Federal Environment Agency) describes examples of biochemical processes in the mammalian organism and how xenobiotics interfere with them. Interference with physiological processes expected to lead to adverse health effects is characterised as "toxicity pathway". The study describes toxicological endpoints not usually covered in routine animal testing and the respective toxicity pathways.

Results and conclusions

Screening for chemicals which exert effects via common toxicity pathways and subsequently conducting targeted short-term tests may generate new information about the toxicity of chemicals without performing extensive substance-by-substance animal experiments. Information on common toxicity pathways may also provide input for the assessment of mixture effects. The U.S. Environmental Protection Agency is working intensely on this concept. It involves the use of enormous amounts of data on relevant biochemical and cellular processes, which are generated by "high-throughput screening" methods, and then are combined with substance-specific kinetic data, experimental apical test outcomes and modelling. Current limitations in the regulatory use of this integrated approach on risk assessment will be outlined.     

Advances in the study of directed evolution for cellulases

If cellulose can be effectively hydrolyzed into glucose by cellulase, the production costs of hydrogen, ethanol or other chemicals from cellulosic materials will be greatly decreased, and economically viable production of biohydrogen and bioethanol will become feasible. Cellulose is degraded into glucoses by multi-component enzyme systems. Nowadays cellulases are widely used in brewing, food, bioenergy, fodder, textiles, paper, pharmaceuticals, environmental protection and other industries. However, existing cellulases have several problems that limit their wider applications, including the low turnover number for solid cellulosic materials, and low stability in adapting to various application conditions. For example, high temperature, low pH, and so on. Application of directed evolution technology may be one of the most effective ways for improving the characteristics of cellulases. This paper presents a brief review of the cellulose hydrolysis mechanism by cellulase, advances in cellulases (endoglucanase and β-glucosidase) improvement by directed evolution for several characteristics (for instance, thermal stability, pH adaptability and enzyme activity), limitations of directed evolution for cellulases, and the outlook for directed evolution for cellulase.     

Ammonium in Fließgewässern des Saale-Einzugsgebietes

Exposure assessment of rarely measured substances or newly identified chemicals requires the usage of mathematical methods. The georeferenced exposure model GREAT-ER was designed to accurately predict the concentration of ‘down-the-drain’ chemicals under consideration of their spatial and temporal variability in surface waters. In the past, successful validations of the model have been performed predominantly for small and middle-sized catchments and were accompanied by extensive monitoring of the detergent-ingredients boron and linear alkylbenzene sulphonate (LAS). A proof of the adaptability of GREAT-ER to large catchments is given here by example of the Saale river basin. Furthermore, it could be shown that ammonium is a suitable parameter for validations of the model. This corroborated the hypothesis that the non-point-emissions of ammonium are of less importance in comparison to the ammonium loads in the effluents of wastewater treatment plants.     

Einstufung und Kennzeichnung: das Instrumentarium von GHS und REACH für das Risikomanagement

For the safe use of chemicals it is necessary to identify risks in different fields of application. Not until then harmful effects to man and the environment can possibly be reduced by adequate measures. Here the identification of intrinsic properties of chemicals is an important fundamental for evaluation. Broad examination of exposition follows. REACH and GHS deliver new instruments which, due to their requirements on information quality and transparency as well as on harmonization, contribute to the improvement of risk management measures (RMM). With the coming into force of the CLP-regulation and the implementation of the GHS within the EU on 20.?1.?2009, as suggested in the white book on European Chemicals policy in 2001, the new system of European chemical law has been completed at a regulatory level. This article shows the development so far from the first directive on the regulation on the labeling of chemicals, to the establishment of application and test procedures, and then to the instruments of risk communication and risk management introduced by REACH and the CLP-regulation.     

生理毒代动力学模型及其在有机污染物水生生态毒理研究中的应用

人类生产和生活使用各种人工合成的化学品,种类和数量急剧增长,对生态系统和人体健康造成了极大威胁。因此,亟需采用高效的方法对数量巨大的化合物进行毒性评价。对生理毒代动力学(PBTK)模型的建立过程及其在污染物生态毒理研究中的应用进行了综述。PBTK模型,又称生理药代动力学(PBPK)模型,是利用生理学和解剖学等原理,将生物体简化为用血流连接的肝、肾和脂肪等各组织器官房室,模拟化合物在生物体内的吸收、分布、代谢和排泄过程。模型参数包括生理参数和生化参数2个部分,可用MATLAB等软件进行模拟。模型已应用于数百余种有机污染物在鱼体等水生生物体的毒代动力学模拟。已有模拟结果能够预测化合物在生物体内的有效剂量,对化合物毒性进行评估,并可用于不同物种、不同剂量和不同暴露途径间的外推,有力推进了污染物生态毒理研究工作的开展。     

Effect of dietary factors and environmental chemicals on intestinal drug metabolizing enzymes

The liver is the major site of metabolism of foreign chemicals, but contribution from intestinal biotransformation can influence the overall disposition of chemicals. The intestinal drug‐metabolizing enzymes are located in the endoplasmic reticulum and they possess biochemical properties similar to those of the hepatic system. In general, the rate of in vitro metabolism of drug substrates in intestines is lower than in the liver. There seem to be differences in regulation and induction of hepatic and intestinal drug‐metabolizing enzymes. The in vitro intestinal metabolism of foreign chemicals is affected by several factors including the nutritional status of the animal. Dietary components such as vitamins, lipids and vegetables can modify the activities of intestinal drug‐metabolizing enzymes. Phenobarbital or 3‐methyl‐cholanthrene (3‐MC) pre‐treatment induces the hepatic metabolism of a wide variety of drug substrates in a number of species, while the stimulation of intestinal enzymes is both substrate and species specific. Rabbit intestinal drug‐metabolizing enzymes seem to be resistant to induction by foreign chemicals.     

理论毒理学研究进展

毒理学是近代发展起来的科学,由于工农业生产的迅速发展,化学物质剧增,迄今登记在册的化学物质已超过2 600万种,每年还新增2 000多种,因此传统的毒性鉴定已远远不能满足时代的要求,针对各种化学物质的细致的毒理学研究更是难以实现。因此毒理学必须在理论层面实现突破,缩短研究时间,减少研究经费及人力、物力的消耗,同时可使化学物质得到更安全的应用。另外,动物保护已列入议事日程,不再允许大量使用动物做毒理方面的实验,这些促进了理论毒理学的发展。     

A foundation for developing a methodology for social network sampling

Researchers are increasingly turning to network theory to understand the social nature of animal populations. We present a computational framework that is the first step in a series of works that will allow us to develop a quantitative methodology of social network sampling to aid ecologists in their social network data collection. To develop our methodology, we need to be able to generate networks from which to sample. Ideally, we need to perform a systematic study of sampling protocols on different known network structures, as network structure might affect the robustness of any particular sampling methodology. Thus, we present a computational tool for generating network structures that have user-defined distributions for network properties and for key measures of interest to ecologists. The user defines the values of these measures and the tool will generate appropriate network randomizations with those properties. This tool will be used as a framework for developing a sampling methodology, although we do not present a full methodology here. We describe the method used by the tool, demonstrate its effectiveness, and discuss how the tool can now be utilized. We provide a proof-of-concept example (using the assortativity measure) of how such networks can be used, along with a simulated egocentric sampling regime, to test the level of equivalence of the sampled network to the actual network. This contribution is part of the special issue “Social Networks: new perspectives” (Guest Editors: J. Krause, D. Lusseau and R. James).     

Interactions among plant defense compounds: a method for analysis

Summary. Plants contain an enormous diversity and quantity of secondary metabolites, some of which are toxic and deterrent to herbivores and pathogens. This impressive diversity of plant compounds suggests a high probability of interactions among them. Synergistic interactions are those in which the combined activity of two or more chemicals is greater than that expected given their individual activities. On the other hand, antagonistic interactions are those in which the combined activity of two or more chemicals is less than that expected given their individual activities. Synergistic interactions could increase plant fitness whereas antagonistic interactions could decrease plant fitness. Interactions are thus potentially very important, not only in explaining the diversity of defense compounds within individual plants, but also in providing insight into plant defense strategies. Although synergistic interactions have received increased attention in the ecological literature in the last decade, the number of documented cases of synergy remains small and antagonistic interactions are rarely considered. The primary reason for this scarcity may be the difficulty of detecting, analyzing and displaying such interactions. Analysis by ANOVA, though sometimes used, often is not appropriate. We introduce a simple technique, isobolographic analysis, that is used in pharmacology for detecting and rigorously quantifying synergy and antagonism and provide an example using the brine shrimp toxicity assay. More statistically sophisticated approaches, such as isobolographic analysis, will allow ecologists to effectively document the role of chemical synergy and antagonism in interactions between species. Such chemical interactions may ultimately provide insight into longstanding, ecological questions. Received 26 October 1998; accepted 24 March 1999.     

Die von REACH ausgelösten Veränderungen im Hinblick auf die neu definierte Verantwortung von Herstellern und industriellen Nutzern

The changes initiated by REACH towards the newly defined responsibility of producers and industrial users are presented. The data acquisition for ‘old chemicals’, and hereby the improvement of risk assessment, will start in 2007, though will take more than ten years. The data material shows gaps in the area of occupational health and safety. The protection of consumers from substances in products remains insufficient. Nevertheless, for chemicals policy, REACH is a big step forward.     

Toxicity of acidization fluids used in California oil exploration

There has been considerable public interest regarding the toxicity of chemicals used in hydraulic fracturing, but little is known about its sister technique, acidizing. Little to no research has been done on what the chemicals of acidization are and what impact they could have on humans and the environment. This paper discusses the differences between three acidizing techniques (acid maintenance, matrix acidization, and acid fracturing) and quantifies the amounts of the chemicals used for each. Washington State's Quick Chemical Assessment Tool is used to identify F-graded toxins, which are known carcinogens, mutagens, reproductive toxins, developmental toxins, endocrine disruptors, or high acute toxicity chemicals. The analysis of the present data shows that there have been over 600 instances of acidizing in urbanized Southern and Central California from April 2013 to August 2015. Although most of the chemicals of acidizing are similar to hydraulic fracturing, those used most frequently are different. There are close to 200 specific chemicals used in acidization, with at least 28 of them being F-graded hazardous chemicals. Some are used frequently in the range of 100–1000 kg per treatment, such as hydrofluoric acid, xylene, diethylene glycol, and ethyl benzene. Close to 90 more chemicals are identified using non-specific names as trade secrets or reported with no quantity. Unlike hydraulic fracturing the chemical concentrations in acidizing are high, ranging from 6% to 18%, and the waste returns can be highly acidic, in the range of pH 0–3. With this paper it is hoped that acidization becomes part of the larger discussion on concerns with oil exploration and be evaluated by appropriate authorities.     

Parasitismus und ‘Endokrine Disruption’ in Fischen

Background

Since the 1960s the scientific community has become increasingly aware of the need for integrative and holistic approaches to solve environmental issues. It has not only been recognized that changing environmental conditions can alter toxicological properties of pollutants but also that susceptibility of organisms to man-made chemicals strongly depends on environmental factors. This is especially true with respect to the endocrine control of reproductive processes in many aquatic species including fish, which are mainly influenced by changes in the surrounding environment such as day length, temperature, water flow, etc. Thus, it is astounding that the use of integrative approaches to address the question of the ecotoxicological relevance of the disruption of endocrine and related reproductive functions is rate. As a consequence of this shortcoming, there is increasing demand both among scientists and politicians regarding more holistic approaches in the endocrine disruptor research.

Aim

This contribution aims to critically discuss current strategies and approaches as well as to identify alternative strategies in context with the environmental risk assessment of endocrine disruptors. This will be exemplified using an ecotoxicological study with bream (Abramis brama) that was conducted along a major European river, the Elbe.

Results and Discussion

Local bream (Abramis brama) populations collected along the river Elbe were characterized by different magnitudes and/or types of endocrine alterations. Although there is a relatively extensive data set available regarding its contamination with wide range of chemicals in the Elbe, it has not been possible to conclusively relate the observed endocrine effects to the exposure to individual compounds or mixtures of chemicals. However, during the gross morphological evaluations of the fish it was observed that at some locations a great number of the individuals caught were parasitized with the tapeworm Ligula intestinalis. Furthermore, statistical analysis revealed that a relatively great percentage of the variation of the biological endpoints observed both among individuals and sampling sites could be explained by the occurrence of this parasite. Overall, the findings of these studies indicate that there is a complex interaction not only among the exposure to chemicals and parasitism but also of both of these aspects with the occurrence of biological effects in fish.

Conclusions

The gaps in our current knowledge as well as the findings from the few studies available indicate, the there is a need to revise our current approaches to characterize and evaluate exposure scenarios regarding their potential to cause endocrine disruption in wild organisms. Given the complexity of most environmental exposure scenarios, involving multiple factors including anthropogenic and natural influences and their interactions, I therefore see the urgent need to initiate a discussion on more integrative approaches in this field in favor of true ‘ecotoxicological studies’ that integrate both ecology and toxicology.     

Inorganic chemicals in domestic water of the United Arab Emirates

The concentration of selected inorganic chemicals was determined for 396 samples of bottled water, desalinated water, and groundwater used for drinking and domestic purposes in the United Arab Emirates (UAE). The objective of this study was to compare the concentrations of inorganic chemicals in different domestic water types used in the UAE with the World Health Organization (WHO) limits for drinking water. Results of the present study revealed a wide variation in the concentrations of major, minor, and trace inorganic chemicals in domestic water of the UAE. For example, the bottled water sold for drinking is depleted in major ions and the total dissolved solids (TDS) in some brands do not exceed 100 mg/l. On the other hand, some of the domestic water used may contain as much as 3,000 mg/l TDS, which is above the WHO recommended limit for drinking water (500–1,500 mg/l TDS). Similarly, while bottled water is almost free of trace ions and minor constituents, some natural groundwater may have concentrations higher than the WHO recommended limits for drinking water. The cause of this variation is related to the different water sources and the large number of companies producing and distributing drinking and domestic water. Moreover, it is clear that the current controls on domestic water quality in some areas, namely conformance of pH and electrical conductivity measurements with prescribed ranges of values, are currently inadequate. These two parameters are not enough to judge if water is suitable for drinking or not and some consumers may receive domestic water of uncertain quality.     

Toxizitätsdaten aus einer ökotoxikologischen Testbatterie

The influence of industrial chemicals in the environment is strongly determined by the condition of the soil. Considering the complex interrelationships of soil condition and the specific parameters of the material as influential to bioavailability and decompositional reactions, it is necessary to reproduce various situations via a selected battery of ecotoxicological tests. The use of such batteries has already proved to be suitable for the examination of sediments. In order to make statements about the dangerous potential of chemicals in the soil, samples of natural soil were exposed to industrial chemicals (surfactants, mineral oil hydrocarbons, an antibiotic and a pesticide), and examined regularly in test batteries over a period of four weeks. This microcosm works as a degradation test of environmental relevance, monitoring the effects and reactions of industrial chemicals in natural soil. All test results collected over this period of time come to a very complex and multi-dimensional compilation of data which needs to be considered in full before an assessment is possible. The main goal in analysing the data is to extract the maximum possible information from the matrix. Aside from the graphic presentation, mathematic graphs of the data will be introduced. This method aims to provide a structural and logical relationship to the data, in order to build up a classification system and an order of precedence, which should make it possible to estimate potential risk.     

受体功能区结构与环境内分泌干扰效应生物差异的关系

环境中存在的多种内分泌干扰物能够与生物体内的天然激素受体选择性结合并产生多种生物效应,由于受体功能区三维结构的不同,其内分泌干扰活性存在着种间、种内、组织间等的种种差异,限制了不同物种间毒性效应的外推研究,增加了环境内分泌干扰物筛选和风险评价的难度.论文综述了基于受体介导的环境内分泌干扰物生物活性与相应受体选择性及受体功能区结构关系的研究进展,并利用分子模拟方法分析探讨了雌激素受体与部分化合物结合作用模式,讨论了目前存在的问题,对以后有关方面的研究提出了建议.