Registration of polymers in accordance with directive 67/548/EEC

This paper clarifies how polymers are dealt with under the Directive 67/548/EEC. Polymers are a particular group of substances under the Directive 67/548/EEC [1] and amendments [2,3] as they are not listed in the European INventory of Existing Commercial chemical Substances (EINECS [4]) which otherwise lists all substances which were on the European Community Market between 1 January 1971 and 18 September 1981, the ‘existing substances’. Instead, in EINECS polymers are registered under their ultimate building blocks. With the 6th amendment to the Directive [2] polymers became notifiable substances if containing 2% or more of new substance(s) (i.e. as a general rule substances not listed in EINECS), and the reporting criteria were used as definition. With the 7th amendment to the Directive [3] an exact definition was introduced and a special test package, given in Directive 93/105/EEC [5], was designed for polymers to take into account their particular properties. Changing the definition of polymers created a group of substances which under the 6th amendment had been defined as polymers, and could no longer be regarded as polymers under the 7th amendment, the No‐Longer‐Polymers.     

Utility of the QSAR modeling system for predicting the toxicity of substances on the European inventory of existing commercial chemicals∗

Many chemicals are in common commercial use for which no information on the environmental fate or toxicity exists. Recent legislation requires that many substances be assessed for their toxicity to aquatic organisms within a very short time and determine which of these chemicals need to be studied in greater detail. It would be impossible to measure the acute and chronic effects of all of these compounds on a single organism, let alone a battery of different types of organisms, communities or ecosystems. Initially, the chemicals on the European Inventory of Existing Commercial Chemical Substances (EINECS) need to be screened and relative hazard to the environment determined. In response to OECD directives, there has been a great deal of activity by government and industry scientists. At the International Workshop on Advances in Environmental Hazard and Risk Assessment it was concluded that quantitative structure activity relationships (QSAR) could and should be used in the hazard assessment process. Papers published in that volume outline the advantages, disadvantages, limitations, advances and research requirements.

The QSAR, structure‐activity based chemical modeling and information system, which was developed by the US‐Environmental Protection Agency was used to predict the acute toxicity of 113 substances from the “Old Substances”; list of the German government to the four commonly used aquatic toxicity test organisms: Daphnia magna (DM), fathead minnow (FHM), rainbow trout (RBT), and blue‐gill sunfish (BG).

Of these compounds the QSAR system predicted the acute toxicity of 87 substances towards fathead minnow. For the other three species examined the QSAR system could be used to predict toxicity for 78 compounds.

The predicted toxicities were compared to observed toxicities of compounds which have been evaluated and stored in the “Aquire”; data base. Observed toxicity values were available for at least one species for 38 compounds. The toxicities of some compounds are well predicted while those of other compounds were not well predicted. Overall, the QSAR system accurately classified the acute toxicity ranges of 50%, 64%, 56% and 56% of the compounds investigated for DM, FHM, RBT and BG, respectively. Of the compounds studied 10 were very poorly predicted, of these the QSAR system overpredicted the toxicity of three, while underpredicting the toxicity of seven. Of these seven compounds, five contained amino groups.     

Ein Indikator für den Einsatz gefährlicher Stoffe in Produkten und Prozessen: Monoethylenglykol-Äquivalente

In order to quantify hazardous substance use in production processes, a special methodology has been designed within the context of the EcoGrade integrated environmental assessment method developed by the Öko-Institut, Institute for Applied Ecology. This methodology uses monoethylene glycol (MEG) equivalents as an indicator value for hazardous substance use. MEG equivalents permit direct, noxious-substance-focussed comparison of processes and products (Bunke 2001). The assessment is based upon the standardized risk phrases assigned to the component substances. The MEG equivalent methodology is a refinement and application of the potency factor model (Wirkfaktorenmodell) of the German Technical Rule for Hazardous Substances (Technische Regel für Gefahrstoffe, TRGS) 440 (AGS 2001). The data required for the assessment procedure are available within companies (safety data sheets) or are readily accessible publicly (hazardous substance databanks). A further benefit is that inventory analysis of hazardous substances using the method presented here makes it possible to take hazardous substance use into account in a systematic manner within life-cycle assessment (LCA) studies. The methodology has been tested for the example of residential buildings. Note: The terms ‘hazardous substance’, ‘noxious substance’ and ‘hazardous constituent’ are used in this paper in the sense of substances that have one of the hazard attributes set out in Article 3 of the German Chemicals Act (Chemikaliengesetz).     

Molecular size as a limiting characteristic for bioconcentration in fish

The relationships between the bioconcentration factor (BCF) of chemicals in fish and their size, as characterized by molecular weight (MW), effective cross sectional diameter (Deff), and maximum diameter (Dmax) have been investigated using an experimental data set of 737 new and 441 existing chemicals monitored by the Japanese Chemical Substances Control Law (CSCL). Substances with BCF > or = 5000 (very high bioconcentration potential) typically have MW < 550, Deff < 1.1 nm and Dmax < 2.0 nm, respectively and the substances with BCF > or = 1000 (high bioconcentration potential) have MW < 550, Deff < 1.4 nm and Dmax < 2.9 nm, respectively Therefore, the previously suggested threshold values for Deff (0.95 nm) and Dmax (1.5 nm) used for discriminating between bioconcentrative and non-bioconcentrative substances were found to be somewhat small. We found that many substances with BCF > or = 1000 and Dmax > or = 1.5 nm have Deff < 0.95 nm.     

Distribution and behaviour of radiocaesium in Scottish freshwater loch sediments

The distribution and behaviour of radiocaesium have been studied in the sediments of two contrasting freshwater lochs: Round Loch of Glenhead, an acidified loch in south-west Scotland, with organic-rich sediments (≈20%C) and Loch Lomond, 35 km north-west of Glasgow, where sediments are low in organic matter (1–6%C, southern basin), but with a relatively high clay content. In the sediments of Scottish freshwater lochs,¹³⁷Cs [half life (t_1/2) = 30.23 yr] originates from fallout from nuclear weapons’ testing (1950s and 1960s) and from the Chernobyl reactor accident in 1986, which is also the source of the shorter-lived¹³⁴Cs [half life (t_1/2) = 2.05 yr]. Use of the characteristic¹³⁴Cs/¹³⁷Cs activity ratio of radiocaesium emitted from Chernobyl enables resolution of sedimentary radiocaesium profiles into the two component sources. In the organic-rich sediment of Round Loch, downward diffusion of radiocaesium in porewaters obscures its pattern of input to the loch. In the more clay-rich sediments of Loch Lomond, separate radiocaesium concentration peaks, related to atmospheric deposition maxima, are clearly discernible, although an influence of partial mixing is apparent. While the derived Chernobyl fallout inventory of radiocaesium in Round Loch sediments is broadly comparable with that for Loch Lomond, the corresponding weapons testing inventory is an order of magnitude lower than in Loch Lomond. Although Round Loch is situated in an area of known elevated Chernobyl deposition, the inventory is much lower than literature values of atmospheric deposition, indicating significant loss of radiocaesium from this loch. The weapons testing inventory in Round Loch is also lower than reported estimates, whereas in Loch Lomond the established inventories from both sources are similar to, or greater than, fallout deposition. The differences between the distribution and inventories in the two lakes confirms that radiocaesium is much less efficiently bound and is correspondingly much more mobile in the organic sediments of Round Loch of Glenhead than in the more clay-rich sediments of Loch Lomond.     

Pharmaceutical compounds in aquatic environment in China: locally screening and environmental risk assessment

An environmental risk assessment was performed for pharmaceutical compounds present in the aquatic environment of China. Predicted environmental concentration (PEC) of the compounds were calculated according to European Medicines Evaluation Agency (EMEA) guidelines. Available ecotoxicological data compromised by applying a very conservative assessment factor (AF) were employed to calculate the predicted no-effect concentration (PNEC). The screening principle and the risk assessment were based on risk quotient (RQ), which derived from the PEC and related PNEC values. PEC results indicated that all the compounds except sulfadimethoxine and levocarnitine, should carry out phase II risk assessment in EMEA guideline. RQ values suggested that more than 36 pharmaceuticals may be imposed health threats to the aquatic environment; especially the antibiotic therapeutic class including amoxicillin, sulfasalazine, trimethoprim, oxytetracycline and erythromycin showed high RQ values. These substances with high RQ value (RQ≥1) were regarded as top-priority pharmaceuticals for control in the aquatic environment of China. However, the antibiotic substances which had low risk quotient (RQ <1), should be reassessed by its potentially induced resistance under low concentration in future.     

长江口水体中取代芳烃类污染物的生态风险评价

通过对采集于长江口水体15个不同采样点水样中的主要6种取代芳烃类化合物的浓度分析,依据3个基础营养级水平(藻、溞、鱼)的急性毒性效应[L(E)C50],采用欧盟适用于现有化学物质与新化学物质的风险评价技术指南(TGD)中的商值法对长江口水体中的1,3-二氯苯、1,4-二氯苯、1,2-二氯苯、六氯苯、2,4-二硝基甲苯、...     

Chemische tarnung. Die stoffliche grundlage der anpassung von anemonenfischen an riffanemonen

Dissolved amino acids (³H-phenylalanine, ³H-proline) were accumulated and incorporated into proteins and glycoproteins by sea anemones. On objects (glass rods, pipe cleaners or filter paper) which had touched labelled anemones, tritiated substances could be detected. The mucus of labelled anemones was analysed by disc-electrophoresis. Tritium activity was found in the bands (stained by amino black). Anemone fishes adapted to labelled anemones had 4 times more tritium activity on their surface than control fishes. Most radioactivity was found on those regions which made closest contact with the anemones. The mucus of anemone fishes adapted to labelled anemones was also analysed by disc-electrophoresis. The analysis revealed protein-containing fractions in which ³H-amino acids were incorporated. The pattern of tritium activity in disc-electropherograms from labelled anemones corresponds to that of fishes adapted to those anemones. Anemones produce specific substances which influence the discharge of their nematocytes. These substances have special functions in the normal behaviour of the anemones. The substances provide protection against self-nettling and prevent the discharge of nematocytes into nearby objects which the tentacles continuously contact. The production of these substances by anemones is completely separate from the association with anemone fishes. The fishes thus simply exploit a mechanism existing independently in the anemones. Therefore, it is possible to form, in an aquarium, unnatural associations between anemone fishes and anemone species which never live in association with fishes in their natural biotope. On the basis of previous information, as well as on these new data, it is possible to develop a model which explains the control of nematocyte discharge: Substances with inhibitory qualities (protecting substances) are produced by the anemones themselves, and de-sensitize the sensory inputs of the anemones (nematocytes and sensory cells). Sensitization takes place as soon as the anemones come into contact with “stimulating substances”. This happens if anemones are touched by food objects or by anemone fishes which have been previously isolated from anemones. The surfaces of these fishes are not impregnated with protecting substances. Adapted anemone fishes, neighbouring anemones of the same species and other “adapted” objects are coated with the inhibitory substances and thus do not induce nematocyte discharge.     

Erfahrungen des Umweltbundesamtes mit der EU-Biozid-Richtlinie

Biocides are active substances and products which are intended to destroy (…) any harmful organism by chemical or biological means. Typical applications are for instance wood preservatives, antifouling products or disinfectants. In the European Union the use of biocidal products is regulated since 1998 by the Biocidal Product Directive 98/8/EG (BPD). The BPD was transposed into German law in 2001 by the “Biozid-Gesetz”. The Federal Environment Agency is responsible for the environmental risk assessment of biocidal active substances and products under the “Biozid-Gesetz” in Germany. The European Commission has to evaluate the BPD seven years after endorsement and if necessary, has to submit a proposal for the revision of the directive. It is expected that the European Commission will publish soon a review of the enforcement of the BPD together with suggestions for the revision of the directive. In this article the German Federal Environment Agency summarises suggestions for the revision of the BPD based on its ten years experience with the directive: The scope of the BPD needs an exact clarification of borderlines in order to avoid confusion with other legislation. Food and feeding stuff together with natural products like lavender branches and cedar wood, which are used as attracting or repellent agents, have to be excluded from the scope of the BPD. Special data requirements for natural oils and pheromones should be developed to take the complex composition of these substances into account. The advantages of a centralised and decentralised authorisation procedure are discussed for biocidal products in special product types. Furthermore we stipulate that biocidal active substances which are nano particles are treated as separate active substances with own identities. Due to animal welfare reasons it should be obligatory to share data from vertebrate animal studies as it is already mandatory under the REACH regulation. The import of articles treated with biocidal active substances into the European market should only be allowed, if the active substance is approved for their biocidal use within the EU. Finally we suggest to implement an obligation to report the market shares or consumption rates of biocidal active substances and products. Together with procedural simplifications and adaptation in the scope of the directive, changes of the data requirements will be the key issues during the revision of the BPD. Most important, these changes should not reduce but ideally increase the level of protection for human health and the environment.     

POPs — Stand der Entwicklung zur Emissionsinventarisierung

The measures undertaken for reducing the impact of POPs on the environment are discussed in international conventions concerned with these substances and are related to the reporting of obligations which should ensure the control of their implementation and verify the effects of these measures on the environment. An essential element of this reporting involves the data concerning the emissions and environmental impact of these substances in emission inventories. A summary of the current status of emission inventories for POPs with a special focus on atmospheric emissions under EMEP is also presented. There are considerable uncertainties of reported emission data by the individual countries and in expert evaluations regarding marine and atmospheric impacts. Harmonized instruments for emission evaluation are required and under development in the form of guidance documents for the marine environment in ‘Harmonized Quantification and Reporting Procedures for Hazardous Substances (HARP-HAZ)’ and under EMEP in the ‘Atmospheric Emission Inventory Guidebook for UNECE/LRTAP’. The problems and the reasons for uncertainties in the quantification of environmental impacts are presented using the example of lindanes (hexachlorocyclohexane, HCH), polychlorinated biphenyls (PCB), polycyclic aromatic hydrocarbons (PAH) und hexachlorobenzene (HCB).     

中国城市温室气体排放清单编制和方法概述

介绍中国国家层面的温室气体排放清单编制现状,概述了中国城市层面温室气体排放清单研究进展,总结国际通用的城市清单方法(Urban Inventory Methods),包括以排放为中心的IPCC和WRI/WBCSD温室气体排放模型、以需求为中心的混合生命周期方法和中国现状城市温室气体排放清单编制方法,阐述在目前的城市温室...     

Kenntnisdefizite bei Stoffeigenschaften und ihre Folgen

The data situation to chemical substances is unsatisfactory— in spite of in part considerable efforts in the last decades. One knows still very little on the subject of the dangerous characteristics of chemical substances. The consequences of this ignorance have primarily the employees to carry. They get sick due to a dealing with substances whose characteristics were not completely enlightened. But as well the enterprises have to suffer under it, after all, lose her experienced staff member and have to pay the costs about the Berufsgenossenschaften for these knowledge deficits. In the EU, the future European chemical policy is therefore discussed. The contribution explains the range of the sicknesses through dealing with substances with unknown characteristics.     

离子液体氯化1-辛基-3-甲基咪唑对酵母细胞增殖生长和细胞膜通透性的影响

为探讨咪唑类离子液体氯化1-辛基-3-甲基咪唑([C₈mim][Cl])对酵母细胞的增殖生长和细胞膜通透性的影响,以不同浓度的[C₈mim][Cl]处理酵母细胞,研究离子液体对酵母细胞增殖和菌落形成的影响,通过测定酵母细胞外液蛋白质和核酸的含量,判断膜通透性的大小和[C₈mim][Cl]对细胞膜性结构的损伤。结果显示,0.1 mmol·L^-1的[C₈mim][Cl]延长了酵母细胞到达对数生长期的时间,在6～9 h之间对酵母细胞的增殖存在明显的抑制作用。1 mmol·L^-1的[C₈mim][Cl]使酵母细胞增殖不能到达对数生长期,对酵母细胞的增殖一直具有较强的抑制作用。随着离子液体浓度的增加,小菌落的数量增多。当平板内[C₈mim][Cl]浓度达到10 mmol·L^-1时,完全抑制了菌落的形成。[C₈mim][Cl]处理酵母细胞后,细胞外液中OD₂₈₀、OD₂₆₀的值显著升高。研究表明,细胞膜等膜性结构通透性的增加是离子液体[C₈mim][Cl]抑制酵母细胞增殖生长的原因之一。     

以污水流行病学监测广西某市12个污水处理厂服务区域精神活性物质的消耗量

精神活性物质滥用和使用量逐年递增正成为社会稳定、环境健康新的关注点。准确地估算某一地区这类化合物的消耗总量是管理这类物质的关键。本研究对中国广西某市12个污水处理厂(wastewater treatment plants,WWTPs)服务区域中的8种精神活性物质消耗量进行了调查。首先,采用固相萃取-液相色谱-串联质谱法测定了广西某市12个WWTPs进水中8种精神活性物质的浓度,检测到在<方法检测(method detection limit,MDL)至170.9 ng·L^-1范围内的5种精神活性物质。然后,依据污水流行病学(wastewater-based epidemiology,WBE)进行消耗量反算。结果表明,氯胺酮(ketamine,KET)、吗啡(morphine,MOR)、冰毒(methamphetamine,METH)、摇头丸(3,4-methylenedioxymethamphetamine,MDMA)是主要检出的精神活性物质,平均消耗量分别为682.4、167.8、44.6、11.3 mg·d^-1·1000inh^-1;而可卡因(cocaine,COC)、苯甲酰爱康宁(benzoylecgonine,BE)、甲卡西酮(methcathinone,MC)没有被检出。对WWTPs进水中精神活性物质的残留进行分析,估算这些物质在特定区域的消耗量,为防控风险提供支持。     

Priorisierung von bioziden Wirkstoffen aufgrund der potenziellen Gefährdung schweizerischer Oberflächengewässer

Background, Aim and Scope Active substances for use in biocidal products can potentially occur as micropollutants in natural waters. Biocides, which are used in Switzerland for non-agricultural applications, should be evaluated and prioritized with regard to their respective environmental risks. The following questions were emphasized: Which active substances are used for which purposes and in which amounts? Is there discharge to the aquatic environment? What are the environmental behaviours and ecotoxicological effects of these biocides? How can a prioritization be achieved? Which active substances should be suggested for further assessments? Methods Manufacturing firms, sales organisations, users and environmental experts were identified as key stakeholders for the issues of this project. Chemical identities, product compositions, used amounts, product types, ways and places of applications were elucidated. A database was established with information on approximately 1760 products with totally 277 active substances. A prioritization procedure was established, providing a distinction of the active substances. For priority setting, water pollution risks by biocides were evaluated based on potential environmental emissions as well as on environmental behaviour and ecotoxic effects. Results In the European Union 372 active substances were notified for biocidal products, which accounted for use of 7500 tons per year in Switzerland. More than 95?% of the total use bases on 30 active substances, of which seven are rapidly biodegradable. A group of experts determined 22 substances as candidates for an extended assessment. It became evident that many active biocidal substances are highly ecotoxic und could, therefore, cause an augmented environmental risk Discussion It could be shown which active substances are applied in Switzerland in substantial amounts. Although close to 300 active biocidal substances are used, only about 30 substances are employed in relevant amounts of more than 5000?kg per year. For 22 active substances with low biodegradability, a potential environmental risk for natural surface waters can be inferred. These active substances are used at amounts comparable to the pesticides.     

离子液体氯化1-辛基-3-甲基咪唑对洋葱的遗传毒性作用

为探讨咪唑类离子液体氯化1-辛基-3-甲基咪唑([C_8mim][C1])对洋葱的遗传毒性,用浓度分别为2.5、5、10和20mmol·L~(-1)的[C_8mim][C1]处理洋葱内表皮细胞和洋葱根尖8 h,用浓度为10 mmol·L~(-1)的[C_8mim][C1]处理洋葱内表皮细胞和洋葱根尖4 h、8 h、12 h和24 h,研究[C_8mim][C1]对洋葱内表皮细胞核的影响和对洋葱根尖有丝分裂指数和染色体畸变的影响。结果显示,与对照组相比,随着[C_8mim][Cl]处理浓度和时间的增加,洋葱内表皮细胞核偏移率明显升高,根尖细胞有丝分裂指数显著降低,染色体畸变现象明显,畸变率升高。研究表明,当浓度达到2.5 mmol·L~(-1)时,[C_8mim][Cl]对洋葱具有遗传毒性。     

Lead and cadmium uptake by sulfur-containing modified silica gels

We compared mercaptopropyl fonctionalized silica, SiSH, with two aminoethanethiol modified silica gels, SiNS and SiNMeS, for their ability to remove Cd²⁺ and Pb²⁺ from aqueous solutions. Adsorption was performed using a batchwise process. The maximum adsorption capacities were obtained for lead and cadmium. The adsorption isotherms followed the Langmuir model. The calculated parameters indicated a similar removal capacity of Si[2-[3-(triethoxysilyl)propylamino]ethanethiol] and Si-[1-methyl-2-[3-(triethoxysilyl) propylamino]ethanethiol]. This study underscores the different behaviour of the aminoethanethiol modified silica gels compared to the mercaptopropyl modified silica for lead and cadmium uptake.     

QuEChERS-超高效液相色谱-串联质谱法测定鱼血清中的精神活性物质

本文建立了一种同时测定鱼血清中19种精神活性物质的分析方法.该方法基于QuEChERS方法对样品进行提取和净化,待测物采用超高效液相色谱-串联质谱法(UPLC-MS/MS)进行分析,检测的19种精神活性物质均采用同位素内标法定量.该方法的方法检测限(MDL)范围为0.02-0.06 ng.mE-1,基质效应处于76.7...     

The importance of age-related decline in forest NPP for modeling regional carbon balances.

We show the implications of the commonly observed age-related decline in aboveground productivity of forests, and hence forest age structure, on the carbon dynamics of European forests in response to historical changes in environmental conditions. Size-dependent carbon allocation in trees to counteract increasing hydraulic resistance with tree height has been hypothesized to be responsible for this decline. Incorporated into a global terrestrial biosphere model (the Lund-Potsdam-Jena model, LPJ), this hypothesis improves the simulated increase in biomass with stand age. Application of the advanced model, including a generic representation of forest management in even-aged stands, for 77 European provinces shows that model-based estimates of biomass development with age compare favorably with inventory-based estimates for different tree species. Model estimates of biomass densities on province and country levels, and trends in growth increment along an annual mean temperature gradient are in broad agreement with inventory data. However, the level of agreement between modeled and inventory-based estimates varies markedly between countries and provinces. The model is able to reproduce the present-day age structure of forests and the ratio of biomass removals to increment on a European scale based on observed changes in climate, atmospheric CO2 concentration, forest area, and wood demand between 1948 and 2000. Vegetation in European forests is modeled to sequester carbon at a rate of 100 Tg C/yr, which corresponds well to forest inventory-based estimates.     

Rapid control of black and odorous substances from heavily-polluted sediment by oxidation: Efficiency and effects

Oxidants were proposed to rapidly control black and odorous substances in sediments. NaClO and KMnO₄ had excellent efficiency to remove black and odorous substances. NaClO dramatically accelerated the release of organics, NH₄⁺-N, P, and heavy-metals. Moderate oxidation had a limited effect on microbial communities. NaClO of 0.2 mmol/g was viewed to be the optimum option. The control of black and odorous substances in sediments is of crucial importance to improve the urban ecological landscape and to restore water environments accordingly. In this study, chemical oxidation by the oxidants NaClO, H₂O₂, and KMnO₄ was proposed to achieve rapid control of black and odorous substances in heavily-polluted sediments. Results indicate that NaClO and KMnO₄ are effective at removing Fe(II) and acid volatile sulfides. The removal efficiencies of Fe(II) and AVS were determined to be 45.2%, 94.1%, and 93.7%, 89.5% after 24-h exposure to NaClO and KMnO₄ at 0.2 mmol/g, respectively. Additionally, rapid oxidation might accelerate the release of pollutants from sediment. The release of organic matters and phosphorus with the maximum ratios of 22.1% and 51.2% was observed upon NaClO oxidation at 0.4 mmol/g. Moreover, the introduction of oxidants contributed to changes in the microbial community composition in sediment. After oxidation by NaClO and KMnO₄ at 0.4 mmol/g, the Shannon index decreased from 6.72 to 5.19 and 4.95, whereas the OTU numbers decreased from 2904 to 1677 and 1553, respectively. Comparatively, H₂O₂ showed a lower effect on the removal of black and odorous substances, pollutant release, and changes in sediment microorganisms. This study illustrates the effects of oxidant addition on the characteristics of heavily polluted sediments and shows that chemical oxidants may be an option to achieve rapid control of black and odorous substances prior to remediation of water environments.