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.     

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。     

Reduction of Cr(VI) by peat and coal humic substances

The reduction of Cr(VI) by humic substances from leonardite and peat was investigated by capillary zone electrophoresis at various pHs. Both humic materials reduced Cr(VI) at pH 5.4, but not at basic pH. The capacity of leonardite humic substances to reduce Cr(VI) was lower than that of peat humic substances. Fe(III) accelerated the reduction of Cr(VI) by peat humic substances, but not by leonardite humic substances. Cr(VI) reduction mechanisms are proposed. The coal humic substances seem more suitable for remediation of Cr(VI)-contaminated sites.     

Humic substances as surfactants

Humic substances from soils and sediments can be defined as surface active substances based on the surface tension measurements. Although there are several micellar structural models of humic substances currently available, few studies evaluating humic substances as surfactants have been conducted to date. Therefore, we evaluated the ability of humic substances and their derivatives to influence surface tension. We found that the ability of a humic substance to influence the surface tension of a solution depends on its origin. Many industrially produced humic materials exerted little or no impact on surface tension, whereas humic substances isolated from natural environments (water, soil, peat, sediments, sludge from wastewater treatment facilities) exerted a large impact on surface tension. These findings indicate that the modification of humic substances can enable their use as surfactants. In addition, these findings indicate that solutions of humic substances and their derivatives can be used to increase the solubility of organic compounds.     

嫌气条件下土壤中有机还原性物质的动态变化

利用示差脉冲伏安法研究了不同有机物料在嫌气培养条件下产生的有机还原性物质的动态变化．结果表明：在培养起始阶段，强还原性有机物质的数量迅速增加，以后逐渐下降．不同有机物料所产生的有机还原性物质的强度和数量各不相同。培养初期，有机还原性物质种类较多，长时间培养后，部分还原能力较弱的有机物质消失。长时间培养后。嫌气培养液中强还原性有机物质可能与金属离子作用，使其活性降低。     

Physiologically based pharmacokinetic modeling of perfluoroalkyl substances in the human body

Currently, there are limited data on the levels of perfluoroalkyl substances other than perfluorooctane sulfonic acid and perfluorooctanoic acid in the human body. Most of this information has been extracted from biological monitoring of plasma while the occurrence of perfluoroalkyl substances in other human tissues is rarely studied. The objective of the present study was to develop a physiologically based pharmacokinetic model to assess the concentration of perfluoroalkyl substances in human tissues, based on an existing model previously validated for perfluorooctane sulfonic acid and perfluorooctanoic acid. Experimental data on concentrations of perfluoroalkyl substances in human tissues from individuals in Tarragona County (Catalonia, Spain) were used to estimate the values of some distribution and elimination parameters needed for the simulation. No significant correlations were found between these parameters and the chain lengths. The model was finally validated for five perfluoroalkyl substances.     

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.     

Recovering humic substances from the dewatering effluent of thermally treated sludge and its performance as an organic fertilizer

The biologic treatment of the dewatering effluent from thermally treated sludge is difficult due to the high concentration of refractory humic substances. On the other hand, humic substances are an important source of organic fertilizer. In this study, a novel process using ferric coagulant was developed to recover humic substances from dewatering effluent for use as an organic fertilizer. When ferric coagulant was applied to raw dewatering effluent, up to 70% of humic substances were enmeshed by hydrolyzed ferric ions at an optimum pH of 4.5. The proper mass ratio of iron ions to humic substances was 0.6. In the recovered material, humic substances accounted for 24.2% of the total dry solids, and the amount of phosphorus (equivalent phosphorus pentoxide) was 6.2%. Heavy metals and other components all met the legal requirements for organic fertilizer. When the recovered material was applied to soybeans, the germination and growth of the seeds was significantly improved.     

Huminstoffe in Sedimentporenwässern ausgewählter Bundeswasserstraßen

Humic substances are an important component of organic carbon in natural waters. Their character and properties are determined by the sources and the processes of their origin. Humic substances are not exclusively refractory compounds, but they are involved in several transformation processes in the water. It is not possible to directly analyze humic substances, therefore several methods were applied for their characterization. The presented LC-OCD-technique is a size-exclusion-chromatography with online UV- and carbon detection. Carbon fractions, e.?g. humic substances were differentiated by their molecular size. The portion of humic substances in sediment porewaters of the rivers Elbe, Rhine, Danube, Oder, Müritz-Elde-Waterway was determined. With only a few exceptions it ranges from 50 to 67?% of the dissolved organic carbon. The high molecular weight fraction accounts for 10 to 34?%, and the fraction of the low molecular weight substances was from 7 to 37?%. The ratio between the spectral absorption coefficient (254?nm) and the organic carbon is called SUVA (L/mg × m) and is an inidicator of the proportion of unsaturated bonds in the humic substances. Both high molecular herbal components (e.?g. cellulose, lignin) and biological degradiation products (e.?g. amino acids, sugar) are involved in sediment porewater transformation and degradiation processes. This demonstrates the distribution of the dissolved organic carbon between the fractions.     

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.     

Schadstoffbelastete Erzeugnisse im Verbraucherbereich: Wird REACH zu Verbesserungen führen?

Aim and Background Currently, the protection from hazardous substances occurring in consumer articles is often insufficient. In this paper, we discuss whether this situation will improve relevantly in the course of the implementation of the new European regulation on chemical substances (REACH). Changes under REACH may be heterogeneous. Therefore, differential effects depending on the tonnage as placed on the market, on the amount of substances contained in an article, and depending on timelines and exemptions for meeting the legal requirements, are discussed in this paper, together with a presentation of some uses of substances serving as examples. Discussion and Conclusions If substances are adequately registered, all identified and supported uses including their use in articles should be assessed. Therefore, where the full implementation of the registration conditions applies a substantial improvement may be expected due to REACH. Usually, producers or importers of articles are not required to register substances contained in these articles. Instead, the manufacturer or importer of the respective substance is usually responsible for registration, if exposure to the substance cannot be excluded and emission of the substance from an article is not the intended purpose. This may differ for substances intentionally released from articles. Additional obligations for substances not intentionally released mainly apply to substances of very high concern (SVHC). For the latter, the producer or importer of articles has to notify the European Chemicals Agency (ECHA) on the occurrence of the respective SVHC in articles. This information is important, especially because substances in imported articles may not be registered in advance. Authorisation within REACH is a very far reaching and effective tool of the legislation. However, authorisation is not required for SVHC imported as components of articles. Therefore, one main effect intended by REACH, i.?e. the substitution of SVHC, may possibly be undermined by importers of SVHC in articles. Restrictions, as specified in Annex XVII of REACH, offer a powerful opportunity to improve health and environmental safety with respect to hazardous substances. We support an extended understanding of what is defined as a “substance of concern” in the context of restrictions. This definition should be broader than just what is currently covered by the term SVHC. Consequences of restrictions may equally apply to European producers and importers of articles from outside of Europe, which contain such substances of concern. Another instrument currently closely linked to SVHC (in its more restricted definition), is the obligation of the producer or importer of articles to provide information according to article 33 (REACH). The downstream recipient of an article has to be informed on the content of SVHC in this article and how its safe use is ensured. Warehouses, wholesalers and other traders may therefore be aware of the SVHC contained in articles and may look for substitutes without such ingredients. Also, consumers may request this information on SVHC (just provided on demand) and are thus enabled to decide to buy other articles with less hazardous properties.     

The molecular composition of humic substances extracted from green composts and their potential for soil remediation

Humic substances play empirically several essential functions in biogeochemical cycles such as storage of carbon, pollutants, nutrients and water, yet the underlying mechanisms remain poorly known because their precise molecular structure is largely unknown so far. Here, we extracted humic substances from biomass waste of bell pepper, fennel, artichoke, coffee ground, coffee husks, and nursery residues. We analyzed humic extracts by ultra-high resolution Orbitrap Fusion Lumos Tribrid 1 M mass spectrometry, using both positive photoionization and negative electrospray ionization modes, and by ¹³C cross polarization/magic angle spinning nuclear magnetic resonance spectroscopy. We identified 5000–7000 unique organic compounds in humic substances by integrating photoionization with electrospray ionization. The chemical distribution of all components was depicted by nuclear magnetic resonance. Humic substances from green composts are composed by a wide variety of hydrophilic and hydrophobic moieties, thus providing the required biosurfactant properties for effective soil washing capacities, with carboxyl-rich alicyclic molecules, fatty acids, and phenolic acids as major constituents. Overall, our findings provide a major insight in the molecular structure of humic substances, thus opening research on mechanisms ruling the origin, fate and behavior of humic substances.

     

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.     

Pollution extents of organic substances from a coal gangue dump of Jiulong Coal Mine,China

This paper addresses the distribution and occurrence of harmful organic substances in coal gangue dump from Jiulong Coal Mine and its influence on the environment. The samples were taken from the coal gangue dump and coal waste water stream and analyzed by organic geochemical methods. The results indicate that the coal gangues contain abundant harmful organic substances like polycyclic aromatic hydrocarbons. The TOC and sulfur contents of the samples are much higher than those of the background sample except Sample JL7. The contents of organic bulk parameters are relatively high. Ten carcinogenic PAHs were identified and these harmful organic substances have influenced the surrounding area. Along the waste water stream, organic substances pollute at least 1,800 m far from the coal gangue dump.     

水中天然有机物的臭氧氧化处理特性

通过小型实验和液相色谱分析，研究了水中天然有机物的臭氧氧化反应的特性和反应前后有机物分子量的变化情况。结果表明，臭氧氧化的主要功效不在于降低以TOC为代表的水中有机物总量，而是改变了有机物的性质和结构。通过臭氧氧化处理，水中大分子有机物分解氧化为小分子有机物分解氧化为小分子有机物，且具有饱和构造的有机物成分明显增加。     

Photosensitivity sources of dissolved organic matter from wastewater treatment plants and their mediation effect on 17α-ethinylestradiol photodegradation

● EE2 photodegradation behavior in the presence of four WWTPs’ DOM was explored. ● The ³DOM* played a major role in the EE2 photodegradation mediated by WWTPs’ DOM. ● The A²/O process DOM contained more aromatic and oxygen-containing substances. ● Possible photosensitivity sources of DOM in the A²/O process were proposed. Dissolved organic matter (DOM) from each treatment process of wastewater treatment plants (WWTPs) contains abundant photosensitive substances, which could significantly affect the photodegradation of 17α-ethinylestradiol (EE2). Nevertheless, information about EE2 photodegradation behavior mediated by DOM from diverse WWTPs and the photosensitivity sources of such DOM are inadequate. This study explored the photodegradation behavior of EE2 mediated by four typical WWTPs’ DOM solutions and investigated the photosensitivity sources of DOM in the anaerobic-anoxic-oxic (A²/O) process. The parallel factor analysis identified three varying fluorescing components of these DOM, tryptophan-like substances or protein-like substances, microbial humus-like substances, and humic-like components. The photodegradation rate constants of EE2 were positively associated with the humification degree of DOM (P < 0.05). The triplet state substances were responsible for the degradation of EE2. DOM extracted from the A²/O process, especially in the secondary treatment process had the fastest EE2 photodegradation rate compared to that of the other three processes. Four types of components (water-soluble organic matter (WSOM), extracellular polymeric substance, humic acid, and fulvic acid) were separated from the A²/O process DOM. WSOM had the highest promotion effect on EE2 photodegradation. Fulvic acid-like components and humic acid-like organic compounds in WSOM were speculated to be important photosensitivity substances that can generate triplet state substances. This research explored the physicochemical properties and photosensitive sources of DOM in WWTPs, and explained the fate of estrogens photodegradation in natural waters.     

Per- and polyfluoroalkyl substances and obesity,type 2 diabetes and non-alcoholic fatty liver disease: a review of epidemiologic findings

Abstract

Per- and polyfluoroalkyl substances, a group of fluoro-surfactants widely detected in the environment, wildlife, and humans, have been linked to adverse health effects. A growing body of literature has addressed their effects on obesity, diabetes and non-alcoholic fatty liver disease/non-alcoholic steatohepatitis. This review summarizes the brief historical use and chemistry of per- and polyfluoroalkyl substances, routes of human exposure, as well as the epidemiologic evidence for associations between exposure to per- and polyfluoroalkyl substances and the development of obesity, diabetes and non-alcoholic fatty liver disease/non-alcoholic steatohepatitis. We identified 22 studies on obesity and 32 studies on diabetes, while only 1 study was found for non-alcoholic fatty liver disease/non-alcoholic steatohepatitis by searching PubMed for human studies. Approximately two-third of studies reported positive associations between per- and polyfluoroalkyl substances exposure and the prevalence of obesity and/or type 2 diabetes. Causal links between per- and polyfluoroalkyl substances and obesity, diabetes and non-alcoholic fatty liver disease/non-alcoholic steatohepatitis, however, require further large-scale prospective cohort studies combined with mechanistic laboratory studies to better assess these associations.     

Compilation of EINECS: Descriptions and definitions used for substances,impurities and mixtures

The European INventory of Existing commercial Chemical Substances (EINECS) lists all substances which were on the European Community Market between 1 January 1971 and 18 September 1981. Substances on EINECS are known as ‘existing’ substances. The EINECS inventory was drawn up by the European Commission to meet the requirements of article 13 of Directive 79/831/EEC [1]. EINECS was published in the Official Journal of the European Communities in 1990 [2]. This paper describes how individual substances, impurities and mixtures were defined and dealt with when registered for the EINECS inventory. It is the first in a series of such papers.     

植物修复土壤重金属污染中外源物质的影响机制和应用研究进展

重金属进入土壤后难以被降解,并通过食物链在生物体内富集,长此以往会导致中毒、癌症、畸形、突变,严重影响了人类生产活动及地球生态系统的稳定。植物修复技术是一种经济有效的重金属污染修复技术,其依靠超富集植物强大的自身抗性机制,从土壤中提取或稳定重金属,达到污染治理的目的。然而修复土壤重金属污染的超富集植物通常生长缓慢、生物量低,其抗性机制也会受到植物本身对重金属胁迫的阈值限制,当胁迫超过这个阈值,植物修复的效率就会大大降低甚至失去修复功能。文章在解析植物重金属相互作用机制的基础上,综述了添加外源物质对重金属毒害植物的缓解效应以及其在强化植物修复土壤重金属污染中的应用研究进展;介绍了应用外源物质调控植物吸收转运重金属的3种途径,分别为提高土壤重金属生物利用度、促进植物生长以及增强植物耐性。提出了应用外源物质作为强化植物修复措施的潜力及今后的研究方向,其未来的研究应着重于以下方面:明确外源物质的应用浓度、时期、方式与植物吸收转运重金属之间的关系;从植物内源激素及信号分子间的互作、抗逆基因表达、内生及根际微生物等不同层面上揭示外源物质对植物积累重金属的调控机理;开展外源物质与其他植物修复强化技术的联合应用研究。这些研究可为土壤重金属污染的植物修复技术及其强化措施研究提供科学依据,同时也对植物修复工程技术的发展实践具有一定的指导意义。     

Risikobewertung von Perfluortensiden als Beitrag zur aktuellen Diskussion zum REACH-Dossier der EU-Kommission

Background

The analysis of the intrinsic effects of perfluorinated organic surfactants shows the group to have a characteristic overall picture:

-high polarity

-high thermal and chemical stability

-ubiquitous distribution

-non-biodegradability

-multiple toxicity

In addition, certain substances belonging to this group (e.g. PFOS) exhibit a very long retention time in the human body. Toxic properties vary and, like the mechanisms for global distribution, have not been fully clarified. In the meantime, individual members of this substance group have been (are being) removed from the market. This report shows that in future the planned EU chemicals law (REACH) can be used to prevent such substances being regulated after they have been distributed in the environment and thus after damage has already occurred. To this end, however, the requirements for registration for low tonnage substances (1–10 tonnes/a) must be supplemented with specific tests (in particular on biodegradability)

Aim and Scope

The aim of the work was to analyse the intrinsic properties and risks of a subgroup of fluorinated organic substances.

Results

A summarising article describes the toxic effects and properties of a group of substances selected from the approximately 30,000 existing substances. With regard to the ongoing debate on revising the European regulations of existing substances (REACH). it is apparent that standardised test requirements cannot be applied to impact and risk analyses which are at times highly complex. For governments, REACH only provides the starting points for this process in the form of prescribed standard tests. If a substance (or a substance group) draws attention, more detailed tests must be carried out by the industry itself in the framework of responsible care and in the framework of the evaluation step of REACH. It is therefore important that the standard requirements of REACH are selected appropriately. In this respect, the study reveals some serious deficiencies in the Commission proposal.

Conclusion

The standard information for low tonnage substances (1–10 tonnes/a) must be supplemented in particular with an obligatory test on biodegradability. The possibility provided by the REACH dossier to evaluate substances on the basis of group observarions (SAR, QSAR e.g.) is to be welcomed.