Influence of Dissolved Organic Matter On the Bio-Availability and Toxicity of Metals in Soils and Aquatic Systems

Cations in soil are essential for the growth of plants and micro-organisms. Their availability is dependent on soil organic matter. Soil organic matter (SOM) is heterogeneous comprising amino, aliphatic and phenolic acids, but particularly humic substances. All these substances can complex cations selectively. Mechanisms of complexation with dissolved organic matter are discussed. Such complexation can lead to the apparently contradictory observations that dissolved organic matter (DOM) can either increase the concentration of some less soluble nutrients, making them more available for plant uptake, or make them less available and hence less toxic. the importance of DOM is discussed in relation to soil solution, particularly the rhizosphere, and also in relation to aquatic systems. the latter systems contain mainly dissolved humic substances whereas in the soil, non-humic substances assume a greater importance.

SOM in the rhizosphere is derived from plant, microbial and animal remains but much, especially the water-soluble compounds, are acquired through root exudation. Exudation has important consequences for enhanced nutrient availability as a result of the production of non-humic substances such as amino, aliphatic and phenolic acids. in future, the role of root exudation in relation to DOM and nutrient availability should be investigated more fully, particularly as predicted elevated CO₂ levels are likely to have a major impact on root exudation, nutrient availability, and possibly ecosystem community structure and functioning. It is likely that more information will become available on aquatic systems as more highly sensitive techniques and equipment capable of dealing with low concentrations of DOM in these systems become available.     

Influence of Dissolved Organic Matter On the Bio-Availability and Toxicity of Metals in Soils and Aquatic Systems

Cations in soil are essential for the growth of plants and micro-organisms. Their availability is dependent on soil organic matter. Soil organic matter (SOM) is heterogeneous comprising amino, aliphatic and phenolic acids, but particularly humic substances. All these substances can complex cations selectively. Mechanisms of complexation with dissolved organic matter are discussed. Such complexation can lead to the apparently contradictory observations that dissolved organic matter (DOM) can either increase the concentration of some less soluble nutrients, making them more available for plant uptake, or make them less available and hence less toxic. the importance of DOM is discussed in relation to soil solution, particularly the rhizosphere, and also in relation to aquatic systems. the latter systems contain mainly dissolved humic substances whereas in the soil, non-humic substances assume a greater importance.

SOM in the rhizosphere is derived from plant, microbial and animal remains but much, especially the water-soluble compounds, are acquired through root exudation. Exudation has important consequences for enhanced nutrient availability as a result of the production of non-humic substances such as amino, aliphatic and phenolic acids. in future, the role of root exudation in relation to DOM and nutrient availability should be investigated more fully, particularly as predicted elevated CO₂ levels are likely to have a major impact on root exudation, nutrient availability, and possibly ecosystem community structure and functioning. It is likely that more information will become available on aquatic systems as more highly sensitive techniques and equipment capable of dealing with low concentrations of DOM in these systems become available.     

Chemical exergy based evaluation of water quality

The thermodynamic concept of chemical exergy is introduced for water quality evaluation, to develop unified objective indicators in contrast to conventional indicators characteristic of subjectivity. While a quantity termed specific standard chemical exergy based on the global reference substances is used to evaluate the standard water quality, an indicator as specific relative chemical exergy with reference to a spectrum of substances associated with some specified water quality standard is developed for practical water quality evaluation, with related concepts of carrying deficit and carrying capacity well embodied in exergy terms. Based on the data collected in the GEMS/WATER project, water qualities of 72 rivers and 24 lakes over the world are evaluated, as a detailed case study to illustrate the adaptability of the chemical exergy based indicators for water quality evaluation.     

A new polystyrene-latex-based and EPS-containing synthetic sludge

Since the living microorganisms in activated sludge continuously change, it is difficult to conduct controlled experiments and achieve reproducible results for evaluating sludge characteristics. Synthetic sludge, as a chemical surrogate to activated sludge, could be used to investigate the sludge physicochemical properties, and it is desirable to prepare synthetic sludge with similar structure and properties to real activated sludge to explore the flocculation and settlement processes in activated sludge systems. In this work, a high-strength synthetic sludge was prepared with functional polystyrene latex particles as the framework and extracellular polymeric substances (EPS) to modify its surface. The flocculation and settling characteristics of the microspheres and the prepared synthetic sludge were tested. Compared with other three functional polystyrene latex microspheres, the synthetic sludge prepared with EPS-modified polystyrene latex microspheres showed good settling characteristics and a significantly higher strength. They could be used for studying the physicochemical properties of activated sludge.     

Geophagy in animals and geology of kudurs (mineral licks): a review of Russian publications

This paper reviews from the geological and biological perspectives the achievements of Russian researchers in the field of geophagy, which have not been published in English. It is focused on publications in Russian language about (1) animal behavior related to geophagy, (2) mineral and chemical composition as well as geological characteristics and biological effects of the earths, eaten by animals in various locations in Russia and neighboring countries. The authors argue that the Russian term “solonetz” (salt lick) is too limiting, as animals consume not just salt but many other minerals too. The more general term “kudur” is used for places where animals eat earths. The geological nature and biological properties of kudurites (the common name given to biologically active mineral-crystal substances consumed by animals) and gastroliths (stones consumed by birds and reptiles) are addressed. On the basis of the reviewed data, the authors propose their own views regarding the causes of geophagy.     

化学农药与环境激素

环境激素是指有可能干扰人与脊椎动物内分泌的外因性化学物质。在已知的６７ 种（或类）环境激素有机物中,化学农药（包括除草剂、杀虫剂、杀菌剂）及其代谢产物共占４４ 种,几近三分之二。在已进行环境调查的４７ 种环境激素中,已检出的有２４ 种,占二分之一。列举了环境激素对人类和动物生育、生理功能的影响,并指出研制开发“安全化学农药”的思路是不可取的。     

Effect of dilution rate on dynamic and steady-state biofilm characteristics during phenol biodegradation by immobilized Pseudomonas desmolyticum cells in a pulsed plate bioreactor

Continuous pulsed plate bioreactor (PPBR) was used for phenol biodegradation. Pseudomonas desmolyticum cells immobilized on granular activated carbon was used. Dynamic and steady state biofilm characteristics depend on dilution rate (DR). Lower DR favour phenol degradation and uniform, thick biofilm formation. Exo polymeric substance production in biofilm are favoured at lower dilution rates. Pulsed plate bioreactor (PPBR) is a biofilm reactor which has been proven to be very efficient in phenol biodegradation. The present paper reports the studies on the effect of dilution rate on the physical, chemical and morphological characteristics of biofilms formed by the cells of Pseudomonas desmolyticum on granular activated carbon (GAC) in PPBR during biodegradation of phenol. The percentage degradation of phenol decreased from 99% to 73% with an increase in dilution rate from 0.33 h?1 to 0.99 h?1 showing that residence time in the reactor governs the phenol removal efficiency rather than the external mass transfer limitations. Lower dilution rates favor higher production of biomass, extracellular polymeric substances (EPS) as well as the protein, carbohydrate and humic substances content of EPS. Increase in dilution rate leads to decrease in biofilm thickness, biofilm dry density, and attached dry biomass, transforming the biofilm from dense, smooth compact structure to a rough and patchy structure. Thus, the performance of PPBR in terms of dynamic and steady-state biofilm characteristics associated with phenol biodegradation is a strong function of dilution rate. Operation of PPBR at lower dilution rates is recommended for continuous biologic treatment of wastewaters for phenol removal.     

不同泥龄下活性污泥絮体性状的研究

采用序批式反应器对不同泥龄下污泥絮体的化学性状(胞外聚合物成分及含量)、物理性状(表面电荷)、形态性状(粒度分布、分形维数)等进行了对比研究.结果表明:泥龄对胞外聚合物总量及各组分含量的影响规律并不明显;多糖/蛋白质愈大,污泥絮体表面电负性愈强;污泥絮体的平均粒径随泥龄的延长呈逐渐减小的趋势,且粒度分布愈来愈均匀;不同泥龄下,污泥絮体形态结构亦不相同,泥龄短时,絮体表面粗糙,结构开放疏松;泥龄长时,絮体表面平滑,结构紧凑;随着泥龄的增大,絮体分形维数逐渐增加.由于不同泥龄下所表现出的污泥絮体性状的差异,直接影响了污泥的絮凝和沉降性能.     

攀枝花市水系沉积物与土壤中重金属的地球化学特征比较

水系沉积物和土壤都是表生作用的产物,是环境中污染物质的重要受纳体,但两者在物质来源和受纳污染物方面又有不同。重金属通过不同方式进入到水系沉积物和土壤之中产生污染,对于区域环境具有重要的影响。为了了解攀枝花市水系沉积物和土壤中重金属元素地球化学特征的异同和污染状况,在攀枝花市范围内系统采集了水系沉积物和土壤样品,从环境地球化学角度,应用地球化学方法研究了攀枝花市水系沉积物及土壤中重金属的地球化学特征,应用地质累积指数法评价了污染情况,并对二者进行了比较研究。结果表明,攀枝花市水系沉积物中重金属的含量普遍高于土壤;水系沉积物和土壤中重金属的分布具有相似的特征;水系沉积物中重金属的污染程度高于土壤,但总体上来说,重金属的污染程度较小。两者的污染程度不同是因为接受污染物的方式不同;两者的分布趋势相同,说明具有相同或相近的污染来源。     

Speciation and carcinogenic classification—some limits of assessment and prevention procedures—the case of “nickel”

The speciation of nickel is of the highest importance for the definition of lists of substances for regulatory activity in terms of prevention, regarding possible cancer risk. A review is made of the different attitudes of outstanding administrations in front of nickel speciation. Some of them show a maximum of care in chemical definition, others reflect a lack of scientific rigor leading to generic classifications, more or less abusive. The great complexity of the chemistry and physicochemistry of nickel imposes the “two‐level speciation concept” (chemical and physicochemical), at least for compliance with the “Good Laboratory Practice” as far as experimental toxicology is concerned. Recommendations are exposed for the attention of toxicologists and regulators who have been for some years now extremely solicited for prevention aims.     

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.     

应对地震灾害山谷型城市空间布局的对策

应对地震灾害时山谷型城市空间布局表现出很大的局限性,而合理完善的城市空间布局对生命财产的安全以及震后救援是相当重要的。依据山谷型城市面对灾害时的空间特点,以生命安全为根本目的,依据系统观从微观空间、中观空间、宏观空间3个层面进行了探讨,提出山谷型城市空间布局一些对策来应对地震灾害。微观空间层面的对策重点在于逃生,中观空间层面的对策重点在于安全转移和避难,宏观空间层面的对策重点在于对外联系。     

Insect chemical communication: Pheromones and exocrine glands of ants

Summary Chemical communication plays a very important role in the lives of many social insects. Several different types of pheromones (species-specific chemical messengers) of ants have been described, particularly those involved in recruitment, recognition, territorial and alarm behaviours. Properties of pheromones include activity in minute quantities (thus requiring sensitive methods for chemical analysis) and specificity (which can have chemotaxonomic uses). Ants produce pheromones in various exocrine glands, such as the Dufour, poison, pygidial and mandibular glands. A wide range of substances have been identified from these glands.     

Östrogene Wirkung von Xenobiotika

A number of xenobiotic organic substances are known which, in cases of prenatal exposition, may produce an estrogenic effect leading subsequently to serious reproductive disorders in the male progeny. Damage of this kind which is seen to occur in wildlife populations leads to the assumption that environmental chemicals exerting such estrogenic effects may be responsible for these disorders. Listed here are environmental chemicals which are known to date to exert an estrogenic effect. The article provides a review of papers and hypotheses on the estrogenic effects of xenobiotic substances. This is followed by a discussion concerning the significance of chemical estrogenicity on environmental and chemical policies as well as on the possibilities and limitations of test systems for the verification of estrogenicity.     

Anwendung differenzierter Untersuchungsmethoden zur Sedimentbewertung

The aquatic sediments have special significance as habitats of species-rich biocoenoses and as the place where manifold transformation processes occur. Because of their high potential for accumulation of contaminants, sediments are particularly sensitive to anthropogenic impacts, which may disturb the natural state of sediments. In order to protect the aquatic life community, such impacts must be identified, assessed, and the chemical causes of toxic effects must be found. Since the end of the 1980s, the interest for a possibly comprehensive assessment of sediments has increased. This problem can be tackled only by an integrated approach, which combines the detection of toxicity under standardized laboratory conditions with chemical data and biologicalin situ studies into a holistic view. The information value of the results depends essentially on the selection of a diversity of test methods, which are able to indicate contaminant effects differentially. This paper presents results from a comprehensive test approach, which integrates standardized methods (DIN) with pore waters and eluates, as well as tests using the whole sediment. To cover a wider variety of contaminants in the sediment, solvent extracts and fractions thereof were also examined by different bioassays. Chemical analyses examined the structural parameters and identified priority contaminants. Non-target screening could detect a variety of further substances and substance classes. The model organisms of the bioassays responded very differentially and sometimes very intensively to the contaminants in the various investigation media. Especially in sediment extracts, some fractions, and consequently also substances and groups of substances, proved to be particularly toxic. It could be shown that the selected chemical, ecotoxicological, and biological study methods contribute to a holistic assessment. Further, possibly very sensitive bioassays and benthos-biological parameters should be examined aiming to optimize the very wide battery of tests.     

有害结局路径(AOP)框架在水体复合污染监测研究中的应用

水体复合污染包含低浓度、种类复杂的毒害化学污染物,威胁人类健康和生态安全。监测并识别水体关键毒害污染因子是进行水质管理的前提,也是复合污染研究的难点。目前国内外在水复合污染毒性监测研究上主要基于动物活体试验或者生物体外测试。由于受限于毒理学测试方法,常见的应用通常仅关注于某方面的毒性效应或者少数的分子指标,因而受到质疑和挑战。有害结局路径(Adverse outcome pathway,AOP)的概念将化学污染物的结构、致毒的分子启动事件和生物毒性的有害结局建立关联,为污染物的毒性测试、预测和评估提供了新的模式。本文旨在论述有害结局路径在复合污染毒性评估和关键毒害物质鉴别中的指导性价值和意义。在有害结局路径的指导框架下,借助于生物体外高通量测试技术、化学分析的靶向和非靶向分析技术和生物信息学技术,可以系统地分析化学混合物在分子、细胞水平上健康相关指标的响应水平,评估水体中复杂结构污染物,与不同生态和健康有害结局之间的关联,为水环境评价和优先污染物的筛选管理提供有效支撑。本文通过综述AOP框架在复合水体中毒害物质风险研究的现状和优势,对AOP在水环境环境管理上的应用前景提出展望。     

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.     

有害结局路径(AOP)框架在水体复合污染监测研究中的应用

由于包含复杂的毒害化学污染物质,水体复合污染一直威胁着人类健康和水生生态安全。对复合污染水体进行监测、评估和治理是水环境管理的重点之一。监测并识别水体关键毒害污染因子是进行水质管理的前提,也是复合污染研究的难点。目前国内外在水复合污染毒性监测研究上主要基于动物活体试验或者生物体外测试。由于受限于毒理学测试方法,常见的应用通常仅关注于某方面的毒性效应或者少数的分子指标,因而受到质疑和挑战。有害结局路径(Adverse outcome pathway, AOP)的概念将化学污染物的结构、致毒的分子启动事件和生物毒性的有害结局建立关联,为污染物的毒性测试、预测和评估提供了新的模式。本文旨在论述有害结局路径在复合污染毒性评估和关键毒害物质鉴别中的指导性价值和意义。在有害结局路径的指导框架下,借助于生物体外高通量测试技术、化学分析的靶向和非靶向分析技术、和生物信息学技术,可以系统地分析化学混合物在分子、细胞水平上健康相关指标的响应水平,评估水体中复杂结构污染物,与不同生态和健康有害结局之间的关联,为水环境评价和优先污染物的筛选管理提供有效支撑。本文通过综述AOP框架在复合水体中毒害物质风险研究的现状和优势,对AOP在水环境环境管理上的应用前景提出展望。     

Soils and geomedicine

Geomedicine is the science dealing with the influence of natural factors on the geographical distribution of problems in human and veterinary medicine. Discussions on potential harmful impacts on human and animal health related to soil chemistry are frequently focused on soil pollution. However, problems related to natural excess or deficiency of chemical substances may be even more important in a global perspective. Particularly problems related to trace element deficiencies in soils have been frequently reported in agricultural crops as well as in livestock. Deficiencies in plants are often observed for boron, copper, manganese, molybdenum, and zinc. In animals deficiency problems related to cobalt, copper, iodine, manganese, and selenium are well known. Toxicity problems in animals exposed to excess intake have also been reported, e.g., for copper, fluorine, and selenium. Humans are similar to mammals in their relations to trace elements and thus likely to develop corresponding problems as observed in domestic animals if their supply of food is local and dependent on soils providing trace element imbalances in food crops. In large parts of Africa, Asia, and Latin America, people depend on locally grown food, and geomedical problems are common in these parts of the world. Well-known examples are Keshan disease in China associated with selenium deficiency, large-scale arsenic poisoning in Bangladesh and adjacent parts of India, and iodine deficiency disorders in many countries. Not all essential elements are derived only from the soil minerals. Some trace elements such as boron, iodine, and selenium are supplied in significant amounts to soils by atmospheric transport from the marine environment, and deficiency problems associated with these elements are therefore generally less common in coastal areas than farther inland. For example, iodine deficiency disorders in humans are most common in areas situated far from the ocean. There is still a great need for further research on geomedical problems.     

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.