Beschreibung der Desorption von Zink aus Flußsedimenten mittels Freundlich- und Langmuir-Isothermen Mathematical Description of the Desorption of Zinc from River Sediments by NTA Using Freundlich and Langmuir Equations

Remobilization of zinc from sediments from Rhine and Neckar rivers with nitrilotriacetic acid (NTA) in water has been studied in order to obtain a mathematical relation between quantities of mobilized zinc on sediments and concentration of zinc and NTA in aqueous solution. Remobilization has been measured by stirring the sediments for 70 hours in polyethylene flasks and analyzing dissolved zinc by AAS. Concentration of free zinc ions in solution is correlated with amount of zinc fixed on the sediments in form of adsorption equations by Freundlich and Langmuir and the linear equation. Whereas for the Rhine river sediment all correlations are of similar quality, the standard deviation for the linear correlation with the Neckar sediment is about twice as large as for the others. The adsorption energies on both sediments are similar, however, the adsorption capacity and therefore, the remobilized amount of zinc is larger for the Rhine sediment. For mathematical modelling of technical processes, eg., for technical decontamination of sediments the linear correlation may be recommended.     

Zielvorgaben für Pflanzenschutzmittelwirkstoffe und andere Schadstoffe in Oberflächengewässern

Quality Targets for Pesticides and Other Pollutants in Surface Waters Surface waters are not only adversely affected by industrial and municipal wastewaters but also by diffuse sources. For the control of the ecological water quality, so‐called quality targets are set. The quality targets are threshold concentrations for hazardous substances related to the protected goods like water ecosystems, drinking water supply, sediments, or fishing. In this paper, quality targets for the protection of aquatic life in surface waters were derived on the basis of a concept developed by the International Commission for the Protection of the Rhine (Internationale Kommission zum Schutze des Rheins – IKSR). The quality targets for the selected hazardous substances, which mainly belong to the chemical class of pesticides, were calculated using ecotoxicological results for species of bacteria, algae, fish, and small crustaceans, as the four trophic standards of the water ecosystem. In cooperation with the Federal Environmental Agency (Umweltbundesamt – UBA) the effect data were taken from ecotoxicological data bases. According to the concept of the IKSR, the lowest test result for the most sensitive species was multiplied by an assessment factor. This proceeding concerns the difficulty in describing the complex interactions in water ecosystems with toxicity data of single laboratory experiments for a few organisms. For seven pesticides quality targets below 0.1 μg/L were proposed. These results show that the ecotoxicologically based quality targets might be even lower than the limit values for pesticides in drinking water of 0.1 μg/L. But for most of the substances the determined values are significantly higher. The great concentration range of quality targets demonstrates distinctly that one standard concentration for all pesticides could not be given with regard to the different effects on aquatic organisms.     

Self‐purification in Upland and Lowland Streams

Ecological investigations at four streams in Saxony‐Anhalt have shown that there are considerable differences between the self‐purification power of upland and lowland streams. This result is reflected in chemistry and in microbiology. The structure of the bottom substrate mainly influences the degree of self‐purification in connection with rate of flow and flow velocity. The results and differences are demonstrated using the example of Katzsohlbach in the landscape unit “Mittel‐ and Unterharz” and the stream Olbe in the landscape unit “Magdeburger Börde”.     

Die EG‐Wasserrahmenrichtlinie: Ausweisung und Bewertung künstlicher und erheblich veränderter Gewässer

Designation and Assessment of Artificial and Heavily Modified Water Bodies under the EC Water Framework Directive The EC Water Framework Directive allows the Member States to designate artificial and heavily modified water bodies under specific conditions. For those water bodies the ecological assessment and the resulting programmes of measures will be based on the “maximum ecological potential” as reference conditions and not on the “high ecological status”, which has to be used for natural water bodies. Such designation is possible only, if the hydromorphology of the water bodies concerned has been substantially changed in character to maintain specified uses. The criteria for the designation are fulfilled, if restoration measures needed to meet the high ecological status would have significant adverse effects on the uses and if no other better environmental options would exist to maintain the specified uses. In late 1999 the EC‐Working Group on Heavily Modified Water Bodies (HMWB) has been established to develop criteria for the designation of artificial and heavily modified water bodies as well as for the determination of the maximum ecological potential. The working group has produced the guidance document “Identification and Designation of Artificial and Heavily Modified Water Bodies” in November 2002, which has been agreed by the European Water Directors on 21 November 2002 in Copenhagen. The guidance document is focusing on two time borders, the provisional identification of heavily modified water bodies until 2004 and the legally binding designation as artificial and heavily modified in the first river basin management plan in 2009 at the latest. The guidance document considered the main findings of 34 case studies for rivers, lakes, transitional and coastal waters carried out in 11 European countries. The results of the case studies as well as a summarizing synthesis were used as a fundamental basis to produce the guidance document. The practical examples given by the case studies were compiled as a toolbox which supplements the guidance for the purpose of its better application.     

Developmental,Reproductive, and Demographic Alterations in Aquatic Wildlife: Establishing Causality between Exposure to Endocrine‐active Compounds (EACs) and Effects

This brief overview discusses the difficulty of demonstrating causal associations between exposure to endocrine active compounds (EACs) and the occurrence of developmental, reproductive, or demographic disturbances in aquatic wildlife. While for biological responses at the suborganism level correlational or causal evidence of an EAC etiology has been established in a number of cases, well proven examples of ecological consequences of endocrine disruption are rather few in number. The attribution of causality is complicated due to (i) lack of data on EAC exposure and bioaccumulation, (ii) lack of specific biomarkers and endpoints, together with insufficient knowledge on the mechanisms and conditions by which EAC‐induced disruption of endocrine functions translates into impaired organism development and reproduction, and (iii) insufficient understanding of the importance of species diversity in endocrine physiology and life histories for the consequences of endocrine disruption. Future research should address these gaps in our understanding of EAC exposure and effects, but additionally needs to pay more attention (i) to ecological determinants influencing the population‐level consequences of the endocrine disruption of developÍmental and reproductive functions, and (ii) to the use of epidemiological principles and approaches.     

Wasserqualität durch höhere Wasserpflanzen. — Übersicht zur ökotechnologischen Anwendung —

Improving Water Quality by submerged and emergent Macrophytes. — A Review of Ecotechnological Application. Measures of ecotechnology using submerged and emergent macrophytes in native stands or planted littoral stands on the one hand, ingenious swimming plant mats on the other, may be assessed to be successful if applied in combination with additional measures, for instance — reorganization (sanition) of all the area collecting water — biomanipulation of pelagic food chains. Plantation of submerged macrophytes as oxygenators in standing and impounded waters to improve water quality should be avoided. To the contrary, the strategy should be taking measures in order to maximize the light penetrated euphotic zone (z_eu) and simultaneously minimize the mixed zone (z_mix) in order to improve spontaneous settlements of submerged macrophyte stands.     

Vorkommen natürlicher und synthetischer östrogener Steroide in Wässern des süd‐ und mitteldeutschen Raumes

Distribution of Natural and Synthetic Estrogenic Steroid Hormones in Water Samples from Southern and Middle Germany Natural and synthetic hormones can reach surface waters via domestic sewage effluents. For drinking water production, bank filtration of river waters is a common procedure and hormone contaminations can potentially reach groundwater levels and drinking water sources. In order to analyse steroid hormones in the different aquatic compartments (raw sewage and effluent, surface water, groundwater, raw and drinking water) of South and Middle Germany, a sensitive analytical method was developed and employed to detect the natural steroid hormones estradiol (E2) and estrone and the synthetic estrogen ethinylestradiol (EE2). Samples which were taken in two subsequent series were subjected to clean‐up and enrichment procedure and subsequently analysed by HPLC‐MS. The limit of quantitation for the method was determined to be 0.05 to 0.5 ng/L, depending on the matrix. By treating the samples with glucuronidases/arylsulfatases, conjugates were amenable to analysis and the sum of conjugates and unconjugated steroids was calculated. In raw sewage, the median of the concentrations of the unconjugated steroids was 7 ng/L for EE2, 1.5 ng/L for E2, and 5.5 ng/L for estrone. After cleavage of conjugates, the medians of total steroids were 9.5 ng/L (EE2), 3 ng/L (E2), and 13 ng/l (estrone). Conjugates therefore contributed up to 50 % of the total steroid concentration in raw sewage. In treated effluents, the concentrations of steroids were much lower than in the raw sewage. The medians of free steroids were determined to be 0.3 ng/L for EE2, 0.2 ng/L for E2, and 2.5 ng/L for estrone. Overall the medians in the effluent were thus less than 10% of those in the influent. Conjugates still contributed significantly (40% and more) to the steroid concentrations (medians: EE2: 0.5 ng/L, E2: 0.8 ng/L, and estrone: 8 ng/L).     

Endocrine Disrupters in the Aquatic Environment: An Overview

Although a relatively new area of environmental research, the field of endocrine disruption has grown very rapidly, and currently many hundreds, perhaps even a few thousand, papers are published annually on the many different aspects covered by the field. As far as endocrine disruption in wildlife is concerned, most attention has been focused on aquatic organisms, for two reasons. Firstly, the aquatic environment receives most of the pollutants intentionally released into the environment, through effluents from wastewater treatment plants, and secondly because many of the best documented examples of endocrine disruption in wildlife are of partially or completely aquatic species. These two reasons are probably not unconnected, of course. Hence, aquatic organisms can receive continuous exposure to endocrine‐disrupting chemicals throughout their lives, albeit usually to low concentrations of these chemicals. Analysis of effluents has identified many of the endocrine‐disrupting chemicals present, and shown that these are both natural and man‐made, and vary greatly in potency. Most attention has been directed to identifying the main estrogenic chemicals, because many of the effects reported in wildlife appear to be a consequence of ‘feminization’ of males. However, chemical analysis of effluents has also demonstrated that chemicals with other types of endocrine activity are present, such as androgens, anti‐androgens, progestagens, etc. The effects (if any, of course) of such chemicals on aquatic organisms are unknown, and largely uninvestigated, presently. Much of the biological research has centred on the effects of estrogenic chemicals, especially to fish. These effects, such as elevated vitellogenin concentrations and intersexuality, have to date been studied almost exclusively at the level of the individual, and hence whether endocrine‐disrupting chemicals cause population‐level consequences is largely unknown (the undeniable effects of TBT on molluscs, leading to local extinctions, being the exception). It is my opinion that rather too much of the recent research has not advanced our understanding of endocrine disruption a great deal, and we are probably not much further forward now than we were five years or so ago. It is surely time to tackle some of the outstanding, unresolved issues, such as the impact of endocrine disruption at the population level, and the issue of how organisms respond when exposed to complex mixtures of endocrine active chemicals. Such research will not be easy, and will require multidisciplinary teams, including people with expertise in areas not yet involved in the field of endocrine disruption, such as mathematical modellers. However, until such research is done, it will not be possible to decide how important an issue endocrine disruption is to wildlife, and how that importance compares to the other factors adversely affecting wildlife, such as habitat loss, climate change, and the introduction of exotic species and novel diseases.     

Die neue EG‐Wasserrahmenrichtlinie: Bewertung der chemischen und ökologischen Qualität von Oberflächengewässern

The New EC Framework Water Directive: Assessment of the Chemical and Ecological Status of Surface Waters The main objective of the draft EC Framework Water Directive is the good quality of all surface waters. The directive provides for an assessment of the chemical status of surface waters (EU‐wide valid environmental quality standards for approximately 30 priority substances) and a five‐stage ecological classification of waters, comprising the stages high, good, moderate, poor, and bad. The starting point for the assessment are the reference conditions, which are defined as corresponding to high water quality and characterising a water status with no significant anthropogenic impact. The reference sites in the various water body types are to be selected using hydromorphological and physico‐chemical parameters and subsequently characterised by means of biological parameters. For surface waters, three groups of characteristics are provided for, namely: 1. with priority the biology – in the case of surface waters – with the four elements phytoplankton, macrophytes/phytobenthos, benthic invertebrate fauna, and fish fauna; 2. supporting the hydromorphology, e.g. flowing waters with the three elements hydrological regime, river continuity, and morphological conditions and 3. supporting the physico‐chemical conditions with the three elements general conditions, specific synthetic pollutants, and specific non synthetic pollutants (other than the priority substances of the chemical status).     

Use of Chemotaxonomy To Study the Influence of Benzalkonium Chloride on Bacterial Populations in Biodegradation Testing

Contradictory results are reported for the behaviour of quaternary ammonium compounds (QACs) in sewage treatment plants (STPs). QACs may sorb onto activated sludge. Only little information is available with respect to effects of QACs against bacteria in STPs. Only 5 to 15 % of bacteria present in sewage sludge can be detected by means of culture dependent microbiological methods. The shift of the bacterial populations due to effects of test compounds have not been studied up to now with culture independent methods. The microbial populations shift was studied in situ using culture independent chemotaxonomy profiling ubiquinones and polyamines. Additionally, toxic effects of QACs against bacteria present in the test vessels of the Zahn‐Wellens test (OECD 302 B) were assessed with a toxicity control in the test. The ubiquinone profiles representing changes in Gram‐negative populations mainly showed that the activated sludge was affected only in test vessels containing benzalkonium chloride. According to chemotaxonomy Acinetobacter or/and some members of Pseudomonas spp. have been selected by benzalkonium chloride after some adaptation period (8 to 12 days).     

Konzepte zur Mobilitätsabschätzung von Schadstoffen in Boden- und Abfallmaterialien

Concepts for the Evaluation of Contaminant Mobility in Soil and Waste Materials Elution tests (S4, pH_stat, and SDS test) are presented, enabling the evaluation of the mobility of hydrophilic/hydrophobic and inorganic/organic contaminants in soil and waste materials. While elution tests for estimation of the mobilization potential of hydrophilic substances are performed following the pH_stat method, for hydrophobic species surfactant-containing eluents are used. The individual parameters of the elution process are selected assuming a "worst-case" scenario. In principle, because of economic reasons, detailed analytical investigations should be preceded by relevant screening tests.     

Applicability of Single and Sequential Extractions for Assessing the Potential Mobility of Heavy Metals in Contaminated Soils

Heavy metal polluted sites are bearing an acute hazardous risk for the groundwater, but also a potential one. While the acute risk can be assessed directly via seepage water measurements, determination of the potential risk is much more complex. It results from the sum of all reactions that are capable to mobilize heavy metals under worst case environ-mental conditions. Using a fourfold sequential extraction (SE₄) such a worst case was simulated for four soils highly contaminated with Pb, Zn, and Cu. The resulting potential mobilizable amounts ϕ_pm have been compared with those derived from 6 single extractions. By means of variance analyses, it is shown that ϕ_pm of lead can be represented by a single extraction with NH₂OH. In contrary, ϕ_pm of zinc can be represented using the pH_stat test or an extraction with aqua regia, while ϕ_pm of copper can be represented only by aqua regia extraction. The water-soluble amounts deriving from the DEV-S4 test do not correlate with the potential mobilizable amounts of any metal. Therefore, an assessment of contaminated sites should include an aqua regia extraction additionally to the seepage water analysis.     

Anthropogenic Eutrophication and Red Tide Outbreak in Lacustrine Systems of the Kashmir Himalaya

Red tide, a recurrent phenomenon has become conspicuous in several Kashmir lake ecosystems since 1991. The responsible organism (Euglena pedunculata), a rare flagellate rediscovered in the Kashmir Himalaya (Khan 1993) caused first and unprecedented red tide outbreak, constituting a maximum of 96% of resident numerical phytoplankton density in Dal Lake. At present, conflicting hypotheses exist on the generation of causal assemblage(s) imparting redness to waters: Jeeji Bai (1991) linked its origin to acid precipitation – a fallout of burning oil‐fields during the Gulf War – whilst Khan (1993) holds local factor(s) responsible. Field/experimental studies support the latter contention that the influx of untreated sewage, in unison with warm temperatures, high levels of PhAR, iron and interruption to hydrological flow‐pattern together with absence/or reduction in grazing activity created conducive environmental milieu for red tide outbreak. Dal Lake “red tide” drifted the bloom‐inoculum to other waters, including Lake Wular, where additional ecological niches were carved out, threatening the aesthetic value and biological diversity of Kashmir lakes. Ecological monitoring indicates frequent seasonal red tide occurrence in Dal Lake (including summer‐autumn event of 1998) which testifies its unabated eutrophication status. Further studies are needed on ecological adaptability and biogeographic distribution of this rare and unique red tide‐causing flagellate.     

Description of Ecosystem of the Lower Odra and the Odra Estuary

Environmental conditions of the lower river Odra and its estuary show a high variability of chemical and biological parameters, related to the dynamics of the river, its mouth area, the Lake Dabie-Szczecin Lagoon system, and the Pomeranian Bay. Water chemistry, affected by the total sum of industrial, urban, and agricultural pollution discharged from the direct drainage area is discussed. This pollution load influences the composition and ecological structures of terrestrial, frequently unique, phytal communities associated with aquatic areas, phyto- and zooplankton, benthos, fish fauna, and avifauna. The current status of the terrestrial and aquatic ecosystems is described; elements of cultural infrastructure existing within the Lower Odra Valley in Western Pomerania are mentioned as well.     

Verringerung der Schwermetall‐ und Sulfatbelastung in sauren bergbaubelasteten Gewässern durch Aluminiumpräzipitate

Attenuation of Heavy Metals and Sulfate by Aluminium Precipitates in Acid Mine Drainage During the mixing of acid mine waters with nearly neutral tributaries, often precipitates are formed which are high in iron or aluminium. These precipitates cover the river bed for many kilometres. Near the town of Lehesten (Thuringian slate mining area), leachates of slate quarries and waste rock dumps contain high amounts of aluminium, sulfate, copper, nickel, zinc, manganese, and H⁺ ions as a result of the oxidation of incorporated pyrite. These leachates enter the brooks Loquitz, Kleine Sormitz, and Rehbach leading to the phenomenon named above. The contribution of the forming aluminium‐rich precipitates on the attenuation of sulfate and heavy metals by sorption or coprecipitation was studied by analysing the composition of water and sediment samples as well as samples of suspended matter. Sulfate is often considered as conservative tracer in acid mine drainage. However, sulfate does not behave conservatively in this system what might be explained by the adsorption of sulfate to the aluminium precipitates. Instead, conservative behaviour was found for calcium, potassium, chloride, zinc, manganese, and nickel. A formation of jurbanite can be excluded because of the low sulfate contents. The sulfate content of the sediment depends on the pH. At low pH values (4.8) the S/Al ratio corresponds to the theoretical ratio in basaluminite and decreases with rising pH. Sulfate is weakly bound to the solid phase and can easily be replaced by OH^– ions. A formation of basaluminite is possible at low pH values with a fluent transition to aluminium hydroxide. Therefore the precipitates are assumed to consist predominantly of aluminium hydroxide with sulfate being adsorbed to the surface.     

Saisonales Vorkommen von Arten der Saprolegniales und Leptomitales im Auesee und in der Fulda in Kassel (Hessen) unter Berücksichtigung fischpathogener Arten

Seasonal Occurrence of Species of Saprolegniales and Leptomitales in Lake Aue and the River Fulda in Kassel (Hesse) with Special Consideration of Fish Pathogenic Species In this study, we examined the occurrence of species of aquatic Oomycetes of Saprolegniales und Leptomitales in Lake Aue and the river Fulda in Kassel (Hesse, Germany) with special consideration of fish pathogenic species. We monthly collected water samples of both water bodies from July 2003 to June 2004. The baiting method was used to gain an insight into the specific seasonal occurrence of aquatic Oomycetes. Some species show a seasonal periodicity. Nine of 11 species of Saprolegniales isolated from the two water bodies, and Leptomitus lacteus (Roth) C. Agardh, one of the two species of Leptomitales, were already documented on fish according to references. Additionally, 7 of 10 species could according to references already be detected on fish species present in the two water bodies. Simultaneous measurements of limnological‐chemical parameters were done during the sampling of water for the isolation of aquatic Oomycetes. The results of some measurements, concerning the river Fulda, were additionally compared with the predetermined guideline values and limit values of water bodies of fish of the “Cyprinid region”.     

Modelling the Kinetics of Calcium Hydroxide Dissolution in Water

In water treatment calcium hydroxide is used in softening and decarbonization techniques as well as in stabilization processes. Due to its slight solubility calcium hydroxide is applied as suspension. The dissolution kinetics plays a major role in these processes. For the characterization of calcium hydroxide dissolution empirical methods exist. These methods allow relative comparison of different calcium hydroxide products. Thus in this study a dissolution rate model is presented that is based on the chemical reactions determining the dissolution. This model allows to predict the dissolution with respect to particle diameter and temperature. However, the most important factor is the particle diameter i.e. the total surface of particles in solution. Furthermore an effect of the dosed amount of calcium hydroxide particles on the solubility was found.     

Effects of the Herbicide Metazachlor on Phytoplankton and Periphyton Communities in Outdoor Mesocosms

The effects of the chloroacetanilide herbicide metazachlor have been investigated in outdoor artificial mesocosms. Decreasing phytoplankton densities were caused by the application, however, the communities recovered after 30 to 35 days. Periphyton growth was found to be affected not only by the herbicide application but by the presence of species with different ability to grow on artificial substrates. Zooplankton diversity was small due to low density of ingestible algae species. Oxygen saturation was found to be correlated with the dosage levels of the herbicide in the second half of the study.     

Tsunami deposit associated with the 2011 Tohoku‐oki tsunami in the Hasunuma site of the Kujukuri coastal plain,Japan

We describe the detailed sedimentary characteristics of a tsunami deposit associated with the 2011 Tohoku‐oki tsunami in Hasunuma, a site on the Kujukuri coastal plain, Japan. The thick tsunami deposit was limited to within 350 m from the coastline whereas the inundation area extended about 1 km from the coastline. The tsunami deposit was sampled by excavation at 29 locations along three transects and studied using peels, soft‐X imaging and grain‐size analysis. The deposit covers the pre‐existing soil and reached a maximum measured thickness of 35 cm. It consists mainly of well‐sorted medium to fine sand. On the basis of sedimentary structures and changes in grain size, we divided the tsunami deposit into several sedimentary units, which may correspond to multiple inundation flows. The numbers of units and their sedimentary features vary among the three transects, despite the similar topography. This variation implies a considerable influence of local effects such as elevation, vegetation, microtopography, and distance from footpaths, on the tsunami‐related sedimentation.     

Adsorbed and Bound Residues in Fulvic Acid Fractions of a Contaminated Groundwater – Isolation:, Chromatographic and Spectroscopic Characterization

Humic substances (HS) were isolated from two contaminated groundwater samples (B22 and B53) from a site of a former gas facility. The isolation yielded almost only the fulvic acid fractions (FA). For characterization spectroscopic (UV, fluorescence) and chromatographic techniques (hydrophobic interaction chromatography – HIC as well as size-exclusion chromatography – SEC) were applied. The sample designated B22 FA was collected from the contamination plume whereas the sample B53 FA was collected downstream. Distinct differences were exhibited by these samples. The UV and fluorescence spectra as well as the HIC and SEC chromatograms of the B53 FA sample resemble those of the FA fraction obtained from natural water (groundwater, bog). The HIC and SEC chromatograms reveal the presence of organic compounds in B22 FA which can be derived from coal tar contaminants or their metabolites. Some of the compounds can be extracted from the FA fraction with non-polar organic solvents indicating adsorptive forces between the contaminants and the FA fraction.