Managing contaminated sediments

Remediation techniques on contaminated sediments are generally much more limited than for most other solid waste materials, except for mine wastes. The widely diverse contamination sources in larger catchment areas usually produce a complex mixture of contaminants that is more difficult to treat than an industrial waste. In the first two chapters, additional information will be presented onin- situ treatment methods, which were the central topic in the Spittelwasser Case Study (JSS - Journal of Soils and Sediments, Vol. 1, No. 3, pp. 181–187), and on the development of ecologically sound dredging and processing techniques, where practical applicability had to be demonstrated as part of an integrated remediation chain. In the latter respect, mechanical separation of less strongly contaminated fractions may be a useful step prior to the final storage of the residues (chapter 2, Treatment of Strongly Contaminated Dredged Materials) For most sediments from maintenance dredging, there are more arguments in favor of ‘disposal’ rather than ‘treatment’ (chapter 3, Subaqueous Storage and Capping). Consideration about the comparative assessment of the two basic management options ofin- situ capping and dredging followed by sub-aqueous disposal are discussed on a legislative, economic and technical-environmental basis. The concept of capping of contaminated sedimentsin- situ has been developed in the last two decades as an ecologically sound and economic alternative to more costly remediation techniques. The main characteristics are related to the passive character of this concept, which minimizes labor and process costs. Mechanisms of contaminant retention in sediment caps is discussed with special regard to the chemical isolation component. From this consideration, the development of the active barrier concept is derived that denotes the use of reactive additives in capping layers to chemically bind one or more contaminants specifically.     

Evaluation of two bacterial delivery systems for in-situ remediation of PAH contaminated sediments

Intention, Goal and Background  Contaminated sediments represent a significant, worldwide environmental problem since they contain a mixture of different xenobiotics and heavy metals. The presence of mixed contamination presents a unique set of obstacles for remediation efforts. Often sediment remediation occurs as an ex-situ application (i.e., after dredging) in an attempt to minimize some of the problems. However, dredging poses it’s own issues. It does not address contaminated water and often material is not completely removed thereby leaving a long-term residual contamination source in the waterway. Objective  The potential of bio remediation to treat sediments contaminated with polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls, and heavy metals was addressed. The primary objective was to assess two delivery mechanisms for microbial inoculation to facilitate in-situ remediation of PAH contaminated sediments. Methods  Simulated river beds were constructed to mimic the Mahoning River. Contaminated sediment from the river was added to each reactor at a uniform depth, followed by the addition of river water. Fifteen inoculation points were used in each simulated river bed to ensure adequate microbial populations. One tank was inoculated with an acclimated bacteria solution as a free suspension. The other tank was inoculated with an attached growth biofilm system. Sediment samples were taken throughout the experiment and the percent PAH degradation determined. Water characteristics (DO, pH, bacterial activity, etc.) were also tracked as corroborating evidence. Results and Discussion  The monitoring sites indicated that an attached growth system was more effective, and achieved a 99% PAH degradation efficiency at some of the sampling sites. Tracking individual PAH compounds also indicated a higher overall microbial activity with the attached growth system. This activity was evident by the formation and subsequent biodegradation of lower molecular weight degradation byproducts. However, more of the sediment area was treated by the free suspension inoculum due to the ease of microbial migration. Conclusions  The applicability of using an aerobic microbial consortium composed ofMycobacterium sp., Pseudomonas aeruginosa, andPseudomonas flourescens to treat contaminated sediment was demonstrated. In addition, it was found that introducing the consortium as an attached growth was more effective than when delivered as a free suspension. Recommendation and Outlook  The results demonstrated that the consortium was effective at treating the PAHs present in the contaminated soil. An additional study to evaluate the consortium’s effectiveness at remediating the PCB present in the sediment is warranted. Optimization of the consortium-nutrient combination could enable a treatment approach to effective for all the organic contaminants present. Although this would not address the heavy metals present in the sediment, it would afford a great opportunity at remediating a severely contaminated sediment system.     

Manging contaminated sediments

Management of contaminated sediments, i.e. linking risk assessment and problem solutions, needs both quality criteria respecting recent findings on bioavailability of pollutants and in-depth knowledge on processes controlling their particular hydrological and biogeochemical dynamics. In thefirst part of our review, new insights into ‘diagenetic’ mechanisms on particles including ageing and their effects on biological interactions were presented. These findings clearly indicate the need to refine bioavailability models including equilibrium partitioning. A set of bioassays is a powerful supplement to assess sediment quality. In thesecond part, an interdisciplinary process approach relating to the release of DOC, nutrients and pollutants into the open water is described, which has been derived from the evaluation of the international state-of-the-technology with three major themes: ‘experimental techniques’, ‘processes and properties’ and ‘development and validation of models’. Special study targets are the formation of aggregates in turbulent water, flocs and biofilms from organic reactions, and formation of new surfaces for readsorption of dissolved pollutants. Of greatest importance is the degradation of organic matter, which affects both hydrodynamic processes and geochemical redox cycles, thus providing driving forces, e.g. for metal mobilization. Models for predicting pollutant transport in rivers are still dominated by hydromechanical parameters. A first step for extending these models could involve typical milieu factors such as competing ions, complexing agents, redox conditions and pH-values. The next steps would include binding constants and other factors describing solid/solution interactions of critical chemicals in a multicomponent system. In theforthcoming issues of JSS — J Soils and Sediments, two practical fields of application will be discussed: in-situ sediment treatment — natural attenuation approach (Part III) and subaquous storage/capping of dredged material (Part IV). The abstracts of both parts can be found in the appendix.     

Sediment remediation: U.S. focus on capping and monitored natural recovery

The Battelle Conferences series represent the state-of-the-art of emerging technologies, science and management issues for contaminated sediment remediation. In the 2007 Conference held in Savannah, GA, two in situ technologies for cleanup sites were at the centre of interest: Sediment capping, a form of in situ containment, which involves the placement of a subaqueous covering of clean sediment and/or other materials to isolate contaminated sediments, and monitored natural recovery (MNR), where natural processes are used to mitigate the transfer of particle-bound contaminants into the water phase and/or biota. A third priority technology in the Superfund program, recommended by the U.S. Environmental Protection Agency (EPA), is environmental dredging, i.e., removing the sediments from the aquatic environment. About 30 platform or poster presentations dealt with in situ capping as a technology, reflecting the rapid developments in this field, both in assessments and enhancements of ‘classic’ passive caps and the development and demonstration of active capping technologies. Issues relevant to monitored natural recovery were spread throughout many sessions; e.g., contaminant source identification, control, remediation strategies; innovative characterization and assessment, chemical/toxicological/biological measurements and characterization, bioavailability of contaminants, contaminant fate and transport and remediation effectiveness: defining, monitoring, and demonstrating success. Presentations addressing the role of science and stakeholder input were complemented by discussions on the importance of data quality considerations, uncertainty analysis, and careful selection of reference sites highlighted the complex nature of these multidisciplinary assessments. Case studies, in which site-specific information was linked to regional management objectives, various approaches to watershed-scale assessment and management, and the role of ecosystem considerations, were all discussed in these sessions, as well as in a complementary panel discussion. One compelling feature of the Savannah Conference 2007 (relative to the first couple of meetings) is that there were a much larger number of presentations that provided the tools, models, case studies, etc to fill in the lines of evidence that allow a fair comparison between removal and in situ management when appropriate, and evidence of a growing acceptance that the residuals and impacts of removal approaches can at times offset perceived benefits, so that in situ management can be considered if exposure risk can be properly assessed.     

Managing Contaminated Sediments

Management of contaminated sediments, i.e. linking risk assessment and problem solutions, needs both quality criteria respecting recent findings on the bioavailability of pollutants and in-depth knowledge on processes controlling their particular hydrological and biogeochemical dynamics. To understand bioavailability is the key issue for managing contaminated sediments. Therefore, scrutiny of the geochemical situation, toxicity, and biodegradability is needed. The first part of this review refers to the new insights into ‘diagenetic’ mechanisms on particles including ageing and their effects on biological interactions. Chemical and physical methods are described to quantify the retarded desorption behaviour of hydrophobic organic substances and toxic metals. Results of analyses on the extractability of particle-bound pollutants (e.g. solid phase micro-extraction) can be correlated with the bioavailability. Some techniques recently developed to mimic bioavailabilty are briefly summarised. As can be derived from this review, there is a clear need to refine bioavailability models including equilibrium partitioning. A set of bioassays is a powerful supplement to assess sediment quality. Consequently, a paradigm shift should be initiated for the evaluation of biological data. All information of a survey have to be implemented in an assessment scheme. Multivariate statistics and fuzzy mathematics provide promising means to interpret multiple data pattern.     

Sediments in the Catchment-coast Continuum (7 pp)

-  Dedicated to Prof. Dr. Ulrich Förstner on his 65th birthdayBackground   Sediments pose problems at their deposition sites when there is too little sediment (e.g. wetlands) or too much sediment (e.g. navigable waterways) and, additionally, when they are contaminated. These problems often have their origin upstream in the river catchment. Objective   Global aspects of changes concerning sediment quantity and quality, as they affect downstream areas, are reviewed. A case study of estuarine sediments demonstrates how a holistic approach helps in understanding and predicting their present and future quality. Results and Conclusions   Globally, large reservoirs intercept between 25 and 30% of the sediment and consequently supply the coast with impacts on wetlands and coastal morphology. In estuaries, the composition of sediments is determined by the mixing of marine sediments supplied from the coast and the supply by rivers. Natural tracers can be used to predict mixing ratios of marine to fluvial sediments in estuaries, and hence their contamination. Scenarios on implementation of pollution abatement, the implementation of regulations as well as climate change are needed to predict future sediment quality in downstream areas. The results show, even for a ‘green’ scenario, that sediment quality in the Rhine catchment will pose future problems due to the temporal storage of contaminants in soils and sediments.Recommendations and Outlook   The current methods applied make use of existing models linking sediment transport with point and diffuse sources in the river catchments and scenarios on the development of strength of point and diffuse sources. However, more effort is needed to come to a uniform framework which includes land use changes and links with more advanced scenario methodology for long to medium-term management of sediment quality and quantity in river catchments.     

From risk assessment to sediment management an international perspective

Contaminated sediment management is complex and multivariate, involving a careful balance of science, politics and economics. As is true for most such complex issues, there is not a single correct way to address a problem, but rather the approach should be driven by the ecological, political and economic goals of all interested parties. However, because the choices made have far-reaching implications, it is useful for countries, regions or communities to develop standard approaches for sediment assessment and management to meet agreed-upon goals. This paper provides a brief review of a number of sediment assessment frameworks from around the world. Their main similarities and differences, and some of the reasons behind them, are addressed. Aspects of assessing and managing sediments are discussed, as well as why these are (or should be) driven by sediment management goals. Finally, suggestions are made to support the development of a European framework for sediment management and environmental quality. This paper was originally an invited address for the Risk Management and Communication Workgroup WG5 at the European Sediment Research Network (SedNet) Inaugural Conference, Venice, Italy, April 22–23, 2002     

The multispecies freshwater biomonitor a potential new tool for sediment biotests and biomonitoring

Behavioural changes are used as early warning systems for water quality monitoring or as rapid and sensitive endpoints in toxicity bioassays. In this study, the automated measurement of behavioural patterns of the thrichopteranHydropsyche angustipennis (Curtis 1834) has been recorded for the first time in sediment with the Multispecies Freshwater Biomonitor, MFB. The MFB recorded different types of behaviour in sediment with the same accuracy as in water. Behavioural differences of the larvae exposed to ‘water only’ and ‘sediment only’ have been described. In ‘choice’ experiments, the larvae preferred the ‘water only’ compartment.     

Historical Contaminated Sediments and Soils at the River Basin Scale

Background, Aims, and Scope  

Data from the Elbe River and its tributaries indicate, despite extensive improvement in water quality during the last 15 years, that the respective sediment situation of many priority pollutants has not reached an acceptable level. For the coming decades, risks for downstream sites and stakeholders will persist, mainly due to secondary sources originating from historical pollution of soils and sediments in the catchment area. In practice, a catchment-wide assessment of historical contaminated soil and sediment should apply a three-step approach: (i) Identification of substances of concern (s.o.c.) and their classification into ’hazard classes of compounds’; (ii) identification of areas of concern (a.o.c.) and their classification into ‘hazard classes of sites’; (iii) identification of areas of risk (a.o.r.) and their assessment relative to each other with regard to the probability of polluting the sediments in the downstream reaches. The conversion of this concept has to consider the underlying philosophy of the EU Water Framework Directive, particularly with respect to the analysis and monitoring of priority substances in solid matrices. However, major deficiencies are still in the assessment and prognosis of resuspension processes, and potential approaches to fill this gap are described both in theory and from examples of the Elbe River.     

A Novel Particle Contact Assay with the Yeast Saccharomyces cerevisiae (8 pp)

Goal, Scope and Background   Numerous xenobiotics released into surface waters are transferred to suspended particulate matter and finally attached to sediments. Aquatic organisms may be exposed to them by direct particle feeding, by physical contact with contaminated surfaces as an exposure route, and by the uptake of dissolved contaminants after equilibration via the free water phase. In order to assess potential sediment toxicity, each of these exposure routes has to be addressed. This paper presents a newly developed particle contact assay that uses the fermentation performance of a specific Saccharomyces cerevisiae strain for the assessment of toxic effects in sediments. The test procedure is based on the characteristic feature of growing yeast cells to attach to sediment particles, which are also relevant for the accumulation of contaminants. The physical contact with lipophilic contaminants mirrors an exposition pathway for the direct uptake into the cells. In order to quantitatively characterize the toxic effects of particle attached pollutants on the fermentation performance, unpolluted native reference sediment was spiked with representatives for widely distributed anthropogenic contaminants. Methods   Saccharomyces cerevisiae was established as sensitive eukaryotic microorganism for the ecotoxicological assessment of particle attached anthropogenic contaminants in freshwater sediments. For this purpose, yeast cells were cultivated in sediment samples and the resulting fermentation performance was continuously measured. Sediments artifically spiked with HCB, PCB, g-HCH, DDT, and benzo(a)pyrene and solutions of each contaminant were comparatively investigated by means of their adverse effects on yeast fermentation performance. Additionally, four native river sediments characterized by increasing levels of pollution were assessed by the yeast particle contact assay, and simultaneously by standard aquatic tests with algae, daphniae, and luminescent bacteria using pore water and elutriates. Results of the bioassays were related to specific sediment contamination with respect to metals and organic priority pollutants. Results and Discussion   In sediments spiked with PCB and benzo(a)pyrene fermentation, performance was affected extensively below concentrations inhibiting fermentation in contaminant solutions. This suggests a high efficiency of the exposure route by physical contact. The fermentation performance was only slightly affected by single lipophilic pollutants, whereas mixtures of individually spiked sediments caused critically reduced fermentation performance suggesting additive synergistic effects. Native river sediments modestly to critically polluted by hazardous organic compounds lead to a slightly to dangerously reduced fermentation performance in the yeast contact assay. These inhibitory effects were much less pronounced in the standard bioassays conducted with algae, daphniae and luminescent bacteria, applying pore waters and elutriates as sample matrices. Using pore water, inhibition was measured only in the most polluted sediment, elutriates lead to a slight inhibition of the algal growth in the undiluted sample only. These results indicate an improved sensitivity of the yeast particle contact assay compared to the standard assays, due to uptake and physical cell contact as additional routes of exposure. Conclusion   The yeast particle contact assay is a valuable tool for the assessment of ecotoxicological potential in freshwater sediments. Since the assay addresses physical contact as an exposure route, it indicates bioavailability of lipophilic compounds in sediments. Outlook   The sensitive indication of bioavailable contaminants associated to sediment particles by the newly developed yeast particle contact assay recommends it as a complementary microbial bioassay in a test battery for assessing major pathways of contaminants in whole sediments.     

The assessment of sediment screening risk in Venice Lagoon and other coastal areas using international sediment quality guidelines

Background, Aims and Scope  A number of studies carried out in recent years have shown the presence of a wide range of contaminants in the Venice Lagoon. It is important to have a good understanding of the ecological quality of Venice Lagoon sediments, in order to: i) define and locate areas where a threat to the environment is present and therefore an intervention is needed (i.e. in situ assessment and management); and ii) define sustainable and environmentally correct ways of managing sediments which are to be dredged for navigational purposes or in relation to other interventions (i.e., ex situ management). Methods  To examine how various regional and international SQGs ‘classed’ screening risk in Venice Lagoon sediments, data on median contaminant levels in surface sediments in Venice Lagoon resulting from a literature review were compared to a range of local and international sediment quality guidelines (SQGs). Then data on sediment contaminant levels in various areas and sub-basins of Venice Lagoon (main Lagoon, Porto Marghera and Venice City Canals) and in other regional and international transitional and coastal ecosystems with various levels of human impact (urbanization and industrialization) were evaluated based upon a selected consensus-based SQG. Finally, screening sediment quality for all of Venice Lagoon was mapped and contoured, relative to this consensus-based SQG and briefly compared with direct toxicity measurement through a battery of bioassays. Results  SQGs allow the sediment areas to be put in terms of potential, or screening, risk. Although there were some differences depending upon which specific SQGs were applied, the Venice SQGs and other international SQGs provided the same general picture of screening risk in Venice Lagoon despite geographic differences. Venice Lagoon South has the lowest screening risk levels, Venice Lagoon Central/North has the highest (and is nearest to the Porto Marghera and Venice City Canals sites). Discussion  The Venice Lagoon sediments have hazard quotients on the low end of the range of moderately urbanized and industrialized sites and higher than background case studies reviewed. Hg levels in the Venice Lagoon were generally higher than equivalent sites, while other contaminants were either equivalent or lower. In Porto Marghera (PM) and Venice City Canals (VC), for many contaminants of interest, PM, and for some, VC sediments have the highest levels of any case study reviewed. Ranges are high, so in all cases, remedial or disposal decisions should be based upon site-specific (and preferably tiered) data. Conclusions  The use of hazard quotients makes it possible to compare screening risks due to different mixes of contaminants within and between sites, but results should be interpreted with caution. How these sites rank when compared to some of the other highly industrialized sites depends upon how data are synthesized and communicated. Actual risk must be evaluated using a weight of evidence (WOE) approach, as site-specific bioavailability and background levels will differ both regionally and internationally. Recommendations and Perspectives  Whilst there are subtle differences, the current Venice sediment classifications (A, B and C) ‘performed’ in a similar manner to SQGs in similar classes, suggesting that regions of Venice Lagoon would not be classified much differently if other SQGs such as TEL, ERL, PEL, ERM or AET were adopted. The Italian sediment quality objectives, on the other hand, are significantly more conservative than any other SQGs examined, with the exception of the Flemish Reference values. A number of European nations are considering criteria based upon contaminant levels in relatively pristine modern sites, or based upon derivations of historical (pre-anthropogenic) contaminant levels. When used as a standard, such an approach lacks discriminating power, designating almost all sediments within an urbanized or industrialized region as of concern, or even, in many cases, mandating action or prohibiting various management approaches in a large percentage of sediments. While generally based upon the laudable desire to return sites to unimpacted levels, there is a risk that overprotective criteria have the opposite effect: by designating too large a percentage of sediments as requiring management or control, limited resources may be improperly allocated. Which set of SQGs is most ‘appropriate’ for the Venice Lagoon sediments depends upon the questions being asked. However, the Venice classifications are currently being used as pass-fail criteria, without consideration of site-specific conditions. The fact that they performed similarly to SQGs in similar classes suggests that any work to develop more site-specific SQGs (with the same general decision classes) would probably not make much difference in how sediments were ultimately classified and managed unless the fundamental approach was changed from a pass-fail to a tiered and WOE approach integrated in a comprehensive decision framework. For Venice Lagoon, and for other regions, although SQGs should be developed with care, in a scientifically defensible and risk-based manner, an equally or more important issue to be addressed is their role in overall decision frameworks. ESS-Submission Editor: Dr. Marc Babut (marc.babut@cemagref.fr)     

Sediment management options for the lower Ebro River and its delta

Background, Aim and Scope  Past and present management of the Ebro catchment have altered water, sediment and nutrient fluxes of the lower Ebro River and its delta. The construction of the Mequinensa and Riba-Roja dams during the 1960s disrupted the sediment transport continuity. As a result, the lower Ebro River and its delta are facing a reduction in sediment delivery which is estimated to be up to 99% of its original yield (about 3 × 10⁷ t/yr). Consequently, about 45% of the emerged delta will be under the mean sea level by 2100 due to subsidence and sea level rise, whereas the delta coast is retreating at a rate of several meters per year in the mouth area. This paper aims to establish the basis for a sediment management plan directed to offset the effects of the sediment delivery deficit of the Ebro delta. Main Features  A new management plan named ‘Integrated Plan for the Protection of the Ebro Delta’ (PIPDE) is being presently elaborated in order to develop sustainable management of the Ebro River and delta through an integrated management of water, sediment and habitats, in order to achieve European Union (EU) Water Framework Directive (WFD) requirements. Among other aspects, the plan aims to restore the sediment flux of the lower Ebro River by means of both the removal of the sediment trapped behind the dams and the transport of the sediment downstream of the reservoirs to the river mouth and delta plain. Results  Preliminary studies show that the ‘flushing flood’ method has lower costs and is the most adapted method to transfer the sediments retained into the Riba-Roja dam. The required sediment load to stop coastal retreat in the mouth area and to compensate relative sea level rise represents 10 times the present suspended load (0.021 g/l), but is 10 times lower than the total volume of sediment delivered to the sea under natural conditions. Sediment delivery to the delta plain can be accomplished through the rice irrigation system, a method used prior to dam construction. Discussion  Problems of achieving a sustainable management of water and sediment are mostly linked to reservoir management. Technical problems associated with by-passing sediments through the reservoirs can be solved through operational and structural changes. Benefits of sediment flow recovery are multiple, including maintenance of the reservoir capacity, possible decline of invasive species, reduction of elevation loss and coastal retreat in the delta. Conclusions  The partial restoration of sediment fluxes in the lower Ebro River and its delta is technically feasible and environmentally desirable, but further detailed studies need to be carried out before the plan can be implemented. Perspectives  Overall, the sustainability of the lower Ebro River and delta can only be guaranteed by the implementation of a new reservoir management concept where the ecological and morphological values, as well as the economical and social values, have to be taken into consideration.     

Determining the bioavailability of contaminants and assessing the quality of sediments

Background, Aims and Scope  Our study determined the role of light, aeration, grain size, amount of sediments and of water, density of animals and presence of additional food on the movement of Ilyanassa obsoleta. Spiked relative to reference sediments were also tested for avoidance or preference by the mud snails. Our goal was to develop exposure conditions to be used in future assessment studies of the environmental quality of sediments inhabited by mud snails. The behavioural response of the snails towards different concentrations of contaminated Halifax Harbour sediments placed in one half of a tank relative to reference sediments in the other half is examined in Part 2 and a chemical link investigated. Methods  Animals were exposed in 7 L aquaria at 12°C to their native sediments placed in one or two halves of a tank and the effect due to the presence of a light source, air bubbles, sediment grain size, added algae examined relative to the snails’ behaviour. Preference or avoidance of one half of a tank relative to the second half, the immersed or dry glass surface represented the various media to be chosen by snails. After choosing the optimum set up, exposures were performed in triplicate, under slightly differing initial placement of the snails to compare means and variability in the results. Three specific biogenic chemicals, cholesterol, coprostanol and a fatty acid methyl ester (FAME) were spiked at 0.002, 0.01, 0.05, 0.25 and 1.2 mg/g, dry weight of sediment. A hexane, dichloromethane and methanol extract of harbour sediment were also spiked in reference sediments. In all cases, the location of the snails was recorded over a period extending up to 96 hrs. Results  Twenty snails exposed during a 72 hrs period in commercial 7 L tanks containing 50 g of sediments (wet weight) in the bottom half of a tank filled half way with seawater represented the chosen conditions to test the avoidance/preference behaviour of snails for part of a tank. The presence of additional food on sediments attracted snails within 24 hrs of exposure. Discussion  A general lack of preference was indicated in exposures to three biologically derived compounds spiked in reference sediments, i.e. a C-18 FAME, cholesterol and coprostanol. The repelling properties of a harbour sediment extract pointed to a role for non polar chemicals. Conclusions  It is proposed that behaviour reflects a balance between the repelling effects of contaminants and the attractive value of food. The present study provides a robust green assessment tool that is easy to set up to assess the quality of sediments. Recommendations and Perspectives  The interpretation of field observations regarding the abundance of animals during environmental assessments must consider both nutritional and toxicological causes. Additional laboratory exposures are needed to determine which chemicals play a role in the field.     

BMBF-research-focus ‘percolation water prognosis’ concept and current activities

The 41 participants of the BMBF-research-focus ‘percolation water prognosis’ are working out the scientific basis of the methods, which are needed to carry out this ‘percolation water prognosis’. They are either focussing on the further development of methods for determining the source strength of materials or on improving existing models for predicting the contaminant transport through soils. Validity and transferability of these developed methods/models are evaluated by including the core projects ‘reference materials’ and ‘lysimeter experiments’ . Scientific co-ordination is carried out at the HSL, where — among other activities — a central database will be created to compare and interpret the results of the different projects. A routine procedure for carrying out the ‘percolation water prognosis’ in most cases must be easily applicable and generally accepted. Nevertheless, the research projects are examining the arising questions from different perspectives and apply highly sophisticated methods in order to provide a sound scientific basis [8]. Most of the projects have started in the course of the year 2001, so first results may be expected during 2002.     

Contaminated sediments as a potential source of Zn, Pb, and Cd for a river system in the historical metalliferous ore mining and smelting industry area of South Poland

Background, aim, and scope  Elevated levels of heavy metals in the aquatic and soil systems can be caused by the weathering of mineralized rocks. This enrichment is often considerably enlarged by historical and current mining and smelting activities. In Poland, the most contaminated river systems are those in the Silesia region. The metalliferous ore mining and smelting industries have been the main sources of heavy metal pollutions over the last 100–170 years. The previous and present studies have shown very high concentrations of heavy metals in the bottom sediments of the Mala Panew River, the most polluted tributary of the Oder River. The main objective of this work was to study temporary changes of selected metal (Zn, Pb, and Cd) concentrations in upper layer of bottom sediments at the measuring point near the outlet of the Mala Panew River into the Oder River, and to determine the vertical distribution of the metals in the sediment cores from the most polluted middle part of this river. The mobility of the metals and their potential bioavailability were assessed based on metal partitioning in the sediments and metal concentrations in pore waters. The presented data were compared with metal concentrations in aquatic sediments from similar historical mining and smelting sites in Poland and other countries. Methods  The upper layer of bottom sediment samples from the same Mala Panew River measuring point were collected six times in the period 1997–2005, while five sediment cores were collected once from the middle course of Mala Panew River in 2006. Abiotic parameters such as pH and Eh have been determined in situ. Metal contents were determined in the <20 and <63 μm size fractions of sediments after digestion in a microwave oven with aqua regia or concentrated nitric acid. Metal mobility was assessed in the selected sediment cores by the chemical forms of metals (sequential extraction method) and their concentrations in pore waters were investigated. Results  The concentrations of Cd, Pb, and Zn in the upper layer of sediments varied, depending on both the season and the year of sampling. Their mean concentrations (from six samplings) are [mg/kg]: Zn 1,846, Pb 229 and Cd 73. The metal concentrations in the sediment cores varied with the depth in the range of [mg/kg]: 0.18–559 for Cd, 26.2–3,309 for Pb and 126–11,153 for Zn, although the highest accumulations generally could be observed in the deeper layers. The most mobile metal fractions, i.e., exchangeable, carbonate and easily reducible fractions, are typical of Zn and Cd. Cadmium was found to be the most mobile metal and its relative contribution ranges from 84 to 96%, while in the case of Zn it ranged from 45 to 94%. Lead is mainly associated with the moderately reducible fraction (30–60%). Relative contributions of metal chemical forms slightly vary with the depth in the sediment profile. The results obtained for the pore water samples show very high concentrations of the metals studied, especially in the case of Cd (31–960 μg/dm³) and Zn (300–4,400 μg/dm³). Discussion  Accumulation of Cd, Pb, and Zn in the upper layer of the bottom sediments and in the sediment core samples from the Mala Panew River is very high, considerably exceeding the local geochemical background. High contributions of mobile Cd and Zn and the toxicity of cadmium can cause environmental risk. Our measurements also suggest that mobile metals can migrate into groundwater, whereas the groundwater itself can leach some chemicals from river sediments, because of a relatively high water table in the study area, especially during rainfall periods. Comparison of the results obtained with the literature data from the last decade shows that the concentrations of Cd and Zn in the sediments from the Mala Panew River are the highest among other submersed sediments in Poland and other regions (e.g., the Mulde River, Germany). Conclusions  The Mala Panew River is one of the most polluted rivers when compared with similar historical mining and smelting areas in Poland and elsewhere. The sediments studied are strongly polluted with the metals analyzed. In the upper layer of the bottom sediments there has been no reduction of Zn and Cd amounts over the last decade, which could suggests a long-term migration and a secondary contamination. Considerably higher accumulations of metals in overbank sediment cores and in the deeper core section could result from strong contamination in previous decades and translocation of Cd and Zn (secondary pollutants). The relatively high concentrations of the two metals in pore waters support these findings. Cadmium is crucial in the environmental risk assessment because of its high mobility and toxicity. These data are important for water/sediment management in the transboundary Oder River catchment, situated in Poland, Germany and the Czech Republic. Recommendations and perspectives  It is important to assess mobility phase and pore water in the contaminated historical aquatic sediments. Such studies may help explain the changes, which take place in the sediment layers as well as at the water–sediment interface. Obtained results should be used for the risk assessment of the historical contaminated sediments at the local river-basin scale. The treatment of contaminated sediments, e.g., dragging activity, should be considered as very important in management strategies in order to avoid remobilization of metals.     

Source apportionment of lake bed sediments to watersheds in an Upper Mississippi basin using a chemical mass balance method

Sediment samples were collected from three known sources contributing to a depositional basin of the Upper Mississippi River, USA. The heavy silt fraction (2–63 μm, density >2.95) isolated from the sediments was analyzed for 42 elements by inductively coupled plasma-mass spectrophotometry (ICP-MS) to give signature profiles characteristic of each source catchment. Known proportions of heavy silt fractions from each source were mixed and the composite samples analyzed in the same way. The proportions of components in the composite samples were compared to their apportionments calculated statistically using the US Environmental Protection Agency (USEPA) chemical mass balance (CMB) air quality receptor model. This showed that the CMB technique can apportion sediments to their catchment sources reliably. The technique was then applied to dated sediments of Lake Pepin, in the Upper Mississippi basin, to apportion them to their contributing catchments. The results show that almost all the recent sediments deposited in the basin originated in the Minnesota River catchment, and that the sediment load increased over time as anthropogenic impacts increased. This technique could be used elsewhere to determine sediment provenance and identify changes in sediment sources over time.     

Sediment Properties for Assessing the Erosion Risk of Contaminated Riverine Sites. An approach to evaluate sediment properties and their covariance patterns over depth in relation to erosion resistance. First investigations in natural sediments (11 pp)

Background, Aim and Scope   Riverine sediments store large quantities of hazardous contaminants, remaining a 'legacy of the past' world-wide. Natural events such as floods may cause the resuspension of polluted sediments and accordingly, the former immobilized contaminants might become bioavailable and toxic again. Hence, a comprehensive erosion risk assessment of contaminated sites is of crucial importance. The present study aimed to implement 'master-variables' for a reliable, easy-to-manage and economically more viable determination of stability in cohesive sediments. Materials and Methods: A wide range of physico-chemical (bulk density, water content, particle size, mineral composition, cation exchange capacity / CEC, total organic matter / TOC, liquid and plastic limits of a soil) and biological (macrofauna abundances, microalgal biomass and species composition, bacterial cell numbers, EPS fractions such as carbohydrates and proteins) properties were determined simultaneously over depth spanning the zone between 0-35 cm. The data were related to sediment stability, determined as the 'critical shear stress for mass erosion' in the SETEG (Stroemungskanal zur Ermittlung der tiefenabhaengigen Erosionsstabilitaet von Gewaessersedimenten) - flume. The investigations were done on natural sediments, thereby covering vertical (over depth), spatial (different study sites) and temporal (different seasons) aspects to ensure the transferability of the data. Here, first data originating from three contaminated reservoirs in the lock-regulated River Neckar / Germany are presented. Results: Comparison of the rather low critical shear stress values (resisting force of sediment, determined in SETEG) with the possibly occurring natural bottom shear stresses (attacking force, calculated for different hydraulic scenarios) at the three reservoirs indicated a severe risk of sediment erosion even under moderate hydraulic conditions and was not restricted to the surface. Critical shear stress was characterised by the following sediment properties of depth, grain size, CEC (Cation Exchange Capacity) and concentrations of TOC (Total Organic Carbon), proteins as well as carbohydrates (water- and resin-extractable). Firstly, biological stabilisation by extracellular polymeric substances (EPS) could be shown for riverine sediments, even over depth. Secondly, erosion resistance was determined by the inter-particles forces, an interplay of the biologically produced compounds constituting active surfaces and the binding capacity as well as charge densities of the sediments. The combined influence of sedimentological and biological properties on sediment stability over depth was assessed by PCA (Principal Component Analysis). Discussion: Hence, a better correlation coefficient between sediment stability and the master variables could be achieved (Main component II: Polymeric substances, R = 0.7, Main component III: Grain size, TOC, CEC, R = 0.9) compared to single correlations. Conclusions: The present paper revealed the combined influence of physico-chemical and biological properties on sediment stability over depth by simultaneous investigation and statistical evaluation. It can be shown, that inter-particle forces, determined by particles size classes, CEC, TOC and polymeric substances such as proteins and carbohydrates, affected sediment stability most. Thereby, the impact of biogenic sediment mediation on riverine sediment stabilisation became evident, even over depth, where mostly sedimentological parameters were considered as important before. Recommendations and Perspectives: The importance of a comprehensive risk assessment of contaminated riverine sites was again highlighted in the present study by the comparison of natural occurring bottom shear stresses with the determined sediment erosion resistance. If a realistic risk assessment is to be derived, the stabilizing potential of micro-organisms needs to be taken into account and the covariance patterns of biological and physico-chemical sediment properties have to be addressed.     

Temporal Dynamics of Sediment Sources in an Urbanizing Mediterranean Catchment

The identification of sediment sources is important for catchment management, but few studies have been performed in Mediterranean areas. This study uses a multiproxy sediment fingerprinting approach to explore sources and dynamics of fluvial sediments in a rapidly urbanizing Portuguese peri‐urban catchment. X‐ray fluorescence was used to characterize the elemental geochemistry of sediments collected within the stream network after three storm events in 2012 and 2015. A range of statistical techniques, including hierarchical cluster analysis, was used to identify discriminant sediment properties and similarities between fine bed sediment samples of tributaries and downstream sites. Quantification of sediment supply from upstream sub‐catchments was undertaken using established sediment fingerprinting approaches. The geochemistry of the sediments was found to be influenced by both lithology and land‐use changes. In 2012, the sandstone sub‐catchment provided 75% of the <63 μm and 94% of the 63–125 and 125–2000 μm sediment, mostly from an Enterprise Park site undergoing deforestation and construction (covering 5% of the catchment area), with most of the remaining sediment deriving from the construction of a major road (1% of the catchment) in the limestone sub‐catchment. In 2015, planned and accidental retention basins below the Enterprise Park and major road sites, respectively, prevented some sediment from reaching the stream network, thereby reducing their importance as sediment sources. Sediment mobilization in urban areas with paved roads was small in comparison, but characterized by high heavy metal concentrations. The sediment fingerprinting approach adopted shows promise in identification of the main sources of sediments, necessary to underpin improved peri‐urban management strategies. Copyright © 2017 John Wiley & Sons, Ltd.     

CLPP and EEA profiles of microbial communities in salt marsh sediments

Objective  Microbial communities are a central component of trophic dynamics and biogeochemical processes on coastal systems, since most of the processes in sediments are mediated by microorganisms and carried out by enzymes. Microorganisms play a key role in decomposition processes in salt marsh sediments, although the significance of microbial dynamics is largely unexplored. A culture-dependent (Ecoplate) and a culture-independent (extracellular enzyme activity [EEA]) approaches were evaluated in their ability to distinguish the catabolic potential among sediments from Tagus estuary salt marshes with different proximities to anthropogenic sources. Methods  Ecoplate was used to analyse the salt marsh community-level physiological profiles (CLPPs). Results were expressed as the net area under the curve for each of the 31 response wells over a 3-day incubation period in two sediment horizons. The catabolic profiles for salt marsh samples were analysed by Principal Component Analysis (PCA) and hierarchic clustering methods. EEA was analysed by fluorescein diacetate (FDA) hydrolysis in two sediment horizons. The FDA is catalysed by extracellular enzymes, i.e. esterases, lipases and partially by proteases. Results were expressed as μg g⁻¹d wt h⁻¹. Results and Discussion  In this study the CLPP and EEA data were not generally correlated. In Corroios salt marsh only in surface sediments higher net areas corresponded to higher extracellular enzymatic activity, and in Alcochete deep sediments lower net areas corresponded to lower enzymatic activity. Although EEA profiles more directly reflect the inherent activity of resident community in each salt marsh sample, the CLPP profiles provide better assessments of diversity. ESS-Submission Editor: Prof. Dr. Peter Schroeder, Institute of Soil Ecology, Department of Rhizosphere Biology, GSF — National Research Center for Environment & Health, Ingolstaedter Landstrasse 1, 85758 Neuherberg, Germany (peter.schroeder@gsf.de)     

A new sediment contact assay to assess particle-bound pollutants using zebrafish (<Emphasis Type="Italic">danio rerio</Emphasis>) embryos

Goal, Scope and Background. Based on a bioassay battery covering only primary producers and consumers as well as degraders, the potential ecological hazard of sediments to vertebrates cannot be estimated comprehensively. Therefore, there is an urgent need to develop and standardize integrated vertebrate-based test systems for sediment investigation strategies. Whereas vertebratebased in vitro systems have frequently been used for the investigation of aqueous samples, there is a significant lack of whole sediment assays. Thus, the purpose of the present study was: (1) to develop a rapid and reliable, but comprehensive method to investigate native sediments and particulate matters without preceding extraction procedures; (2) to compare the hazard potential of solid phase sediments to the effects of corresponding pore waters and organic extracts in order to characterize the bioavailability of the particle-bound pollutants; and (3) to relatively evaluate the embryotoxic effects of sediments from the catchment areas of the rivers Rhine, Neckar and Danube. Methods (or Main Features).  To investigate the toxicity of sediment samples on vertebrates, the standard embryo toxicity test with the zebrafish (Danio rerio; Hamilton-Buchanan 1922) according to DIN 38415-6 was modified with respect to exposure scheme and toxicological endpoints. Sediments from the catchment area of the Neckar River were assessed using pore waters, acetonic extracts and native sediments in order to get inside into the potential bioavailability of particle-bound pollutants. A comprehensive test protocol for the investigation of native sediments in the embryo toxicity test with the zebrafish is presented. Results and Discussion.  The fish embryo assay with Danio rerio can be carried out with both aqueous and organic sediment extracts as well as native (whole, solid phase) sediment samples. Elongation of exposure time from 48 to up to 196 h significantly increased the mortality. Using the fish egg assay with native sediments, a broad range of embryotoxic effects could be elucidated, including clear-cut dose-response curves for the embryotoxic effects of contaminated sediments; in contrast, absence of embryotoxic effects could be demonstrated even for the highest test concentrations of unpolluted sediments. With native sediments, embryotoxicity was clearly higher than with corresponding pore waters, thus corroborating the view that — at least for fish eggs — the bioavailability of particle-bound lipophilic substances in native sediments is higher than generally assumed. The relative ranking of sediment toxicity was identical using both native sediments and sediment extracts, EC₂₀ values of the latter, however, being eight time lower higher than with the native sediments. A comparison of the embryo toxic effects of samples from the Neckar area with locations along the Rhine and Danube rivers elucidated a broad range of results, thus indicating different levels of contamination. Conclusions.  A modified protocol of the zebrafish embryo test allows the assessment of sediment toxicity in both aqueous extracts and native sediments. The isolated investigation of pore waters may result in a clear-cut underestimation of the bioavailability of lipophilic particle-bound substances (as determined by native sediments). Recommendations and Perspectives.  The zebrafish embryo test with native (whole, solid phase) sediments appears very promising for the evaluation of the bioavailable fraction of lipophilic particle-bound substances and can therefore be recommended for the evaluation of vertebrate toxicity in tiered sediment test strategies and dredging directives such as the HABAB-WSV. Whereas acetone extracts may be tested as a rough estimation of embryotoxicity, native sediment samples will provide a more comprehensive and realistic insight into the bioavailable hazard potential