The occurrence of xenoestrogens in the Elbe river and the North Sea

The xenoestrogens Bisphenol A (BPA), p-alkylphenols and p-alkylphenol ethoxylates were determined in water samples of the North Sea, the Elbe river, and its tributaries Schwarze Elster, Mulde, Saale and the Weisse Elster. The sampling sites of the Elbe river reached from Schmilka at the German-Czech border to Cuxhaven at the estuary. Samples of the North Sea were taken in the German Bight. Additionally, freshly deposed sediments of the River Elbe and its tributaries were analyzed. Partitioning coefficients of these compounds for the distribution between suspended particulate matter (SPM) and the aqueous phase were calculated for samples of the River Elbe at sampling site Geesthacht. The analytical procedure consisted of liquid-liquid extractions of the acidified water samples using dichloromethane. Sediments and SPM samples were extracted by Accelerated Solvent Extraction with n-hexane/acetone. Following a clean-up by HPLC, the analytes were derivatized with heptafluorobutyric acid anhydride and quantified using GC-MSD. The concentration ranges of the compounds analyzed in water samples of the Elbe river were as follows (in ng l(-1)): BPA 9-776, alkylphenols 10-221 and alkylphenol ethoxylates 18-302. In sediment samples the concentrations were (in microg kg(-1) dry mass): BPA 66-343, alkylphenols 17-1378 and alkylphenol ethoxylates 30-1797. In samples of the North Sea the concentrations were generally about 1 order of magnitude lower. As shown by the concentration profiles following the River Elbe into the North Sea, the Elbe river must be considered as a major pollution source for the North Sea concerning the compounds analyzed. The SPM/water-partitioning coefficients calculated (mean values) amounted to: BPA 4.50, alkylphenols 5.52-5.58 and alkylphenol ethoxylates 5.60-6.38. A comparison of the results with data from other surface waters showed that concentrations of these xenoestrogens in the River Elbe and its tributaries were relatively low. The evaluation of the data based on the lowest observable effect concentration (LOEC) for alkylphenols (endpoint: vitellogenin synthesis in male trout) indicated that the concentrations were well below the effectivity threshold.     

Seasonal variation of sediment toxicity in the Rivers Dommel and Elbe

Contaminated sediment in the river basin has become a source of pollution with increasing importance to the aquatic ecosystem downstream. To monitor the temporal changes of the sediment bound contaminants in the River Elbe and the River Dommel monthly toxicity tests were applied to layered sediment and river water samples over the course of 10 months. There is an indication that contaminated sediments upstream adversely affected sediments downstream, but this process did not cause a continuous increase of sediment toxicity. A clear decrease of toxic effects in water and upper layer sediment was observed at the River Elbe station in spring related to high water discharge and algal blooms. The less obvious variation of sediment toxicity in the River Dommel could be explained by stable hydrological conditions. Future monitoring programmes should promote a more frequent and intensive sampling regime during these particular events for ecotoxicological evaluation.     

Spatial and temporal variability of sediment deposition on artificial-lawn traps in a floodplain of the River Elbe

Artificial-lawn mats were used as sediment traps in floodplains to measure sediment input and composition during flood events. To estimate the natural variability, 10 traps were installed during two flood waves at three different morphological units in a meander loop of the River Elbe. The geochemical composition of deposited and suspended matter was compared. The sediment input showed weak correlations with concentration and composition of river water. It also correlated poorly with flood duration and level as well as distance of trap position from the main river. This is due to the high variability of the inundation, different morphological conditions and the variability of sources. The composition of the deposits and the suspended matter in the river water was comparable. Hence, for the investigated river reach, the expected pollution of the floodplain sediments can be derived from the pollution of the suspended matter in the river during the flood wave.     

Geochemical techniques on contaminated sediments-river basin view

The big flood in the upper Elbe River catchment area has revealed a wide spectrum of problems with contaminated sediments. So far, an effective strategy for managing contaminated sediments on a river basin scale is still missing and it seems that not much has been learned from the lessons received during the last decade. In the following overview, special emphasis is given to the utilization of geochemically-based techniques for sediment remediation, which can be applied in different parts of a river basin. The examples presented here are mostly from the Elbe River catchment area. In general, new technical problem solutions need a set of practical process knowledge that uses a wide range of simulation techniques, as well as models in different spatial and temporal scales. The evaluation of recent flood events clearly demonstrates the importance of chemical expertise in the decision-making process for the sustainable development in river basins.     

Influence of storage time on toxicity of freshwater sediments to benthic macroinvertebrates

Guidance concerning recommended storage times for sediments to be used in toxicity tests generally has not been based upon systematically collected experimental data. The objective of this study was to better define the effects of storage time on toxicity of a series of freshwater sediments. Sixteen sediments with varying types of contaminants were collected, homogenized and stored at 4 degrees C in 1 liter aliquots, which were periodically tested for toxicity to the amphipod Hyalella azteca and the midge Chironomus tentans after storage times of up to 101 weeks. The sediments ranged from non-toxic to extremely toxic (100% mortality) in 10-day assays, with several of the samples displaying an intermediate degree of toxicity (e.g. partial mortality, reduced growth). Biological responses in most of the samples did not vary with time relative to their statistical relationship to control values; samples identified initially as toxic (or non-toxic) tended to remain toxic (or non-toxic) regardless of when they were tested. The variations that were observed in biological responses over time generally were not systematic; that is, there were no apparent trends in samples becoming more (or less) toxic in the 10-day assays. This suggests that the source of at least some of the temporal changes in toxicity were due to inherent biological variability of the assays used to assess the sediments, rather than the effects of storage. In C. tentans tests with the least toxic sediments, among-replicate variability tended to be greater in initial assays than in tests with samples that had been stored for some period of time. This may have been due to the presence of indigenous competitive or predatory organisms that did not survive during prolonged storage.     

Changes in toxicity and Ah receptor agonist activity of suspended particulate matter during flood events at the rivers Neckar and Rhine — a mass balance approach using in vitro methods and chemical analysis

Background, aim, and scope  

As a consequence of flood events, runoff and remobilized sediments may cause an increase of ecotoxicologically relevant effects from contaminant reservoirs. Aquatic and terrestrial organisms as well as cattle and areas of settlement are exposed to dislocated contaminants during and after flood events. In this study, the impacts of two flood events triggered by intense rain at the rivers Neckar and Rhine (Southern Germany) were studied. Effects in correlation to flood flow were assessed at the river Neckar using samples collected at frequent intervals. River Rhine suspended particulate matter (SPM) was sampled over a longer period at normal flow and during a flood event. Three cell lines (H4L1.1c4, GPC.2D.Luc, RTL-W1) were used to compare Ah receptor agonist activity in different biotest systems. Multilayer fractionation was performed to identify causative compounds, focusing on persistent organic contaminants.     

Levels of PCDDs and PCDFs in Korean river sediments and their detection by biomarkers

Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) are a group of toxic halogenated aryl hydrocarbons inducing various physiological disorders against biological organisms. Here, we investigated their levels in sediment samples taken from 12 different rivers in Korea. The levels of PCDD/PCDFs in sediment samples were expressed as concentrations and international TEQ values. Among 17 PCDD/PCDFs selected as target compounds in this study, the 1,2,3,4,7,8-HxCDD and OCDD were found in all river sediments with significant variation in various congener profiles of PCDD/PCDFs in sediments. PCDD/PCDFs could be monitored by sensitive biomarkers using insect immune system. Out of 12 river sediment samples, the biomarkers reported four spots (up, middle, and down Singil sites and Ansan) as putative contamination areas. When comparing both chemical and biological monitoring results, two methods agreed three spots of Singil as contamination areas (above 10ppt levels) as well as six river sediment samples as relatively less-contaminated areas, but differed in the results in Ansan and Miho, probably due to relative non-specificity of biomarkers. Despite some disparity between bio- and chemical monitoring results, the biomarkers can be recommended as a device warning the contamination of dioxins in the environment because of a fast and inexpensive detection method.     

Evaluating toxicity of Asana XL (esfenvalerate) amendments in agricultural ditch mesocosms

Agricultural ditches primarily serve to remove and store excess water associated with irrigation and storm events. The ability of these ecosystems to mitigate potential contaminants is not well understood. Five sites along a 650-m agricultural ditch located in the Mississippi Delta Management Systems Evaluation Area (MDMSEA) were used to measure fate and effects of an esfenvalerate (insecticide) exposure. Following a 0.64-cm simulated storm event, samples were collected from water and sediments and analyzed spatially from five sites and temporally from 0.5 h to 56 d. Results of aqueous toxicity bioassays indicated that lethality progressed downstream throughout all sampling intervals, while sediment toxicity bioassays only elicited biological responses at the point of pesticide application to the ditch (0 m). Significant reductions in survival of Ceriodaphnia dubia and Pimephales promelas in water were measured at the 0-, 20-, and 80-m sites following application. Ten-day solid phase sediment testing of Chironomus tentans indicated persistent toxicity only at the point of application (0 m) and throughout 56 d (mean=14.4% survival). No lethality or significant reduction in midge growth was measured for remaining downstream sites. These measurements were used to evaluate the potential of agricultural ditches to reduce potential deleterious effects of contaminants in agricultural drainage systems that precede receiving streams.     

Phytoremediation as a management option for contaminated sediments in tidal marshes, flood control areas and dredged sediment landfill sites

Background, aim and scope  

Polluted sediments in rivers may be transported by the river to the sea, spread over river banks and tidal marshes or managed, i.e. actively dredged and disposed of on land. Once sedimented on tidal marshes, alluvial areas or control flood areas, the polluted sediments enter semi-terrestrial ecosystems or agro-ecosystems and may pose a risk. Disposal of polluted dredged sediments on land may also lead to certain risks. Up to a few years ago, contaminated dredged sediments were placed in confined disposal facilities. The European policy encourages sediment valorisation and this will be a technological challenge for the near future. Currently, contaminated dredged sediments are often not valorisable due to their high content of contaminants and their consequent hazardous properties. In addition, it is generally admitted that treatment and re-use of heavily contaminated dredged sediments is not a cost-effective alternative to confined disposal. For contaminated sediments and associated disposal facilities used in the past, a realistic, low cost, safe, ecologically sound and sustainable management option is required. In this context, phytoremediation is proposed in the literature as a management option. The aim of this paper is to review the current knowledge on management, (phyto)remediation and associated risks in the particular case of sediments contaminated with organic and inorganic pollutants.     

BIOCHEM-ORCHESTRA: a tool for evaluating chemical speciation and ecotoxicological impacts of heavy metals on river flood plain systems

The chemical speciation model BIOCHEM was extended with ecotoxicological transfer functions for uptake of metals (As, Cd, Cu, Ni, Pb, and Zn) by plants and soil invertebrates. It was coupled to the object-oriented framework ORCHESTRA to achieve a flexible and dynamic decision support system (DSS) to analyse natural or anthropogenic changes that occur in river systems. The DSS uses the chemical characteristics of soils and sediments as input, and calculates speciation and subsequent uptake by biota at various scenarios. Biotic transfer functions were field-validated, and actual hydrological conditions were derived from long-term monitoring data. The DSS was tested for several scenarios that occur in the Meuse catchment areas, such as flooding and sedimentation of riverine sediments on flood plains. Risks are expressed in terms of changes in chemical mobility, and uptake by flood plain key species (flora and fauna).     

Occurrence and possible sources of polychlorinated biphenyls in surface sediments from the Wuhan reach of the Yangtze River, China

Twenty-seven surface sediment samples were collected from the mainstream and eight tributaries of the Wuhan reach of the Yangtze River, China, in 2005, in order to assess the distribution, possible sources, and potential risk of polychlorinated biphenyls (PCBs) in the environment. The total concentrations of PCBs (the sum of 39 congeners) ranged from 1.2 to 45.1 ng g⁻¹ dry weight, with a mean value of 9.2 ng g⁻¹. Sediment samples with the highest PCB concentrations came from the tributary sites, which are closer to PCB sources. Conversely, PCB concentrations in the sediment from the mainstream sites of Yangtze River were relatively low. The observed PCB levels were higher than those found in the sediments of other rivers in China, but lower than those in river sediments from other urban areas and harbors around the world. Low-chlorinated PCBs, dominated by tetra-PCBs and penta-PCBs, were identified as being prevalent in the surface sediments. Correlation analyses between the PCBs and the geochemistry and heavy metal content of the sediments suggest that the washing of these compounds from the land into the river by floods and heavy rains, or industrial wastewater and domestic sewage, may be the major sources of the PCBs. According to established sediment quality guidelines, the risk of adverse biological effects from the levels of PCBs recorded at most of the studied sites should be insignificant, although the higher concentrations at other sites could cause acute biological damage.     

The influence of the scale of mining activity and mine site remediation on the contamination legacy of historical metal mining activity

Globally, thousands of kilometres of rivers are degraded due to the presence of elevated concentrations of potentially harmful elements (PHEs) sourced from historical metal mining activity. In many countries, the presence of contaminated water and river sediment creates a legal requirement to address such problems. Remediation of mining-associated point sources has often been focused upon improving river water quality; however, this study evaluates the contaminant legacy present within river sediments and attempts to assess the influence of the scale of mining activity and post-mining remediation upon the magnitude of PHE contamination found within contemporary river sediments. Data collected from four exemplar catchments indicates a strong relationship between the scale of historical mining, as measured by ore output, and maximum PHE enrichment factors, calculated versus environmental quality guidelines. The use of channel slope as a proxy measure for the degree of channel-floodplain coupling indicates that enrichment factors for PHEs in contemporary river sediments may also be the highest where channel-floodplain coupling is the greatest. Calculation of a metric score for mine remediation activity indicates no clear influence of the scale of remediation activity and PHE enrichment factors for river sediments. It is suggested that whilst exemplars of significant successes at improving post-remediation river water quality can be identified; river sediment quality is a much more long-lasting environmental problem. In addition, it is suggested that improvements to river sediment quality do not occur quickly or easily as a result of remediation actions focused a specific mining point sources. Data indicate that PHEs continue to be episodically dispersed through river catchments hundreds of years after the cessation of mining activity, especially during flood flows. The high PHE loads of flood sediments in mining-affected river catchments and the predicted changes to flood frequency, especially, in many river catchments, provides further evidence of the need to enact effective mine remediation strategies and to fully consider the role of river sediments in prolonging the environmental legacy of historical mine sites.     

Vertical profile of PCDD/Fs, dioxin-like PCBs, other PCBs, PAHs, chlorobenzenes, DDX, HCHs, organotin compounds and chlorinated ethers in dated sediment/soil cores from flood-plains of the river Elbe, Germany

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and other organic micropollutants were determined in dated sediment/soil cores collected from the flood-plain of the river Elbe near Pevestorf (PT), approximately 125 km upstream of Hamburg, and Heuckenlock (HL) in southeast of Hamburg. Concentrations of PCDD/Fs peaked sharply at PT in the 1950s and at HL at the end of the 1940s. Cluster analyses provide evidence that the region of Bitterfeld-Wolfen (about 350-400 km upstream of Hamburg) could be the source of the PCDD/F contamination existing in the cores PT and HL since the 1940s. Obviously it is caused by sediments of the river Elbe of a similar composition. Whereas the PCDD/Fs, HCHs (hexacyclohexane isomers), DDX (DDT, DDD, DDE), and tetrachlorinated ethers in PT and HL presumably originated predominantly from the Bitterfeld-Wolfen region, organotin compounds in HL and dichlorinated haloethers in HL during the 1940s and 1950s can probably largely be attributed to emissions from the Hamburg region. Although they are separated by a large distance, in both sediment cores PT and HL concentrations and composition patterns of most organic micropollutants analyzed widely match. Inductively it can be concluded that similar contaminations will be found in many of the river bank soils between the Bitterfeld-Wolfen region and Hamburg. Excavation of top soils may uncover highly contaminated materials. Since the dated sediment cores show the variation in contaminants in the Elbe sediments over a defined time period, it is possible to make an approximate assessment of the actual degree of contamination to be expected in areas where in previous decades contaminated dredged sediments from the Elbe and from the Port of Hamburg have been deposited on land and used for building plots or for agricultural purposes.     

Environmental impact of flood: the study of arsenic speciation in exchangeable fraction of flood deposits of Warta river (Poland) in determination of "finger prints" of the pollutants origin and the ways of the migration

The paper presents the application of the hyphenated technique - high-performance liquid chromatography with atomic absorption spectrometry detection with hydride generation (HPLC-HG-AAS) - in the determinations of inorganic forms of arsenic: As(III) and As(V) in the exchangeable fraction of flood deposits. The separation of analytical signals of the determined arsenic forms was obtained using an ion-exchange column in a chromatographic system with the atomic absorption spectrometer as a detector, at the determination limits of 5 ng g⁻¹ for As(III) and 10 ng g⁻¹ for As(V). Flood deposits were collected after big flood event in valley of the Warta river which took place in summer 2010. Samples of overbank deposits were taken in Poznań agglomeration and vicinity (NW Poland). The results of determinations of arsenic forms in the exchangeable fraction of flood deposits allowed indication of a hypothetical path of deposits migration transported by a river during flood and environmental threats posed by their deposition by flood.     

Spatial and temporal trends of metals and arsenic in German freshwater compartments

Cadmium, lead, mercury, copper, nickel, zinc, and arsenic were analyzed in suspended particulate matter (SPM), zebra mussels, and bream sampled yearly under the program of the German Environmental Specimen Bank (ESB) in the rivers Rhine, Elbe, Danube, Saar, Mulde, and Saale and in Lake Belau. Temporal and spatial trends were analyzed, correlations between metal levels in different specimen types assessed, and sampling sites ranked according to their metal levels by calculating a Multi-Metal Index (MMI) for every specimen type and site. SPM: Highest metal loads were detected in Mulde, Saale, and Elbe right downstream of the Saale confluence. In the Elbe, metal loads in SPM were mostly highest in the upper and middle section of the river while in Rhine and Saar concentrations increased downstream. Temporal trends since 2005 were detected only at three sites. Zebra mussel: MMIs were highest in the tidal section of the Elbe and the lower Rhine and lowest in Lake Belau and the upper Danube. Different temporal trends were detected since the early 1990s depending on site and metal. Bream: As, Pb, Cu, and Hg were analyzed in muscle tissue and Pb, Cd, Cu, and Zn in liver. For both tissues, MMIs were highest in Mulde and Saale and the lower and middle Elbe. Since the early 1990s, Hg, Pb, and Cu decreased in bream muscle at many sites while As increased at 6 of the 17 sites. The findings indicate that Hg, Pb, and Cu have obviously decreased in many freshwater ecosystems in recent years, whereas As and Ni levels have increased at several sites. Metal levels and temporal trends mostly differed between the specimen types under investigation and only few correlations between specimen types were detected. This underlines the importance of including different components of an ecosystem when assessing its environmental quality.     

Longer-term and short-term variability in pollution of fluvial sediments by dioxin-like and endocrine disruptive compounds

Changes in pollutant loads in relatively dynamic river sediments, which contain very complex mixtures of compounds, can play a crucial role in the fate and effects of pollutants in fluvial ecosystems. The contamination of sediments by bioactive substances can be sensitively assessed by in vitro bioassays. This is the first study that characterizes detailed short- and long-term changes in concentrations of contaminants with several modes of action in river sediments. One-year long monthly study described seasonal and spatial variability of contamination of sediments in a representative industrialized area by dioxin-like and endocrine disruptive chemicals. There were significant seasonal changes in both antiandrogenic and androgenic as well as dioxin-like potential of river sediments, while there were no general seasonal trends in estrogenicity. Aryl hydrocarbon receptor-dependent potency (dioxin-like potency) expressed as biological TCDD-equivalents (BIOTEQ) was in the range of 0.5–17.7 ng/g, dry mass (dm). The greatest BIOTEQ levels in sediments were observed during winter, particularly at locations downstream of the industrial area. Estrogenicity expressed as estradiol equivalents (EEQ) was in the range of 0.02–3.8 ng/g, dm. Antiandrogenicity was detected in all samples, while androgenic potency in the range of 0.7–16.8 ng/g, dm dihydrotestosterone equivalents (DHT-EQ) was found in only 30 % of samples, most often during autumn, when antiandrogenicity was the least. PAHs were predominant contaminants among analyzed pollutants, responsible, on average, for 13–21 % of BIOTEQ. Longer-term changes in concentrations of BIOTEQ corresponded to seasonal fluctuations, whereas for EEQ, the inter-annual changes at some locations were greater than seasonal variability during 1 year. The inter- as well as intra-annual variability in concentrations of both BIOTEQ and EEQ at individual sites was greater in spring than in autumn which was related to hydrological conditions in the river. This study stresses the importance of river hydrology and its seasonal variations in the design of effective sampling campaigns, as well as in the interpretation of any monitoring results.     

Assessment of nematode community structure as a bioindicator in river monitoring

Nematode communities from river water and sediments were assessed for the abundance, feeding types, maturity indices and nematode channel ratio (NCR). The sampling sites studied included different levels of pollution and contamination from agricultural, industrial and sewage sources. The nematode abundance found in the sediment samples was more than that in the water samples. The lowest nematode abundance in sediment samples and the lowest NCR in water samples were both found at the industrial pollution site. Water samples showed positive correlation between the NCR and river pollution index (RPI). Mean maturity indices in sediment samples were inversely correlated with RPI. The pollutant source determined the relationship between NCR and pollution level, while maturity index always showed negative correlation with pollutant level regardless of the pollutant sources. The nematode abundance and its community structure were both reliable bioindicators for monitoring long-term river pollution in both qualitative and quantitative aspects.     

Distribution of pesticides and bisphenol A in sediments collected from rivers adjacent to coral reefs

To investigate the deteriorating health of coral reefs in Okinawa, Japan, natural sediment samples were analyzed for diuron, Irgarol 1051, chlorpyrifos, and bisphenol A (BPA) which are hazardous to corals. Samples were analyzed by solid-phase extraction (SPE) followed by high-performance liquid chromatography with tandem mass spectrometry (LC–MS–MS). Although diuron and chlorpyrifos usage is only well recorded for farms and not for cities, these chemicals were detected in both rural and urban areas. Additionally, diuron concentration in urban areas was in some cases higher than in rural areas, which might be caused by greater consumption of these chemicals in home gardens in city areas. Irgarol 1051 was detected in downstream river areas, which are situated far from the source sites such as pier or fishery harbor (0.6–3.2 km). This result suggested that Irgarol 1051 could be transported from the river mouths to the sampling sites during flood tides. High BPA concentrations were associated with urban areas (<1.2–22.0 μg kg⁻¹), while low concentrations were associated with rural areas (nd–6.8 μg kg⁻¹). The river sediments under study are delivered to coral reefs in large quantity through runoff caused by typhoons and other heavy rains. The highly hazardous chemicals are carried into coral reefs on these sediments. Therefore, these hazardous chemical substances may already be influencing the coral reefs.     

Evaluation of HCH isomers and metabolites in soils, leachates, river water and sediments of a highly contaminated area

In this work we evaluate the contamination caused by HCH residues in the soil, leachates, river water and sediments of an industrial estate of the NW of Spain. We study the distribution of the isomers in the different matrices, analysing 37 soil samples, collected in eight points at several depths, six natural leachates, four river water samples and three river sediments. Soil and leachate samples present very high levels of HCH isomers, higher than the established by legislation, and some pesticides were also detected in the analysed river water whereas no pesticides were detected in the river sediments. The distribution of isomers was different depending on the matrix analysed. Some natural degradation products and also other organochlorine pesticides were detected in the samples analysed.     

Identifying primary stressors impacting macroinvertebrates in the Salinas River (California, USA): relative effects of pesticides and suspended particles

Laboratory dose-response experiments with organophosphate and pyrethroid pesticides, and dose-response experiments with increasing particle loads were used to determine which of these stressors were likely responsible for the toxicity and macroinvertebrate impacts previously observed in the Salinas River. Experiments were conducted with the amphipod Hyalella azteca, the baetid mayfly Procloeon sp., and the midge Chironomus dilutus (Shobanov, formerly Chironomus tentans). The results indicate the primary stressor impacting H. azteca was pesticides, including chlorpyrifos and permethrin. The mayfly Procloeon sp. was sensitive to chlorpyrifos and permethrin within the range of concentrations of these pesticides measured in the river. Chironomus dilutus were sensitive to chlorpyrifos within the ranges of concentrations measured in the river. None of the species tested were affected by turbidity as high as 1000 NTUs. The current study shows that pesticides are more important acute stressors of macroinvertebrates than suspended sediments in the Salinas River.