Assessing the Hazard of Metals and Inorganic Metal Substances in Aquatic and Terrestrial Systems

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Since HOCs are usually related to lipid content, this parameter should also be determined in the sample [ 31 ]. In both inorganic and organic analyses, the results are often transferred from one data processing level to another e. Regarding the new priority substances that have to be measured in biota for compliance checking with the WFD, European member states are presently elaborating guidelines for monitoring new EQS biota.

Environmental contaminants are monitored in aquatic organisms, particularly in fish, for compliance checking with regulatory directives.

Furthermore, national directives such as the German regulation on tolerable levels of contaminants in food [ 36 ] also define maximum allowable concentrations in food. Monitoring chemicals in aquatic biota for food surveillance purposes differs from environmental monitoring: In food surveillance, the subject of protection is solely the human being as consumer.

Usually fish, fishery products or seafood are obtained from commercial markets so that the allocation to the ecosystem often remains unclear. In general, chemicals are measured in muscle tissue and refer to fresh weight of the sample.

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Depending on the consumption pattern, analysing muscle tissue with skin may even be appropriate. In the European water framework directive, however, the subjects of protection are either humans or predators [ 37 ]. The latter mainly feed on the whole body of smaller fish. If comparing data from food surveillance and environmental monitoring, such aspects need to be considered.

In Europe, member states have to measure chemicals in aquatic biota for compliance checking with EQS biota [ 2 , 3 ]. The guidance document for chemical monitoring of sediment and biota [ 37 ] gives recommendations for implementing this monitoring. In fish, contaminant concentrations are usually measured in muscle tissue and refer to the fresh weight of the sample.


Since the common eel Anguilla anguilla accumulates high amounts of chemicals due to its food habits and its high lipid content, monitoring data are often presented separately for this species. In the Rhine River, for example, next to the common eel, the white fish species roach Rutilus rutilus , common bream Abramis brama and chub Squalius cephalus are often monitored [ 39 ]. In this context, sampling the same species as well as comparable size and age of fish are particularly important since these parameters affect bioaccumulation and may confound or even superimpose temporal trends.

For chemicals that show increased levels in liver compared with muscle tissue of fish, analysing liver tissue may be advantageous.

Testing of chemicals

In contrast to compliance monitoring with fish, an investigative monitoring with zebra mussels Dreissena polymorpha in Bavaria Germany has shown that mercury concentrations in this species is generally below EQS biota. Mussels can hint at more local pollution events, e.

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Only at one site, the EQS biota for mercury was exceeded in zebra mussels in to indicating a very local input of mercury [ 41 ]. Another example for the identification of chemical sources is monitoring triphenyltin TPT in Lower Saxony Germany : After finding high tributyltin TBT and TPT concentrations in sediments and biota from a marina, concentrations of both chemicals were measured in fish at around stations in Lower Saxony Germany in TPT that has been used until the mids as component in antifouling paints as well as fungicide showed higher levels in fish livers than TBT.

Monitoring bioaccumulation can also support risk assessment of various natural or anthropogenic events such as floods or dredging activities. For the maintenance of waterways, dredging of sediments may be necessary. As an example, the amount of sediments had increased to an unacceptable level in the Hamburg Port in In consequence, 6. To assess the potential ecological impacts on the marine environment, a comprehensive monitoring program has been established [ 43 ].

Bioaccumulation in aquatic systems: methodological approaches, monitoring and assessment

Among many other parameters, bioaccumulation of metals and organic chemicals has been measured in two benthic invertebrates mussels white furrow shell, Abra alba and snails common whelk, Buccinum undatum and fish dab, Limanda limanda sampled in and around the disposal site as well as in reference sites. These species were selected since they are abundant in the monitoring area and they represent different trophic levels. Since , significantly increased levels of the organotin compounds monobutyltin MBT and dibutyltin DBT were detected in snails from the disposal site hinting at an increased bioavailability of contaminants due to the sediment disposals.

Sediment disposals had, in contrast to snails, no clear effect on concentrations of chemicals in fish and mussels. This shows that the selection of monitoring species can influence the outcome of monitoring studies. Species-specific differences in bioaccumulation potential also have to be considered when the same species is not available in the whole monitoring area, such as the different river basins within Europe. In addition to species, bioaccumulation depends on further biotic e. Passive sampling suffers less from the variability connected to biota and may in some cases complement biota monitoring.

Passive sampling devices have a sampling phase, usually a polymer that accumulates chemicals when exposed in the environment or to an environmental sample. By quantifying concentrations of target analytes in the polymer of the sampler, freely dissolved concentrations c free are determined that are a measure of contaminant bioavailability.

Due to the enrichment of target analytes within the passive sampling polymer, quantification limits of passive sampling techniques are often lower than those for conventional techniques e. Passive sampling in the water phase is generally conducted in the kinetic uptake regime, and time averaged concentrations can then be determined by in situ calibration with performance reference compounds [ 47 , 48 ].

These are dosed to the sampling phase prior to exposure, and their release in water is measured to calculate uptake rates of target compounds [ 49 ]. Since , monitoring by passive sampling in water has been applied in parallel to a mussel watch program in the coastal area of the Netherlands. A non-target application of passive samplers on laboratory scale is the investigation of waste water for the detection of potentially bioaccumulative substances according to OSPAR's whole effluent assessment concept [ 51 ]. In sediments, c free of HOCs can be quantified by equilibrium sampling devices [ 54 ]: The polymer of the sampling device is brought in contact with the sediment until equilibrium of the target analytes between sediment and polymer is attained.

Provided that the polymer does not deplete the analyte concentration in the sediment, analyte concentrations in polymer c polymer can be translated to freely dissolved concentration c free in sediment interstitial water:. Partitioning coefficients, K polymer,water and K lipid,polymer , that are essential for passive sampling and derivation of, e.

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Indeed, for emerging chemicals as well as for many polymers that are applied for passive sampling, appropriate partition coefficients are often not yet available. Nonetheless, direct measurements of c free with equilibrium sampling techniques have the potential to substantially improve risk assessment and management of sediments contaminated with HOCs [ 57 ]. DGTs are kinetic regime sampling devices that consist of a thin hydrogel layer that constrains diffusive transport of solutes into a binding layer [ 58 ].

The chemical mass absorbed by the binding layer in a given time is used for calculating c free in water, sediment or soil.

DGT devices can also be applied for assessing the long-term release and bioavailable fraction of metal loid s from construction products in hydraulic engineering e. In contrast to standardised batch experiments that require the repeated renewal of the water phase, in DGT-based long-term batch experiments, the amount of ionic metal loid species is continuously reduced to avoid equilibrium in the test medium which impacts the further release from the test material [ 63 ].

The significance of bioaccumulation for assessing the chemical status of bodies of water is increasingly acknowledged as exemplified by setting new EQS biota in the amended WFD EQS directive. Implementing the monitoring for compliance checking with these new EQS biota is one of the challenges for the EU member states in the near future. As previously stated by Fuerhacker [ 64 ], the EQS directive is valuable for approaching a good chemical status of bodies of water even though new chemicals are not adequately considered.

We further suggest that for bioaccumulative and non-metabolisable substances, EQS biota are more relevant to chemical water quality than EQS water since internal chemical concentrations are more related to a chemical's uptake and toxicity. Additionally, biota monitoring results can be related to ecological water quality as demonstrated by Van Ael et al. The authors showed that for most investigated chemicals, ecological water quality being assessed by fish community structure was lower when chemical concentrations in fish were elevated.

However, due to limited resources, the European member states have implemented biota monitoring for compliance checking with the WFD on a smaller scale than monitoring of the water phase and sediment. Next to compliance checking with regulatory directives, chemical concentrations in biota can be used for identifying sources of contamination and event-related monitoring. Since bioaccumulation of chemicals is closely linked with their toxicity, monitoring bioaccumulation can improve risk assessment of environmental contamination.

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When monitoring chemical concentrations in biota, various abiotic and biotic factors that can affect bioaccumulation have to be considered. Since monitoring programs have different conceptual and methodological approaches, these have to be taken into account when comparing data from different programs. Assessing bioaccumulation of hydrophobic organic chemicals can be improved by additionally measuring lipid content of the analysed tissue.

We further suggest to elaborate consensual standardised protocols for chemical analyses of biota and to perform quality assurance by inter-laboratory exercises. We have highlighted that passive sampling can complement biota monitoring that aims at protecting human health and predators. It can also be helpful in spatial and temporal trend monitoring of chemical status of bodies of waters since samplers with standardised partition properties can be used over a wide geographical and temporal range. Strategies for assessing bioaccumulation potential of chemicals need to be further optimised and harmonised for different regulations and groups of chemicals.

In vitro tests are needed for preliminary testing of bioaccumulation potential. Monitoring data can in principle be used for bioaccumulation assessment of chemicals, but monitoring programs have to be improved to deliver all necessary data. Further, communication between monitoring and risk assessment communities needs to be improved to create awareness for critical issues and to mutually benefit from technical expertise and scientific findings. Scientific support is necessary for establishing new monitoring programs for bioaccumulation.

Assessing the Hazard of Metals and Inorganic Metal Substances in Aquatic and - Google книги

Bioakkumulation in aquatischen Systemen: Methoden, Monitoring und Bewertung. European Communities. Bioaccumulation in fish: aqueous and dietary exposure.