No abstract

Geographical and temporal variations in metal speciation were calculated and water-type specific sensitivities were derived for a range of aquatic species, using surveillance water chemistry data that cover almost all surface water types in The Netherlands. Biotic ligand models for Cu, Zn, and Ni were used to normalize chronic no-effect concentrations (NOEC) determined in test media toward site-specific NOEC for 372 sites sampled repeatedly over 2007-2010. Site-specific species sensitivity distributions were constructed accounting for chemical speciation. Sensitivity of species as well as predicted risks shifted among species over space and time, due to changes in metal concentrations, speciation, and biotic ligand binding. Sensitivity of individual species (NOEC) and of the ecosystem (HC5) for Cu, Ni, and Zn showed a spatial variation up to 2 orders of magnitude. Seasonality of risks was shown, with an average ratio between lowest and highest risk of 1.3, 2.0, and 3.6 for Cu, Ni, and Zn, respectively. Maximum risks of Cu, Ni, and Zn to ecosystems were predicted in February and minimum risks in September. A risk assessment using space-time specific HC5 of Cu and Zn resulted in a reduction of sites at risk, whereas for Ni the number of sites at risks increased.

After the scientific development of Biotic Ligand Models (BLMs) in recent decades these models are now considered suitable for implementation in regulatory risk assessment of metals in freshwater bodies. The approach has been developed over several years and has been described in many peer-reviewed publications. The original complex BLMs have been applied in prospective risk assessment reports for metals and metal compounds and are also recommended as suitable concepts for the evaluation of monitoring data in the context of the European Water Framework Directive. Currently, several userfriendly BLM-based bioavailability software tools are available for assessing the aquatic toxicity of a limited number of metals (mainly copper, nickel, and zinc). These tools need only a basic set of water parameters as input (e.g., pH, hardness, dissolved organic matter and dissolved metal concentration). Such tools seem appropriate to foster the implementation in routine water quality assessments. This work aims to review the existing bioavailability-based regulatory approaches and the application of available BLM-based bioavailability tools for this purpose. Advantages and possible drawbacks of these tools (e.g., feasibility, boundaries of validity) are discussed, and recommendations for further implementation are given.

The aim of this study is to predict the solid-solution partitioning of heavy metals in river flood plain soils. We compared mechanistic geochemical modeling with a statistical approach. To characterize the heavy metal contamination of embanked river flood plain soils in The Netherlands, we collected 194 soil samples at 133 sites distributed in the Dutch part of the Rhine and Meuse river systems. We measured the total amounts of As, Cd, Cr, Cu, Ni, Pb, and Zn in the soil samples and the metal fraction extractable by 2.5 mM CaCl2. We found a strong correlation between heavy metal contamination and organic matter content, which was almost identical for both river systems. Speciation calculations by a fully parametrized model showed the strengths and weaknesses of the mechanistic approach. Cu and Cd concentrations were predicted within one log scale, whereas modeling of Zn and Pb needs adjustment of some model parameters. The statistical fitting approach produced better results but is limited with regard to the understanding it provides. The log RMSE for this approach varied between 0.2 and 0.32 for the different metals. The careful modeling of speciation and adsorption processes is a useful tool for the investigation and understanding of metal availability in river flood plain soils.

The sediment or fauna incubation experiment (SOFIE) is an experimental research tool that was developed to analyze concentrations and chemical speciation of heavy metals in pore waters of natural, undisturbed sediments or water-sediment interfaces over time, while simultaneously conducting exposure tests with sediment-dwelling organisms. In this way, concentrations of chemical species are directly linked to accumulation by biota. It is shown that discrete gradients of redox-sensitive metals and nutrients occur over very small intervals. These gradients differ from those of free metal ion activities. Speciation affects the uptake of metals by sediment-dwelling organisms, which, in their turn, have a significant effect on metal speciation. With reaction kinetics that differ per metal, uptake of metals by organisms from the water phase may be hindered (e.g., Cu, Zn) or promoted (e.g., Ni, As). Time-varying exposure concentrations of metals were incorporated in uptake and elimination models. Body concentrations of Cd, Cu, Ni, and Zn in the aquatic oligochaete Limnodrilus could best be described by the time-varying free ion concentration in the overlying water. Body concentrations of As and Pb were best described by sediment pore water concentrations. It is concluded that SOFIE provides the necessary experimental tool to support, in a mechanistic way, environmental risk assessments of contaminants.