In this study, the combined effects of pH, water hardness, and dissolved organic carbon (DOC) concentration and type on the chronic (72-h) effect of copper on growth inhibition of the green alga Pseudokirchneriella subcapitata were investigated. Natural dissolved organic matter (DOM) was collected at three sites in Belgium and The Netherlands using reverse osmosis. A full central composite test design was used for one DOM and a subset of the full design for the two other DOMs. For a total number of 35 toxicity tests performed, 72-h effect concentration resulting in 10% growth inhibition (EbC10s) ranged from 14.2 to 175.9 micrograms Cu/L (factor 12) and 72-h EbC50s from 26.9 to 506.8 micrograms Cu/L (factor 20). Statistical analysis demonstrated that DOC concentration, DOM type, and pH had a significant effect on copper toxicity; hardness did not affect toxicity at the levels tested. In general, an increase in pH resulted in increased toxicity, whereas an increase of the DOC concentration resulted in decreased copper toxicity. When expressed as dissolved copper, significant differences of toxicity reduction capacity were noted across the three DOM types tested (up to factor 2.5). When expressed as Cu2+ activity, effect levels were only significantly affected by pH; linear relationships were observed between pH and the logarithm of the effect concentrations expressed as free copper ion activity, that is, log(EbC50Cu2+) and log(EbC10Cu2+): (1) log(EbC50Cu2+)= - 1.431 pH + 2.050 (r2 = 0.95), and (2) log(EbC10cu2+) = -1.140 pH -0.812 (r2 = 0.91). A copper toxicity model was developed by linking these equations to the WHAM V geochemical speciation model. This model predicted 97% of the EbC50dissolved and EbC10dissolved values within a factor of two of the observed values. Further validation using toxicity test results that were obtained previously with copper-spiked European surface waters demonstrated that for 81% of tested waters, effect concentrations were predicted within a factor of two of the observed. The developed model is considered to be an important step forward in accounting for copper bioavailability in natural systems.

The chronic Cu biotic ligand model (CuBLM) provides a means by which the bioavailability of Cu can be taken into account in assessing the potential chronic risks posed by Cu at specific freshwater locations. One of the barriers to the widespread regulatory application of the CuBLM is the perceived complexity of the approach when compared to the current systems that are in place in many regulatory organizations. The CuBLM requires 10 measured input parameters, although some of these have a relatively limited influence on the predicted no-effect concentration (PNEC) for Cu. Simplification of the input requirements of the CuBLM is proposed by estimating the concentrations of the major ions Mg2+, Na+, K+, SO4(2-), Cl- , and alkalinity from Ca concentrations. A series of relationships between log10 (Ca, mg l(-1)) and log10 (major ion, mg l(-1)) was established from surface water monitoring data for Europe, and applied in the prediction of Cu PNEC values for some UK freshwater monitoring data. The use of default values for major ion concentrations was also considered, and both approaches were compared to the use of measured major ion concentrations. Both the use of fixed default major ion concentrations, and major ion concentrations estimated from Ca concentrations, provided Cu PNEC predictions which were in good agreement with the results of calculations using measured data. There is a slight loss of accuracy when using estimates of major ion concentrations compared to using measured concentration data, although to a lesser extent than when fixed default values are applied. The simplifications proposed provide a practical evidence-based methodology to facilitate the regulatory implementation of the CuBLM.

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Larvae of Mytilus spp. are among the most Cu sensitive marine species. In this study we assessed the combined effect of salinity and dissolved organic carbon (DOC) on Cu accumulation on mussel larvae. Larvae were exposed for 48 h to three Cu concentrations in each of nine salinity/DOC treatments. Synchrotron radiation X-ray fluorescence was used to determine the Cu concentration in 36 individual larvae with a spatial resolution of 10 × 10 μm. Cu body burden concentrations varied between 1.1 and 27.6 μg/g DW larvae across all treatments and Cu was homogeneously distributed at this spatial resolution level. Our results indicate decreasing Cu accumulation with increasing DOC concentrations which can be explained by an increase in Cu complexation. In contrast, salinity had a nonlinear effect on Cu. This cannot be explained by copper speciation or competition processes and suggests a salinity-induced alteration in physiology.

Predicting copper (Cu) toxicity in marine and estuarine environments is challenging because of the influence of anions on Cu speciation, competition between Cu(2+) and other cations at the biotic ligand and the effect of salinity on the physiology of the organism. In the present study the combined effect of salinity and dissolved organic carbon (DOC) on Cu toxicity to larvae of Mytilus galloprovincialis was assessed. Two statistical models were developed and used to elucidate the relationship between Cu toxicity, salinity, and DOC. All models based on dissolved Cu indicate a decrease in Cu toxicity with increasing DOC concentrations, which can partly be explained by complexation of Cu(2+) ions with DOC. These models also indicate an increase in Cu toxicity (modeled with dissolved Cu or Cu(2+) activity) with increasing salinity, suggesting a salinity-induced alteration in the physiology of the mussel larvae. When based on Cu body burdens, neither of the models indicates an effect of salinity or DOC. This shows that the Cu body burden is a more constant predictor of Cu toxicity, regardless of the water chemistry influencing Cu speciation or competition and possible physiological alterations or changes in Cu speciation or competition.