Investigating speciation and toxicity of heavy metals in anoxic marine sediments-a case study from a mariculture bay in Southern China

The pollution of marine sediments by heavy metals is still a major concern, especially in zones affected by industry or mariculture. Toxicity of sediment heavy metal contents may be assessed using sequential extraction (SE) procedures, minding inherent constraints of such approaches. In this study, we investigated heavy metal speciation and toxicity in anoxic marine sediments in Zhelin Bay, a mariculture bay in Southern China, using an SE and acid volatile sulfur-simultaneously extracted metals (AVS-SEM) approach. Speciation of Cd, Cu, Ni, Pb, and Zn were studied by a modified SE of five fractions, adapted to separate organic and sulfidic metal fractions in anoxic sediments: F1 weak acid soluble (readily available), F2 reducible fraction, F3 organic matter-bound fraction, F4 sulfide-bound fraction, and F5 residually bound fraction. Toxicity predictions based on the sum of non-residual (NR) metal fractions from sequential extraction were compared to predictions based on AVS-SEM. Results showed that Cd, Ni, and Pb predominantly occurred in the weak acid soluble fraction (F1), residual fraction (F5), and sulfide-bound fraction (F4), respectively; Cu and Zn were mainly obtained in F4 and F5. Based on the distribution of indicator elements for metal fractions, the SEM from AVS extraction included different yields of non-residual and residual fractions besides the sulfidic fraction. Estimates for potential heavy metal toxicity based on NR metals of the SE procedure were thus based on a better-defined speciation compared to the simplistic approach of the AVS-SEM method. Based on the contents of NR metals and normalizing them by organic matter content, toxic effects are not expected for any of the sampling sites, irrespective of the presence or absence of mariculture. Using Pearson correlation analysis to identify predominant fractions influencing toxicity, we conclude that toxicity of heavy metals in anoxic sediments can be well predicted by their non-residual heavy metal contents.