A critical evaluation of using bulk sediment instead of fine fraction in environmental marine studies, investigated on example of Rijeka harbor, Croatia

This work tested the preferential use of fine (< 63 mu m) or bulk sediment (< 2 mm) in environmental research of marine sediments in the Eastern Adriatic. Fine fraction sediment containing silt and clay (< 63 mu m), predominating in the studied area, was examined to evaluate past and present anthropogenic inputs and to test our hypothesis that investigation of bulk sediment should be preferred. Following aqua regia digestion, chemical analyses of 58 elements were performed by ICP/OES, ICP-MS and cold vapor AAS, and statistical analysis was performed. The concentrations of the majority of the analyzed elements increased with age of the sediment, except for Ag and Sn, which had higher concentrations in recent sediments. The previous main sources of metal contamination in Rijeka harbor were now abandoned municipal-sewage outflow and oil refinery, and continuing harbor activities and antifouling paint use. All activities except of antifouling paint use have been decreasing significantly. Anomalies of selected elements were determined by the box-plot method. More anomalies were found in the bulk sediment than in the fine fraction. Results of Q-modality clustering and factor analysis in the fine fraction almost correlate with that applied on bulk sediments. Thus, it can be said that the differences between the element distribution in the bulk and fine fraction are not statistically significant. Our conclusion is that analysis of bulk marine sediment gives a better insight into the state of pollution and supports previous recommendations to use bulk sediment as a chosen media for environmental studies.