Chlorinated hydrocarbons in the open mediterranean ecosystem and implications for mass balance calculations

Studies on the biogeochemical cycling of organic contaminants in the Mediterranean have demonstrated the importance of polychlorinated biphenyls (PCBs) as relatively stable markers of recent anthropogenic influence in ocean systems. This paper presents results of hydrocarbon analyses of deep water profiles, sediments and their associated surface flocculent layers, and zooplankton samples collected in the western basin. Seawater concentrations were higher than those previously reported for the eastern basin and were consistent with the presence of industrial sources in the northwestern segment. In the water column, the percent of PCBs associated with filterable particles was related to the ambient concentrations of total suspended matter, distance from coastal input sources and on depth. The occurrence of deep water residues primarily in the dissolved phase and observations of subsurface maxima in seawater concentrations during a season of high surface productivity were consistent with the predictions of vertical transport models based on residues associated with sinking particles and equilibrium partitioning. Flocculent layers at the sea/sediment interface contained two and three orders of magnitude, respectively, more PCBs and petroleum hydrocarbons (PHCs) than their associated surface sediments. The flocculent particles also contained several biogenic hydrocarbons presumably originating from plankton and relatively soluble and labile contaminants such as hexachlorohexane isomers (HCH) and hexachlorobenzene (HCB), thus confirming that the majority of the flux of hydrocarbons to sediments is carried on rapidly settling large particles. By combining the sediment and flocculents data with published sedimentation rates for the deep basins of the Mediterranean, a yearly flux rate of PCBs to the open sea sediments was estimated as 13 μg m⁻² yr⁻¹ or less than half of the rate measured in a coastal sediment trap experiment. Analytical results are placed in the context of other distribution data for PCBs and long-term flux studies to construct a partial mass balance budget for this semi-enclosed sea. The computed coastal inventory showed that about 35% remains suspended in the water column while the majority of residues are deposited in coastal sediments. However in the open sea, the deep water column may contain up to 70% of the total inventory and may be a continually increasing reservoir of stable organic contaminants reaching the ocean. The budget shows that priority for improved research and monitoring efforts in ocean systems should be given to continued advancement in techniques for the precise measurement of deep water concentrations and for measuring current atmospheric inputs and sedimentation rates in order to develop more accurate ocean flux models.