An evaluation of the distributions of polychlorinated biphenyls and organic matter in coastal sediments

The objective of this thesis is to improve the understanding of what processes and mechanism affects the distribution of polychlorinated biphenyls (PCBs) and organic carbon in coastal sediments. Because of the strong association of hydrophobic organic contaminants (HOCs) such as PCBs with organic matter in the aquatic environment, these two entities are naturally linked. The coastal environment is the most complex and dynamic part of the ocean when it comes to both cycling of organic matter and HOCs. This environment is characterised by the largest fluxes and most diverse sources of both entities. A wide array of methods was used to study these processes throughout this thesis. In the field sites in the Stockholm archipelago of the Baltic proper, bottom sediments and settling particulate matter were retrieved using sediment coring devices and sediment traps from morphometrically and seismically well-characterized locations. In the laboratory, the samples have been analysed for PCBs, stable carbon isotope ratios, carbon-nitrogen atom ratios as well as standard sediment properties. From the fieldwork in the Stockholm Archipelago and the following laboratory work it was concluded that the inner Stockholm archipelago has a low (≈ 4%) trapping efficiency for freshwater-derived organic carbon. The corollary is a large potential for long-range waterborne transport of OC and OC-associated nutrients and hydrophobic organic pollutants from urban Stockholm to more pristine offshore Baltic Sea ecosystems. Theoretical work has been carried out using Geographical Information Systems (GIS) and statistical methods on a database of 4214 individual sediment samples, each with reported individual PCB congener concentrations. From this work it was concluded that the continental shelf sediments are key global inventories and ultimate sinks of PCBs. Depending on congener, 10-80% of the cumulative historical emissions to the environment are accounted for in continental shelf sediments. Further it was concluded that the many infamous and highly contaminated surface sediments of urban harbours and estuaries of contaminated rivers cannot be of importance as a secondary source to sustain the concentrations observed in remote sediments. Of the global shelf PCB inventory < 1% are in sediments near population centres while ≥ 90% is in remote areas (> 10 km from any dwellings). The remote sub-basin of the North Atlantic Ocean contains approximately half of the global shelf sediment inventory for most of the PCBs studied.

Models of the Distribution of Persistent Organic Pollutants in the Marine Environment

Persistent organic pollutants (POPs) is a group of chemicals that are toxic, undergo long-range transport and accumulate in biota. Due to their persistency the distribution and recirculation in the environment often continues for a long period of time. Thereby they appear virtually everywhere within the biosphere, and poses a toxic stress to living organisms. In this thesis, attempts are made to contribute to the understanding of factors that influence the distribution of POPs with focus on processes in the marine environment. The bioavailability and the spatial distribution are central topics for the environmental risk management of POPs. In order to study these topics, various field studies were undertaken. To determine the bioavailable fraction of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated naphthalenes (PCNs), and polychlorinated biphenyls (PCBs) the aqueous dissolved phase were sampled and analysed. In the same samples, we also measured how much of these POPs were associated with suspended particles. Different models, which predicted the phase distribution of these POPs, were then evaluated. It was found that important water characteristics, which influenced the solid-water phase distribution of POPs, were particulate organic matter (POM), particulate soot (PSC), and dissolved organic matter (DOM). The bioavailable dissolved POP-phase in the water was lower when these sorbing phases were present. Furthermore, sediments were sampled and the spatial distribution of the POPs was examined. The results showed that the concentration of PCDD/Fs, and PCNs were better described using PSC- than using POM-content of the sediment. In parallel with these field studies, we synthesized knowledge of the processes affecting the distribution of POPs in a multimedia mass balance model. This model predicted concentrations of PCDD/Fs throughout our study area, the Grenlandsfjords in Norway, within factors of ten. This makes the model capable to validate the effect of suitable remedial actions in order to decrease the exposure of these POPs to biota in the Grenlandsfjords which was the aim of the project. Also, to evaluate the influence of eutrophication on the marine occurrence PCB data from the US Musselwatch and Benthic Surveillance Programs are examined in this thesis. The dry weight based concentrations of PCB in bivalves were found to correlate positively to the organic matter content of nearby sediments, and organic matter based concentrations of PCB in sediments were negatively correlated to the organic matter content of the sediment.