Assessing PCB pollution in the Baltic Sea - An equilibrium partitioning based study.

Sediment cores and bottom water samples from across the Baltic Sea region were analyzed for freely dissolved concentrations (Cfree), total sediment concentrations (CT) and the dissolved aqueous fraction in water of seven indicator PCBs. Ex-situ equilibrium sampling of sediment samples was conducted with polydimethylsiloxane (PDMS) coated glass fibers that were analyzed by automated thermal desorption GC-MS, which yielded PCB concentrations in the fiber coating (CPDMS). Measurements of CPDMS and CT were then applied to determine (i) spatially resolved freely dissolved PCB concentrations; (ii) baseline toxicity potential based on chemical activities (a); (iii) site specific mixture compositions; (iv) diffusion gradients at the sediment water interface and within the sediment cores; and (vi) site specific distribution ratios (KD). The contamination levels were low in the Gulf of Finland and moderate to elevated in the Baltic Proper, with the highest levels observed in the western Baltic Sea. The SPME method has been demonstrated to be an appropriate and sensitive tool for area surveys presenting new opportunities to study the in-situ distribution and thermodynamics of hydrophobic organic chemicals at trace levels in marine environments.

Equilibrium passive sampling as a tool to study polycyclic aromatic hydrocarbons in Baltic Sea sediment pore-water systems.

Solid Phase Microextraction (SPME) was applied to provide the first large scale dataset of freely dissolved concentrations for 9 polycyclic aromatic hydrocarbons (PAHs) in Baltic Sea sediment cores. Polydimethylsiloxane (PDMS) coated glass fibers were used for ex-situ equilibrium sampling followed by automated thermal desorption and GC-MS analysis. From the PAH concentrations in the fiber coating we examined (i) spatially resolved freely dissolved PAH concentrations (Cfree); (ii) baseline toxicity potential on the basis of chemical activities (a); (iii) site specific mixture compositions; (iv) diffusion gradients at the sediment water interface and within the sediment cores and (v) site specific distribution ratios. Contamination levels were low in the northern Baltic Sea, moderate to elevated in the Baltic Proper and highest in the Gulf of Finland. Chemical activities were well below levels expected to cause narcosis to benthos organisms. The SPME method is a very sensitive tool that opens new possibilities for studying the PAHs at trace levels in marine environments.

Passive equilibrium sampler for in situ measurements of freely dissolved concentrations of hydrophobic organic chemicals in sediments.

In this study, an equilibrium passive sampling device is introduced that facilitates the in situ measurement of hydrophobic organic chemicals bioavailability in sediments in terms of freely dissolved concentrations. The new field sampler allows SPME fibers and silicone hollow fibers to be immersed and equilibrated in situ, whereas an automated liner exchanger (ALEX) facilitates the quantitative transfer of analytes to the GC without the use of extraction solvents. The sampler was developed for environmental monitoring as follows: (1) It is of very solid construction and can be reused practically ad infinitum. (2) Fibers with varying surface to volume ratios can be exposed in parallel in order to confirm that equilibrium was reached between sampler and sediment. (3) The equilibrium times allow a temporal resolution that is suited for monitoring of both long-term trends and seasonal effects. The automated thermal desorption reduced sample treatment to a minimum and ensured cost- and time-efficient measurements while minimizing potential error sources after the sampling. The sampler is applicable in a multitude of aquatic environments, especially where currents are low and sediments are muddy and well-mixed, e.g. by bioturbation. Examples for such environments are mud flats, harbor basins, river banks, and lakes.