M.Tech. (Chemistry) / Please refer to full text to view abstract

This thesis examines fatty acid (FA) and polychlorinated biphenyl (PCB) dynamics in a marine top predator, the grey seal (Halichoerus grypus,) and their transfer during lactation from mother to offspring. It examines regional and annual variations in FA composition and PCB loads, and also how the physical and chemical characteristics of these molecules (e.g. their polarity and size) can affect the rates of accumulation, mobilization and transfer of specific FAs or PCBs. Two UK grey seal colonies (North Rona (NR) and Isle of May (IOM) were studied during three consecutive years (1996-1998 and 2004-2006). Lactating grey seals and their pups were repeatedly captured during the lactation period and sampled for blubber, serum and milk and analysed for FAs and PCBs. Overall, the two colonies were clearly distinguished from each other, suggesting that the main prey species had different FA composition, and possibly that the seals from these colonies had different diets . These differences are probably a direct consequence of differences in prey community structure in the two regions where seals from these two colonies are thought to feed. Within each colony, annual differences could be detected between some years but not between others. During 1996-98, IOM seals showed a clear change in their FA profiles while NR seals did not. In contrast, during 2004-2006 NR seals showed a clear change while IOM seals did not. The changes observed in IOM during 1996-1998 are consistent with the large-scale regime shift that occurred in the North Sea during the 1990‟s. The relative proportions of each FA that were mobilized from blubber and transferred to the milk during lactation were very similar between colonies, and could be explained to a large degree by their physico-chemical properties. For a given carbon chain length the mobilization increased with increasing number of double bonds; and for a given number of double bonds the mobilization decrease with increasing carbon chain length. However, the mobilization also appeared to be influenced by the specific nutritional requirements of the growing pups. For instance, FAs that are considered essential for pup development or efficient energy storage (e.g. saturated FAs) were more highly mobilised than expected. This selectivity was also reflected in the FA composition of the different body compartments (maternal blubber and milk, pup blubber) that persisted throughout lactation. These changes were also similar between the colonies. Colonies could also be clearly distinguished by their blubber PCB profiles. IOM seals had higher total concentrations on average than NR seals (1327.9 vs. 680.2 ng/g lipid in 2005 and 1199.7 vs. 819.0 ng/g lipid in 2006). IOM seals also had higher total amounts in both years (79.2 vs. 38.0 mg in 2005 and 61.7 vs. 53.4 mg in 2006). One of the main differences between colonies was that females from IOM had higher concentrations of highly chlorinated congeners than NR seals. PCB concentrations in blubber increased towards the end of lactation. Serum and milk PCB concentrations also increased rapidly, especially for the highly chlorinated congeners. These results were consistent with other studies showing the increase in concentrations as a result of lipid loss. Serum concentrations stayed constant during the first part of lactation and increased at late lactation. This was also observed in milk PCB concentrations. The changes in the PCB profiles in the three body compartments were very similar between colonies. However IOM seals always had higher total concentrations of PCBs in all of the body compartments. The concentrations of individual congeners relative to PCB-153 showed that blubber contained higher proportions of the highly chlorinated PCBs relative to other tissues. There were no clear changes in these proportions in blubber during lactation, but the relative proportions of highly chlorinated PCB In serum and milk increased throughout lactation while the less chlorinated PCBs stayed constant. The highly chlorinated PCBs were found in lower concentration in the milk compared to the less chlorinated compounds suggesting a selective release from blubber to blood and a selective transfer of PCBs to the milk.