Accumulation,solid partitioning and remobilisation of 99Tc in subtidal and intertidal sediments in the Irish Sea

Recent studies have shown that accumulation of ⁹⁹Tc in seabed sediments labelled by authorised radioactive liquid discharges into the NE Irish Sea from the Sellafield reprocessing complex is greater than previously thought. In this paper, new data on ⁹⁹Tc concentration profiles in subtidal and intertidal sediments from the eastern and western Irish Sea are provided with a view to elucidating the processes responsible for the incorporation and retention of ⁹⁹Tc in the seabed. The data show that substantial amounts of ⁹⁹Tc have accumulated in the fine-grained subtidal sediments off the Cumbrian coast, particularly after increased releases from Sellafield following the commissioning of the Enhanced Actinide Removal Plant (EARP) in 1994. In all the cores taken in this area, ⁹⁹Tc has been found to be present to depths in excess of 30 cm. Analysis of ¹³⁷Cs and ²⁴¹Am profiles, together with other supporting geochemical data, show a high degree of homogenisation of the sediments down to these depths as a result of physical and biological processes, and confirm that incorporation of ⁹⁹Tc into the sediment compartment is actually the result of mixing and reworking, rather than active sediment accumulation. In contrast, active deposition of material transported from this mixed pool of sediment appears to be the dominant mechanism controlling ⁹⁹Tc profiles in intertidal areas close to the Sellafield discharge outfall.Data obtained from the analysis of subtidal sediment cores from the western Irish Sea mud basin suggest that similar mixing processes to those occurring in the subtidal sediments of the eastern Irish Sea are also active in this area. Time-series data on ⁹⁹Tc concentrations in surficial sediments from this basin, gathered in the period 1988–2004, inclusive, show a clear increase in concentrations, by a factor of ～2, between samples collected pre-EARP and post-EARP. The constancy of ⁹⁹Tc concentrations in surface sediments throughout the 1980s and the early-1990s suggests that little redissolution and export of ⁹⁹Tc occurred over this extended period. A similar observation applies to the post-EARP period, when concentrations remained relatively constant despite the reported steady decrease in ⁹⁹Tc concentrations in the overlying waters.This apparent lack of remobilisation is consistent with data from sequential extraction analyses, which indicate that the bulk of the ⁹⁹Tc is strongly bound to non-labile geochemical phases, with only a small proportion associated with exchangeable and acido-soluble phases. Further, these analyses show that ⁹⁹Tc is not associated with oxygen-sensitive and highly-reactive acid-volatile sulphides (AVS) to any significant extent.