Trace metals in the central and southern North Sea

Measurements of both dissolved and particulate trace metals (Cd, Co, Cu, Fe, Mn, Ni, Pb and Zn) were made on samples collected simultaneously in the central and southern North Sea (below 56°N), during four cruises covering the seasonal cycle. Analyses of trace metals in both phases were undertaken using similar analytical protocols, and the data subjected to rigorous quality controls. Clean techniques were used throughout sampling and analysis. Trace metal concentrations ranged from those characteristic of waters entering the shelf region from the North Atlantic Ocean to values which in some cases were two orders of magnitude higher. Marked increases in concentrations were often associated with waters directly influenced by riverwaters, but the results showed that the distributions could be influenced by processes other than fluvial inputs. The redox-sensitive metals, Fe and Mn, were influenced at some sites, including those overlying areas of fine-grained sediments, by benthic inputs associated with seasonal changes in oxidation-reduction conditions in the benthic interfacial zone. The behaviour of metals which are not redox-sensitive (Cd, Zn) in some cases paralleled those of Fe and Mn, suggesting an association with Mn-or Fe-rich solid phases, or with organic matter. However, seasonal variations in concentrations of Cd and Zn were not directly linked to the cycle of biological utilization and regeneration of nutrients, suggesting that their geochemistry is more influenced by boundary inputs. Resuspension of Pb-rich sediments, long-range transport of Pb-rich suspended particulate matter (SPM), and enhanced, though diffuse, atmospheric inputs of lead were considered to have contributed to the elevated concentrations of particulate Pb (mass metal/mass sediment) in the water column during winter. Estimates of partitioning (K D s) were derived from the dissolved and particulate data for each of the metals over the seasonal cycle. For the more particle-reactive metals (Co, Fe, Mn, Pb), transport in the suspended particulate phase is a significant, sometimes dominant factor. In contrast, for Cd, Cu and Zn, transport in solution will dominate under almost all conditions in the southern North Sea. Furthermore, the values of K D , for a particular metal, varied widely, partly in response to seasonal differences in the relative contributions of lithogenous and biogenous particles to the particles in suspension. Only for Cu and Zn during the winter could the partitioning be described by a narrow range of K D values covering the observed concentrations of SPM. The data from this study give unique information concerning the contemporaneous distribution of dissolved and particulate trace metals in the southers North Sea and they provide a baseline against which the effects of reductions of inputs into the North Sea may be more accurately assessed. Viewed in combination, the dissolved and particulate data have yielded new insights into mechanisms affecting trace metal cycling and transport, essential in the development of coupled hydrodynamic-geochemical models.