Trace metal speciation in North Sea coastal waters

Highlights: @@@ Trace metal (TM) speciation was assessed using DGT and active sampling techniques. @@@ DGT gives labile fractions and shows different trends than the dissolved non-labile. @@@ TM speciation shows both seasonal and spatial variation on the Belgian Coastal Zone. @@@ @@¹³C signatures was used to trace the origin suspended organic matter. -- Abstract: Most trace metals exhibit a dual role in marine waters, acting as nutrients at low concentration and being toxic at high concentration. But besides concentration range, speciation is also an important factor. They both show both seasonal and spatial variations. A thorough comparison between total dissolved and particulate concentrations estimated from manual sampling and an assessment of the bioavailability using Diffusive Gradients in Thin Films (DGT) has been performed in this work for Cd, Co, Cu, Ni and Pb, at several sampling points of the Belgian Coastal Zone (BCZ). Additional information to trace back the origin and identify the anthropogenic fingerprint of Suspended Particulate Matter (SPM) was measured using stable carbon isotope measurements in particulate organic matter. Our results show that: (i) particulate and total dissolved metal concentrations are higher at two stations, one in the harbor of Oostende and one offshore; (ii) dissolved and particulate trace metal concentrations do not correlate with the dissolved labile fractions; and (iii) SPM in the harbor zone is likely from allochthonous sources, while in the offshore station marine origin has been evidenced. Our results indicate that, even though contamination is higher in the harbor zones, the trace metal toxicity, which is linked to the metal bioavailability, is most likely not higher than in the open sea. However, with increasing acidification of the ocean, a shift from particulate to dissolved phase might lead to increasing adverse effects on the coastal environment.