Total Co (3–22 ppm), Ni (4–160 ppm), V (4–168 ppm), and Cr (8–241 ppm) concentrations vary regionally and with textural differences in the sediments of the St. Lawrence estuary and Gulf of St. Lawrence. They are, except for local anomalies, at or near natural levels relative to their source rocks and other marine sediments.Chemical partition and mineralogical analyses indicate that small but biochemically significant quantities (2–24%) of the total element concentrations are potentially available to the biota and are most likely held by fine-grained organic material, hydrous iron oxides, and ion exchange positions in the sediments. In the upper estuary, nondetrital Ni, Cr, and V supplied from natural and anthropogenic (Cr) sources are apparently preferentially scavenged from solution by terrestrial organic matter and hydrous oxides and concentrated in fine-grained sediments deposited below the turbidity maximum. In the lower estuary, the fine-grained sediments are relatively enriched in nondetrital V supplied from anthropogenic sources in the Saguenay system. Elsewhere the sedimentation intensities of the nondetrital elemental contributions have remained relatively constant with fluctuations in total sediment intensity.Seventy-six to 98% of the total Co, Ni, Cr, and V is not, however, available to the biota, but held in various sulphide, oxide, and silicate minerals. The host minerals have accumulated at the same rate as other fine-grained detrital material except for some local anomalies. In the upper estuary, detrital V concentrations are highest in the sands as an apparent result of an enrichment of ilmenite and titaniferous magnetite from a nearby mineral deposit. In the open gulf, relatively high concentrations of Ni, Cr, and V occur in sediments from the Bay of Islands, Newfoundland, and probably result from the seaward dispersal of detrital Ni, Cr, and V bearing minerals from nearby ultrabasic rocks.