Trace-element deposition in the Cariaco Basin, Venezuela Shelf, under sulfate-reducing conditions: A history of the local hydrography and global climate, 20 ka to the present

Abstract

A sediment core from the Cariaco Basin on the Venezuelan continental shelf, which recovered sediment that has been dated back to 20 ka (thousand years ago), was examined for its major-element-oxide and trace-element composition. Cadmium (Cd), chromium (Cr), copper (Cu), molybdenum (Mo), nickel (Ni), vanadium (V), and zinc (Zn) can be partitioned between a siliciclastic, terrigenous-derived fraction and two seawater-derived fractions. The two marine fractions are (1) a biogenic fraction represented by nutrient trace elements taken up mostly in the photic zone by phytoplankton, and (2) a hydrogenous fraction that has been derived from bottom water via adsorption and precipitation reactions. This suite of trace elements contrasts with a second suite of trace elements—barium (Ba), cobalt (Co), gallium (Ga), lithium (Li), the rare-earth elements, thorium (Th), yttrium (Y), and several of the major-element oxides—that has had solely a terrigenous source. The partitioning scheme, coupled with bulk sediment accumulation rates measured by others, allows us to determine the accumulation rate of trace elements in each of the three sediment fractions and of the fractions themselves. The current export of organic matter from the photic zone, redox conditions and advection of bottom water, and flux of terrigenous debris into the basin can be used to calculate independently trace-element depositional rates. The calculated rates show excellent agreement with the measured rates of the surface sediment. This agreement supports a model of trace-element accumulation rates in the subsurface sediment that gives a 20-kyr history of upwelling into the photic zone (that is, primary productivity), bottom-water advection and redox, and provenance. Correspondence of extrema in the geochemical signals with global changes in sea level and climate demonstrates the high degree to which the basin hydrography and provenance have responded to the paleoceanographic and paleoclimatic regimes of the last 20 kyr. The accumulation rate of the marine fraction of Mo increased abruptly at about 14.8 ka (calendar years), from less than 0.5 µg cm -2 yr -1 to greater than 4 µg cm -2 yr -1 . Its accumulation rate remained high but variable until 8.6 ka, when it decreased sharply to 1 µg cm -2 yr -1 . It continued to decrease to 4.0 ka, to its lowest value for the past 15 kyr, before gradually increasing to the present. Between 14.8 ka and 8.6 ka, its accumulation rate exhibited strong maxima at 14.4, 13.0, and 9.9 ka. The oldest maximum corresponds to melt-water pulse IA into the Gulf of Mexico. A relative minimum, centered at about 11.1 ka, corresponds to melt-water pulse IB; a strong maximum occurs in the immediately overlying sediment. The maximum at 13.0 ka corresponds to onset of the Younger Dryas cold event. This pattern to the accumulation rate of Mo (and V) can be interpreted in terms of its deposition from bottom water of the basin, the hydrogenous fraction, under SO 4 2- -reducing conditions, during times of intense bottom-water advection 14.8 ka to 11.1 ka and significantly less intense bottom-water advection 11 ka to the present. The accumulation rate of Cd shows a pattern that is only slightly different from that of Mo, although its deposition was determined largely by the rain rate of organic matter into the bottom water, a biogenic fraction whose deposition was driven by upwelling of nutrient-enriched water into the photic zone. Its accumulation exhibits only moderately high rates, on average, during both melt-water pulses. Its highest rate, and that of upwelling, occurred during the Younger Dryas, and again following melt-water pulse IB. The marine fractions of Cu, Ni, and Zn also have a strong biogenic signal. The siliciclastic terrigenous debris, however, represents the dominant source, and host, of Cu, Ni, and Zn. All four trace elements have a consid-erably weaker hydrogenous signal than biogenic signal. Accumulation rates of the terrigenous fraction, as reflected by accumulation rates of Th and Ga, show strong maxima at 16.2 and 12.7 ka and minima at 14.1 and 11.1 ka. Co, Li, REE, and Y have a similar distribution. The minima occurred during melt-water pulses IA and IB, the maxima during the Younger Dryas and the rise in sea level following the last glacial maximum.