Description: In order to quantify changes in export production and carbonate dissolution over the past 1 Myr in the central equatorial Pacific Ocean we analyzed Ba, P, Al Ti, and Ca in 1106 samples from five piston cores gathered from 5°S to 4°N at 140°W. We focused on Ba/Ti, Al/Ti, and P/Ti ratios as export proxies and employed areally integrated time slice as well as time series strategies. Carbonate maxima from 0-560 kyr are characterized by 15-30% greater export than carbonate minima. The increases in export fall on glacial delta18O transitions rather than glacial maxima. From 560-800 kyr, overlapping with the mid-Pleistocene transition, there is a very large increase in total export yet no glacial-interglacial variability. The highest latitudes (5°S and 4°N) record minimal absolute export change from glacials to interglacials and yet record the most extreme minima in percent CaCO3, indicating that carbonate records there are dominated by dissolution, whereas near the equator they are more influenced by changes in export.

Description: Ocean Drilling Program Site 1002 in the Cariaco Basin was drilled in the final two days of Leg 165 with only a short transit remaining to the final port of San Juan, Puerto Rico. Because of severe time constraints, cores from only the first of the three long replicate holes (Hole 1002C) were opened at sea for visual description, and the shipboard sampling was restricted to the biostratigraphic examination of core catchers. The limited sampling and general scarcity of biostratigraphic datums within the late Quaternary interval covered by this greatly expanded hemipelagic sequence resulted in a very poorly defined age model for Site 1002 as reported in the Leg 165 Initial Reports volume of the Proceedings of the Ocean Drilling Program. Here, we present for the first time a new integrated stratigraphy for Site 1002 based on the standard of late Quaternary oxygen-isotope variations linked to a suite of refined biostratigraphic datums. These new data show that the sediment sequence recovered by Leg 165 in the Cariaco Basin is continuous and spans the time interval from 0 to ~580 ka, with a basal age roughly twice as old as initially suspected from the tentative shipboard identification of a single biostratigraphic datum. Lithologic subunits recognized at Site 1002 are here tied into this new stratigraphic framework, and temporal variations in major sediment components are reported. The biogenic carbonate, opal, and organic carbon contents of sediments in the Cariaco Basin tend to be high during interglacials, whereas the terrigenous contents of the sediments increase during glacials. Glacioeustatic variations in sea level are likely to exert a dominant control on these first-order variations in lithology, with glacial surface productivity and the nutrient content of waters in the Cariaco Basin affected by shoaling glacial sill depths, and glacial terrigenous inputs affected by narrowing of the inner shelf and increased proximity of direct riverine sources during sea-level lowstands.

Description: Records of long-term sediment deposition in the Caribbean Sea were recovered during Ocean Drilling Program Leg 165. Samples from the Cayman Rise (Site 998), the Colombian Basin (Site 999), and the Hess Escarpment (Site 1001) were analyzed for calcium carbonate (CaCO3) by coulometry and for selected major and trace elements by X-ray fluorescence and inductively coupled plasma-emission spectrometry. These data were used to quantify in the bulk sediment the absolute concentrations of CaCO3, terrigenous matter, and dispersed ash (as opposed to discrete ash layers). The weight percent of terrigenous matter was computed using a Cr-based normative calculation, and dispersed ash content was calculated by difference; the assumption of a three component system (CaCO3, ash, and terrigenous matter) is justified by and consistent with petrographic analysis. Sites 998 and 999 broadly exhibit the same pattern of terrigenous accumulation. Both show a general decrease in terrigenous accumulation rates during the Oligocene and early Miocene, except for a sharp increase at Site 998 during the early Oligocene (30-40 Ma) and significant increases in the late Miocene and late Pliocene/early Pleistocene. The same pattern in terrigenous accumulation is recorded at Sites 925 and 929 in the Ceara Rise (Atlantic Ocean), which receives input from an Amazon River source, demonstrating that Sites 925, 929, 998, and 999 collectively provide a circum-Andean record of tectonic uplift, with the Leg 165 sites responding to inputs from the Magdelena River system. Both Sites 998 and 999 appear to be responding to South and Central American inputs, particularly after the middle Miocene; however, the variation in the terrigenous, carbonate, and dispersed ash at Site 998 point to an erosional event during the Oligocene that is apparently unique to this site's location. Dispersed ash commonly accounts for 15-20 wt% of the bulk sediment, and in some cases up to 45 wt%. The accumulation of dispersed ash typically leads the accumulation of discrete layers by 2-10 m.y. These changes in sediment composition could signify (1) the distance from the source of volcanism, (2) periods of small volume volcanic activity preceding the large eruptions, or (3) the transportation to the deep sea of terrestrially deposited ash preceding the large eruptions.

Description: Leg 165 of the Ocean Drilling Program afforded a unique opportunity to investigate organic and inorganic geochemistry across a wide gradient of sediment compositions and corresponding chemical pathways. The solid fractions at Sites 998, 999, 1000, and 1001 reveal varying proportions of reactive carbonate species, a labile volcanic ash fraction occurring in discrete layers and as a dispersed component, and detrital fluxes that derive from continental weathering. The relative proportions and reactivities of these end-members strongly dictate the character of the diagenetic profiles observed during the pore-water work of Leg 165. In addition, alteration of the well-characterized basaltic basement at Site 1001 has provided a strong signal that is reflected in many of the dissolved components. The relative effects of basement alteration and diagenesis within the sediment column are discussed in terms of downcore relationships for dissolved calcium and magnesium. With the exception of Site 1002 in the Cariaco Basin, the sediments encountered during Leg 165 were uniformly deficient in organic carbon (typically 〈0.1 wt%). Consequently, rates of organic oxidation were generally low and dominated by suboxic pathways with subordinate levels of bacterial sulfate reduction and methanogenesis. The low rates of organic remineralization are supported by modeled rates of sulfate reduction. Site 1000 provided an exception to the generally low levels of microbially mediated redox cycling. At this site the sediment is slightly more enriched in organic phases, and externally derived thermogenic hydrocarbons appear to aid in driving enhanced levels of redox diagenesis at great depths below the seafloor. The entrapment of these volatiles corresponds with a permeability seal defined by a pronounced Miocene minimum in calcium carbonate concentration recognized throughout the basin and with a dramatic downcore increase in the magnitude of limestone lithification. The latter has been tentatively linked to increases in alkalinity associated with microbial oxidation of organic matter and gaseous hydrocarbons. Recognition and quantification of previously unconstrained large volumes and frequencies of Eocene and Miocene silicic volcanic ash within the Caribbean Basin is one of the major findings of Leg 165. High frequencies of volcanic ash layers manifest as varied but often dominant controls on pore-water chemistry. Sulfur isotope results are presented that speak to secondary metal and sulfur enrichments observed in ash layers sampled during Leg 165. Ultimately, a better mechanistic understanding of these processes and the extent to which they have varied spatially and temporally may bear on the global mass balances for a range of major and minor dissolved components of seawater.

Description: Al/Ti and K/Al ratios in bulk sediment are used to interpret wind-blown and hemipelagic sources of deposition to a 578 kyr record in the Cariaco Basin, Venezuela (Ocean Drilling Program site 1002). Graphical and cross-spectral analyses indicate that these ratios vary extremely closely with planktonic foraminiferal d18O, with both ratios being significantly higher during interglacials and lower during glacials. K/Al indicates that during glacials the lower sea level that results in relative basin isolation increases the relative proportion of kaolinite derived from local rivers draining the relatively humid Venezuelan margin. Al/Ti decreases during glacials, suggesting greater proportions of eolian rutile sourced from the northern Sahara (due to increased wind strength and/or aridity). This interpretation is consistent with previous studies of the chemistry and mineralogy of Saharan-derived eolian matter in the Caribbean and with a mass balance determining the effect of changes in eolian rutile accumulation on the bulk sedimentary Al/Ti ratio.