Chemistry of biogenic sediments from the equatorial Pacific

To increase our understanding of the mechanisms that control the distribution of Al and Ti within marine sediment, we performed sequential extractions targeting the chemical signatures of the loosely bound, exchangeable, carbonate, oxide, organic, opal, and residual fraction of sediment from a carbonate-dominated regime (equatorial Pacific) and from a mixed opal-terrigenous regime (West Antarctic Peninsula). We observe a systematic partitioning of Al and Ti between sediment phases that is related to bulk Al/Ti. We show that, where we can quantify an Al(excess) component, the dissolved Al is preferentially affiliated with the oxide fraction, resulting in Al/Ti molar ratios of 500-3000. This is interpreted as the result of surface complexation in the water column of dissolved Al onto oxyhydroxides. We also observe a previously undetected Ti(excess) with as much as 80% of the total Ti in the organic fraction, which is most likely a function of metal-organic colloidal removal from the water column. In samples where the excess metals are obscured by the detrital load, the Al and Ti are almost exclusively found in the residual phase. This argues for the paired removal of Al (preferentially by the oxide component) and Ti (preferentially by the organic component) from the water column by settling particulate matter. This research builds upon earlier work that shows changes in the bulk ratio of Al to Ti in carbonate sediment from the central-equatorial Pacific that coincide with changes in the sedimentary bulk accumulation rate (BAR). The ratios that are observed are as much as three times higher than typical shale values, and were interpreted as the result of scavenging of dissolved Al onto particles settling in the water column. Because this non-terrigenous Al(excess) accounts for up to 50% of the total sedimentary Al inventory and correlates best with BAR, the bulk Al/Ti may be a sensitive tracer of particle flux and, therefore, export production. Because we show that the excess metals are the result of scavenging processes, the bulk Al/Ti may be considered a sensitive proxy for this region.

Geochemistry of sediment cores from the Rainbow vent site

A geochemical investigation was carried out on two sediment cores collected at 2 and 5 km from the Rainbow hydrothermal vent site. Bulk sediment compositions indicate that these cores record clear enrichments in Fe, Cu, Mn, V, P and As from hydrothermal plume fallout (Cave et al., 2002, doi:10.1016/S0016-7037(02)00823-2). Sequential dissolution of the bulk sediments has been used to discriminate between a leach (biogenic and oxy-hydroxide) component and a residual phase (detrital and sulphide/sulphate fractions). Major element data (Al, Fe, Ti, Mn, Mg, Ca, Si and index%) reveal that the hydrothermal input, as recorded in the leach phase, is much stronger than apparent from bulk sediment analyses alone. REE patterns for the leach phase record contributions from both biogenic carbonate (mimicking seawater REE patterns) and hydrothermal oxy-hydroxides, with the latter exhibiting positive Eu anomalies (hydrothermal derived) and negative Ce anomalies (seawater derived). Based on major element and REE data, the residue contains contributions from aeolian dust input, local MORB material and a hydrothermal component. Ternary REE mixing calculations indicate that most of the REE within the residual fraction (~80%) is derived from hydrothermal material, while detrital contributions to the REE budget, as deep-sea clay and volcanic debris, are <20%. By combining bulk and REE data for the various end-member components of the residue, we calculate that the chemical composition of the residue hydrothermal end-member is high in Ca (6-15%) and with a Nd/Sr ratio of 0.004. These characteristics indicate the presence of low-solubility hydrothermal sulphate (rather than sulphide) material within the residue component of Rainbow hydrothermal sediments.

Contents and isotopic speciation of sedimentary carbon and nitrogen in sediment core MD01-2404, the Okinawa Trough

Total organic carbon to total nitrogen ratio (C/N) and their isotopic composition (d13CTOC vs. d15NTN) are oft-applied proxies to discern terrigenous from marine sourced organics and to unravel the ancient environmental information. In high depositional Asian marginal seas, matrixes, including N-bearing minerals, dilution leads to illusive and even contradictive interpretations. We use KOH-KOBr to separate operationally defined total organic matter into oxidizable (labile) and residual fractions for content and isotope measurements. In a sediment core in the Okinawa Trough, significant amounts of carbon and nitrogen existed in the residual phase, in which the C/N ratio was ~9 resembling most documented sedimentary bulk C/N ratios in the China marginal seas. Such similarity creates a pseudo-C/N interrupting the application of bulk C/N. The residual carbon, though composition unknown, it displayed a d13C range (-22.7 to -18.9 per mil, mean -20.7 per mil) similar to black carbon (-24.0 to -22.8 per mil) in East China Sea surface sediments. After removing residual fraction, we found the temporal pattern of d13CLOC in labile fraction (LOC) was more variable but broadly agreed with the atmospheric pCO2-induced changes in marine endmember d13C. Thus, we suggested adding pCO2-induced endmember modulation into two-endmember mixing model for paleo-environment reconstruction. Meanwhile, the residual nitrogen revealed an intimate association with illite content suggesting its terrestrial origin. Additionally, d15N in residual fraction likely carried the climate imprint from land. Further studies are required to explore the controlling factors for carbon and nitrogen isotopic speciation and to retrieve the information locked in the residual fraction.