The sedimentary fingerprint of an open-marine iron shuttle

We present iron (Fe) concentration and Fe isotope data for a sediment core transect across the Peru upwelling area, which hosts one of the ocean's most pronounced oxygen minimum zones (OMZs). The lateral progression of total Fe to aluminum ratios (FeT/Al) across the continental margin indicates that sediments within the OMZ are depleted in Fe whereas sediments below the OMZ are enriched in Fe relative to the lithogenic background. Rates of Fe loss within the OMZ, as inferred from FeT/Al ratios and sedimentation rates, are in agreement with benthic flux data that were calculated from pore water concentration gradients. The mass of Fe lost from sediments within the OMZ is within the same order of magnitude as the mass of Fe accumulating below the OMZ. Taken together, our data are in agreement with a shuttle scenario where Fe is reductively remobilized from sediments within the OMZ, laterally transported within the anoxic water column and re-precipitated within the more oxic water below the OMZ. Sediments within the OMZ have increased 56Fe/54Fe isotope ratios relative to the lithogenic background, which is consistent with the general notion of benthic release of dissolved Fe with a relatively low 56Fe/54Fe isotope ratio. The Fe isotope ratios increase across the margin and the highest values coincide with the greatest Fe enrichment in sediments below the OMZ. The apparent mismatch in isotope composition between the Fe that is released within the OMZ and Fe that is re-precipitated below the OMZ implies that only a fraction of the sediment-derived Fe is retained near-shore whereas another fraction is transported further offshore. We suggest that a similar open-marine shuttle is likely to operate along many ocean margins. The observed sedimentary fingerprint of the open-marine Fe shuttle differs from a related transport mechanism in isolated euxinic basins (e.g., the Black Sea) where the laterally supplied, reactive Fe is quantitatively captured within the basin sediments. We suggest that our findings are useful to identify OMZ-type Fe cycling in the geological record.

Chromatographic fractionation of bitumen from sediments and presence of glycerol ethers in immature sediments (Table 2)

Alkanes having unusual saturated isoprenoidal and methyl-branched structures have been isolated from the bitumen of several sediments. The methanogenic biomarkers 2,6,10,15,19-pentamethyleicosane and squalane were found in sediments which also contained bacteriogenic glycerol ethers. However, in one ether-containing sediment, 2,6,10,13,17,21-hexamethyldocosane was tentatively identified and this compound was found in place of the established alkane biomarkers. Other hydrocarbons found were regular C21 and C23 isoprenoid alkanes, compounds which cannot be derived from phytol; two isoprenoids of the type 3,7,11.-polymethylalkane, previously reported only in petroleums; 8-methylheptadecane, a probable biomarker for cyanobacteria and a number of its homologs and other methyl-branched alkanes. Ubiquitous branched-chain alkylbenzenes and a homology of trimethylalkylbenzenes were also isolated. Most, or all, of the compounds reported here are probably not catagenetic products but may represent direct algal or bacterial bioinputs.

(Table 1) Organic geochemistry at DSDP Leg 71 Holes

Forty-three core samples from Sites 511 through 514 of DSDP Leg 71 were analyzed geochemically. The black shales at the bottom of Hole 511, in the basin province of the Falkland Plateau, contain an average of 1590 ppm extractable organic matter (EOM) and 120 ppm hydrocarbons. Whereas molecular type-carbon number distributions of mono- and polynuclear aromatic hydrocarbons and their sulphur and oxygen analogues in the black shale "aromatic hydrocarbon" fractions are very similar to those of many crude oils, other data - gas chromatography (GC) fingerprint, pyrolysis GC, visual kerogen analysis, H/C ratio - suggest the black shale section is thermally immature. Together, these observations imply that many of the hydrocarbons were deposited with the original sediments or are diagenetic products of other biological compounds. Pyrograms of the humic acid and kerogen fractions from the black shale interval are typical of geopolymers derived from marine algal material. It appears that these humic acids and kerogens are derived from the same lipid stock.

Biomarkers in turbidites at ODP Sites 157-951 and 157-952

Free and ester-bound lipid biomarkers were analysed in oxidised and unoxidised parts of four distinct turbidites from the Madeira Abyssal Plain (MAP), which contained 1 to 2% organic carbon homogeneously distributed throughout the turbidites at the time they were deposited. These turbidites are well suited to study the effects of oxic degradation on lipid biomarkers without the complicating influence of varying organic matter sources, sedimentation rates, or bioturbation. One sample from the oxidised turbidite was compared with two samples from the unoxidised part of each turbidite. Postdepositional oxic degradation decreased concentrations of biomarkers by several orders of magnitude. The ester-bound lipids were degraded to a far lesser extent than their free counterparts were. The extent of degradation of different compounds differed substantially. Within a specific class of biomarkers, degradation also took place to a different extent, altering their distributions. This study shows that oxic degradation of the organic matter may have a profound effect on the biomarker fingerprint and may result in a severe bias in, for example, the interpretation of organic matter sources and the estimation of the palaeoproductivity of specific groups of phytoplankton.