Amino acids from ODP Holes 117-722B and 177-724C

Sedimentary d15N records are valuable archives of ocean history but they are often modified during early diagenesis. Here we quantify the effect of early diagenetic enrichment on sedimentary N-isotope composition in order to obtain the pristine signal of reactive N assimilated in the euphotic zone. This is possible by using paired data of d15N and amino acid composition of sediment samples, which can be applied to estimate the degree of organic matter degradation. We determined d15N and amino acid composition in coeval sediments from Ocean Drilling Program (ODP) Hole 772 B in the central Arabian Sea and from Hole 724 C situated on the Oman Margin in the western Arabian Sea coastal upwelling area. The records span the last 130 kyr and include two glacial-interglacial cycles. These new data are used in conjunction with data available for surface sediments that cover a wide range of organic matter degradation states, and with other cores from the northern and eastern Arabian Sea to explore spatial variations in the isotopic signal. In order to reconstruct pristine N values we apply the relationship between organic matter degradation and 15N enrichment in surface sediments to correct the core records for early diagenetic enrichment. Reconstructed d15N values suggest a significant role of N2-fixation during glacial stages. An evaluation of two preservation indices based on amino acid composition (Reactivity Index, RI; Jennerjahn and Ittekkot, 1997; and the Degradation Index, DI; Dauwe et al., 1999) in both recent sediments and core samples suggests that the RI is more suitable than the DI in correcting Arabian Sea d15N records for early diagenetic enrichment.

Stable isotope ratios and organic carbon accumulation rates of late Pleistocene sediments of ODP Hole 117-724C

Stable isotope records of coexisting benthic foraminifers Uvigerina spp. and Cibicidoides spp. and planktonic G. ruber (white variety) from Site 724 are used to study the late Pleistocene evolution of surface and intermediate water hydrography (593 m water depth) at the Oman Margin. Glacial-interglacial d18O amplitudes recorded by the benthic foraminifers are reduced when compared to the estimated mean ocean changes of d18Oseawater . Epibenthic d13C remains at its modern level or is increased during glacial times. This implies that Red Sea outflow waters which are enriched in d18Oseawater and d13C (Sum CO2) have been replaced during glacial periods by intermediate waters still positive in d13C (Sum CO2) but more negative in d18Oseawater. Glacial-interglacial amplitudes of the planktonic d18O record exceed those of the mean ocean d18Oseawater variation and imply decreased surface water temperatures (SST) during glacial times. Throughout most of the records these cooling events correlate with enhanced rates of carbon accumulation. However, both negative (colder) SST and positive Corg accumulation rate anomalies do not correlate with potential physical upwelling maxima as inferred from the orbital monsoon index. This is in conflict with the established hypothesis that upwelling in the estern Arabia Sea should be strongest during maxima of the southwest monsoon.

Inorganic geochemical record of ODP Holes 117-722B and 117-724C

High-resolution sampling from late Pleistocene (last 400 k.y.) sediments of Site 722 (upper 16 m) and Site 724 (upper 70 m), and subsequent inorganic geochemical analysis, has defined the history of productivity in the northwest Arabian Sea. Eolian dust input from the Arabian Peninsula and Somalia is characterized by the record of Ti/Al and Cr/Al. This dust record displays strong precessional periodicity (cycles at 25 k.y.) suggesting the Southwest Monsoon and associated winds play a key role in transporting terrigenous material from the land. High biological productivity results in the accumulation of biogenic CaCO3 and opal in the sediments, the latter having an unexpectedly minor contribution to the total mass flux. Due to dilution of the CaCO3 record by the terrigenous component, the record of biological productivity is best exemplified by Ba. Its record, together with that of other metals recording biological association and redox variability (Cu, Ni, Zn, V, U) clearly identifies the interglacial episodes as being more biologically productive. The striking agreement between Ba and the d18O record in planktonic foraminifers suggests that the supply of nutrients during these periods of high productivity is linked to ocean-wide changes in ocean fertility, and not just local upwelling conditions. High levels of phosphate accumulation in interglacial sediments is attributed to both diagenetic phosphorite formation and biogenic skeletal debris. This study provides a detailed record of productivity variation in the northwest Arabian Sea during the late Pleistocene.

Pliocene to Pleistocene calcium carbonate and organic carbon record of ODP Hole 117-722B

Site 722 provides high resolution records of percent CaCO3, magnetic susceptibility, d18O, organic carbon, and coarse fraction for the past 3.4 m.y. from the crest of the Owen Ridge, northwestern Arabian Sea. Within this time interval, most of the carbonate percent variations can be attributed to terrigenous dilution and do not reflect changes in the carbonate system. From the late Pliocene to Present, the average rate of calcium carbonate accumulation increases from 1 to 3 g/cm**2/k.y. and the average accumulation of organic carbon decreases from 75 to 30 mg/cm**2/k.y. The carbonate component is more dissolved in the older interval. The long-term variations in carbonate accumulation may reflect a greater input of organic matter in the late Pliocene, which decomposes to produce CO2 and dissolve carbonate. Magnetic susceptibility and % noncarbonate (100 - CaCO3%) reflect changes in the amount of the lithogenic component in the sediments. The period of variation of lithogenic material is the same period as the original forcing of the regional summer monsoon, however, the timing matches global aridity patterns and global ice volume (sea level) changes. This preliminary analysis suggests that the high frequency variation of lithogenic material persists for at least the last 3.4 m.y. Within the last million years, calcium carbonate accumulation has a large amplitude signal that covaries with major changes in ice volume. Both calcium carbonate and noncarbonate (mostly terrigenous) accumulation are greatest during glacial stages. Interglacial intervals are characterized by low mass accumulation rates, increased foraminifer fragmentation, and increased opal concentration. The accumulation of organic carbon matches the high frequency changes in sedimentation rates. We attribute this high correlation to enhanced preservation of organic carbon by increased sedimentation rate. Of the three major biological components studied, only opal exhibits the variations expected for a biological productivity system forced by monsoonal upwelling driven by changes in northern hemisphere summer radiation.