Organic properties of sediments and amino acids in iterstitial waters of ODP Holes 111-677A and 111-678B

The basement at Ocean Drilling Program (ODP) Sites 677 and 678 originated from the Galapagos spreading center of the Costa Rica Rift and has moved about 200 km over the last 6 m.y. (Fig. 1) (Shipboard Scientific Party, 1987, 1988; Scientific Drilling Party, 1987). Sediments about 300 m thick cover basement so young that basal sediments at Sites 677 and 678 have been reheated up to 60?-70?C at Site 677 and altered to limestone and/or chert (Shipboard Scientific Party, 1988). Sediments from both sites indicate (1) a high sedimentation rate (about 48 m/m.y.) and (2) biogenic silica and carbonate as the main constituents of sediments (Table 1) (Shipboard Scientific Party, 1988). Heatflow observations and measurements of interstitial water chemistry around the sites show that Site 677 is in a lower heatflow zone (166 mW/m**2; 1°12.14'N, 83°44.22'W) whereas Site 678 is located in a zone of higher heat flow (250 mW/m**2; 1°13.01'N, 83°43.39'W) (Langseth et al., 1988; Shipboard Scientific Party, 1988). In the flank hydrothermal systems, circulating solution is moving upward through the sedimentary column in zones of higher heat flow while it is moving downward in zones of lower heat flow (Anderson and Skilbeck, 1981). The chemistry of the interstitial waters is modified by several processes such as (1) diagenetic reactions and (2) advective and (3) diffusive transports of dissolved constituents. Analyses of Ca2+ and Mg2+ in interstitial waters from Sites 677 and 678 show that their profiles are mainly controlled by advective transport (Shipboard Scientific Party, 1988). In contrast, the interstitial-water profiles for NH4+, Si, and PO4[3-] are highly affected by reactions in the sediments. Site 677 offers a good opportunity to investigate amino acids in the interstitial waters because sediments of similar compositions have been deposited at constant rates of sedimentation. There are few previous works on amino acid distributions in interstitial waters (Henrichs and Parrington, 1979; Michaelis et al., 1982; Henrichs et al., 1984; Henrichs and Farrington, 1987; Ishizuka et al., 1988). In this chapter, we report (1) Rock-Eval analysis and (2) the composition of total hydrolyzable and dissolved free amino acids (THAA and DFAA, respectively) in the interstitial waters. Our objectives are to discuss (1) the possible origin of organic materials, (2) the characteristics of THAA and DFAA, and (3) their relationships in interstitial waters.

Physical properties and bulk organic geochemical results for sediments from DSDP Hole 96-619

The concentration and carbon isotopic composition (d13C) of sedimentary organic carbon (C_org), N/C ratios, and terrigenous and marine d13C_org endmembers form a basis from which to address problems of Late Quaternary glacial-interglacial climatic variability in a 208.7 m hydraulic piston core (DSDP 619) from the Pigmy Basin in the northern Gulf of Mexico. While interpretations of sedimentary d13C_org time series records are often not unique, paired analyses of d13C_org and N/C are consistent with the hypothesis that the C_org in the Pigmy Basin is a climatically determined mixture of C3-photosynthetic terrigenous and marine organic matter, confirming the earlier d13C_org model of Sackett (1964). A high resolution (~1.4-2.9 Ka/sample) d13C_org record shows that sedimentary organic carbon in interglacial oxygen isotope (sub)stages 1 and 5a-b are enriched in 13C (average +/-1 sigma values are -24.2+/-1.2? and -22.9+/-0.7? relative to PDB, respectively) while glacial isotope stage values 2 are relatively depleted (-25.6+/-0.5?). Concentrations of terrigenous and marine sedimentary organic carbon are calculated for the first time using d13C_org and C_org measurements, and empirically determined terrigenous and marine d13C_org endmembers. The net accumulation rate of terrigenous organic carbon is 4.3+/-2.6 times higher in isotope stages 2-4 than in (sub)stages 1 and 5a-b, recording higher erosion rates of terrigenous organic material in glacial times. The concentration and net accumulation rates of marine and terrigenous C_org suggest that the nutrient-bearing plume of the Mississippi River may have advanced and retreated across the Pigmy Basin as sea level fell and rose in response to glacial-interglacial sea level change.

Sedimentology, organic geochemistry, and stable isotopes of core PS2138-1

We studied variations in terrigenous (TOM) and marine organic matter (MOM) input in a sediment core on the northern Barents Sea margin over the last 30 ka. Using a multiproxy approach, we reconstructed processes controlling organic carbon deposition and investigated their paleoceanographic significance in the North Atlantic-Arctic Gateways. Variations in paleo-surface-water productivity are not documented in amount and composition of organic carbon. The highest level of MOM was deposited during 25-23 ka as a result of scavenging on fine-grained, reworked, and TOM-rich material released by the retreating Svalbard/Barents Sea ice sheet during the late Weichselian. A second peak of MOM is preserved because of sorptive protection by detrital and terrigenous organic matter, higher surface-water productivity due to permanent intrusion of Atlantic water, and high suspension load release by melting sea ice during 15.9-11.2 ka.

Description of sediments, epoch, calcium carbonate, orgnic carbon, geolipids and mass accumulation rate at DSDP Holes 92-597A, 92-600 and 92-601B

Low concentrations of organic carbon in slowly accumulating sediments from Sites 597, 600, and 601 reflect a history of low marine productivity in the subtropical South Pacific since late Oligocene times. The distributions of n-alkanes, n-alkanoic acids, and n-alkanols provide evidence of the microbial alteration of sediment organic matter. Landderived hydrocarbons, possibly from eolian transport, dominate n-alkane distributions in these samples.

(Tables 1, 3) Component composition of organic particles in samples from ODP Site 131-808

Analysis of the palynofacies and miospore thermal alteration indices (TAI) of sediments from ODP Site 808 in the Nankai Trough was undertaken to determine (1) the source, depositional environment, and diagenesis of organic matter in the accreted sediments, and (2) the thermal structure and history of the prism and its relationship to fluid flow. Using the Hartax classification system, two palynofacies were recognized in the sedimentary sequence. Facies 1 occurs within the upper 600 m of trench-wedge turbidites (sedimentation rate > 1 km/m.y.) and contains >50% inertite particles. The rest of the assemblage is dominated by well-preserved phytoclasts and contains small amounts of poorly preserved phytoclasts and well-preserved scleratoclasts. Facies 2 occurs within the Shikoku Basin hemipelagites (600-1300 m below seafloor; sedimentation rate <150 m/m.y.) and contains over two-thirds inertite particles. The rest of the assemblage is dominated by poorly preserved phytoclasts. Miospores and marine phytoplankton compose only a small percentage of both palynofacies. Degraded organic matter is most noticeable in Facies 2, whereas its presence in Facies 1 is overshadowed by the high influx of well-preserved primary organic matter. Most of the degraded organic matter and inertite is interpreted to be reworked. Some of the degraded organic matter may be primary, and may have experienced more biodegradation and thermal alteration in Facies 2 than in Facies 1. TAI values indicate an immature stage of organic maturation (< 2) down to about 900 mbsf. Below this, samples show an increase with depth to a mature stage, reaching peak levels of about 3 just above basement. Samples from within the thrust fault and decollement zones do not show levels of maturity significantly greater than those of surrounding samples, leaving uncertain whether hot fluids have migrated along these fault boundaries in the past.

Geochemistry of organic carbon at DSDP Sites 75-530 and 75-532

CHN analyses of sediments and rocks sampled during DSDP Leg 75 in the South Atlantic have provided concentrations of organic carbon and atomic C/N ratios of organic matter from two sites. High values of organic carbon were measured in sediments deposited during Neogene and Cretaceous times at Site 530 in the Angola Basin; sediments deposited at other times contain less than 0.5% organic carbon. Development of the Benguela Current and associated upwelling-supported biological productivity is recorded in late Miocene to Holocene sediments which contain 1 to 7% organic carbon. These sediments include debris flows and turbidites composed of predominantly biogenic materials originally deposited on the Walvis Ridge and on the African continental margin. Organic-carbon-rich black shales containing up to 17% organic carbon occur in late Albian to Coniacian turbidite sequences. These Cretaceous black shale layers are commonly several centimeters thick and are separated by bioturbated fine-grained organic-carbon-poor turbidites which are usually much thicker. At Site 532 on the Walvis Ridge, biogenic sediments deposited between late Miocene and Holocene times contain 1 to 9% organic carbon. Fluctuations in the intensity of high biological productivity associated with the Benguela Current are preserved in alternating light and dark layers of sediments. C/N ratios of organic matter in sediments from both sites are typical of marine sources

Mass fluxes and organic carbon fluxes at four stations off Cape Blanc, NW Africa (Mauritania)

Vertical carbon fluxes between the surface and 2500 m depth were estimated from in situ profiles of particle size distributions and abundances me/asured off Cape Blanc (Mauritania) related to deep ocean sediment traps. Vertical mass fluxes off Cape Blanc were significantly higher than recent global estimates in the open ocean. The aggregates off Cape Blanc contained high amounts of ballast material due to the presence of coccoliths and fine-grained dust from the Sahara desert, leading to a dominance of small and fast-settling aggregates. The largest changes in vertical fluxes were observed in the surface waters (<250 m), and, thus, showing this site to be the most important zone for aggregate formation and degradation. The degradation length scale (L), i.e. the fractional degradation of aggregates per meter settled, was estimated from vertical fluxes derived from the particle size distribution through the water column. This was compared with fractional remineralization rate of aggregates per meter settled derived from direct ship-board measurements of sinking velocity and small-scale O2 fluxes to aggregates measured by micro-sensors. Microbial respiration by attached bacteria alone could not explain the degradation of organic matter in the upper ocean. Instead, flux feeding from zooplankton organisms was indicated as the dominant degradation process of aggregated carbon in the surface ocean. Below the surface ocean, microbes became more important for the degradation as zooplankton was rare at these depths.

Uranium radionuclides and organic biomarkers in sediment core RC27-42

Uranium series radionuclides and organic biomarkers, which represent major groups of planktonic organisms, were measured in western Arabian Sea sediments that span the past 28 ka. Variability in the past strength of the southwest and northeast monsoons and its influence on primary productivity, sea surface temperature (SST), and planktonic community structure were investigated. The average alkenone-derived SST for the last glacial period was ~3°C lower than that measured for the Holocene. Prior to the deglacial, the lowest SSTs coincide with the highest measured fluxes of organic biomarkers, which represent primarily a planktonic suite of diatoms, coccolithophorids, dinoflagellates, and zooplankton. We propose that intensification of winter northeast monsoon winds during the last glacial period resulted in deep convective mixing, cold SSTs and enhanced primary productivity. In contrast, postdeglacial (<17 ka) SSTs are warmer during times in which biomarker fluxes are high. Associated with this transition is a planktonic community structure change, in which the ratio of the average cumulative flux of diatom biomarkers to the cumulative flux of coccolithophorid biomarkers is twice as high during the deglacial and Holocene than the average ratio during the last glacial period. We suggest that this temporal transition represents a shift from a winter northeast monsoon-dominated (pre-17 ka) to a summer southwest monsoon-dominated (post-17 ka) wind system.

Geochemistry of labile organic matter in sediments and interstitial waters of ODP Sites 107-651 and 107-653

Sediment and interstitial water from Sites 651 and 653 (ODP Leg 107) were investigated by organic geochemical methods to characterize labile organic compound classes (amino compounds and carbohydrates) and to evaluate their progressive diagenetic and thermal degradation in deep-sea sediments. Downhole distribution of dissolved organic carbon (DOC) appears related to redox zones associated with bacterial activity and of diagenetic recrystallization of biogenic tests and not so much to organic matter concentrations in ambient sediments. DOC ranges from 250 to 8300 µmol/L (3-100.1 ppm). Amino acids contribute 10%-0.3% of DOC; carbohydrates range from 78 to 5 µmol/L. Rate of degradation of amino acids by thermal effects and/or bacterial activity at both sites (significantly different in sedimentation rates: average 41 cm/1000 yr in the top 300 m at Site 651, average 3.9 cm/1000 yr in the Pliocene/Quaternary sequence at Site 653 to 220 mbsf) is more dependent on exposure time rather than on the depth within the sediment column. Variability in neutral, acidic, and basic amino acid fractions of total amino acids (with a range of 1.1-0.02 µmol/g sediment; up to 2.5% of organic carbon) varies with carbonate content and by differences in thermal stability of amino acids. Distribution patterns of monosaccharides are interpreted to result from differences in organic matter sources, sedimentation rates, and the degree of organic matter decomposition prior to and subsequent to burial. Total particulate carbohydrates range from 1.82 to 0.21 µmol/g sediment and contribute about 8% to the sedimentary organic matter. Investigation of trace metals in the interstitial waters did not show any correlation of either DOC, amino compounds, or carbohydrates.