Sediment and pore water geochemistry of sediment cores, Potter Cove, King George Island

Redox-sensitive trace metals (Mn, Fe, U, Mo, Re), nutrients and terminal metabolic products (NO3-, NH4+, PO43-, total alkalinity) were for the first time investigated in pore waters of Antarctic coastal sediments. The results of this study reveal a high spatial variability in redox conditions in surface sediments from Potter Cove, King George Island, western Antarctic Peninsula. Particularly in the shallower areas of the bay the significant correlation between sulphate depletion and total alkalinity, the inorganic product of terminal metabolism, indicates sulphate reduction to be the major pathway of organic matter mineralisation. In contrast, dissimilatory metal oxide reduction seems to be prevailing in the newly ice-free areas and the deeper troughs, where concentrations of dissolved iron of up to 700 µM were found. We suggest that the increased accumulation of fine-grained material with high amounts of reducible metal oxides in combination with the reduced availability of metabolisable organic matter and enhanced physical and biological disturbance by bottom water currents, ice scouring and burrowing organisms favours metal oxide reduction over sulphate reduction in these areas. Based on modelled iron fluxes we calculate the contribution of the Antarctic shelf to the pool of potentially bioavailable iron (Feb) to be 6.9x10**3 to 790x10**3 t/yr. Consequently, these shelf sediments would provide an Feb flux of 0.35-39.5/mg/m**2/yr (median: 3.8 mg/m**2/yr) to the Southern Ocean. This contribution is in the same order of magnitude as the flux provided by icebergs and significantly higher than the input by aeolian dust. For this reason suboxic shelf sediments form a key source of iron for the high nutrient-low chlorophyll (HNLC) areas of the Southern Ocean. This source may become even more important in the future due to rising temperatures at the WAP accompanied by enhanced glacier retreat and the accumulation of melt water derived iron-rich material on the shelf.

Geochemistry on Holocene sediments from the Mediterranean

The enhanced accumulation of organic matter in Eastern Mediterranean sapropels and their unusually low d15N values have been attributed to either enhanced nutrient availability which led to elevated primary production and carbon sequestration or to enhanced organic matter preservation under anoxic conditions. In order to evaluate these two hypothesis we have determined Ba/Al ratios, amino acid composition, N and organic C concentrations and d15N in sinking particles, surface sediments, eight spatially distributed core records of the youngest sapropel S1 (10-6 ka) and older sapropels (S5, S6) from two locations. These data suggest that (i) temporal and spatial variations in d15N of sedimentary N are driven by different degrees of diagenesis at different sites rather than by changes in N-sources or primary productivity and (ii) present day TOC export production would suffice to create a sapropel like S1 under conditions of deep-water anoxia. This implies that both enhanced TOC accumulation and d15N depletion in sapropels were due to the absence of oxygen in deep waters. Thus preservation plays a major role for the accumulation of organic-rich sediments casting doubt on the need of enhanced primary production for sapropel formation.

Sedimentology and geochemistry of Oxygen Isotope Stage 3 and Holocene sediments from Laguna Potrok Aike, Patagonia

Seismic reflection studies in the maar lake Laguna Potrok Aike (51°58? S, 70°23? W) revealed an erosional unconformity associated with a sub-aquatic lake-level terrace at a water depth of 30m. Radiocarbon-dated, multi-proxy sediment studies of a piston core from this location indicate that the sediment below this discontinuity has an age of 45kyr BP (Oxygen Isotope Stage 3), and was deposited during an interval of high lake level. In comparison to the Holocene section, geochemical indicators of this older part of the record either point towards a different sediment source or to a different transport mechanism for Oxygen Isotope Stage 3 sediments. Holocene sedimentation started again before 6790cal. yr BP, providing a sediment record of hydrological variability until the present. Geochemical and isotopic data indicate a fluctuating lake level until 5310cal. yr BP. During the late Holocene the lake level shows a receding tendency. Nevertheless, the lake level did not drop below the 30m terrace to create another unconformity. The geochemical characterization of volcanic ashes reveals evidence for previously unknown explosive activity of the Reclús and Mt. Burney volcanoes during Oxygen Isotope Stage 3.

Sedimentology and geochemistry of late glacial and Holocene sediments from Laguna Potrok Aike, Patagonia

A high-resolution multiproxy geochemical approach was applied to the sediments of Laguna Potrok Aike in an attempt to reconstruct moist and dry periods during the past 16 000 years in southeastern Patagonia. The age-depth model is inferred from AMS 14C dates and tephrochronology, and suggests moist conditions during the Lateglacial and early Holocene (16 000-8700 cal. BP) interrupted by drier conditions before the beginning of the Holocene (13 200-11 400 cal. BP). Data also imply that this period was a major warm phase in southeastern Patagonia and was approximately contemporaneous with the Younger Dryas chronozone in the Northern Hemisphere (12 700-11 500 cal. BP). After 8650 cal. BP a major drought may have caused the lowest lake level of the record. Since 7300 cal. BP, the lake level rose and was variable until the 'Little Ice Age', which was the dominant humid period after 8650 cal. BP.

Geochemistry at DSDP Leg 74 Holes

Clay mineralogical and inorganic geochemical data from the Campanian to the Pleistocene provide information bearing on the evolution of both continental and marine paleoenvironments in the Walvis Ridge area. (1) Alteration processes of basalts occurred under subaerial conditions during the Campanian and Maestrichtian and were virtually absent in deeper marine environments. (2) Strong tectonic effects were present during the Campanian and persisted until the early Eocene. (3) Subsidence of this part of the Walvis Ridge became important during the late Maestrichtian and continued into the Paleocene and Eocene. (4) The influence of global climatic cooling was evident from the late Eocene on. (5) Modification of oceanic circulation and the increasing influence of surface and deep water masses on the sedimentation characterized the Cenozoic.

Interstitial water d13C and sediment geochemistry of ODP Leg 166 sites

A review of interstitial water samples collected from Sites 1003-1007 of the Bahamas Transect along with a shore-based analysis of oxygen and carbon isotopes, minor and trace elements, and sediment chemistry are presented. Results indicate that the pore-fluid profiles in the upper 100 meters below seafloor (mbsf) are marked by shifts between 20 and 40 mbsf that are thought to be caused by changes in sediment reactivity, sedimentation rates, and the influence of strong bottom currents that have been active since the late Pliocene. Pore-fluid profiles in the lower Pliocene-Miocene sequences are dominated by diffusion and do not show significant evidence of subsurface advective flow. Deeper interstitial waters are believed to be the in situ fluids that have evolved through interaction with sediments and diffusion. Pore-fluid chemistry is strongly influenced by carbonate recrystallization processes. Increases in pore-fluid Cl- and Na+ with depth are interpreted to result mainly from carbonate remineralization reactions that are most active near the platform margin. A lateral gradient in detrital clay content observed along the transect, leads to an overall lower carbonate reactivity, and enhances preservation of metastable aragonite further away from the platform margin. Later stage burial diagenesis occurs at slow rates and is limited by the supply of reactive elements through diffusion.

Geochemistry and soil characteristics of sediment core GeoB4234

Stable isotopes of sedimentary nitrogen and organic carbon are widely used as proxy variables for biogeochemical parameters and processes in the water column. In order to investigate alterations of the primary isotopic signal by sedimentary diagenetic processes, we determined concentrations and isotopic compositions of inorganic nitrogen (IN), organic nitrogen (ON), total nitrogen (TN), and total organic carbon (TOC) on one short core recovered from sediments of the eastern subtropical Atlantic, between the Canary Islands and the Moroccan coast. Changes with depth in concentration and isotopic composition of the different fractions were related to early diagenetic conditions indicated by pore water concentrations of oxygen, nitrate, and ammonium. Additionally, the nature of the organic matter was investigated by Rock-Eval pyrolysis and microscopic analysis. A decrease in ON during aerobic organic matter degradation is accompanied by an increase of the 15N/14N ratio. Changes in the isotopic composition of ON can be described by Rayleigh fractionation kinetics which are probably related to microbial metabolism. The influence of IN depleted in 15N on the bulk sedimentary (TN) isotope signal increases due to organic matter degradation, compensating partly the isotopic changes in ON. In anoxic sediments, fixation of ammonium between clay lattices results in a decrease of stable nitrogen isotope ratio of IN and TN. Changes in the carbon isotopic composition of TOC have to be explained by Rayleigh fractionation in combination with different remineralization kinetics of organic compounds with different isotopic composition. We have found no evidence for preferential preservation of terrestrial organic carbon. Instead, both TOC and refractory organic carbon are dominated by marine organic matter. Refractory organic carbon is depleted in 13C compared to TOC.

Organic geochemistry of ODP Leg 104 holes

The Leg 104 organic geochemistry program consisted of monitoring (a) hydrocarbon gases, (b) organic and inorganic carbon, and (c) parameters resulting from Rock-Eval pyrolysis at three sites on the Voring Plateau. The results amplify some of those obtained earlier on Deep Sea Drilling Project (DSDP) Leg 38. In a regional sense there is an inverse correlation between amounts of hydrocarbon gas and organic carbon. For example, significant concentrations of methane are present only at Site 644 in the inner part of the plateau where organic carbon contents are always less than 1%; in contrast, at Site 642 on the outer plateau, methane concentrations are very low (ppm range) whereas amounts of organic carbon approach 2%. Only at Site 644 are the environmental conditions such that methanogenesis is an active diagenetic process. Because of the importance of routine gas analyses to the Ocean Drilling Program (ODP), a procedure was devised to improve the use of Vacutainers for collection of gas samples. Comparison of methods for determining organic carbon showed that at Sites 643 and 644 Rock-Eval TOC could be used as a measure of organic carbon, but not at Site 642. Although no liquid or solid hydrocarbons were encountered at any of the sites, a catalog of potential organic geochemical contaminants was developed in anticipation of such a discovery.

Stable isotope geochemistry of pore waters and marine sediments from the New Jersey shelf: Methane formation and fluid origin

Interstitial water and sediment samples of the Integrated Ocean Drilling Program (IODP) expedition 313 "New Jersey Shallow Shelf" were analyzed for chemical composition and stable isotope ratios. A total of 222 water samples were collected from the cores by Rhizon samplers and squeezing of fresh core material. Water was analyzed for its stable oxygen and hydrogen isotope geochemistry (d2H and d18O) at sites M0027A and M0029A, and the carbon isotope composition of the dissolved inorganic carbon (d13CDIC) (all sites). In addition, organic material (Corg) and inorganic carbonates from sediments were analyzed for their carbon ratios (d13Corg and d13Ccarb), and in case of the carbonates also for oxygen (d18Ocarb). Carbon isotopes were also analyzed in samples containing enough methane gas (d13Cmeth). Pore fluids from site M0027A were analyzed for the sulfur isotope composition of dissolved sulfate (d34S). The combination of isotope analyses of all phases (interstitial water, sediment, and gas) with pore water chemistry is expected to enable a better understanding of processes in the sediment and will help to identify the origin of fluids under the New Jersey shelf.

Geochemistry and isotopes at DSDP Leg 80 Holes

Thirty-eight samples from DSDP Sites 549 to 551 were analyzed for major and minor components and trace element abundances. Multivariate statistical analysis of geochemical data groups the samples into two major classes: an organic-carbon- rich group (> 1% TOC) containing high levels of marine organic matter and certain trace elements (Cu, Zn, V, Ni, Co, Ba, and Cr) and an organic-carbon-lean group depleted in these components. The greatest organic and trace metal enrichments occur in the uppermost Albian to Turanian sections of Sites 549 to 551. Carbon-isotopic values of bulk carbonate for the middle Cenomanian section of Site 550 (2.35 to 2.70 per mil) and the upper Cenomanian-Turonian sections of Sites 549 (3.35 to 4.47 per mil) and 551 (3.13 to 3.72 per mil) are similar to coeval values reported elsewhere in the region. The relatively heavy d13C values from Sites 549 and 551 indicate that this interval was deposited during the global "oceanic anoxic event" that occurred at the Cenomanian/Turonian boundary. Variation in the d18O of bulk carbonate for Section 550B-18-1 of middle Cenomanian age suggests that paleosalinity and/or paleotemperature variations may have occurred concurrently with periodic anoxia at this site. Climatically controlled increases in surface-water runoff may have caused surface waters to periodically freshen, resulting in stable salinity stratification