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.

Accumulation rates and composition of organic matter in sediments off Peru

Deep-sea sediment samples from three Ocean Drilling Program (ODP) Leg 112 sites on the Peru continental margin were investigated, using a number of organic geochemical and organic petrographic techniques, for amounts and compositions of the organic matter preserved. Preliminary results include mass accumulation rates of organic carbon at Site 679 and characteristics of the organic facies for sediments from Sites 679, 681, and 684. Organic-carbon contents are high, with few exceptions. Particularly high values were determined in the Pliocene interval at Site 684 (4%-7.5%) and in the early Pliocene to Quaternary section of Hole 679D (2%-9%). Older sediments at this site have distinctively lower organic-carbon contents (0.2%-2.5%). Mass accumulation rates of organic matter at Site 679 are 0.02 to 0.07 g carbon/cm**2/k.y. for late Miocene to early Pliocene sediments and higher by a factor of 5 to 10 in the Quaternary sediments. The organic matter in all samples has a predominantly marine planktonic and bacterial origin, with minor terrigenous contribution. Organic particle sizes are strikingly small, so that only a minor portion is covered by visual maceral analysis. Molecular organic-geochemical data were obtained for nonaromatic hydrocarbons, aromatic hydrocarbons (including sulfur compounds), alcohols, ketones, esters, and carboxylic acids. Among the total extractable lipids, long-chain unsaturated ketones from Prymnesiophyte algae strongly predominate among the gas chromatography (GC) amenable components. Steroids are major constituents of the ketone and free- and bound-alcohol fractions. Perylene is the most abundant aromatic hydrocarbon, whereas in the nonaromatic hydrocarbon fractions, long-chain n-alkanes from higher land plants predominate, although the total terrigenous organic matter proportion in the sediments is small.

Stable carbon and nitrogen isotope composition of organic matter in sediments of the Oman Margin

Stable isotopic compositions of carbon and nitrogen and organic carbon content of sediments ranging from the Pliocene to the Pleistocene-Holocene in age from the Oman Margin (ODP Sites 724 and 725) are reported. In general, the organic carbon content is greater than 2% at Site 724. Prior to the Pleistocene-Holocene at this site, sediments with higher content of organic matter were deposited owing to favorable preservation conditions and/or higher productivity. In the Pleistocene, lower amounts of organic matter have been preserved; this material generally has more enriched nitrogen isotopic compositions. This may indicate intensification of the Oxygen Minimum Zone and denitrification with the onset of the Pleistocene. A correlation of carbon isotope content of these sediments with oxygen isotope stages at Site 724 indicates an enrichment in 13C during glacial events. Based on the stable isotope evidence of both carbon and nitrogen, there does not appear to be major input of terrigenous-derived allochthonous material in this marine environment. The timing and extent of monsoon winds on the productivity of this region are not evident, but require further studies for collaborative interpretation of small-scale features in the isotopic and carbon content of this environment.

Dissolved organic carbon concentrations, amino sugar concentrations and highly significantly correlating FT-ICR mass peak magnitudes obtained from solid phase extracted marine dissolved organic matter during POLARSTERN cruise ANT-XXV/1

Dissolved organic matter (DOM) was extracted with solid phase extraction (SPE) from 137 water samples from different climate zones and different depths along an Eastern Atlantic Ocean transect. The extracts were analyzed with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) with electrospray ionization (ESI). D14C analyses were performed on subsamples of the SPE-DOM. In addition, the amount of dissolved organic carbon was determined for all water and SPE-DOM samples as well as the yield of amino sugars for selected samples. Linear correlations were observed between the magnitudes of 43% of the FT-ICR mass peaks and the extract D14C values. Decreasing SPE-DOM D14C values went along with a shift in the molecular composition to higher average masses (m/z) and lower hydrogen/carbon (H/C) ratios. The correlation was used to model the SPE-DOM D14C distribution for all 137 samples. Based on single mass peaks a degradation index was developed to compare the degradation state of marine SPE-DOM samples analyzed with FT-ICR MS. A correlation between D14C, degradation index, DOC values and amino sugar yield supports that SPE-DOM analyzed with FT-ICR MS reflects trends of bulk DOM. A relative mass peak magnitude ratio was used to compare aged SPE-DOM and fresh SPE-DOM regarding single mass peaks. The magnitude ratios show a continuum of different reactivities for the single compounds. Only few of the compounds present in the FT-ICR mass spectra are expected to be highly degraded in the oldest water masses of the Pacific Ocean. All other compounds should persist partly thermohaline circulation. Prokaryotic (bacterial) production, transformation and accumulation of this very stable DOM occurs probably primarily in the upper ocean. This DOM is an important contribution to very old DOM, showing that production and degradation are dynamic processes.

Layer description, carbon and nitrogen content and stable isotope record of bulk sedimentary organic matter from Laguna Potrok Aike

An investigation of stable isotope (d13C TOC and d15N TN) and elemental parameters (TOC, TN contents and TOC/TN ratios) of bulk organic matter (<200 µm) from sediment cores recovered from the Patagonian lake Laguna Potrok Aike (Argentina) in the framework of the ICDP deep drilling project PASADO provided insights into past changes in lake primary productivity and environmental conditions in South Patagonia throughout the last Glacial-Interglacial transition. Stratigraphically constrained cluster analyses of all proxy parameters suggest four main phases. From ca 26,100 to 17,300 cal. years BP, lacustrine phytoplankton was presumably the predominant organic matter source in an aquatic environment with low primary productivity rates. At around 17,300 cal. years BP, abrupt and distinct shifts of isotopic and elemental values indicate that the lacustrine system underwent a rapid reorganization. Lake primary productivity (phytoplankton and aquatic macrophytes) shows higher levels albeit with large variations during most of the deglaciation until 13,000 cal. years BP. The main causes for this development can be seen in improved growing conditions for primary producers because of deglacial warming in combination with expedient availability of nutrients and likely calm wind conditions. After 13,000 cal. years BP, decreased d13C TOC values, TOC, TN contents and TOC/TN ratios indicate that the lake approached a new state with reduced primary productivity probably induced by unfavourable growing conditions for primary producers like strengthened winds and reduced nutrient availability. The steady increase in d15N TN values presumably suggests limitation of nitrate supply for growth of primary producers resulting from a nutrient shortage after the preceding phase with high productivity. Nitrate limitation and consequent decreased lacustrine primary productivity continued into the early Holocene (10,970-8400 cal. years BP) as reflected by isotopic and elemental values.

Organic matter deposition along the Kara and Laptev Seas continental margin (eastern Arctic Ocean) during last deglaciation and Holocene

Organic petrologic (maceral analysis) and bulk organic-geochemical studies were performed on five sediment cores from the Eurasian continental margin to reconstruct the environmental changes during the last not, vert, similar13 000 yr. The core stratigraphy is based on AMS-14C dating, and correlation by magnetic susceptibility and lithostratigraphic characteristics. Variations in terrigenous, freshwater, and marine organic matter deposition document paleoceanographic and paleoclimatic changes during the transition from the last deglaciation to the Holocene. Glacigenic diamictons deposited in the St. Anna Trough (northern Kara Sea) during the Last Glacial Maximum (LGM) are characterized by reworked terrigenous organic matter. In contrast, the Laptev Sea shelf was not covered by an ice-sheet, but was exposed by the lowered sea level. Increased deposition of marine organic matter (MOM) during deglaciation indicates enhanced surface-water productivity, possibly related to influence of Atlantic waters. The occurrence of freshwater alginite gives evidence for river discharge to the Kara and Laptev Seas after the LGM. At the eastern Laptev Sea slope, the first influence of Atlantic water masses is indicated by an increase in the contents of MOM and dinoflagellate cysts, with Operculodinium centrocarpum prior to not, vert, similar10 000 yr BP. High sedimentation rates in the Kara and the Laptev Seas with the adjacent slope at the beginning of the Holocene are presumably related to increased freshwater and sediment discharge from the Siberian rivers. Evidence for elevated Holocene freshwater discharge to the Laptev Sea has been found between not, vert, similar9.8 and 9 kyr BP, at not, vert, similar5 kyr BP and at not, vert, similar2.5 kyr BP. In the Kara Sea, an increased freshwater signal is obvious at not, vert, similar8.5 kyr BP and at not, vert, similar5 kyr BP. Higher portions of MOM were accumulated in the St. Anna Trough and at the Eurasian continental margin at several intervals during the Holocene. Increased primary productivity during these intervals is explained by seasonally ice-free conditions possibly associated with increased inflow of Atlantic waters.

Communities and microhabitats of living benthic foraminifera from the tropical East Atlantic

Living (Rose Bengal stained) benthic foraminifera were collected with a multicorer from six stations between 2°N and 12°S off West Africa. The foraminiferal communities in the investigated area reflect the direct influence of different productivity regimes, and are characterized by spatially and seasonally varying upwelling activity. At five stations, foraminiferal abundance coincides well with the gradient of surface productivity. However, at one station off the Congo River, the influence of strong fresh water discharge is documented. Although this station lies directly in the center of an upwelling area, foraminiferal standing stocks are surprisingly low. It is suggested that the Congo discharge may induce a fractionation of the organic matter into small and light particles of low nutritional content, by contrast to the relatively fast-sinking aggregates found in the centers of high productivity areas. Quality and quantity of the organic matter seem to influence the distribution of microhabitats as well. The flux of organic carbon to the sea-floor controls the sequence of degradation of organic matter in sediment and the position of different redox fronts. The vertical foraminiferal stratification within sediment closely parallels the distribution of oxygen and nitrate in porewater, and reflects different nutritive strategies and adaptation to different types of organic matter. The epifauna and shallow infauna colonize oxygenated sediments where labile organic matter is available. The intermediate infauna (M. barleeanum) is linked to the zone of nitrate reduction in sediments where epifaunal and shallow infaunal species are not competitive anymore, and must feed on bacterial biomass or on metabolizable nutritious particles produced by bacterial degradation of more refractory organic matter. The deep infauna shows its maximum distribution in anoxic sediments, where no easily metabolizable organic matter is available.

(Appendix) Total organic carbon, pyrolysis characteristics, and organic matter types at DSDP Holes 77-535 and 77-540

Lower to middle Cretaceous sediments in the eastern Gulf of Mexico are richer in organic matter and have a more marine organic facies than their counterparts in the nearby western North Atlantic, suggesting that the Gulf was the more productive of the two areas. As in the western North Atlantic, the rate of supply of terrestrial organic matter was high when the rate of supply of noncarbonate clastic materials was high (at times of low sea level) and diminished as sea level rose. The rate of supply of marine organic matter was lower in the Early Cretaceous than in the Cenomanian, perhaps in response to the global rise in sea level over this period. Where they are thermally mature, the organic matterrich units drilled at Sites 535 and 540 should be excellent sources for liquid hydrocarbons. The Pleistocene sediments of the eastern Gulf are dominated by terrestrial organic matter representing Mississippi River effluent.

Concentrations of organic carbon and organic matter isotopic compositions of sapropels and adjacent marls from ODP Hole 161-974B in the Tyrrhenian Basin (Table 1)

Multiple layers of sapropels occur widely in the sedimentary record of the Mediterranean Sea and record repetitions of paleoclimatic conditions that favored increased production and preservation of marine organic matter. A combination of hydrogen and carbon isotope analyses of Pleistocene sapropels from the Tyrrhenian Sea reveals new aspects of the factors leading to their deposition. Organic matter dD values that are significantly more negative in sapropels than in adjacent marls indicate a combination of dilution of surface waters by meteoric waters and increased burial of lipid-rich organic matter during periods of sapropel deposition. Organic d13C values in sapropels that are less negative than those in marls suggest periods of markedly elevated marine biological production. The opposite but concordant excursions of these two isotopic parameters imply that the sapropel layers formed from increased export of marine organic matter from the photic zone to the sea floor during periods of greater fluvial delivery of continental nutrients to the Mediterranean Sea. Furthermore, the isotopic evidence indicates that periods of wetter climate were widespread in southern Europe at the same times as in northern Africa.

Granulometry, mineralogy and organic matter content of permafrost core 5011-3

The combination of permafrost history and dynamics, lake level changes and the tectonical framework is considered to play a crucial role for sediment delivery to El'gygytgyn Crater Lake, NE Russian Arctic. The purpose of this study is to propose a depositional framework based on analyses of the core strata from the lake margin and historical reconstructions from various studies at the site. A sedimentological program has been conducted using frozen core samples from the 141.5 m long El'gygytgyn 5011-3 permafrost well. The drill site is located in sedimentary permafrost west of the lake that partly fills the El'gygytgyn Crater. The total core sequence is interpreted as strata building up a progradational alluvial fan delta. Four macroscopically distinct sedimentary units are identified. Unit 1 (141.5-117.0 m) is comprised of ice-cemented, matrix-supported sandy gravel and intercalated sandy layers. Sandy layers represent sediments which rained out as particles in the deeper part of the water column under highly energetic conditions. Unit 2 (117.0-24.25 m) is dominated by ice-cemented, matrix-supported sandy gravel with individual gravel layers. Most of the Unit 2 diamicton is understood to result from alluvial wash and subsequent gravitational sliding of coarse-grained (sandy gravel) material on the basin slope. Unit 3 (24.25-8.5 m) has ice-cemented, matrix-supported sandy gravel that is interrupted by sand beds. These sandy beds are associated with flooding events and represent near-shore sandy shoals. Unit 4 (8.5-0.0 m) is ice-cemented, matrix-supported sandy gravel with varying ice content, mostly higher than below. It consists of slope material and creek fill deposits. The uppermost metre is the active layer (i.e. the top layer of soil with seasonal freeze and thaw) into which modern soil organic matter has been incorporated. The nature of the progradational sediment transport taking place from the western and northern crater margins may be related to the complementary occurrence of frequent turbiditic layers in the central lake basin, as is known from the lake sediment record. Slope processes such as gravitational sliding and sheet flooding occur especially during spring melt and promote mass wasting into the basin. Tectonics are inferred to have initiated the fan accumulation in the first place and possibly the off-centre displacement of the crater lake.