Chemical and isotopic analysis of bulk organic matter and hydrocarbon biomarkers from IODP Holes 311-U1327C, 311-U1328B and 311-U1328C

The chemical and isotopic compositions of sedimentary organic matter (SOM) from two mid-slope sites of the northern Cascadia margin were investigated during Integrated Ocean Drilling Program (IODP) Expedition 311 to elucidate the organic matter origins and identify potential microbial contributions to SOM. Gas hydrate is present at both locations (IODP Sites U1327 and U1328), with distinct patterns of near-seafloor structural accumulations at the cold seep Site U1328 and deeper stratigraphic accumulations at the slope-basin Site U1327. Source characterization and evidence that some components of the organic matter have been diagenetically altered are determined from the concentrations and isotopic compositions of hydrocarbon biomarkers, total organic carbon (TOC), total nitrogen (TN) and total sulfur (TS). The carbon isotopic compositions of TOC (d13C TOC = -26 to -22 per mil) and long-chain n-alkanes (C27, C29 and C31, d13C = -34 to -29 per mil) suggest the organic matter at both sites is a mixture of 1) terrestrial plants that employ the C3 photosynthetic pathway and 2) marine algae. In contrast, the d15N TN values of the bulk sediment (+4 to +8 per mil) are consistent with a predominantly marine source, but these values most likely have been modified during microbial organic matter degradation. The d13C values of archaeal biomarker pentamethylicosane (PMI) (-46.4 per mil) and bacterial-sourced hopenes, diploptene and hop-21-ene (-40.9 to -34.7 per mil) indicate a partial contribution from methane carbon or a chemoautotrophic pathway. Our multi-isotope and biomarker-based conclusions are consistent with previous studies, based only on the elemental composition of bulk sediments, that suggested a mixed marine-terrestrial organic matter origin for these mid-slope sites of the northern Cascadia margin.

Geochemistry of ODP Sites 123-765 and 123-766

The sediments of the Argo and Gascoyne abyssal plains are generally lean in organic matter, are immature, and contain hydrocarbons trapped during sediment deposition rather than those generated during sediment catagenesis. TOC concentrations in the Argo Abyssal Plain Cenozoic sediments are 0.5 wt%, and organic matter appears to be from mixed marine and reworked, degraded, organic matter sources, with the latter being contributed by turbidity flows from the nearby continental margin. TOC concentrations within the Cenozoic sediments of the Gascoyne Abyssal Plain are mostly undetectable (<0.1 wt%). Biomarker distributions determined by gas chromatography (GC) and gas chromatography-mass spectrometry (GCMS) indicate that organic matter extracted from the Lower Cretaceous sediments from both sites is predominantly marine with varying contributions from terrestrial organic matter. The specific marine biomarker, 24-n-propylcholestane is in relatively high abundance in all samples. In addition, the relatively high abundance of the 4-methylsteranes with the 23,24-dimethyl side chain (in all samples) indicates significant dinoflagellate contributions and marine organic matter. The ratios of n-C27/n-C17 reflect relative contributions of marine vs. terrestrial organic matter. TOC, while generally low at Argo, is relatively high near the Barremian/Aptian boundary (one sample has a TOC of 5.1 wt%) and the Aptian/Albian boundary (up to 1.3 wt% TOC), and two samples from the Barremian and Aptian sections contain relatively high proportions of terrestrial organic carbon. TOC values in the Lower Cretaceous sediments from Gascoyne Abyssal Plain are low (<0.1 wt%) near the Aptian/Barremian boundary. TOC values are higher in older sediments, with maxima in the upper Barremian (1.02 wt%), the Barremian/Hauterivian (0.6 wt%), and Valanginian (1.8 wt%). Sediments from the upper Barremian contain higher amounts of terrestrial organic carbon than older sediments.

Organic facies of Cenozoic and Cretaceous sediments at DSDP Leg 80 Holes

The organic facies of Cenozoic sediments cored at DSDP Sites 548-551 along the Celtic Sea margin of the northern North Atlantic (Goban Spur) is dominated by terrestrially derived plant remains and charcoal. Similar organic facies also occur in the Lower and Upper Cretaceous sections at these sites. Mid-Cretaceous (uppermost Albian-Turonian) sediments at Sites 549-551, however, record two different periods of enrichment in organic material, wherein marine organic matter was mixed with terrestrial components. The earlier period is represented only in the uppermost Albianmiddle Cenomanian section at the most seaward site, 550. Here, dark laminated marly chalks rich in organic matter occur rhythmically interbedded with light-colored, bioturbated marly chalks poor in organic matter, suggesting that bottom waters alternated between oxidizing and reducing conditions. A later period of enrichment in organic material is recorded in the upper Cenomanian-Turonian sections at Sites 549 and 551 as a single, laminated black mudstone interval containing biogenic siliceous debris. It was deposited along the margin during a time of oxygen deficiency associated with upwelling-induced intensification and expansion of the mid-water oxygen-minimum layer. In both the earlier and later events, variations in productivity appear to have been the immediate cause of oxygen depletion in the bottom waters.

Siliceous phytoplankton in Late Quaternary sediments of ODP Site 175-1077

Late Quaternary fluctuations in the intensity of Congo River freshwater load were reconstructed using three different proxies (marine and freshwater diatoms, and the delta18O record of Globigerinoides ruber) preserved in the sediments of Ocean Drilling Program (ODP) Site 1077, located at the northern rim of the Congo River fan (5°10'S, 10°26'E). An abrupt change in the diatom assemblage is evident at Termination II: a two- to four-fold increase in (a) the relative abundance of a marine planktonic diatom tolerant of low salinity conditions (Cyclotella litoralis), and (b) in the concentration of freshwater diatoms. The microfossil data suggest a change in the environmental conditions surrounding Site 1077 from predominantly marine to mixed marine/brackish/fresh. The delta18O record of the planktic foraminifera G. ruber (pink) revealed negative deviations from the global oxygen isotope signal since Termination II which occurred during warm stage 1 and substages 3.2, 5.1, 5.3, and 5.5. Comparison of the isotopic signal of ODP Site 1077 with the record from a pelagic location (core GeoB1041 at 3°48'S, 7°05'W) confirms these results. The construction of an artificial delta18O curve using alkenone-derived sea surface temperature (SST) data from a nearby core (GeoB1008 at 6°S, 10°E) allowed us to estimate salinity and temperature effects on the ODP Site 1077 isotopic signal. Although increased SSTs may account for lighter delta18O values during warmer periods, they do not explain the extremely light values documented in the sediments of Site 1077. We used the oxygen isotope difference (Delta delta18O) between our site and GeoB1041 as a proxy for freshwater input. A general trend in the Delta delta18O was observed, with more negative values since Termination II. In addition, conspicuous Delta delta18O negative pulses coincided with periods of northern hemisphere summer insolation maxima over the African continent, suggesting an increase in the freshwater discharge from the Congo River due to enhanced precipitation on the hinterland. Here we propose that the abrupt change in environmental conditions at Site 1077 since Termination II is a consequence of a major reorganization in the depositional environment of the Congo River delta. This reorganization involved sustained equatorward displacement of the Angola-Benguela Front causing a northward deflection of the Congo River plume thus moving plume waters further north than normal and over Site 1077.

Organic geochemistry at DSDP Leg 80 Holes

The four sites drilled on the Irish continental margin (Goban Spur) yielded sediments ranging in age from Holocene to Barremian. Most of the sediments were deposited in well oxygenated waters, and the small amounts of organic matter they contain are highly oxidized. During a few time intervals from the Cenomanian to earliest Turonian, however, the oxygen content of the bottom waters reached very low levels, resulting in the deposition of homogeneous or laminated black sediments containing from 0.5 to 11% total organic carbon (TOC). The original organic matter was of mixed marine and terrestrial origin. The oxidizing-reducing cycles represented by interbedded black and light sediments are probably a result of changes in both circulation and productivity. The black sediments at Sites 550, 551, and 549 were probably deposited near the lower end, middle, and upper end, respectively, of an expanded oxygen-minimum layer. The oil and gas source potential of the laminated black sediments is very good to excellent. The organic-carbon-lean sediments deposited under oxidizing conditions have no oil or gas source potential. The thermal maturity of all sediments is low.

Late Cretaceous palynofloras of ODP Hole 120-748C

Pollen, spore, and dinoflagellate cyst floras of Late Cretaceous age were found at Sites 748 (120-748C-62R through -79R) and 750 (120-750B-11W) of Ocean Drilling Program Leg 120 to the Kerguelen Plateau area in the Southern Indian Ocean. The ranges of dinocyst and sporomorph species indicate ages between the Cenomanian and Coniacian (to possibly the early Santonian). The ratio of marine/terrestrial flora elements is extremely variable, showing a trend from highly terrestrial (up to -70%) in the late Cenomanian to highly marine (up to 90%) in the Coniacian/early Santonian. Low sedimentation rates of about 3-5 cm/1000 yr were calculated for the glauconitic sediments of Turonian and Coniacian age at Site 748 (lithologic Subunit IIIB).

Freshwater runoff for Taylor Slough to Florida Bay for 1965 to 2000 for the FATHOM model

The Florida Bay ecosystem supports a number of economically important ecosystem services, including several recreational fisheries, which may be affected by changing salinity and temperature due to climate change. In this paper, we use a combination of physical models and habitat suitability index models to quantify the effects of potential climate change scenarios on a variety of juvenile fish and lobster species in Florida Bay. The climate scenarios include alterations in sea level, evaporation and precipitation rates, coastal runoff, and water temperature. We find that the changes in habitat suitability vary in both magnitude and direction across the scenarios and species, but are on average small. Only one of the seven species we investigate (Lagodon rhomboides, i.e., pinfish) sees a sizable decrease in optimal habitat under any of the scenarios. This suggests that the estuarine fauna of Florida Bay may not be as vulnerable to climate change as other components of the ecosystem, such as those in the marine/terrestrial ecotone. However, these models are relatively simplistic, looking only at single species effects of physical drivers without considering the many interspecific interactions that may play a key role in the adjustment of the ecosystem as a whole. More complex models that capture the mechanistic links between physics and biology, as well as the complex dynamics of the estuarine food web, may be necessary to further understand the potential effects of climate change on the Florida Bay ecosystem.

Geochemistry of carbon at DSDP Leg 60 Holes

The 11 frozen cores from the Mariana Trough area from Holes 452 through 455, 459B, 460, and 460A are characteristically low in organic carbon (less than 0.2%) and contain a predominance of n-alkanes within the saturates fraction. There is no odd-predominance of n-alkanes as is typical of immature recent sediments. However, recent sediments containing immature organic matter with normal distributions of n-alkanes {OEP1 approximately equal to 1) are characteristic of sediments derived from purely marine sources (Brooks, 1970; Powell and McKirdy, 1973; Tissot et al., 1975). This type of sediment is very rare. However, at least one case where an immature sediment contains an OEP of near 1 has been reported in samples similar to those reported herein - that is, the Cariaco Trench (Hunt, 1979).

Investigation of Pliocene foraminifera on sediment core CRP-1 from the Ross Sea, Antarctica

Mixed assemblages of Pliocene and Quaternary foraminifera occur within the Quaternary succession of the CRP-1 drillhole. Pliocene foraminifera are not present in the lowermost Unit 4.1. are rare in Unit 3.1 and 2.3, are relatively common in Units 2.2 and 2.1, and are absent in Unit 1.1. Fifteen and twelve species were documented in two of the samples from Units 2.2 and 2.1 respectively. A census count of foraminifera in a sample at 26.89 mbsf (Unit 2.2) indicated that 39% of the tests were from a Pliocene source, with the remaining 61% tests assigned to the in situ Quaternary assemblage. There appears to be a close correlation between the stratigraphic distribution of ice-rafted sediments and the test number and diversity of Pliocene taxa. It is concluded that Pliocene assemblages were not derived from submarine outcrops on Roberts Ridge, but are more likely to have been rafted to the site via major trunk valley drainage systems such as operated within the Mackay and Ferrar glacial valleys. The co-occurrence of marine biota (including foraminifera), fossil wood, pollen, and igneous clasts in the Quaternary succession of CRP-l, points to the marine and terrestrial facies of the Pliocene Sirius Group as a likely source. A major episode of erosion and transport of sediment into the offshore marine basins at about ~1 Ma may have been triggered by dynamism in the ice sheet-glacier system, an episode of regional uplift in the Transantarctic Mountains, sea level oscillations and associated changes in the land-to-sea drainage baselines, or some combination of these factors.

Sedimentology, foraminiferal assemblage, and isotope record of the Agulhas Bank region

The Agulhas Bank region, south of Africa, is an oceanographically important and complex area. The leakage of warm saline Indian Ocean water into the South Atlantic around the southern tip of Africa is a crucial factor in the global thermohaline circulation. Foraminiferal assemblage, stable isotope and sedimentological data from the top 10 m of core MD962080, recovered from the western Agulhas Bank Slope, are used to indicate changes in water mass circulation in the southeastern South Atlantic for the last 450 kyr. Sedimentological and planktonic foraminiferal data give clear signals of cold water intrusions. The benthic stable isotope record provides the stratigraphic framework and indicates that the last four climatic cycles are represented (i.e. down to marine isotope stage (MIS) 12). The planktonic foraminiferal assemblages bear a clear transitional to subantarctic character with Globorotalia inflata and Neogloboquadrina pachyderma (dextral) being the dominant taxa. Input of cold, subantarctic waters into the region by means of leakage through the Subtropical Convergence, as part of Agulhas ring shedding, and a general cooling of surface waters is suggested by increased occurrence of the subantarctic assemblage during glacial periods. Variable input of Indian Ocean waters via the Agulhas Current is indicated by the presence of tropical/subtropical planktonic foraminiferal species Globoquadrina dutertrei, Globigerinoides ruber (alba) and Globorotalia menardii with maximum leakage occurring at glacial terminations. The continuous presence of G. menardii throughout the core suggests that the exchange of water from the South Indian Ocean to the South Atlantic Ocean was never entirely obstructed in the last 450 kyr. The benthic carbon isotope record and sediment textural data reflect a change in bottom water masses over the core location from North Atlantic Deep Water to Upper Southern Component Water. Planktonic foraminiferal assemblages and sediment composition indicate a profound change in surface water conditions over the core site approximately 200-250 kyr BP, during MIS 7, from mixed subantarctic and transitional water masses to overall warmer surface water conditions.

Isotopic composition of terrestrial plant waxes (dD and d13C of n-alkanes) of sediment core SO188_342 from the Northern Bay of Bengal for the last 18 ka

The Indian Summer Monsoon (ISM) is a major global climatic phenomenon. Long-term precipitation proxy records of the ISM, however, are often fragmented and discontinuous, impeding an estimation of the magnitude of precipitation variability from the Last Glacial to the present. To improve our understanding of past ISM variability, we provide a continuous reconstructed record of precipitation and continental vegetation changes from the lower Ganges-Brahmaputra-Meghna catchment and the Indo-Burman ranges over the last 18,000 years (18 ka). The records derive from a marine sediment core from the northern Bay of Bengal (NBoB), and are complemented by numerical model results of spatial moisture transport and precipitation distribution over the Bengal region. The isotopic composition of terrestrial plant waxes (dD and d13C of n-alkanes) are compared to results from an isotope-enabled general atmospheric circulation model (IsoCAM) for selected time slices (pre-industrial, mid-Holocene and Heinrich Stadial 1). Comparison of proxy and model results indicate that past changes in the dD of precipitation and plant waxes were mainly driven by the amount effect, and strongly influenced by ISM rainfall. Maximum precipitation is detected for the Early Holocene Climatic Optimum (EHCO; 10.5-6 ka BP), whereas minimum precipitation occurred during the Heinrich Stadial 1 (HS1; 16.9-15.4 ka BP). The IsoCAM model results support the hypothesis of a constant moisture source (i.e. the NBoB) throughout the study period. Relative to the pre-industrial period the model reconstructions show 20% more rain during the mid-Holocene (6 ka BP) and 20% less rain during the Heinrich Stadial 1 (HS1), respectively. A shift from C4-plant dominated ecosystems during the glacial to subsequent C3/C4-mixed ones during the interglacial took place. Vegetation changes were predominantly driven by precipitation variability, as evidenced by the significant correlation between the dD and d13C alkane records. When compared to other records across the ISM domain, precipitation and vegetation changes inferred from our records and the numerical model results provide evidence for a coherent regional variability of the ISM from the Last Glacial to the present.

Geochemistry of Cretaceous sediments from Argo and Gascoyne Abyssal Plains

The accumulation of organic matter, ferrous and pyrite iron, and the ratios of organic carbon/total sulfur and organic carbon/total phosphorus in the Lower Cretaceous sediments from the Argo and Gascoyne abyssal plains have been used as indicators of both the source and reactivity of organic matter in the sediments and the depositional environment. Total sulfur, used as an indicator of pyrite sulfur, is more abundant in sediments from the Gascoyne Abyssal Plain than in those from the Argo Abyssal Plain. Sulfur positively correlates with TOC at both sites (although poorly at the Argo Abyssal Plain site, R = 0.48), with an extension of the line of best-fit through the origin, indicating that pyrite (TOC <2 wt%) is diagenetic and deposited from normal marine conditions. The average ratio of C/S for samples of TOC <2 wt% is 5.4 at Argo Abyssal Plain (compared to the modern normal marine value of 2.8) indicating deposition of organic matter probably of mixed terrestrial and oxidized marine sources that is unreactive to the sulfate-reducing bacteria. One sample from the Aptian sediments is rich in TOC (5.1 wt%) and has a C/S ratio of 0.5. The average C/S ratio in Gascoyne Abyssal Plain sediments is 0.8 (R = 0.97), which indicates the formation of abundant pyrite in addition to burial and preservation of relatively fresh organic matter that is reactive to the sulfate-reducing bacteria. Organic carbon to phosphorus ratios (C/P) in the sediments indicate preferential remobilization of organic carbon over phosphorus with increasing water depth. Estimates of the degree of pyritization (DOP) increase with increasing TOC at both sites, indicating iron is not limiting and pyrite is formed diagenetically. The one sample with a TOC content of 5.1 wt%, from the Argo Abyssal Plain near the Barremian-Aptian boundary, is composed mostly of framboidal pyrite, finely laminated and not bioturbated, and hence may have been deposited during a brief period of anoxia in the overlying waters.

Mineralogical assemblage in sediment core GeoB12309-5 and in area samples from the Makran subduction zone

In order to study late Holocene changes in sediment supply into the northern Arabian Sea, a 5.3 m long gravity core was investigated by high-resolution geochemical and mineralogical techniques. The sediment core was recovered at a water depth of 956 m from the continental slope off Pakistan and covers a time span of 5 kyr. During the late Holocene source areas delivering material to the sampling site did, however, not change and were active throughout the year.

Stratigraphic distribution of marine palynomorph species recorded for the Miocene of ODP Hole 105-645E (Table 1)

A total of 145 samples were analyzed for palynology, and all were found to be productive. Residues are dominated by pollen, terrestrial spores, and land plant tissues. Marine palynomorphs occur in all samples, which allowed us to recognize five Miocene dinocyst assemblage zones. Dinocyst assemblages indicate cool-water conditions and suggest a neritic rather than fully oceanic environment, with not only North Atlantic and Norwegian Sea affinities, but also containing both notable protoperidiniacean and possible endemic elements. Dinocyst assemblages indicate an early Miocene age for the bottom of Hole 645E and an age no younger than early late Miocene (Sample 105-645E-24R, CC) near the top of the interval studied. These age assignments provide an estimated initiation of ice rafting in Baffin Bay at between 7.4 and 9.5 Ma. Increased terrigenous influx and apparent disappearance of certain dinocyst taxa occur in the middle to late Miocene and may be related to oceanographic changes or climatic deterioration. Spores and pollen indicate a climate that varied within a temperate regime during the early and middle to early late Miocene, followed by climatic deterioration. Four new dinocyst species are described: Batiacasphaera gemmata, Impletosphaeridium prolatum, Operculodinium vacuolatum, and Selenopemphix brevispinosa. The acritarch genus Cyclopsiella Drugg and Loeblich is emended, and two new combinations have been created: Cyclopsiella granosa (Matsuoka) and Cyclopsiella? laevigata (Chateauneuf). Cyclopsiella granosa (Matsuoka) n. comb. is considered a subjective junior synonym of Cyclopsiella granulata He and Li. Ascostomocystis granulatus Chateauneuf has been provisionally allocated to Cyclopsiella and renamed Cyclopsiella? chateauneufii. Two new acritarch species are described: Cyclopsiella spiculosa and Cymatiosphaera! baffinensis.