Chemistry of biogenic sediments from the equatorial Pacific

To increase our understanding of the mechanisms that control the distribution of Al and Ti within marine sediment, we performed sequential extractions targeting the chemical signatures of the loosely bound, exchangeable, carbonate, oxide, organic, opal, and residual fraction of sediment from a carbonate-dominated regime (equatorial Pacific) and from a mixed opal-terrigenous regime (West Antarctic Peninsula). We observe a systematic partitioning of Al and Ti between sediment phases that is related to bulk Al/Ti. We show that, where we can quantify an Al(excess) component, the dissolved Al is preferentially affiliated with the oxide fraction, resulting in Al/Ti molar ratios of 500-3000. This is interpreted as the result of surface complexation in the water column of dissolved Al onto oxyhydroxides. We also observe a previously undetected Ti(excess) with as much as 80% of the total Ti in the organic fraction, which is most likely a function of metal-organic colloidal removal from the water column. In samples where the excess metals are obscured by the detrital load, the Al and Ti are almost exclusively found in the residual phase. This argues for the paired removal of Al (preferentially by the oxide component) and Ti (preferentially by the organic component) from the water column by settling particulate matter. This research builds upon earlier work that shows changes in the bulk ratio of Al to Ti in carbonate sediment from the central-equatorial Pacific that coincide with changes in the sedimentary bulk accumulation rate (BAR). The ratios that are observed are as much as three times higher than typical shale values, and were interpreted as the result of scavenging of dissolved Al onto particles settling in the water column. Because this non-terrigenous Al(excess) accounts for up to 50% of the total sedimentary Al inventory and correlates best with BAR, the bulk Al/Ti may be a sensitive tracer of particle flux and, therefore, export production. Because we show that the excess metals are the result of scavenging processes, the bulk Al/Ti may be considered a sensitive proxy for this region.

Stable isotope (carbonates), organic carbon, calcium carbonate and occurrence of coccoliths at DSDP Hole 71-511

Thin but discrete pelagic limestone beds intercalated among the black mudstones near the top of the extensive Mesozoic black shale sequence of the Falkland Plateau are reminiscent of similar occurrences in the central and North Atlantic and may be cyclic in nature. They have been studied via carbonate, organic carbon, stable isotope, nannofloral, and ultrastructural analysis in an attempt to determine their mode of origin. Nannofossil diversity and preservation suggest that selective dissolution or diagenesis did not produce the interbedded coccolith-rich and coccolith-poor layers, nor did blooms of opportunistic species play a role. Stable isotope measurements of carbonate do not adequately constrain the origin of the cyclicity; however, the d13C data suggest that the more nannofossil-rich intervals may be due to higher nutrient supply and overturn of deeper waters at the site rather than influxes of well-oxygenated waters into an otherwise anoxic environment. Such an explanation is in accord with the nannofloral evidence

Geochemistry at DSDP Leg 75 Holes

Samples of sediments and rocks collected at DSDP Sites 530 and 532 were analyzed for 44 major, minor, and trace elements for the following purposes: (1) to document the downhole variability in geochemistry within and between lithologic units; (2) to document trace-element enrichment, if any, in Cretaceous organic-carbon-rich black shales at Site 530; (3) to document trace-element enrichment, if any, in Neogene organic-carbon-rich sediments at Site 532; (4) to document trace-element enrichment, if any, in red claystone above basalt basement at Site 530 that might be attributed to hydrothermal activity or weathering of basalt. Results of the geochemical analyses showed that there are no significant enrichments of elements in the organic-carbon-rich sediments at Site 532, but a number of elements, notably Cd, Co, Cr, Cu, Mo, Ni, Pb, V, and Zn, are enriched in the Cretaceous black shales. These elements have different concentration gradients within the black-shale section, however, which suggests that there was differential mobility of trace elements during diagenesis of interbedded more-oxidized and less-oxidized sediments. There is little or no enrichment of elements from hydrothermal activity in the red claystone immediately overlying basalt basement at Site 530, but slight enrichments of several elements in the lowest meter of sediment may be related to subsea weathering of basalt

Geochemical characterization of black shales from the Tarfaya Basin

Organic geochemical and petrological investigations were carried out on Cenomanian/Turonian black shales from three sample sites in the Tarfaya Basin (SW Morocco) to characterize the sedimentary organic matter. These black shales have a variable bulk and molecular geochemical composition reflecting changes in the quantity and quality of the organic matter. High TOC contents (up to 18wt%) and hydrogen indices between 400 and 800 (mgHC/gTOC) indicate hydrogen-rich organic matter (Type I-II kerogen) which qualifies these laminated black shale sequences as excellent oil-prone source rocks. Low Tmax values obtained from Rock-Eval pyrolysis (404-425 MC) confirm an immature to early mature level of thermal maturation. Organic petrological studies indicate that the kerogen is almost entirely composed of bituminite particles. These unstructured organic aggregates were most probably formed by intensive restructuring of labile biopolymers (lipids and/or carbohydrates), with the incorporation of sulphur into the kerogen during early diagenesis. Total lipid analyses performed after desulphurization of the total extract shows that the biomarkers mostly comprise short-chain n-alkanes (C16-C22) and long-chain (C25-C35) n-alkanes with no obvious odd-over-even predominance, together with steranes, hopanoids and acyclic isoprenoids. The presence of isorenieratane derivatives originating from green sulphur bacteria indicates that dissolved sulphide had reached the photic zone at shallow water depths (~100m) during times of deposition. These conditions probably favoured intensive sulphurization of the organic matter. Flash pyrolysis GC-MS analysis of the kerogen indicates the aliphatic nature of the bulk organic carbon. The vast majority of pyrolysis products are sulphur-containing components such as alkylthiophenes, alkenylthiophenes and alkybenzothiophenes. Abundant sulphurization of the Tarfaya Basin kerogen resulted from excess sulphide and metabolizable organic matter combined with a limited availability of iron during early diagenesis. The observed variability in the intensity of OM sulphurization may be attributed to sea level-driven fluctuations in the palaeoenvironment during sedimentation.

Zooplankton and seston in the White Sea and its chemical composition

A technique of zooplankton net sampling at night in the Kandalaksha and Dvinskii Bays and during the full tide in the Onezhskii Bay of the White Sea allowed us to obtain "clean" samples without considerable admixtures of terrigenous particulates. Absence of elements-indicators of the terrigenous particulates (Al, Ti, and Zr) in the EDX spectra allows to conclude that ash composition of tested samples is defined by constitutional elements comprising organic matter and integument (chitin, shells) of plankton organisms. A quantitative assessment of accumulation of ca. 40 chemical elements by zooplankton based on a complex of modern physical methods of analysis is presented. Values of the coefficient of the biological accumulation of the elements (Kb) calculated for organic matter and the enrichment factors (EF) relative to Clarke concentrations in shale are in general determined by mobility of the chemical elements in aqueous solution, which is confirmed by calculated chemical speciation of the elements in the inorganic subsystem of surface waters of Onezhskii Bay.

Micropaleontological investigation of Late Albanian Col de Palluel

The Niveau Breistroffer black shale succession in the Vocontian Basin (SE France) is the regional equivalent of the widely distributed Late Albian Oceanic Anoxic Event 1d. The studied black shale-rich interval at the Col de Palluel section is 6.28 m thick and comprises four black shale units with up to 2.5 wt% total organic carbon (TOC) intercalated with marlstones. Calcareous nannofossil, palynomorph, planktic Foraminifera and stable isotopic data from the Niveau Breistroffer succession suggest that short-term climate changes influenced its deposition, with relatively warm and humid climate during black shale formation in comparison with relatively cool and dry climatic conditions during marlstone deposition. An increase in the terrigenous/marine ratio of palynomorphs indicates enhanced humidity and higher runoff during black shale formation. A nutrient index based on calcareous nannofossils and the abundance pattern of small (63-125 µm) hedbergellid Foraminifera show short-term changes in the productivity of the surface water. Surface-water productivity was reduced during black shale formation and increased during marlstone deposition. A calcareous nannofossil temperature index and bulk-rock oxygen isotope data indicate relative temperature changes, with warmer surface waters for black shale samples. At these times, warm-humid climate and reduced surface-water productivity were accompanied by greater abundances of 'subsurface'-dwelling calcareous nannofossils (nannoconids) and planktic Foraminifera (rotaliporids). These taxa presumably indicate more stratified surface-water conditions. We suggest that the formation of the Niveau Breistroffer black shales occurred during orbitally induced increase in monsoonal activity that led to increasing humidity during periods of black shale formation. This, in turn, caused a decrease in low-latitude deep-water formation and probably an increase in surface-water stratification. The combination of these two mechanisms caused depleted O2 concentrations in the bottom water that increased the preservation potential of organic matter

Geochemistry and Nd-Pb isotope ratios of sediments from the Lesser Antilles arc

The Lesser Antilles arc is a particularly interesting island arc because it is presently very active, it is located perpendicular to the South American continent and its chemical and isotopic compositions display a strong north-south gradient. While the presence in the south of a thick pile of sedimentary material coming from the old South American continent has long been suspected to explain the geochemical gradient, previous studies failed to demonstrate unambiguously a direct link between the arc lava compositions and the subducted sediment compositions. Here, we present new Nd, Sm, Th, U and Pb concentrations and Nd-Pb isotopic data for over 60 sediments from three sites located in the fore arc region of the Lesser Antilles arc. New data for DSDP Site 543 drill core located east of Dominica Island complement the data published by White et al. (1985, doi:10.1016/0016-7037(85)90082-1) and confirm their relatively uniform isotopic compositions (i.e., 206Pb/204Pb between 19.13 and 19.53). In contrast, data obtained on DSDP Site 144 located further south, on the edge of the South American Rise and on sediments from Barbados Island are much more variable (206Pb/204Pb ranges from 18.81 to 27.69). The very radiogenic Pb isotopic compositions are found in a 60 m thick black shale unit, which has no age equivalent in the Site 543 drill core. We interpret the peculiar composition of the southern sediments as being due to two factors, (a) the proximity of the South American craton, which contributes coarse grain old detrital material that does not travel far from the continental shelf, and (b) the presence of older sediments including the thick black shale unit formed during Oceanic Anoxic events 2 and 3. The north-south isotopic change known along the Lesser Antilles arc can be explained by the observed geographical changes in the composition of the subducted sediments. About 1% contamination of the mantle wedge by Site 543 sediments explains the composition of the northern islands while up to 10% sediments like those of Site 144 is required in the source of the southern island lavas. The presence of black shales in the subducted pile provides a satisfactory explanation for the very low Delta8/4 values that characterize the Lesser Antilles arc.

Organic geochemical character and hydrocarbon source potential of selected black shales at DSDP Hole 93-603B

LECO analysis, pyrolysis assay, and bitumen and elemental analysis were used to characterize the organic matter of 23 black shale samples from Deep Sea Drilling Project Leg 93, Hole 603B, located in the western North Atlantic. The organic matter is dominantly gas-prone and/or refractory. Two cores within the Turonian and Cenomanian, however, contained significant quantities of well-preserved, hydrogen-enriched, organic matter. This material is thermally immature and represents a potential oil-prone source rock. These sediments do not appear to have been deposited within a stagnant, euxinic ocean as would be consistent with an "oceanic anoxic event." Their organic geochemical and sedimentary character is more consistent with deposition by turbidity currents originating on the continental shelf and slope.

Messinian and pre-Messinian sediments of ODP Holes 107-652A and 107-654A

Sedimentology, mineralogy, and petrology of the pre-Pliocene sediments drilled at ODP Sites 652 and 654 in the Tyrrhenian Sea (Leg 107) have been studied with emphasis on the lower Messinian to pre-Messinian intervals. Messinian at Site 652 is essentially turbiditic and basinal in character; it was deposited during the syn-rift phase in a strongly subsiding half-graben and is correlatable with emerged coeval sequences; in part with the Laga Formation of the foredeep of Apennines, and in part with the filling of grabens dissecting that chain in the Tyrrhenian portion of Tuscany. The sequence found in Site 654 indicates an upper Tortonian to Messinian transgression accompanying crustal stretching in the western Tyrrhenian Sea and is perfectly correlatable with the so-called "Sahelian cycle" and with "postorogenic" cycles recognized in peninsular Italy and in Sicily.

Composition of carbonaceous sediments from the Late Jurassic Volgian Basin of the East European Platform (Kostroma Region, Russia)

Lithological, geochemical, stratigraphic, and paleoecological features of carbonaceous sediments in the Late Jurassic Volgian Basin of the East European Platform (Kostroma Region) are considered. The shale-bearing sequence studied is characterized by greater sedimentological completeness as compared with its stratotype sections in the Middle Volga region (Gorodishche, Kashpir). Stratigraphic position and stratigraphy of the shale-bearing sequence, as well as distribution of biota in different sedimentation settings are specified. It is shown that Volgian sediments show distinct cyclic structure. The lower and upper elements of cyclites consist of high-carbonaceous shales and clayey-calcareous sediments, respectively, separated by transitional varieties. Bioturbation structures in different rocks are discussed. Microcomponent composition and pyrolytic parameters of organic matter, as well as distribution of chemical elements in lithologically variable sediments are analyzed. Possible reasons responsible for appearance of cyclicity and accumulation of organic-rich sediments are discussed.

Late Albian foraminiferal carbon and oxygen isotope data and biostratigraphic datums from ODP holes 171-1050C and 171-1052E

A late Albian-early Cenomanian record (~103.3 to 99.0 Ma), including organic-rich deposits and a d13C increase associated with oceanic anoxic event 1d (OAE 1d), is described from Ocean Drilling Program sites 1050 and 1052 in the subtropical Atlantic. Foraminifera are well preserved at these sites. Paleotemperatures estimated from benthic d18O values average ~14°C for middle bathyal Site 1050 and ~17°C for upper bathyal Site 1052, whereas surface temperatures are estimated to have ranged from 26°C to 31°C at both sites. Among planktonic foraminifera, there is a steady balance of speciation and extinction with no discrete time of major faunal turnover. OAE 1d is recognized on the basis of a 1.2 per mill d13C increase (~100.0-99.6 Ma), which is similar in age and magnitude to d13C excursions documented in the North Atlantic and western Tethys. Organic-rich "black shales" are present throughout the studied interval at both sites. However, deposition of individual black shale beds was not synchronous between sites, and most of the black shale was deposited before the OAE 1d d13C increase. A similar pattern is observed at the other sites where OAE 1d has been recognized indicating that the site(s) of excess organic carbon burial that could have caused the d13C increase has (have) yet to be found. Our findings add weight to the view that OAEs should be chemostratigraphically (d13C) rather than lithostratigraphically defined.

Geochemistry and mineralogy of selected carbonaceous claystones at DSDP Hole 76-534

Four dominant depositions of carbonaceous claystones are recognized to have occurred during the early Aptian to middle Albian at Site 534. There are correlations of stable isotope ratios with organic carbon content and of clay content with clay mineralogy of the samples. Almost all organic carbon in these sequences has very negative terrestrial isotope ratios, and the clay of that age indicates predominance of aluminous montmorillonite, which is thought to be of terrigenous origin. It is suggested that development of coastal vegetation belts and deltaic outbuilding with consequent outpouring of land-plant detritus and terrigenous elastics into the deep basins probably led to formation of the "black shale" facies.

Rare earth elements of modern seeps from the Gulf of Mexico, the Black Sea, and the Congo Fan

At marine seeps, methane is microbially oxidized resulting in the precipitation of carbonates close to the seafloor. Methane oxidation leads to sulfate depletion in sediment pore water, which induces a change in redox conditions. Rare earth element (REE) patterns of authigenic carbonate phases collected from modern seeps of the Gulf of Mexico, the Black Sea, and the Congo Fan were analyzed. Different carbonate minerals including aragonite and calcite with different crystal habits have been selected for analysis. Total REE content (SumREE) of seep carbonates varies widely, from 0.1 ppm to 42.5 ppm, but a common trend is that the SumREE in microcrystalline phases is higher than that of the associated later phases including micospar, sparite and blocky cement, suggesting that SumREE may be a function of diagenesis. The shale-normalized REE patterns of the seep carbonates often show different Ce anomalies even in samples from a specific site, suggesting that the formation conditions of seep carbonates are variable and complex. Overall, our results show that apart from anoxic, oxic conditions are at least temporarily common in seep environments.

Geochemical processes and rare earth element analysis in cold-seep pore waters of Hydrate Ridge, northeast Pacific Ocean

The concentrations of rare earth elements (REEs), sulphate, hydrogen sulphide, total alkalinity, calcium, magnesium and phosphate were measured in shallow (<12 cm below seafloor) pore waters from cold-seep sediments on the northern and southern summits of Hydrate Ridge, offshore Oregon. Downward-decreasing sulphate and coevally increasing sulphide concentrations reveal sulphate reductionas dominant early diagenetic process from ~2 cm depth downwards. A strong increase of total dissolved REE concentrations is evident immediately below the sediment-water interface, which can be related to early diagenetic release of REEs into pore water resulting from the remineralization of particulate organic matter. The highest pore water REE concentrations were measured close to the sediment-water interface at ~2 cm depth. Distinct shale normalized REE patterns point to particulate organic matter and iron oxides as main REE sources in the upper ~2-cm depth interval. In general, the pore waters have shalenormalized patterns reflecting heavy REE (HREE) enrichment, which suggests preferential complexation of HREEs with carbonate ions. Below ~2 cm depth, a downward decrease in REE correlates with a decrease in pore water calcium concentrations. At this depth, the anaerobic oxidation of methane (AOM) coupled to sulphate reduction increases carbonate alkalinity through the production of bicarbonate, which results in the precipitation of carbonate minerals. It seems therefore likely that the REEs and calcium are consumed during vast AOM-induced precipitation of carbonate in shallow Hydrate Ridge sediments. The analysis of pore waters from Hydrate Ridge shed new light on early diagenetic processes at cold seeps, corroborating the great potential of REEs to identify geochemical processes and to constrain environmental conditions.

Rare earth element data for sediments from ODP Leg 127

The relative effects of paleoceanographic and paleogeographic variations, sediment lithology, and diagenetic processes on the recorded rare earth element (REE) chemistry of Japan Sea sediments are evaluated by investigating REE total abundances and relative fractionations in 59 samples from Ocean Drilling Program Leg 127. REE total abundances (Sum REE) in the Japan Sea are strongly dependent upon the paleoceanographic position of a given site with respect to terrigenous and biogenic sources. REE concentrations at Site 794 (Yamato Basin) overall correspond well to aluminosilicate chemical indices and are strongly diluted by SiO2 within the late Miocene-Pliocene diatomaceous sequence. Eu/Eu* values at Site 794 reach a maximum through the diatomaceous interval as well, most likely suggesting an association of Eu/Eu* with the siliceous component, or reflecting slight incorporation of a detrital feldspar phase. Sum REE at Site 795 (Japan Basin) also is affiliated strongly with aluminosilicate phases, yet is diluted only slightly by siliceous input. At Site 797 (Yamato Basin), REE is not as clearly associated with the aluminosilicate fraction, is correlated moderately to siliceous input, and may be sporadically influenced by detrital heavy minerals originating from the nearby rifted continental fragment composing the Yamato Rise. The biogenic influence is largest at Site 794, moderately developed at Site 797, and of only minor importance at Site 795, reflecting basinal contrasts in productivity such that the Yamato Basin records greater biogenic input than the Japan Basin, while the most productive waters overlie the easternmost sequence of Site 794. Ce/Ce* profiles at all three sites increase monotonically with depth, and record progressive diagenetic LREE fractionation. The observed Ce/Ce* record does not respond to changes in oxygenation state of the overlying water, and Ce/Ce* correlates slightly better with depth than with age. The downhole increase in Ce/Ce* at Site 794 and Site 797 is a passive response to diagenetic transfer of LREE (except Ce) from sediment to interstitial water. At Site 795, the overall lack of correlation between Ce/Ce* and La_n/Yb_n suggests that other processes are occurring which mask the diagenetic behavior of all LREEs. First-order calculations of the Ce budget in Japan Sea waters and sediment indicate that ~20% of the excess Ce adsorbed by settling particles is recycled within the water column, and that an additional ~38% is recycled at or near the seafloor (data from Masuzawa and Koyama, 1989). Thus, because the remaining excess Ce is only ~10% of the total Ce, there is not a large source of Ce to the deeply buried sediment, further suggesting that the downhole increase in Ce/Ce* is a passive response to diagenetic behavior of the other LREEs. The REE chemistry of Japan Sea sediment therefore predicts successive downhole addition of LREEs to deeply-buried interstitial waters.