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.

Migration of C1 to C8 volatile organic compounds in sediments at DSDP Hole 75-530A

The distribution of C1 to C8 hydrocarbons in sediment samples from DSDP Leg 75, Hole 530A, indicates that significant amounts of methane and ethane have migrated from organic-rich to organic-lean shales in close proximity. Most compounds larger than ethane are not migrating out of black shales, where they occur in high concentrations. These results lead to a general model for assessing migration. In addition, three shale types are identified on the basis of organic carbon and pyrolysis products and patterns.

Petrography and geochemistry of organic matter in Triassic and Cretaceous sediments from the Wombat and Exmouth Plateau

Triassic (Carnian-Rhaetian) continental margin sediments from the Wombat Plateau off northwest Australia (Sites 759, 760, 761, and 764) contain mainly detrital organic matter of terrestrial higher plant origin. Although deposited in a nearshore deltaic environment, little liptinitic material was preserved. The dominant vitrinites and inertinites are hydrogen-lean, and the small quantities of extractable bitumen contain w-alkanes and bacterial hopanoid hydrocarbons as the most dominant single gas-chromatography-amenable compounds. Lower Cretaceous sediments on the central Exmouth Plateau (Sites 762 and 763) farther south in general have an organic matter composition similar to that in the Wombat Plateau sediments with the exception of a smaller particle size of vitrinites and inertinites, indicating more distal transport and probably deposition in deeper water. Nevertheless, organic matter preservation is slightly better than in the Triassic sediments. Long-chain fatty acids, as well as aliphatic ketones and alcohols, are common constituents in the Lower Cretaceous sediments in addition to n-alkanes and hopanoid hydrocarbons. Thin, black shale layers at the Cenomanian/Turonian boundary, although present at several sites (Sites 762 and 763 on the Exmouth Plateau, Site 765 in the Argo Abyssal Plain, and Site 766 on the continental margin of the Gascoyne Abyssal Plain), are particularly enriched in organic matter only at Site 763 (up to 26%). These organic-matter-rich layers contain mainly bituminite of probable fecal-pellet origin. Considering the high organic carbon content, the moderate hydrogen indices of 350-450 milligrams of hydrocarbon-type material per gram of Corg, the maceral composition, and the low sedimentation rates in the middle Cretaceous, we suggest that these black shales were accumulated in an area of oxygen-depleted bottom-water mass (oceanwide reduced circulation?) underlying an oxygen-rich water column (in which most of the primary biomass other than fecal pellets is destroyed) and a zone of relatively high bioproductivity. Differences in organic matter accumulation at the Cenomanian/Turonian boundary at different sites off northwest Australia are ascribed to regional variations in primary bioproductivity.

Black shales from the Upper Aptian and Lower Albanian of the Volcontian Basin

Calcareous nannoplankton, palynomorph, benthic foraminifera, and oxygen isotope records from the supraregionally distributed Niveau Paquier (Early Albian age, Oceanic Anoxic Event 1b) and regionally distributed Niveau Kilian (Late Aptian age) black shales in the Vocontian Basin (SE France) exhibit variations that reflect paleoclimatic and paleoceanographic changes in the mid-Cretaceous low latitudes. To quantify surface water productivity and temperature changes, nutrient and temperature indices based on calcareous nannofossils were developed. The nutrient index strongly varies in the precessional band, whereas variations of the temperature index reflect eccentricity. Since polar ice caps were not present during the mid-Cretaceous, these variations probably result from feedback mechanisms within a monsoonal climate system of the mid-Cretaceous low latitudes involving warm/humid and cool/dry cycles. A model is proposed that explains the formation of mid-Cretaceous black shales through monsoonally driven changes in temperature and evaporation/precipitation patterns. The Lower Albian Niveau Paquier, which has a supraregional distribution, formed under extremely warm and humid conditions when monsoonal intensity was strongest. Bottom water ventilation in the Vocontian Basin was diminished, probably due to increased precipitation and reduced evaporation in regions of deep water formation at low latitudes. Surface water productivity in the Vocontian Basin was controlled by the strength of monsoonal winds. The Upper Aptian Niveau Kilian, which has a regional distribution only, formed under a less warm and humid climate than the Niveau Paquier. Low-latitude deep water formation was reduced to a lesser extent and/or on regional scale only. The threshold for the formation of a supraregional black shale was not reached. The intensity of increases in temperature and humidity controlled whether black shales developed on a regional or supraregional scale. At least in the Vocontian Basin, the increased preservation of organic matter at the sea floor was more significant in black shale formation than the role of enhanced productivity.

Contents and accumulation rates of the rare earth and some other elements in metalliferous sediments from DSDP Hole 92-598

The sediments recovered during DSDP Leg 92 (Site 598) include a complete 16 m.y. record of hydrothermal sedimentation along the western flank of the East Pacific Rise at 19°S. Fifty samples from this sediment column were analyzed to test the hypothesis that the REE composition of the hydrothermal component is primarily acquired via scavenging from seawater. Site 598 provides an ideal sample suite for this purpose: the sediments are lithologically "simple," primarily consisting of a mixture of hydrothermal materials and biogenous carbonates; the composition of the hydrothermal component is essentially constant through space and time; and the sediments have undergone minimal diagenetic alteration. The following observations suggest the above-stated hypothesis is true. The Ce anomaly as well as key indices of light and heavy REE behavior all show that the REE pattern of hydrothermal sediments approaches that of seawater with increasing paleodistance from the rise crest. Moreover, shale-normalized REE patterns are similar to that of seawater, varying only in absolute REE content: the REE content increases with distance from the paleo-rise crest and exhibits a pronounced increase in sediments deposited below the paleolysocline. Based on significant correlative relationships between paleodistance from the rise crest and both the concentration and mass accumulation rates (MARs) of REEs and Fe, we conclude the REEs in the hydrothermal component are derived from the interaction of seawater and Fe in the hydrothermal plume.

Cretaceous planktonic foraminifera of the Kerguelen Plateau

An almost complete Upper Cretaceous sedimentary sequence recently recovered on the Kerguelen Plateau (southern Indian Ocean) during ODP Leg 183 was analysed for planktonic foraminifera in order to refine and integrate the zonal schemes previously proposed for the Southern Ocean area. Detailed biostratigraphic analysis carried out on holes 1135A, 1136A and 1138A (poleward of 50°S palaeolatitude during Late Cretaceous time) has allowed recognition of low and mid-high latitude bioevents, useful for correlation across latitudes, in addition to known Austral bioevents. The low latitude biozonation can be applied to Turonian sediments, because of the occurrence of Helvetoglobotruncana helvetica, which marks the boundary between Whiteinella archaeocretacea and Helvetoglobotruncana helvetica zones. The base of the Whiteinella archeocretacea Zone falls within the uppermost Cenomanian-Turonian black shale level in Hole 1138A. The stratigraphic interval from upper Turonian to uppermost Santonian can be resolved using bioevents recognized in the mid-high latitude sections. They are, in stratigraphic order: the last occurrence of Falsotruncana maslakovae in the Coniacian, the first occurrence of Heterohelix papula at the Coniacian/Santonian boundary, the extinction of the marginotruncanids in the late Santonian, and the first occurrence of Globigerinelloides impensus in the latest (?) Santonian. The remainder of the Late Cretaceous fits rather well in the Austral zonal scheme, except that Globigerinelloides impensus exhibits a stratigraphic range in agreement with its record at the mid-high latitude sections and extends further downwards than previously recorded at southern sites. Therefore, despite the poor recovery in certain intervals and the presence of several hiatuses of local and regional importance as revealed by correlation among holes, a more detailed zonal scheme has been obtained (mainly for the less resolved Turonian-Santonian interval). Remarks on some species often overlooked in literature are also provided.

Stable oxygen isotope record and benthic foraminiferal abundances in Cretaceous sediments of Demerara Rise

During the mid-Cretaceous period, the global subsurface oceans were relatively warm, but the origins of the high temperatures are debated. One hypothesis suggests that high sea levels and the continental configuration allowed high-salinity waters in low-latitude epicontinental shelf seas to sink and form deep-water masses (Brass et al., 1982, doi:10.1038/296620a0; Arthur and Natland, 1979; Chamberlin, 1906). In another scenario, surface waters in high-latitude regions, the modern area of deep-water formation, were warmed through greenhouse forcing (Bice and Marotzke, 2001, doi:10.1029/2000JC000561), which then propagated through deep-water circulation. Here, we use oxygen isotopes and Mg/Ca ratios from benthic foraminifera to reconstruct intermediate-water conditions in the tropical proto-Atlantic Ocean from 97 to 92 Myr ago. According to our reconstruction, intermediate-water temperatures ranged between 20 and 25 °C, the warmest ever documented for depths of 500-1,000 m. Our record also reveals intervals of high-salinity conditions, which we suggest reflect an influx of saline water derived from epicontinental seas around the tropical proto-North Atlantic Ocean. Although derived from only one site, our data indicate the existence of warm, saline intermediate waters in this silled basin. This combination of warm saline intermediate waters and restricted palaeogeography probably acted as preconditioning factors for the prolonged period of anoxia and black-shale formation in the equatorial proto-North Atlantic Ocean during the Cretaceous period.

Late Cretaceous benthic foraminiferal assemblages from Demerara Rise, western tropical Atlantic

This paper is based on Santonian-Campanian sediments of Ocean Drilling Program Sites 1257 (2951 mbsl) and 1259 (2353 mbsl) from Demerara Rise (Leg 207, western tropical Atlantic, off Surinam). According to its position, Demerara Rise should have been influenced by the early opening of the Equatorial Atlantic Gateway and the establishment of a bottom-water connection between the central and South Atlantic Oceans during the Late Cretaceous. The investigated benthic foraminiferal faunas demonstrate strong fluctuations in bottom-water oxygenation and organic-matter flux to the sea-floor. The Santonian-earliest Campanian interval is characterised by laminated black shales without benthic foraminifera in the lowermost part, followed by an increasing number of benthic foraminifera. These are indicative of anoxic to dysoxic bottom waters, high organic-matter fluxes and a position within the oxygen minimum zone. At the shallower Site 1259, benthic foraminifera occurred earlier (Santonian) than at the deeper Site 1257 (Early Campanian). This suggests that the shallower site was characterised by fluctuations in the oxygen minimum zone and that a re-oxygenation of the sea-floor started considerably earlier at shallower water-depths. We speculate that this re-oxygenation was related to the ongoing opening of the Equatorial Atlantic Gateway. A condensed glauconitic chalk interval of Early Campanian age (Nannofossil Zone CC18 of Sissingh) overlies the laminated shales at both sites. This interval contains benthic foraminiferal faunas reflecting increasing bottom-water oxygenation and reduced organic-matter flux. This glauconitic chalk is strongly condensed and contains most of the Lower and mid-Campanian. Benthic foraminiferal species indicative of well-oxygenated and more oligotrophic environments characterise the overlying mid- to Upper Campanian nannofossil chalk. During deposition of the nannofossil chalk, a permanent deep-water connection between the central and South Atlantic Oceans is proposed, leading to ventilated and well-oxygenated bottom waters. If this speculation is true, the establishment of a permanent deep-water connection between the central and South Atlantic Oceans terminated Oceanic Anoxic Event 3 "black shale" formation in the central and South Atlantic marginal basins during the Early Campanian (Nannofossil Zone CC18) and led to well-oxygenated bottom waters in the entire Atlantic Ocean during the Late Campanian (at least from Nannofossil Zone CC22 onwards).

Zeolite and silica diagenesis and sandstone petrography at DSDP Sites 57-438 and 57-439

We detected authigenic clinoptilolites in two core samples of tuffaceous, siliceous mudstone in the lower Miocene section of Hole 439. They occur as prismatic and tabular crystals as long as 0.03 mm in various voids of dissolved glass shards, radiolarian shells, calcareous foraminifers, and calcareous algae. They are high in alkalies, especially Na, and in silica varieties. There is a slight difference in composition among them. The Si : (Al+ Fe3+) ratio is highest (4.65) in radiolarian voids, intermediate (4.34) in dissolved glass voids, and lowest (4.26) in voids of calcareous organisms. This difference corresponds to the association of authigenic silica minerals revealed by the scanning electron microscope: There are abundant opal-CT lepispheres in radiolarian voids, low cristobalite and some lepispheres in dissolved glass voids, and a lack of silica minerals in the voids of calcareous organisms. Although it contains some silica from biogenic opal and alkalies from trapped sea water, clinoptilolite derives principally from dissolved glass. Although they are scattered in core samples of Quaternary through lower Miocene diatomaceous and siliceous deposits, acidic glass fragments react with interstitial water to form clinoptilolite only at a sub-bottom depth of 935 meters at approximately 25°C. Analcimes occur in sand-sized clasts of altered acidic vitric tuff in the uppermost Oligocene sandstones. The analcimic tuff clasts were probably reworked from the Upper Cretaceous terrain adjacent to Site 439. Low cristobalite and opal-CT are found in tuffaceous, siliceous mudstone of the middle and lower Miocene sections at Sites 438 and 439. Low cristobalite derives from acidic volcanic glass and opal-CT from biogenic silica. Both siliceous organic remains and acidic glass fragments occur in sediments from the Quaternary through lower Miocene sections. However, the shallowest occurrence is at 700 meters subbottom in Hole 438A, where temperature is estimated to be 21°C. The d(101) spacing of opal-CT varies from 4.09 to 4.11 Å and that of low cristobalite from 4.04 to 4.06 Å. Some opal-CT lepispheres are precipitated onto clinoptilolites in the voids of radiolarian shells at a sub-bottom depth of 950 meters in Hole 439. Sandstone interlaminated with Upper Cretaceous shale is chlorite- calcite cemented and feldspathic. Sandstones in the uppermost Oligocene section are lithic graywacke and consist of large amounts of lithic clasts grouped into older sedimentary and weakly metamorphosed rocks, younger sedimentary rocks, and acidic volcanic rocks. The acidic volcanic clasts probably originated from the volcanic high, which supplied the basal conglomerate with dacite gravels. The older sedimentary and weakly metamorphosed rocks and green rock correspond to the lithologies of the lower Mesozoic to upper Paleozoic Sorachi Group, including the chert, limestone, and slate in south-central Hokkaido. However, the angular shape and coarseness of the clasts and the abundance of carbonate rock fragments indicate a nearby provenance, which is probably the southern offshore extension of the Sorachi Group. The younger sedimentary rocks, including mudstone, carbonaceous shale, and analcime-bearing tuff, correspond to the lithologies of the Upper Cretaceous strata in south-central Hokkaido. Their clasts were reworked from the southern offshore extension of the strata. Because of the discontinuity of the zeolite zoning due to burial diagenesis, an overburden several kilometers thick must have been denuded before the deposition of sediments in the early Oligocene.

Geochemical data from the USGS #1 Portland core, Canon City, Colorado

During the Cretaceous, widespread black shale deposition occurred during a series of Oceanic Anoxic Events (OAEs). Multiple processes are known to control the deposition of marine black shales, including changes in primary productivity, organic matter preservation, and dilution. OAEs offer an opportunity to evaluate the relative roles of these forcing factors. The youngest of these events-the Coniacian to Santonian OAE 3-resulted in a prolonged organic carbon burial event in shallow and restricted marine environments including the Western Interior Seaway. New high-resolution isotope, organic, and trace metal records from the latest Turonian to early Santonian Niobrara Formation are used to characterize the amount and composition of organic matter preserved, as well as the geochemical conditions under which it accumulated. Redox sensitive metals (Mo, Mn, and Re) indicate a gradual drawdown of oxygen leading into the abrupt onset of organic carbon-rich (up to 8%) deposition. High Hydrogen Indices (HI) and organic carbon to total nitrogen ratios (C:N) demonstrate that the elemental composition of preserved marine organic matter is distinct under different redox conditions. Local changes in d13C indicate that redox-controlled early diagenesis can also significantly alter d13Corg records. These results demonstrate that the development of anoxia is of primary importance in triggering the prolonged carbon burial in the Niobrara Formation. Sea level reconstructions, d18O results, and Mo/total organic carbon ratios suggest that stratification and enhanced bottom water restriction caused the drawdown of bottom water oxygen. Increased nutrients from benthic regeneration and/or continental runoff may have sustained primary productivity.