Climatic impact on Al, K, Sc and Ti in marine sediments: Evidence from ODP Site 1144, South China Sea

Al, K, Sc and Ti concentrations of the terrestrial material-dominant sediments from ODP site 1144 were reported. Comparison between the bulk and the acid-leached sediments indicates that about 20~30% of the Al, K and Sc in the bulk sediments are not hosted in terrestrial detritus, rather they are of authigenic origin. However, authigenic Ti is negligible. The results indicate that Ti rather than Al is the best proxy for terrestrial materials. Significant climate controls are displayed in the Al/Ti, K/Ti and Sc/Ti variation patterns both for the bulk and the acid leached sediments. Such variation patterns can be mainly accounted for in terms of climate change in their provenance areas in South China. Elevated Al/Ti, K/Ti and Sc/Ti ratios during interglacial periods indicate that chemical weathering then was stronger than during glacial periods, which might be related to a more humid climate in interglacial periods.

Radiocarbon ages, carbon and oxygen isotopes and Mg/Ca and Sr/Ca ratios of Globigerinoides in sediment core MD99-2203, Cape Hatteras

This study presents high-resolution foraminiferal-based sea surface temperature, sea surface salinity and upper water column stratification reconstructions off Cape Hatteras, a region sensitive to atmospheric and thermohaline circulation changes associated with the Gulf Stream. We focus on the last 10,000 years (10 ka) to study the surface hydrology changes under our current climate conditions and discuss the centennial to millennial time scale variability. We observed opposite evolutions between the conditions off Cape Hatteras and those south of Iceland, known today for the North Atlantic Oscillation pattern. We interpret the temperature and salinity changes in both regions as co-variation of activities of the subtropical and subpolar gyres. Around 8.3 ka and 5.2-3.5 ka, positive salinity anomalies are reconstructed off Cape Hatteras. We demonstrate, for the 5.2-3.5 ka period, that the salinity increase was caused by the cessation of the low salinity surface flow coming from the north. A northward displacement of the Gulf Stream, blocking the southbound low-salinity flow, concomitant to a reduced Meridional Overturning Circulation is the most likely scenario. Finally, wavelet transform analysis revealed a 1000-year period pacing the d18O signal over the early Holocene. This 1000-year frequency band is significantly coherent with the 1000-year frequency band of Total Solar Irradiance (TSI) between 9.5 ka and 7 ka and both signals are in phase over the rest of the studied period.

Geochemistry and radionuclide content of sediment and water samples obtained from the Ob and Irtysh river, Russia

This paper reports the results of the investigations of 2006-2007 on the distribution and migration forms of artificial radionuclides and chemical elements in the Ob-Irtysh water system. Three regions were studied. One of them is a local segment of the Ob River upstream from the confluence with the Irtysh River; its investigation allowed us to estimate the general radioecological state of the aquatic environment affected by the activity of the Tomsk 7 plant. The second region is a local segment of the Irtysh River upstream from its confluence with the Ob River, where the influence of emissions from the NPO Mayak could be estimated. The third region is the water area of the Ob River after its confluence with the Irtysh River. It characterizes the real level of radioactive and chemical contamination of the middle reaches of the Ob River. In order to explain horizontal variations in the distribution of radionuclides in the upper layer of bottom sediments collected at various sites, the results of sorption-kinetic experiments with radioactive tracers in the precipitate-solution system were used. The investigation of the migration forms of trace elements and radionuclides occurring in river water was based on the method of tangential-flow membrane filtration. Chemical element contents were determined in 400-ml water samples. A set of Millipore polysulfone membranes with pore sizes of 8, 1.2, 0.45, 0.1, and 0.025 µm was employed. Taking into account the ultralow specific concentrations of radionuclides in the water, they were analyzed in 300-500 litre samples using Millipore polysulfone membranes with pore sizes of 0.45 µm and 15 kDa. This allowed us to estimate the percentages of cesium-137 and plutonium-239, 240 in the suspended particulate fraction, colloids, and dissolved species.

Whole rock geochemistry and stable isotopes of rocks, fragments and foraminifers from two ODP Leg 166 holes

Total carbon and carbonate contents, quantitative carbonate mineralogy, trace metal concentrations, and stable isotope compositions were determined on a suite of samples from the Miocene sections at Sites 1006 and 1007. The Miocene section at Site 1007, located at the toe-of-slope, contains a relatively high proportion of bank-derived components and becomes fully lithified at a depth of ~300 meters below seafloor (mbsf). By contrast, Miocene sediments at Site 1006, situated in Neogene drift deposits in the Straits of Florida and composed primarily of pelagic carbonates, do not become fully lithified until a depth of ~675 mbsf. Diagenetic and compositional contrasts between Sites 1006 and 1007 are reflected in geochemical data derived from sediment samples from each site.

Major oxides, trace elements and rare earth elements of selected basalt samples at DSDP Hole 83-504B

DSDP Hole 504B is the deepest section drilled into oceanic basement, penetrating through a 571.5-m lava pile and a 209-m transition zone of lavas and dikes into 295 m of a sheeted dike complex. To define the basement composition 194 samples of least altered basalts, representing all lithologic units, were analyzed for their major and 26 trace elements. As is evident from the alteration-sensitive indicators H2O+, CO2, S, K, Mn, Zn, Cu, and the iron oxidation ratio, all rocks recovered are chemically altered to some extent. Downhole variation in these parameters enables us to distinguish five depth-related alteration zones that closely correlate with changes in alteration mineralogy. Alteration in the uppermost basement portion is characterized by pronounced K-uptake, sulfur loss, and iron oxidation and clearly demonstrates low-temperature seawater interaction. A very spectacular type of alteration is confined to the depth range from 910 to 1059 m below seafloor (BSF). Rocks from this basement portion exhibit the lowest iron oxidation, the highest H2O+ contents, and a considerable enrichment in Mn, S, Zn, and Cu. At the top of this zone a stockwork-like sulfide mineralization occurs. The chemical data suggest that this basement portion was at one time within a hydrothermal upflow zone. The steep gradient in alteration chemistry above this zone and the ore precipitation are interpreted as the result of mixing of the upflowing hydrothermal fluids with lower-temperature solutions circulating in the lava pile. Despite the chemical alteration the primary composition and variation of the rocks can be reliably established. All data demonstrate that the pillow lavas and the dikes are remarkably uniform and display almost the same range of variation. A general characteristic of the rocks that classify as olivine tholeiites is their high MgO contents (up to 10.5 wt.%) and their low K abundances (-200 ppm). According to their mg-values, which range from 0.60 to 0.74, most basalts appear to have undergone some high-level crystal fractionation. Despite the overall similarity in composition, there are two major basalt groups that have significantly different abundances and ratios of incompatible elements at similar mg-values. The majority of the basalts from the pillow lava and dike sections are chemically closely related, and most probably represent differentiation products of a common parental magma. They are low in Na2O, TiO2, and P2O5, and very low in the more hygromagmaphile elements. Interdigitated with this basalt group is a very rarely occurring basalt that is higher in Na2O, TiO2, P2O5, much less depleted in hygromagmaphile elements, and similar to normal mid-ocean ridge basalt (MORB). The latter is restricted to Lithologic Units 5 and 36 of the pillow lava section and Lithologic Unit 83 of the dike section. The two basalt groups cannot be related by differentiation processes but have to be regarded as products of two different parental magmas. The compositional uniformity of the majority of the basalts suggests that the magma chamber beneath the Costa Rica Rift reached nearly steady-state conditions. However, the presence of lavas and dikes that crystallized from a different parental magma requires the existence of a separate conduit-magma chamber system for these melts. Occasionally mixing between the two magma types appears to have occurred. The chemical characteristics of the two magma types imply some heterogeneity in the mantle source underlying the Costa Rica Rift. The predominant magma type represents an extremely depleted source, whereas the rare magma type presumably originated from regions of less depleted mantle material (relict or affected by metasomatism).

Element concentrations, and Sr and Os isotope ratios of DSDP Leg 92 metalliferous carbonates

The Os concentration and isotopic composition of metalliferous carbonates deposited on the East Pacific Rise over the past 28 Ma are reported with complimentary Sr isotope data. Variations in the Os isotopic composition of these samples are interpreted as a record of past changes in the Os isotopic composition of seawater. These results are consistent with isotopic analyses of leachable Os in pelagic clays which have also been interpreted as a record of the 187Os/186Os ratio of seawater through time (Pegram et al., 1992, doi:10.1016/0012-821X(92)90132-F). The metalliferous carbonate record clearly shows that seawater Os and Sr isotope systems are partially decoupled from one another over the past 28 Ma. Accelerated weathering of ancient organic-rich sediments is suggested as a possible mechanism to account for this decoupling and the rapid increase in the 187Os//186Os ratio of seawater over the past 15 Ma. This rapid increase suggests that the seawater Os record can potentially be used as a stratigraphic tool in some Neogene marine deposits.

Chemical and Sr isotopic compositions of 3 step leachates and residues of bulk samples, zeolites, and smectites from Lower Miocene sediments at ODP Site 166-1007

Massive clinoptilolite authigenesis was observed at about 1105 meters below sea floor (mbsf) in lower Miocene wellcompacted carbonate periplatform sediments from the Great Bahama Bank [Ocean Drilling Program, ODP Leg 166, Site 1007]. The diagenetic assemblage comprises abundant zeolite crystallized within foraminifer tests and sedimentary matrix, as well as Mg smectites. In carbonate-rich deposits, the formation of the zeolite requires a supply of silica. Thus, the objective of the study is to determine the origin of the silica supply, its diagenetic evolution, and consequently the related implications on interpretation of the sedimentary record, in terms of local or global paleoceanographic change. For lack of evidence for any volcaniclastic input or traces of Si-enriched deep fluids circulation, an in situ biogenic source of silica is validated by isotopic data and chemical modeling for the formation of such secondary minerals in shallow-water carbonate sequences. Geochemical and strontium isotopic data clearly establish the marine signature of the diagenetic zeolite, as well as its contemporaneous formation with the carbonate deposition (Sr model ages of 19.6-23.2 Ma). The test of saturation for the pore fluids specifies the equilibrium state of the present mineralogical assemblage. Seawater-rock modeling specifies that clinoptilolite precipitates from the dissolution of biogenic silica, which reacts with clay minerals. The amount of silica (opal-A) involved in the reaction has to be significant enough, at least 10 wt.%, to account for the observed content of clinoptilolite occurring at the most zeolite-rich level. Modeling also shows that the observed amount of clinoptilolite (~19%) reflects an in situ and short-term reaction due to the high reactivity of primary biogenic silica (opal-A) until its complete depletion. The episodic occurrence of these well-lithified zeolite-rich levels is consistent with the occurrence of seismic reflectors, particularly the P2 seismic sequence boundary located at 1115 mbsf depth and dated as 23.2 Ma. The age range of most zeolitic sedimentary levels (biostratigraphic ages of 21.5-22 Ma) correlates well with that of the early Miocene glaciation Mi-1 and Mi-1a global events. Thus, the clinoptilolite occurrence in the shallow carbonate platform environment far from volcanogenic supply, or in other sensitive marine areas, is potentially a significant new proxy for paleoproductivity and oceanic global events, such as the Miocene events, which are usually recognized in deep-sea pelagic sediments and high latitude deposits.

Geochemical composition of sediments from ODP Site 164-997, Blake Ridge

Twenty-two trace elements in 355 sediment samples from Site 997 on the Blake Ridge were examined by inductively coupled plasma-optical emission spectrometry and inductively coupled plasma-mass spectrometry, for respective fractions of acid-soluble and insoluble compositions. Downhole profiles of these elements exhibit complicated fluctuations throughout late Miocene to Pleistocene, principally due to the variations in the acid-soluble fraction. Noncarbonate composition is given from the acid-insoluble residues, which permits us to recognize secular feature of selected element variance for four intervals. These intervals (I: 0-183 mbsf; II: 183- 440 mbsf; III: 440-618 mbsf; and IV: 618-750 mbsf) are interpreted to have originated from changes in the suite of sediments of particular sources and chemical composition, sedimentation rate, dilution of biogenic carbonate abundance, and possibly the current system that controlled deposition and reworking of the terrigenous materials.

Chemical and isotope compositions of bottom sediments from ODP Leg 168, Eastern Flank of the Juan de Fuca Ridge

Ten sites were drilled in the eastern flank of the Juan de Fuca Ridge (North East Pacific) along a 100 km-long east-west transect during Leg ODP 168. This study focuses on the mineralogical and chemical study of sediments that overly basaltic basement through which seawater circulates. Silicate authigenesis was observed in the sediment layer just above basement at sites located more than 30 km from the ridge axis. This sediment alteration is particularly abundant at ODP Sites 1031 and 1029 where authigenic formation of Fe-Mg rich smectite and zeolite and the dissolution of biogenic calcite are observed. Comparison of the distribution of the alteration in the basal sediment collected along this transect suggests that diffusional transport of aqueous solutes from the basement into the overlying sediment cannot produce the mineralogical and chemical changes in the basal sediments at Sites 1031 located on a basement topographic high, and at Site 1029 located at about 50 km from the ridge axis on a buried basement area. Vertical advection of basement fluid though the sediment section is required to produce this alteration. These processes are still active at Site 1031, based on systematic variations in pore-water profiles and temperatures obtained from stable isotopic data on calcium carbonates and the nature of authigenic minerals. At Site 1029, there is no present-day advection of basement fluids though the sediment section, suggesting that this is a relic site for fluid flow.

Pore-water chemistry of abyssal Arabian Sea surface sediments

Benthic fluxes and pore-water compositions of silicic acid, nitrate and phosphate were investigated for surface sediments of the abyssal Arabian Sea during four cruises (1995-1998). Five sites located in the northern (NAST), western (WAST), central (CAST), eastern (EAST), and southern (SAST) Arabian Sea were revisited during intermonsoonal periods after the NE- and SW-Monsoon. At these sites, benthic fluxes of remineralized nutrients from the sediment to the bottom water of 36-106, 102-350 and 4-16 mmol/m**2/yr were measured for nitrate, silicic acid and phosphate, respectively. The benthic fluxes and pore-water compositions showed a distinct regional pattern. Highest fluxes were observed in the western and northern region of the Arabian Sea, whereas decreasing fluxes were derived towards the southeast. At WAST, the general temporal pattern of primary production, related to the NE- and SW-Monsoon, is reflected by benthic fluxes. In contrast, at sites NAST, SAST, CAST, and EAST a temporal pattern of fluxes in response to the monsoon is not obvious. Our results reveal a clear coupling between the general regional pattern of production in surface waters and the response of the benthic environment, as indicated by the flux of remineralized nutrients, though a spatially differing degree of decoupling during transport and remineralization of particulate organic matter and biogenic opal was observed. This has to be taken into account regarding budget calculations and paleoceanographic topics.