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

Geochemistry, isotopic ratios and mineral composition of samples from ODP Leg 163 sites

Thirty-five samples from the drill core of the three Leg 163 sites (Sites 988, 989, and 990) off the southeast coast of Greenland were analyzed for 27 major, minor, and trace elements by X-ray fluorescence (XRF) and for 25 trace elements, including 14 rare-earth elements (REEs), by an inductively coupled plasma source mass spectrometer (ICP/MS). Sr- and Nd-isotope data are reported for seven samples and oxygen-isotope data are reported for 19 plagioclase separates. In addition, a reconnaissance survey of the composition of the main mineral phases, plagioclase, pyroxene, and oxides was determined on an electron microprobe to provide the basic information required for petrogenetic modeling. Olivine pseudomorphs are present in many of the samples, but in no case was an olivine grain found that was fresh enough to give a reliable analysis. The chemical and isotopic data recorded here were determined to provide a comparison with the larger data sets acquired by the Edinburgh, Copenhagen, and Leicester laboratories from both Legs 152 and 163 drill cores. This will permit a detailed comparison of the North Atlantic flood basalt province as a whole with the better known Columbia River, Deccan, and Karoo continental flood basalt provinces, for which substantial chemical data sets are already available at Washington State University.

Interstitial water d13C and sediment geochemistry of ODP Leg 166 sites

A review of interstitial water samples collected from Sites 1003-1007 of the Bahamas Transect along with a shore-based analysis of oxygen and carbon isotopes, minor and trace elements, and sediment chemistry are presented. Results indicate that the pore-fluid profiles in the upper 100 meters below seafloor (mbsf) are marked by shifts between 20 and 40 mbsf that are thought to be caused by changes in sediment reactivity, sedimentation rates, and the influence of strong bottom currents that have been active since the late Pliocene. Pore-fluid profiles in the lower Pliocene-Miocene sequences are dominated by diffusion and do not show significant evidence of subsurface advective flow. Deeper interstitial waters are believed to be the in situ fluids that have evolved through interaction with sediments and diffusion. Pore-fluid chemistry is strongly influenced by carbonate recrystallization processes. Increases in pore-fluid Cl- and Na+ with depth are interpreted to result mainly from carbonate remineralization reactions that are most active near the platform margin. A lateral gradient in detrital clay content observed along the transect, leads to an overall lower carbonate reactivity, and enhances preservation of metastable aragonite further away from the platform margin. Later stage burial diagenesis occurs at slow rates and is limited by the supply of reactive elements through diffusion.

Geochemistry of felsic rocks and minerals of ODP Hole 135-841B

A felsic volcanic series (605-825 mbsf) overlain by upper Eocene shallow-water sediments (500-605 mbsf) and basalticandesitic sills that intruded into sediments of Holocene to Miocene age (0-500 mbsf) was drilled in the forearc region of the Lau Basin at a water depth of 4810 m. The volcanic sequence at Site 841 includes altered and mineralized calc-alkaline rhyolites and dacites, dacitic tuffs, lapilli tuffs, flow breccias, and welded tuffs. These rocks formed subaerially or in a very shallow-water environment suffering a subsidence of >5000 m since Eocene times. Calculations of gains and losses of the major components during alteration show most pronounced changes in the uppermost 70 m of the volcanic sequence. Here, Al, Fe, Mg, and K are enriched, whereas Si and Na are strongly depleted. Illite, vermiculite, chlorite, and hematite predominate in this part of the hole. Throughout the section, quartz, plagioclase, kaolinite, and calcite are present. Sulfide mineralization (up to 10 vol%) consisting mainly of disseminated pyrite (with minor pyrrhotite inclusions) and marcasite together with minor amounts of chalcopyrite is pervasive throughout. Locally, a few sulfide-bearing quartz-carbonate veins as well as Ti-amphibole replacement by rutile and then by pyrite were observed. Strong variations in the As content of sulfides (from 0 to 0.69 wt%) from the same depth interval and local enrichments of Co, Ni, and Cu in pyrite are interpreted to result from fluctuations in fluid composition. Calculations of oxygen and sulfur fugacities indicate that fO2 and fS2 were high at the top and lower at the bottom of the sequence. Sulfur isotope determinations on separated pyrite grains from two samples give d34S values of +6.4ë and +8.4ë, which are close to those reported from Kuroko and Okinawa Trough massive sulfide deposits and calc-alkaline volcanic rocks of the Japanese Ryukyu Island Arc. Calculated chlorite formation temperatures of 265°-290°C at the top of the sequence are consistent with minimum formation temperatures of fluid inclusions in secondary quartz, revealing a narrow range of 270°-297°C. Chlorite formation temperatures are constant downhole and do not exceed 300°C. The presence of marcasite and 4C-type pyrrhotite indicates a formation temperature of <= 250°C. At a later stage, illite was formed at the top of the volcanic series at temperatures well below 200°C.

Geochemistry of the volcanic basement of ODP Hole 134-831B

The basement of Bougainville Guyot drilled at Site 831 consists of andesitic hyalobreccias derived from a submarine arc volcano. The volcanic sequence has been dated by K/Ar at approximately 37 Ma. The 121 m of andesitic hyalobreccias drilled in Hole 831B have been divided into five subunits of two types: one appears to be primary, and the other contains evidence of reworking and a subaerial clastic input. Variations are attributed to fluctuations in water depth. The distinctive hyalobreccias consist of andesitic blebs with chilled margins and peripheral fractures set in a chaotic greenish matrix that is mainly altered glass, with crystals similar to those in the blebs or clasts. Their formation is attributed to violent reaction of andesitic magma discharged into seawater, in perhaps the submarine equivalent of fire-fountaining. There was limited reworking by currents and debris flows on the flanks of the submarine volcano. The andesite shows no significant compositional variation in phenocryst phases throughout the drilled sequence and contains phenocrysts of plagioclase (An88-43), clinopyroxene (Ca44Mg46Fe10-Ca41Mg40Fe19), orthopyroxene (Ca4Mg79Fe17-Ca3Mg58Fe39), and titanomagnetite. There is a systematic change in volcanic composition with height in the section, from more mafic andesites at the base, to overlying more acid andesites, and strong evidence exists that magma mixing may have played a significant role in the genesis of these lavas. The andesites have affinities with the low-K arc tholeiite series. Trace element and isotopic systematics for these rocks indicate very minor involvement of a LILE- and 87Sr-enriched slab-derived fluid in their petrogenesis. This accords with the previous suggestion that Bougainville Guyot forms part of an Eocene proto-island arc developed along the southern side of the d'Entrecasteaux Zone, above a southward-dipping subduction zone.

Physico-chemical parameters of sediment core PG1972-1 (09-Tik-03) from a Tundra Lake, Northeastern Siberia

Thermokarst lakes in the Siberian Arctic contain sediment archives that can be used for paleoenvironmental inference. Until now, however, there has been no study from the inner Lena River Delta with a focus on diatoms. The objective of this study was to investigate how the diatom community in a thermokarst lake responded to past limnogeological changes and what specific factors drove variations in the diatom assemblage. We analysed fossil diatom species, organic content, grain-size distribution and elemental composition in a sediment core retrieved in 2009 from a shallow thermokarst lake in the Arga Complex, western Lena River Delta. The core contains a 3,000-year record of sediment accumulation. Shifts in the predominantly benthic and epiphytic diatom species composition parallel changes in sediment characteristics. Paleoenvironmental and limnogeological development, inferred from multiple biological and sedimentological variables, are discussed in the context of four diatom zones, and indicate a strong relation between changes in the diatom assemblage and thermokarst processes. We conclude that limnogeological and thermokarst processes such as lake drainage, rather than direct climate forcing, were the main factors that altered the aquatic ecosystem by influencing, for example, habitat availability, hydrochemistry, and water level.

Mineralogy and diagenesis of slope sediments at DSDP Leg 84 holes

The distribution and composition of minerals in the silt and clay fraction of the fine-grained slope sediments were examined. Special interest was focused on diagenesis. The results are listed as follows. (1) Smectite, andesitic Plagioclase, quartz, and low-Mg calcite are the main mineral components of the sediment. Authigenic dolomite was observed in the weathering zones of serpentinites, together with aragonite, as well as in clayey silt. (2) The mineralogy and geochemistry of the sediments is analogous to that of the andesitic rocks of Costa Rica and Guatemala. (3) Unstable components like volcanic glass, amphiboles, and pyroxenes show increasing etching with depth. (4) The diagenetic alteration of opal-A skeletons from etching pits and replacement by opal-CT to replacement by chalcedony as a final stage corresponds to the typical opal diagenesis. (5) Clinoptilolite is the stable zeolite mineral according to mineral stability fields; its neoformation is well documented. (6) The early diagenesis of smectites is shown by an increase of crystallinity with depth. Only the smectites in the oldest sediments (Oligocene and early Eocene) contain nonexpanding illite layers.

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.