Geochemistry of altered smectites

In basalts and volcanogenic sediments from the Indian Ocean, the successive stages of submarine alteration of volcanic rocks and glasses give rise to the incorporation or the relative increase of iron in smectite lattices. During the first stage, the Mg-smectites are the most abundant; they are occasionally associated with Al-smectites. Afterwards, they are gradually replaced by iron-rich smectites. The REE distribution follows the same trend as the mineralogical changes. During the f'trst stage of alteration, REE distribution in clay minerals is the same as in the fresh glasses but, when the iron-rich smectites increase, the Ce has a specific behaviour. The Ce shows a positive anomaly in iron-rich smectites formed early in palagonitized glasses, and a negative one in authigenic smectites formed later from solutions in equilibrium with seawater.

Elemental and stable isotopic composition of some metalliferous and pelagic sediments at DSDP Leg 70 Holes

Nontronite, the main metalliferous phase of the Galapagos mounds, occurs at subsurface depths of about 2 to 20 meters; Mn-oxide material is limited to the upper 2 meters of the mounds. The nontronite forms intervals of up to a few meters' thickness, consisting essentially of 100% nontronite granules, which alternate with intervals of normal pelagic sediment. Electron microprobe analyses of nontronite granules from different core samples indicate that: (1) there is little difference in major element composition between nontronites from varying locations within the mounds, with adjacent granules from a given sample having very similar compositions; (2) individual granules show little internal variation in composition. This indicates that the granules are composed of a single mineral of essentially constant composition, consistent with relatively uniform conditions of Eh and composition during nontronite formation. Mn-oxide crusts have very low Fe contents, a feature characteristic of rapidly deposited Mn-oxide crusts formed under hydrothermal influences. The rare-earth element (REE) abundances of the nontronites are generally extremely low, totalling less than several ppm. Two samples have the negatively Ce anomaly typical of authigenic precipitates formed relatively rapidly from seawater. A Mn-oxide crust sample has low REE contents, typical of Mn-oxide crusts formed under hydrothermal influences, but no negative Ce anomaly. A sample of unusual Mn-Fe-oxide mud has relatively high REE concentrations and a seawater-type pattern; both of these features are also found for metalliferous sediments from the East Pacific Rise. The oxygen and hydrogen isotopic composition of the nontronites define a restricted field within a d18O-dD plot. In manganiferous sediments, d18O and dD appear to decrease with increase in the Mn-oxide content of the sediment. From the d18O values of the nontronites, formation temperatures in the range of about 20-30°C have been estimated. By comparison, temperatures of up to 11.5 °C at a 9-meter depth have been directly measured within the mounds (Corliss et al., 1979), and heat-flow data suggest present basement/sediment interface temperatures of 15-25°C. In a plot of Fe + Mn vs. d18O, the Mn-oxide crust and Mn-Fe-ooze plot near the tie-lines for authigenic Mn nodules and silicate phases, implying that they have formed in isotopic equilibrium with seawater at or close to bottom-water temperatures.

Geochemistry at DSDP Leg 60

Eocene to Pleistocene volcanogenic sediments from the Mariana Trough and the Mariana arc-trench system have been studied by X-ray diffraction, X-ray fluorescence, and atomic absorption, and with a scanning electron microscope with an X-ray-energy-dispersive attachment. The mineralogical composition of the volcaniclastic sediments (tuffs) is the same as that of the other associated sediments (mudstones). Diagenetic alterations are significant and seem to result from two processes. The first (low-temperature alteration) develops with age and depth; it consists of the genesis of pure smectite, coupled with zeolites (phillipsite, clinoptilolite). The second is limited to sediments immediately overlying basalts and to the altered basalts themselves. It consists of the massive development of palygorskite, and seems to be linked with hydrothermal activity in the igneous basement.

Siliceous components of Pliocene-Holocene sediments of the South Atlantic

The Pliocene-Holocene sediments recovered on ODP Leg 114 from Holes 699A, 701C, and 704B are the subject of a detailed investigation to interpret changes in the Oceanographic environment of the South Atlantic in the vicinity of the Polar Front Zone (PFZ). The cores sample sediments at shallow (Hole 704B, 2532 m), intermediate (Hole 699A, 3716 m), and basinal (Hole 701C, 4647 m) depths. Sites 699 and 704 come under the influence of the Antarctic Circumpolar Current (ACC) and Circumpolar Deep Water. It is possible that the upper reaches of Antarctic Bottom Water (AABW) may also affect Hole 699A. Site 701 is influenced by AABW. Closely spaced samples were analyzed for grain-size distribution, sand fraction components, biosiliceous microfossils, organic carbon, and water content. PFZ migrations are traced using changes in bulk sedimentaccumulation rates and the abundance of the diatoms Actiniscus ssp. and Genus et species indet. 1 Fenner (1991), as well as changes in sediment grain size and composition. Diatomaceous sediments of Gilbert age in Hole 699A indicate that the PFZ was positioned over this site, but during the Gauss it migrated north, bringing in less productive Antarctic Surface Water. All cores document a very gradual southerly movement of the PFZ throughout the Matuyama (with some sharp fluctuations of the northen PFZ border over Site 704 between 1.45 and 1.83 m.y.). This regressive shift culminated in the late Matuyama. The latest Matuyama to earliest Brunhes record in Hole 699A has been removed by a hiatus lasting from 1.0 to 0.6 m.y., which was probably caused by intensification of the deep-reaching ACC. The corresponding interval in Hole 704B, the shallowest core, contains evidence of winnowing. Sharp fluctuations of large amplitude and high frequency in the lithology of the sediments from Hole 704B in the eastern South Atlantic, starting at about 0.75 m.y. and characterizing the whole Brunhes Epoch, record the rapid movement of the northern border of the PFZ over the site. These reflect strong glacial/interglacial alternations in climate. To a lesser extent, lithologic fluctuations in Hole 701C reflect the same phenomenon, whereas in Hole 699A the lithology does not vary as dramatically.

Concentrations and accumulation rates of chemical elements and sediment components in sediments of central equatorial Pacific, DSDP data

Accumulation rates of Mg, Al, Si, Mn, Fe, Ni, Cu, Zn, opal, and calcium carbonate have been calculated from their concentrations in samples from equatorial Deep Sea Drilling Project sites. Maps of element accumulation rates and of Q-mode factors derived from raw data indicate that the flux of trace metals to equatorial Pacific sediments has varied markedly through time and space in response to changes in the relative and absolute influence of several depositional influences: biogenic, detrital, authigenic, and hydrothermal sedimentation. Biologically derived material dominates the sediment of the equatorial Pacific. The distributions of Cu and Zn are most influenced by surface-water biological activity, but Ni, Al, Fe, and Mn are also incorporated into biological material. All of these elements have equatorial accumulation maxima similar to those of opal and calcium carbonate at times during the past 50 m.y. Detritus distributed by trade winds and equatorial surface circulation contributes Al, non-biogenic Si, Fe, and Mg to the region. Detrital sediment is most important in areas with a small supply of biogenic debris and low bulk-accumulation rates. Al accumulation generally increases toward the north and east, indicating its continental source and distribution by the northeast trade winds. Maxima in biological productivity during middle Eocene and latest Miocene to early Pliocene time and concomitant well-developed surface circulation contributed toward temporal maxima in the accumulation rates of Cu, Zn, Ni, and Al in sediments of those ages. Authigenic material is also important only where bulk-sediment accumulation rates are low. Ni, Cu, Zn, and sometimes Mn are associated with this sediment. Fe is almost entirely of hydrothermal origin. Mn is primarily hydrothermal, but some is probably scavenged from sea water by amorphous iron hydroxide floes along with other elements concentrated in hydrothermal sediments, Ni, Cu, and Zn. During the past 50 m.y. all of these elements accumulated over the East Pacific Rise at rates nearly an order of magnitude higher than those at non-rise-crest sites. In addition, factor analysis indicates that some of this material is carried substantial distances to the west of the rise crest. Accumulation rates of Fe in basal metalliferous sediments indicate that the hydrothermal activity that supplied amorphous Fe oxides to the East Pacific Rise areas was most intense during middle Eocene and late Miocene to early Pliocene time.

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.

Carbonat-free sediment components of ODP Leg 115 holes

From the equatorial Indian Ocean, carbonate-free portions of sediment samples of Paleocene to Miocene calcareous oozes and chalks from Sites 707, 709, and 711 were studied using X-ray diffraction measurements and the scanning electron microscope. Downhole variations in biogenic opal, quartz, barite, and clinoptilolite were investigated. The abundance patterns of these major mineral phases show several similarities and may be used for additional lithologic correlations. Variations in biogenic opal contents reflect biogenic silica productivity. Beside the general pattern, a succession in biogenic silica decrease through time is generally recorded since the Oligocene. This succession started earliest at northernmost Site 711 and latest at southernmost Site 707, including Site 709 within these two. Opal-A variations as well as the barite distribution may be influenced by the paleoposition of the sites in relation to the high-productivity zone, which today lies south of the equator. Authigenic clinoptilolite apparently formed in two different modes. In deeper sediment intervals, clinoptilolite was the last mineral phase formed associated with enhanced silica diagenesis. In late Oligocene to middle Miocene sediments, clinoptilolite was the only authigenic silica phase encountered where otherwise strong opal dissolution was observed. The sponge spicules showed special dissolution features probably related to microbiological activity. Silica concretions mainly composed of opal-CT and authigenic quartz occur in carbonate-rich environments and are formed during later diagenesis when burial depth causes the sediments to reach higher temperatures. Opal-CT concretions in carbonate-free siliceous oozes were found at Site 711 and are probably formed during an early stage of silica diagenesis.

Clay mineralogy of Cape Roberts sediment cores

The clay mineral assemblages of the ca. 1600 m thick Cenozoic sedimentary succession recovered at the CRP-1, CRP-2/2A and CRP-3 drill sites off Cape Roberts on the McMurdo Sound shelf, Antarctica, were analysed in order to reconstruct the palaeoclimate and the glacial history of this part of Antarctica. The sequence can be subdivided into seven clay mineral units that reflect the transition from humid to subpolar and polar conditions. Unit I (35-33.6 Ma) is characterised by an almost monomineralic assemblage consisting of well crystalline, authigenic smectite, and therefore does not allow a palaeoclimatic reconstruction. Unit II (33.6-33.1 Ma) has also a monomineralic clay mineral composition. However, the assemblage consists of variably crystallized smectite that, at least in part, is of detrital origin and indicates chemical weathering under a humid climate. The main source area for the clays was in the Transantarctic Mountains. Minor amounts of illite and chlorite appear for the first time in Unit III (33.1-31 Ma) and suggest subordinate physical weathering. The sediments of Unit IV (31-30.5 Ma) have strongly variable smectite and illite concentrations indicating an alternation of chemical weathering periods and physical weathering periods. Unit V (30.5-24.2 Ma) shows a further shift towards physical weathering. Unit VI (24.2-18.5 Ma) indicates strong physical weathering under a cold climate with persistent and intense illite formation. Unit VII (18.5 Ma to present) documents an additional input of smectite derived from the McMurdo Volcanic Group in the south.

Composition and distribution of silica in sediments of the Broken Ridge

Within a dipping sequence of middle Cretaceous to Eocene sediments on Broken Ridge, opal-A, opal-CT, and quartz occur as minor constituents in carbonate and ash-rich sediments. Biogenic opal-A is mainly derived from diatoms and radiolarians. Opal-A and almost all siliceous microfossils disappear within a narrow (<20-m-thick) transition zone below which authigenic opal-CT and quartz are present. These latter silica polymorphs occur together within a 750-m-thick interval, but the ratio of quartz/opal-CT increases with increasing age and depth within the pre-rift sediment sequence. The boundary between opal-A- and opal-CT-bearing sediments is also a physical boundary at which density, P-wave velocity, and acoustic impedance change. This physical transition is probably caused by infilling of pore space by opal-CT lepispheres.

Chemical and Sr isotopic compositions and timing of carbonate mineral precipitation, ODP Leg 115

The strontium isotope ratios of authigenic carbonates from Indian Ocean sea-floor basalts have been used to determine the timing of carbonate mineral precipitation and fluid flow. The samples include calcites from 57.2 Ma crust from Ocean Drilling Project (ODP) Site 715, and calcites, aragonites, and siderites from 63.7 Ma crust from ODP Site 707. At Site 715, calcite precipitation may have begun at any time after the basalts cooled, and it continued until approximately 31 Ma, or 26 m.y. after basalt eruption. At Site 707, aragonite and siderite did not begin to precipitate until about 36 Ma, almost 30 m.y. after basalt eruption, and continued to precipitate until at least 30 and 28 Ma, respectively. Calcite precipitation began at approximately 32 Ma and continued until 22 Ma. These ages suggest that vein mineral deposition and low-temperature fluid circulation in the ocean crust may continue for much longer periods of time than previously observed.

Radioisotopes and He accumulation in deep sea sediments of the Ontong Java Plateau

The accumulation of extraterrestrial 3He, a tracer for interplanetary dust particles (IDPs), in sediments from the Ontong Java Plateau (OJP; western equatorial Pacific Ocean) has been shown previously to exhibit a regular cyclicity during the late Pleistocene, with a period of ~100 ka. Those results have been interpreted to reflect periodic variability in the global accretion of IDPs that, in turn, has been linked to changes in the inclination of Earth's orbit with respect to the invariable plane of the solar system. Here we show that the accumulation in OJP sediments of authigenic 230Th, produced by radioactive decay of 234U in seawater, exhibits a 100-ka cyclicity similar in phase and amplitude to that evident in the 3He record. We interpret the similar patterns of 230Th and 3He accumulation to reflect a common origin within the ocean-climate system. Comparing spatial and temporal patterns of sediment accumulation against regional patterns of biological productivity and against the well-established pattern of CaCO3 dissolution in the deep Pacific Ocean leads to the further conclusion that a common 100-ka cycle in accumulation of biogenic, authigenic and extraterrestrial constituents in OJP sediments reflects the influence of climate-related changes in sediment focusing, rather than changes in the rate of production or supply of sedimentary constituents.

Isotope composition of sulfur, oxygen and carbon in Black Sea sediments

Inversion of isotopic composition in the SO4(2-)-H2S system is shown to be universal in Neoeuxine sediments and an explanation of its occurrence is proposed. Change in isotopic composition of sulfate sulfur in Black Sea waters over last 10-15 thousand years is reconstructed. Periods of alteration between aerobic and anaerobic situations are identified, the beginning of entry of Mediterranean waters into the basin is dated, presence of authigenic carbonates in sediments of the sea is established and amounts are determined. Methane generation from carbon dioxide is shown to have been replaced by its generation from acetate in the paleo-Black Sea period.

(Table 2) Chemical composition of phosphates from the Namibian and Chilean shelves

This study on phosphorites of different compositions and ages from shelf sediments and seamounts of the Pacific Ocean by means of analytical electron microscopy showed that these phosphorites contain ultra-microscopic inclusions of authigenic minerals and, more rarely, of rare earth element (REE) minerals. In some of phosphorite samples of Pleistocene-Pliocene age from the Namibian shelf both kinds of minerals were found. Uranium minerals were represented by uraninite, coffinite, and ningioite; those of REE - by monazite, xenotime, and bastnesite, which points to their potential accumulation not only as isomorphous admixtures in calcium phosphate but also as independent mineral phases. Coexistence of the minerals noted in shelf phosphorites is caused by repeated changes in redox conditions during formation and then redeposition of phosphate concretions. Presence of uranium minerals in phosphorites from seamounts shows that during an initial step of formation of these phosphorites environment was rather suboxic or reductive than oxic.

Iron and phosphorus speciations in DSDP Leg 92 sediments

We present a detailed study of the co-diagenesis of Fe and P in hydrothermal plume fallout sediments from ~19°S on the southern East Pacific Rise. Three distal sediment cores from 340-1130 km from the ridge crest, collected during DSDP Leg 92, were analysed for solid phase Fe and P associations using sequential chemical extraction techniques. The sediments at all sites are enriched in hydrothermal Fe (oxyhydr)oxides, but during diagenesis a large proportion of the primary ferrihydrite precipitates are transformed to the more stable mineral form of goethite and to a lesser extent to clay minerals, resulting in the release to solution of scavenged P. However, a significant proportion of this P is retained within the sediment, by incorporation into secondary goethite, by precipitation as authigenic apatite, and by readsorption to Fe (oxyhydr)oxides. Molar P/Fe ratios for these sediments are significantly lower than those measured in plume particles from more northern localities along the southern East Pacific Rise, and show a distinct downcore decrease to a depth of ~12 m. Molar P/Fe ratios are then relatively constant to a depth of ~35 m. The Fe and P speciation data indicate that diagenetic modification of the sediments is largely complete by a depth of 2.5 m, and thus depth trends in molar P/Fe ratios can not solely be explained by losses of P from the sediment by diffusion to the overlying water column during early diagenesis. Instead, these sediments are likely recording changes in dissolved P concentrations off the SEPR, possibly as a result of redistribution of nutrients in response to changes in oceanic circulation over the last 10 million years. Furthermore, the relatively low molar P/Fe ratios observed throughout these sediments are not necessarily solely due to losses of scavenged P by diffusion to the overlying water column during diagenesis, but may also reflect post-depositional oxidation of pyrite originating from the volatile-rich vents of the southern East Pacific Rise. This study suggests that the molar P/Fe ratio of oxic Fe-rich sediments may serve as a proxy of relative changes in paleoseawater phosphate concentrations, particularly if Fe sulfide minerals are not an important component during transport and deposition.