Lithium concentrations and isotope composition of basalt samples from ODP/DSDP Sites from Costa Rica Rift

Ocean Drilling Program (ODP) Hole 504B near the Costa Rica Rift is the deepest hole drilled in the ocean crust, penetrating a volcanic section, a transition zone and a sheeted dike complex. The distribution of Li and its isotopes through this 1.8-km section of oceanic crust reflects the varying conditions of seawater alteration with depth. The upper volcanic rocks, altered at low temperatures, are enriched in Li (5.6-27.3 ppm) and have heavier isotopic compositions (delta7Li=6.6-20.8?) relative to fresh mid-ocean ridge basalt (MORB) due to uptake of seawater Li into alteration clays. The Li content and isotopic compositions of the deeper volcanic rocks are similar to MORB, reflecting restricted seawater circulation in this section. The transition zone is a region of mixing of seawater with upwelling hydrothermal fluids and sulfide mineralization. Li enrichment in this zone is accompanied by relatively light isotopic compositions (-0.8-2.1?) which signify influence of basalt-derived Li during mineralization and alteration. Li decreases with depth to 0.6 ppm in the sheeted dike complex as a result of increasing hydrothermal extraction in the high-temperature reaction zone. Rocks in the dike complex have variable isotopic values that range from -1.7 to 7.9?, depending on the extent of hydrothermal recrystallization and off-axis low-temperature alteration. Hydrothermally altered rocks are isotopically light because 6Li is preferentially retained in greenschist and amphibolite facies minerals. The delta7Li values of the highly altered rocks of the dike complex are complementary to those of high-temperature mid-ocean ridge vent fluids and compatible to equilibrium control by the alteration mineral assemblage. The inventory of Li in basement rocks permits a reevaluation of the role of oceanic crust in the budget of Li in the ocean. On balance, the upper 1.8 km of oceanic crusts remains a sink for oceanic Li. The observations at 504B and an estimated flux from the underlying 0.5 km of gabbro suggest that the global hydrothermal flux is at most 8*10**9 mol/yr, compatible with geophysical thermal models. This work defines the distribution of Li and its isotopes in the upper ocean crust and provides a basis to interpret the contribution of subducted lithosphere to arc magmas and cycling of crustal material in the deep mantle.

Mineralogy, and composition of turbidites and background samples at ODP Sites 166-1003 and 166-1007

The lower slope and toe-of-slope sediments of the western flank of the Great Bahama Bank (Sites 1003 and 1007) are characterized by an intercalation of turbidites and periplatform ooze. In general, turbidites form up to 12% of the total mass of the sedimentary column. Based primarily on data from the Bahamas, it has been postulated that steep-sided carbonate platforms shed most of their sediments into the basin during sea-level highstands when the platforms are flooded. This highstand shedding is assumed to be less pronounced along platforms with a ramp-like depositional profile where sediment production is not restricted to sea-level highstand. Miocene to Pliocene sediments recovered in five drill holes during Leg 166 at the western margin of the Great Bahama Bank reveal that turbidite distribution follows a complex pattern that is dependent on several factors such as sedimentation rates, sea-level changes, and slope morphology. To identify the depositional sequences in the cores, the depths of seismic-sequence boundaries were used. The distribution of turbidites within sedimentary sequences varies strongly. Generally, turbidites are clustered at the upper and/or lower portions of the sequences indicating deposition of carbonate turbidites during both highstand and lowstand of sea level. Analyses of the Miocene turbidites show that (1) during high sea level, 60% of all turbidites were deposited at Site 1003 (309 out of 518 turbidites), while during low sea level, two thirds of all turbidites were deposited at Site 1007 (332 out of 486 turbidites); (2) the average thickness of highstand turbidites is 1.5 times higher than the average thickness of lowstand turbidites; and (3) the turbidites display slight differences in composition and sorting. In general, highstand turbidites are less sorted and contain an abundant amount of shallow-water constituents such as green algae, red algae, shallow-water benthic foraminifers (miliolids), and intraclasts. The lowstand turbidites are better sorted and contain abundant planktonic foraminifers and micrite. To complicate matters, highstand and lowstand turbidites seem to be deposited at different locations on the slope. At the lower slope (Site 1003), more turbidites were deposited during highstands, while at the toe of the slope, turbidites were dominantly deposited during sea-level lowstands. The result is a slope section with laterally discontinuous turbidite lenses within periplatform ooze, which is controlled by the interplay of sea-level changes, sediment production, and platform morphology.

Grain characteristics and XRD raw data of ODP Sites 162-981 and 162-984

Multisensor track data, including magnetic susceptibility, gamma-ray attenuation porosity evaluator (GRAPE) wet bulk density, and natural gamma emission, were collected on all cores recovered during Ocean Drilling Program Leg 162. Data from the upper Pliocene and lower Pleistocene of Sites 981 and 984 are here compared to results from analyses of a limited set of discrete samples, including benthic foraminiferal isotopic composition, grain size, carbonate content, abundance of foraminifers and lithic particles, and clay mineralogy. Natural gamma emission most closely monitors the input of felsic terrigenous material to these two sites. Magnetic susceptibility also tracks felsic terrigenous input at Site 981 but appears to reflect a separate, more mafic, terrigenous component at Site 984. The GRAPE record does not correlate well with any discretely measured variable at Sites 981 or 984.

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.

Clay minerals at DSDP Sites 71-511 and 71-513

The distribution of clay minerals, determined by X-ray diffraction, is given for Jurassic to Holocene sediments recovered at DSDP Sites 511 and 513 in the Southwest Atlantic. These data, plus the lithologic and paleoenvironmental information gathered by the shipboard scientists, are used to subdivide the sedimentary sequence into genetic lithologic facies labeled series, seven for Site 511 and two for Site 513. Sediments of these series reflect the main historical and paleoenvironmental events which other means of study have determined to affect this region; particularly important was the opening of the South Atlantic during the Early Cretaceous.

Calcareous nannofossil abundance of ODP Sites 174A-1071, 174A-1072 and 174A-1073

Calcareous nannofossil range charts for Leg 174A sites on the New Jersey continental margin are presented in this report, and nannofossil biostratigraphy is established. Nannofossil biostratigraphic resolution is low in shallow-water Sites 1071 and 1072, where nannofossils are generally rare or frequently absent. Site 1073 yields generally common to abundant nannofossils, which allows a fairly detailed nannofossil biostratigraphy for the entire Pleistocene through upper Eocene sequence. Quantitative and semiquantitative nannofossil data for the upper Pleistocene section from Site 1073 reveal an average sedimentation rate of about 80 cm/k.y. The unusually high sedimentation rate makes this calcareous section very valuable for high-resolution studies.

Pore water chemistry of ODP Sites 201-1225, 201-1226 and 201-1231

High-resolution analyses of the oxygen isotope ratio (18O/16O) of dissolved sulfate in pore waters have been made to depths of >400 meters below seafloor (mbsf) at open-ocean and upwelling sites in the eastern equatorial Pacific Ocean. d18O values of dissolved sulfate (d18O-SO4) at the organic-poor open-ocean Site 1231 gave compositions close to modern seawater (+9.5 per mil vs. Vienna-standard mean ocean water, providing no chemical or isotopic evidence for microbial sulfate reduction (MSR). In contrast, the maximum d18O values at Sites 1225 and 1226, which contain higher organic matter contents, are +20 per mil and +28 per mil, respectively. Depth-correlative trends of increasing d18O-SO4, alkalinity, and ammonium and the presence of sulfide indicate significant oxidation of sedimentary organic matter by sulfate-reducing microbial populations at these sites. Although sulfate concentration profiles at Sites 1225 and 1231 both show similarly flat trends without significant net MSR, d18O-SO4 values at Site 1225 reveal the presence of significant microbial sulfur-cycling activity, which contrasts to Site 1231. This activity may include contributions from several processes, including enzyme-catalyzed equilibration between oxygen in sulfate and water superimposed upon bacterial sulfate reduction, which would tend to shift d18O-SO4 toward higher values than MSR alone, and sulfide oxidation, possibly coupled to reduction of Fe and Mn oxides and/or bacterial disproportionation of sulfur intermediates. Large isotope enrichment factors observed at Sites 1225 and 1226 (epsilon values between 42 per mil and 79 per mil) likely reflect concurrent processes of kinetic isotope fractionation, equilibrium fractionation between sulfate and water, and sulfide oxidation at low rates of sulfate reduction. The oxygen isotope ratio of dissolved pore water sulfate is a powerful tool for tracing microbial activity and sulfur cycling by the deep biosphere of deep-sea sediments.

Chemical and isotopic compositions of deep-sea carbonate sediments and interstitial waters from DSDP Sites 30-288 and 30-289

Interstitial waters and sediments from DSDP sites 288 and 289 contain information on the chemistry and diagenesis of carbonate in deep-sea sediments and on the role of volcanic matter alteration processes. Sr/Ca ratios are species dependent in unaltered foraminifera from site 289 and atom ratios (0.0012-0.0016) exceed those predicted by distribution coefficent data (~0.0004). During diagenesis Sr/Ca ratios of carbonates decrease and reach the theoretical distribution at a depth which is identical to the depth of Sr isotopic equilibration, where 87Sr/86Sr ratios of interstitial waters and carbonates converge. Mg/Ca ratios in the carbonates do not increase with depth as found in some other DSDP sites, possibly because of diagenetic re-equilibration with interstitial waters showing decreasing Mg(2+)/Ca(2+) ratios with depth due to Ca input and Mg removal by alteration of volcanic matter. Interstitial 18O/16O ratios increase with depth at site 289 to d18O = 0.67? (SMOW), reflecting carbonate recrystallization at elevated temperatures (>/= 20°C), the first recorded evidence of this effect in interstitial waters. Interstitial Sr2+ concentrations reach high levels, up to 1 mM, chiefly because of carbonate recrystallization. However, 87Sr/86Sr ratios decrease from 0.7092 to less than 0.7078, lower than for contemporaneous sea water, showing that there is a volcanic input of strontium at depth. This volcanic component is recorded in the Sr isotopic composition of recrystallized calcites. Isotopic compositions of the unrecrystallized calcites suggests that the rate of increase of the 87Sr/86Sr ratio of sea water with time has been faster since 3 my ago than in the preceding 13 my.

Cenozoic clay mineralogy of DSDP Sites 93-604 and 93-605

Examination of the clay mineralogy of Cenozoic sediment samples from Deep Sea Drilling Project Sites 604 and 605 on the upper continental rise off New Jersey indicates that sediment deposition of two different clay mineral facies has occurred. These sites are marked by Paleogene deposition of illite with subordinate kaolinite and smectite covarying in inverse proportion, and by Neogene deposition dominated by illite with subordinate kaolinite and chlorite. Leg 93 results agree with the clay mineral facies proposed by Hathaway (1972), which defined a "Northern facies" consisting of illite and chlorite, with feldspar and hornblende, from erosion of rocks north of Cape Hatteras, and a "Southern facies" composed of smectite, kaolinite, and mixed-layer illite-smectites. Neogene and Quaternary sediments at Sites 604 and 605 contain the "Northern facies," and Paleogene sediments contain the "Southern facies" minerals. Feldspar is exclusively found in Neogene-Quaternary sediments, as is the majority of the amphibole found in these samples. Widespread Paleogene volcanic source materials are suggested by the presence of smectite throughout the early Paleocenemiddle Eocene sediments recovered at Site 605. The clay mineral stratigraphy at Leg 93 sites is comparable to the record at nearby DSDP sites on the lower continental rise and abyssal plain of the northwestern Atlantic (DSDP Sites 388, 105, and 106), and also with the sediments recovered by drilling on the Mazagan Plateau off northwestern Morocco (DSDP Sites 544-547) in the eastern North Atlantic.

Calcareous nannofossil abundance and datums of sediments from ODP Leg 170 sites

Three Pleistocene, five Pliocene, and thirteen late and middle Miocene calcareous nannofossil datums have been identified in the Leg 170 cored sequences collected from a transect across the Middle America Trench off the Nicoya Peninsula. Although some nannofossil zones could not be delineated, particularly in the Pliocene and upper Miocene, there appears to be a complete or very nearly complete Pleistocene through lower Miocene section at Sites 1039 and 1040. The oldest assemblages, observed at Site 1039 and 1040, are latest early Miocene in age (nannofossil Zone NN4). These assemblages are associated with gabbro intrusions into the basal sediments (one contact metamorphic hornfels sample contains relict nannofossils), indicating an age for the intrusion event of between 15.6 and 18.2 Ma at both Sites 1039 and 1040. Reference Site 1039, located on the Cocos plate, provides the best-preserved sequence of sediments of late Pleistocene to latest early Miocene age. The sediments cored in the prism sections at Sites 1040, 1041, 1042, and 1043 all indicate that the age of nannofossil assemblages in the prism sediments, including the toe, wedge, and apron, are all Pleistocene with a considerable amount of upper Miocene reworking. A period of low sediment accumulation rates (~5.3 m/m.y.) is recorded for Pliocene and upper Miocene sediments at Sites 1039, 1040, and 1043. Pliocene calcareous nannofossil assemblages characteristic of the ~2.5- to 3.75-m.y. time interval (nannofossil Zones NN16 and equivalent nannofossil Subzones CN12b and CN12a) were not resolved at any site. Nannofossil Zones NN15, NN14, NN13, and NN12 (early late Pliocene to early Pliocene) could not be resolved at any site either because of the absence of marker species. Within the Miocene at Sites 1039 and 1040, nannofossil Zones NN10-NN6 were difficult to differentiate because of the absence of several species that define the zonal boundaries. These intervals, where the nannofossil zones have not been resolved or are partially resolved, are primarily composed of carbonate ooze deposited during an ~8.5-m.y. (2.5-11 Ma) low sediment accumulation rate time interval. The absence of many of the marker species is attributed to warmer water conditions during those periods. Many of the same marker species are absent in the sediments recovered from nearby Deep Sea Drilling Project Site 155 in the Panama Basin.

Pore-water chemistry of ODP Sites 124-767 and 124-768

The combination of multiple sediment sources and varying rates of sediment accumulation in the Celebes and Sulu seas have had significant impact on the processes of diagenesis, mineralization, and pore-fluid flow. Isotopic and mass-balance calculations help elucidate the various reactions taking place in these western Pacific basins, where ash alteration and basalt-seawater interactions are superimposed on the effects of sulfate oxidation of organic carbon and biogenic methane and of dolomitization of biogenic carbonates. Based on the shape of the calcium and magnesium depth profiles, two major reactive zones have been identified. The first is located near the zone of sulfate depletion and is characterized by carbonate recrystallization, dolomitization and ash alteration reactions at both Ocean Drilling Program Sites 767 and 768. The second reactive zone corresponds to the bottom of the sedimentary sequence and is characterized by alteration reactions in the basement (Site 767) and in the pyroclastic deposits beneath the sediment column (Site 768).

Geochemistry of Early Cretaceous basaltic rocks from ODP Sites 123-765 and 123-766

The Early Cretaceous basaltic rocks obtained from Sites 765 and 766 in the eastern Indian Ocean floor were mostly iron-rich normal mid-ocean ridge basalts (N-MORB), which were derived from a depleted mantle source having strongly light rare earth element (LREE)-depleted rare-earth patterns and a high titanium/zirconium (Ti/Zr) ratio. Basaltic rocks in the upper part of the Site 765 basement section include megacrysts and gabbroic fragments of widely varying mineral chemistry. These megacrysts range from An90 plagioclase, including highly magnesian basaltic glass coexisting with augite of Mg# (= 100 Mg/[Fe+Mg]) at 85, to An50 plagioclase coexisting with hypersthene. This varying mineralogy of megacrysts and gabbroic fragments indicates that a considerable degree of fractional crystallization took place in the magma chamber. The unusual negative correlation between incompatible elements (e.g., TiO2) and FeO*/MgO observed among Site 765 basement basalts and fresh volcanic glasses suggest source-mantle heterogeneity in terms of FeO*/MgO. Strontium isotope ratios (87Sr/86Sr) of the basaltic rocks from both sites are between 0.7027 and 0.7033 and are comparable to those of mid-Indian Ocean ridge basalts (MIORB). The basalt pebbles encountered in the sedimentary section may have been transported from the basement highs nearer the Australian continent and include basaltic compositions ranging from primitive N-MORBs to evolved enriched (E)-MORBs. Their mantle source was not as depleted as that of the basement basalts. These rocks may be the products of earlier volcanism that took place during the rifting of the Australian continent.

Geochemical and mineralogical analyses of clay-rich intervals in ODP Sites 166-1006 and 166-1007

The western flank of the Great Bahama Bank, drilled during ODP Leg 166 at seven sites, represents a prograding carbonate sequence from late Oligocene to Holocene [Eberli et al., Proc. ODP Init. Reports 166 (1997)]. The signatures of the detrital input and of diagenetic alteration are evident in clay enriched intervals from the most distal Sites 1006 and 1007 in the Straits of Florida. Mineralogical and chemical investigations (XRD, TEM, SEM, ICP-MS) run on bulk rocks and on the clay fractions enable the origin and evolution of silicate parageneses to be characterized. Plio-Pleistocene silt and clay interbeds contain detrital clay assemblages comprising chlorite, illite, interstratified illite smectite, smectite, kaolinite and palygorskite. The greater smectite input within late Pliocene units than in Pleistocene oozes may relate either varying source areas or change in paleoclimatic conditions and weathering intensity. The clay intervals from Miocene-upper Oligocene wackestone sections are fairly different, with prevalent smectite in the fine fraction, whose high crystallinity and Mg contents that point towards an authigenic origin. The lower Miocene section, below 1104 mbsf, at depths where compaction features are well developed, is particularly characterized by abundant authigenic Na-K-clinoptilolite filling foraminifer tests. The authigenic smectite and clinoptilolite paragenesis is recorded by the chemical trends, both of the sediment and the interstitial fluid. This diagenetic evolution implies Si- and Mg rich fluids circulating in deeper and older sequences. For lack of any local volcaniclastic input, the genesis of zeolite and the terms of water rock interaction are discussed. The location of the diagenetic front correlates with that of the seismic sequence boundary P2 dated as 23.2 Ma. This correspondence may allow the chronostratigraphic significance of some specific seismic reflections to be reassessed.

Total organic carbon content, methane isotopic composition and hydrocarbon characteristics of ODP Leg 180 sites

The organic geochemistry of Sites 1108 and 1109 of the Woodlark Basin, offshore Papua New Guinea, was studied to determine whether thermally mature hydrocarbons were present in the penetrated section and, if present, whether they are genetically related to the penetrated "coaly" interval. Both the organic carbon and pyrolysis data indicate that there is no significant hydrocarbon source-rock potential at Site 1108. The hydrocarbons encountered during drilling appear to be indigenous and not migrated products or contaminants. In contrast, the coaly interval at Site 1109 contains zones with significant hydrocarbon-generation potential. Several independent lines of evidence indicate that the coaly sequence encountered at Site 1109 is thermally immature. The Site 1108 methane stable-carbon isotope composition does not display a clear trend with depth as would be expected if it was solely reflecting a maturation profile. The measured isotopic composition of methane has most probably been altered by fractionation during sample handling and storage. This fractionation would result in isotopically heavier values than would be obtained on free gas. The organic geochemical data gathered indicate that Site 1108 can be safely revisited and that the organic-rich sediments encountered at Site 1109 were not the source of the gas encountered at Site 1108.