Primary composition, alteration, and origin of Cretaceous volcaniclastic rocks at DSDP Site 89-585

An upper Aptian to middle Albian series of volcaniclastic rocks more than 300 m thick was drilled at Site 585 in the East Mariana Basin. On the basis of textural and compositional (bulk-rock chemistry, primary and secondary mineral phases) evidence, the volcaniclastic unit is subdivided into a lower (below 830 m sub-bottom) and an upper (about 670-760 m) sequence; the boundary in the interval between is uncertain owing to lack of samples. The rocks are dominantly former vitric basaltic tuffs and minor lapillistones with lesser amounts of crystals and basaltic lithic clasts. They are mixed with shallow-water carbonate debris (ooids, skeletal debris), and were transported by mass flows to their site of deposition. The lower sequence is mostly plagioclase- and olivine-phyric with lesser amounts of Ti-poor clinopyroxene. Mineralogical and bulk-rock chemical data indicate a tholeiitic composition slightly more enriched than N-MORB (normal mid-ocean ridge basalt). Transport was by debris flows from shallow-water sites, as indicated by admixed ooids. Volcanogenic particles are chiefly moderately vesicular to nonvesicular blocky shards (former sideromelane) and less angular tachylite with quench plagioclase and pyroxene, indicating generation of volcanic clasts predominantly by spalling and breakage of submarine pillow and/or sheet-flow lavas. The upper sequence is mainly clinopyroxene- and olivine-phyric with minor plagioclase. The more Ti-rich clinopyroxene and the bulk-rock analyses show that the moderately alkali basaltic composition throughout is more mafic than the basal tholeiitic sequence. Transport was by turbidity currents. Rounded epiclasts of crystalline basalts are more common than in the lower sequence, and, together with the occurrence of oxidized olivine pseudomorphs and vesicular tachylite, are taken as evidence of derivation from eroded subaerially exposed volcanics. Former sideromelane shards are more vesicular than in the lower sequence; vesicularity exceeds 60 vol.% in some clasts. The dominant clastic process is interpreted to be by shallow-water explosive eruptions. All rocks have undergone low-temperature alteration; the dominant secondary phases are "palagonite," chlorite/smectite mixed minerals, analcite, and chabazite. Smectite, chlorite, and natrolite occur in minor amounts. Phillipsite is recognized as an early alteration product, now replaced by other zeolites. During alteration, the rocks have lost up to 50% of their Ca, compared with a fresh shard and fresh glass inclusions in primary minerals, but have gained much less K, Rb, and Ba than expected, indicating rapid deposition prior to significant seafloor weathering.

Alteration and vein logs of ODP Holes 152-917A and 152-918D

This data report provides a systematic documentation of the low-temperature alteration associated with the formation of a volcanic-rifted margin by the quantification of alteration effects and vein mineralogy and distributions in basalts recovered on Leg 152 (Larsen, Saunders, Clift, et al., 1994, doi:10.2973/odp.proc.ir.152.1994). Basaltic rocks from Holes 917A and 918D have been investigated to provide a quantitative description of the extents of recrystallization and secondary mineral abundance resulting from low-temperature alteration and weathering. Only limited descriptions of alteration and secondary mineral distributions were undertaken on board ship during Leg 152, and the data presented here provide an essential complement to the shipboard logs of the limited amount of basalt recovered during Leg 163 from Sites 988, 989, and 990 (Duncan, Larsen, Allan, et al., 1996, doi:10.2973/odp.proc.ir.163.1996).

(Table 1) B content, d11B, d18O, degree of alteration, and lithology of basalts from ODP Hole 504B

Boron contents and boron isotopic compositions were determined for the uppermost 1.3 km section of typical 6.2 Ma oceanic crust from DSDP/ODP Hole 504B, Costa Rica Rift, Galapagos Spreading Center. Both the boron content and the d11B value in the oceanic crust are controlled by two types of alteration: 1. (1) low-temperature alteration (0 to 60°C; Zones I and II) and 2. (2) high-temperature hydrothermal alteration (200 to 400°C; Zones III and IV). Basalts subjected to the low-temperature alteration are characterized by their relatively high boron contents (0.69 to 19.3 ppm) and high d11B values (+2.2 to +10.6?), indicating uptake of boron into secondary phases in equilibrium with seawater or evolved seawater. Hydrothermally altered basalts contain less abundant boron (0.17 to 0.52 ppm) and relatively constant d11B values (?0.1 to +1.0?). Although basalts from the upper part of these hydrothermal zones (<1300 mbsf) show equilibrated boron content and d11B value with aqueous fluid, effective leaching of boron from basalt is predominant in the lower part (>1300 mbsf). Original boron content and d11B value of the Hole 504B MORB were 0.35 ppm and +0.2?, respectively. The present data provide fundamental information in understanding of the distribution of boron and boron isotopes in the oceanic crust.

Isotopic and chemical compositions of rocks and minerals from the TAG hydrothermal mound, ODP Site 957

Strontium- and oxygen-isotopic measurements of samples recovered from the Trans-Atlantic Geotraverse (TAG) hydrothermal mound during Leg 158 of the Ocean Drilling Program provide important constraints on the nature of fluid-rock interactions during basalt alteration and mineralization within an active hydrothermal deposit. Fresh Mid-Ocean Ridge Basalt (MORB), with a 87Sr/86Sr of 0.7026, from the basement beneath the TAG mound was altered at both low and high temperatures by seawater and altered at high temperature by near end-member black smoker fluids. Pillow breccias occurring beneath the margins of the mound are locally recrystallized to chlorite by interaction with large volumes of conductively heated seawater (>200°C). The development of a silicified, sulfide-mineralized stockwork within the basaltic basement follows a simple paragenetic sequence of chloritization followed by mineralization and the development of a quartz+pyrite+paragonite stockwork cut by quartz-pyrite veins. Initial alteration involved the development of chloritic alteration halos around basalt clasts by reaction with a Mg-bearing mixture of upwelling, high-temperature (>300°C), black smoker-type fluid with a minor (<10%) proportion of seawater. Continued high-temperature (>300°C) interaction between the wallrock and these Mg-bearing fluids results in the complete recrystallization of the wallrock to chlorite+quartz+pyrite. The quartz+pyrite+paragonite assemblage replaces the chloritized basalts, and developed by reaction at 250-360°C with end-member hydrothermal fluids having 87Sr/86Sr ~0.7038, similar to present-day vent fluids. The uniformity of the 87Sr/86Sr ratios of hydrothermal assemblages throughout the mound and stockwork requires that the 87Sr/86Sr ratio of end-member hydrothermal fluids has remained relatively constant for a time period longer than that required to change the interior thermal structure and plumbing network of the mound and underlying stockwork. Precipitation of anhydrite in breccias and as late-stage veins throughout most of the mound and stockwork, down to at least 125 mbsf, records extensive entrainment of seawater into the hydrothermal deposit. 87Sr/86Sr ratios indicate that most of the anhydrite formed from ~2:1 mixture of seawater and black smoker fluids (65%±15% seawater). Oxygen-isotopic compositions imply that anhydrite precipitated at temperatures between 147°C and 270°C and require that seawater was conductively heated to between 100°C and 180°C before mixing and precipitation occurred. Anhydrite from the TAG mound has a Sr-Ca partition coefficient Kd ~0.60±0.28 (2 sigma). This value is in agreement with the range of experimentally determined partition coefficients (Kd ~0.27-0.73) and is similar to those calculated for anhydrite from active black smoker chimneys from 21°N on the East Pacific Rise. The d18O (for SO4) of TAG anhydrite brackets the value of seawater sulfate oxygen (~9.5?). Dissolution of anhydrite back into the oceans during episodes of hydrothermal quiescence provides a mechanism of buffering seawater sulfate oxygen to an isotopically light composition, in addition to the precipitation and dissolution of anhydrite within the oceanic basement during hydrothermal recharge at the mid-ocean ridges.

Composition and alteration of volcanic rocks of ODP Hole 119-738C

During ODP Leg 119 one basement hole was drilled at Site 738, on the Southern Kerguelen Plateau. The 38.2 m of basement rocks drilled comprises three basaltic aa-lava flows with basal and top breccias, overlain by Turanian marine carbonates. Site 738 basalts probably erupted near a fracture zone, and were emplaced during the plateau-forming stage of Kerguelen Plateau evolution under quiet, subaerial to shallow water conditions. The basalts are T-MORB, chemically resembling Mesozoic continental flood basalts of the southern hemisphere. Two slightly different magma batches are distinguished by Fe, Ti, Al, Zr, and REE concentrations. Prior to eruption, the magmas had undergone significant olivine and some clinopyroxene fractionation. Incompatible and immobile trace element concentrations and ratios point to a veined upper mantle source, where a refractory mineral assemblage retains Nb, Ta, and the HREE. The basaltic melts derived from this regionally veined, enriched upper mantle have high LREE, and especially Ba and Th concentrations and bear the DUPAL isotopic signature gained from deep- seated, recycled, old oceanic(?) crust. A saponite-celadonite secondary mineral assemblage confines the alteration temperature to <170°C. Alteration is accompanied by net gains of H2O, CO2, K2O, and Rb, higher oxidation, minor Na2O, SiO2 gains, and losses of V and CaO. Released Ca, together with Ca from seawater, precipitated as calcite in veins and vesicles, plumbed the circulation system and terminated the rock/open seawater interaction.

Geochemistry and stable isotope record of the hydtrothermally altered lower sheeted dike complex in ODP Hole 140-504B

Drilling during Legs 137 and 140 of the Ocean Drilling Program deepened Hole 504B, the only hole to penetrate through the volcanic section and into the underlying hydrothermally altered sheeted dike complex, by 438.1 m to a total depth of 2000.4 meters below seafloor. This paper presents the secondary mineralogy, bulk-rock sulfur contents, and stable isotopic (O, S) compositions, plus oxygen isotopic compositions of secondary minerals from the lower sheeted dike complex drilled during Legs 137 and 140. Various evidence indicates higher temperatures of hydrothermal alteration in the lower dikes than in the upper dikes, including: the local presence of secondary clinopyroxene in the lower dikes; secondary anorthite and hornblende in the lower dikes vs. mainly actinolite and albite-oligoclase in the upper dikes; generally increasing Al and Ti contents of amphibole downward in the dike section; and greater 18O depletions of the lower dikes (d18O = 3.6-5.0 per mil) compared with the upper dikes. Early high-temperature alteration stages (T = 350°-500°C) resulted in 18O depletions and losses of metals (Cu, Zn) and sulfur from the rocks. Local incorporation of reduced seawater sulfate led to elevated d34S values of sulfide in the rocks (up to 2.5 per mil). Quartz + epidote formed in crosscutting veins at temperatures of 310°-320°C from more evolved fluids (d18O = 1 per mil). Late-stage lower-temperature (~250°C) reactions producing albite, prehnite, and zeolites in the rocks caused slight 18O enrichments, but these were insufficient to offset the 18O depletions caused by earlier higher-temperature reactions. Addition of anhydrite to the rocks during seawater recharge led to increased S contents of rocks that had previously lost S during axial hydrothermal alteration, and to further increases in d34S values of total S in the rocks (up to 12 per mil). Despite the evidence for seawater recharge to near the base of the sheeted dike complex, the paucity of late zeolites in the lower dikes suggests that late-stage, off-axis circulation was mainly restricted to the volcanics and shallowest dikes, or to localized high-permeability zones (faults) at depth.

Bulk geochemistry, mass change and alteration intensity of basalts from ODP Leg 187 sites and survey dredges

Shipboard studies during Ocean Drilling Program Leg 187 (Australian Antarctic Discordance, AAD) suggested that there was no discernible coincidence between the interpreted age of rocks recovered and the intensity of alteration observed. Samples from the oldest sites occupied appeared to exhibit the least overall effects of alteration, and the intensity of alteration varied from site to site. Previous investigations of low-temperature alteration in oceanic basement samples have been restricted by the myopic perspective provided by single drill holes or dredge collections. Combining core samples from Leg 187 and dredge samples from the AAD collection at Oregon State University (USA) offers the unique opportunity to investigate mineral and bulk chemical changes attending alteration of basalt over a range of ages from 0 to 28 Ma. Results of this research indicate that there is a general increase in the intensity of alteration as the basalts age and mosve off axis, but that this relationship is somewhat veiled by the dominating control on alteration intensity dictated by variations in permeability.

(Table 3) Reduced inorganic sulphur, d34S and nickel content of ODP Leg 165 sites

Leg 165 of the Ocean Drilling Program afforded a unique opportunity to investigate organic and inorganic geochemistry across a wide gradient of sediment compositions and corresponding chemical pathways. The solid fractions at Sites 998, 999, 1000, and 1001 reveal varying proportions of reactive carbonate species, a labile volcanic ash fraction occurring in discrete layers and as a dispersed component, and detrital fluxes that derive from continental weathering. The relative proportions and reactivities of these end-members strongly dictate the character of the diagenetic profiles observed during the pore-water work of Leg 165. In addition, alteration of the well-characterized basaltic basement at Site 1001 has provided a strong signal that is reflected in many of the dissolved components. The relative effects of basement alteration and diagenesis within the sediment column are discussed in terms of downcore relationships for dissolved calcium and magnesium. With the exception of Site 1002 in the Cariaco Basin, the sediments encountered during Leg 165 were uniformly deficient in organic carbon (typically <0.1 wt%). Consequently, rates of organic oxidation were generally low and dominated by suboxic pathways with subordinate levels of bacterial sulfate reduction and methanogenesis. The low rates of organic remineralization are supported by modeled rates of sulfate reduction. Site 1000 provided an exception to the generally low levels of microbially mediated redox cycling. At this site the sediment is slightly more enriched in organic phases, and externally derived thermogenic hydrocarbons appear to aid in driving enhanced levels of redox diagenesis at great depths below the seafloor. The entrapment of these volatiles corresponds with a permeability seal defined by a pronounced Miocene minimum in calcium carbonate concentration recognized throughout the basin and with a dramatic downcore increase in the magnitude of limestone lithification. The latter has been tentatively linked to increases in alkalinity associated with microbial oxidation of organic matter and gaseous hydrocarbons. Recognition and quantification of previously unconstrained large volumes and frequencies of Eocene and Miocene silicic volcanic ash within the Caribbean Basin is one of the major findings of Leg 165. High frequencies of volcanic ash layers manifest as varied but often dominant controls on pore-water chemistry. Sulfur isotope results are presented that speak to secondary metal and sulfur enrichments observed in ash layers sampled during Leg 165. Ultimately, a better mechanistic understanding of these processes and the extent to which they have varied spatially and temporally may bear on the global mass balances for a range of major and minor dissolved components of seawater.

Description of manganese nodules and crust collected from the Hakurei Maru Cruise GH76-1, January-March, 1976, in the Central Pacific Basin

This report of the GH76-1 cruise mainly includes the results of the on-board observations in the survey area of the medial-eastern part of Central Pacific Basin (5 degree -10 degree N, 170 degree -175 degree W) and partly of analytical work at the on-shore laboratory. In addition, the results of some on-board optical and geophysical works along the tracks of Japan-Ogasawara-survey area-Hawaii, are described in appendices. The GH76-1 cruise of the R/V Hakurei-maru was carried out from the 10th January to the 9th March, 1976 as the second phase field work of the Geological Survey of Japan five-year research program of study on the manganese nodule deposits of the Central Pacific Basin and also as a part of the National Research Institute for Pollution and Resources research program of technological study on the exploitation of deep sea mineral resources. The GSJ research program (F.Y. 1974-F.Y. 1978) aims at providing basic information on the manganese nodule distribution and their origin on the deep sea floor of the Central Pacific Basin bounded by the Marshall Ridge to the west, the Christmas Ridge to the east, and the Mid-Pacific Mountains to the north. The first phase of investigation was carried out during the GH74-5 cruise in the eastern part of the area (6 degree -10 degree 30'W, 164 degree 30'-171 degree 30'N)(Mizuno and Chujo, eds., 1975), and the present second phase covered an areas of 5 degree square, just west of the GH74-5 area.

(Table 1) Strontium concentration and isotope ratios of carbonates from DSDP Holes 69-504B as well as 83-504B and fish debris samples from Indian and Pacific Ocean sediments

Recent revisions of the geological time scale by Kent and Gradstein (in press) suggest that, on the average, Cretaceous magnetic anomalies are approximately 10 m.y. older than in Larson and Hilde's (1975) previous time scale. These revised basement ages change estimates for the duration of alteration in the ocean crust, based on the difference between secondary-mineral isochron ages and magnetic isochron-crustal ages, from 3 to approximately 13 m.y. In addition to the revised time scale, Burke et al.'s (1982) new data on the temporal variation of 87Sr/86Sr in seawater allow a better understanding of the timing of alteration and more realistic determinations of water/rock ratios during seawater-basalt interaction. Carbonates from all DSDP sites which reached Layer 2 of Atlantic crust (Sites 105, 332, 417, and 418) are deposited within 10-15 m.y. of crustal formation from solutions with 87Sr/86Sr ratios identical to unaltered or contemporaneous seawater. Comparisons of the revised seawater curve with the 87Sr/86Sr of basement carbonates is consistent with a duration of approximately 10-15 m.y. for alteration in the ocean crust. Our preliminary Sr and 87Sr/86Sr data for carbonates from Hole 504B, on 5.9-m.y.-old crust south of the Costa Rica Rift, suggest that hydrous solutions from which carbonates precipitated contained substantial amounts of basaltic Sr. For this reason, carbonate 87Sr/86Sr cannot be used to estimate the duration of alteration at this site. A basalt-dominated alteration environment at Hole 504B is consistent with heat-flow evidence which indicates rapid sediment burial of crust at the Costa Rica Rift, sealing it from access by seawater and resulting in unusually low water/rock ratios during alteration.

Geochemical analyses of secondary minerals from ODP Leg 115 basalts (Tables 1+2)

Basalts recovered along the Reunion hotspot track on Ocean Drilling Program (ODP) Leg 115 range in age from 34 Ma at Site 706 to 64 Ma at Site 707. They have undergone various degrees of secondary alteration. Within single holes the amount of alteration can vary from a few percent to near complete replacement of phenocrysts and groundmass by secondary minerals. Olivine appears to be the most susceptible to alteration and in some sections it is the only mineral altered. In other sections, olivine, pyroxene and plagioclase phenocrysts, and groundmass have been completely replaced by secondary minerals. Clays are the predominant form of secondary mineralization. In addition to replacing olivine, pyroxene, glass, and groundmass, clays have filled veins, vesicles, and voids. Minor amounts of calcite, zeolites, and K-feldspar were also detected. The clays that filled vesicles and veins often show color zonations of dark, opaque bands near the edges that grade into tan or green transparent regions in the centers of the veins. The electron microprobe was used to obtain chemical analyses of these veins as well as to characterize isolated clays that replaced specific minerals and filled voids and vesicles.

Modern and fossil corals from Palmyra and Christmas islands

The relationship between decadal to centennial changes in ocean circulation and climate is difficult to discern using the sparse and discontinuous instrumental record of climate and, as such, represents a large uncertainty in coupled ocean-atmosphere general circulation models. We present new modern and fossil coral radiocarbon (D14C) records from Palmyra (6°N, 162°W) and Christmas (2°N, 157°W) islands to constrain central tropical Pacific ocean circulation changes during the last millennium. Seasonally to annually resolved coral D14C measurements from the 10th, 12th-17th, and 20th centuries do not contain significant interannual to decadal-scale variations, despite large changes in coral d18O on these timescales. A centennial-scale increase in coral radiocarbon from the Medieval Climate Anomaly (~900-1200 AD) to the Little Ice Age (~1500-1800) can be largely explained by changes in the atmospheric D14C, as determined with a box model of Palmyra mixed layer D14C. However, large 12th century depletions in Palmyra coral D14C may reflect as much as a 100% increase in upwelling rates and/or a significant decrease in the D14C of higher-latitude source waters reaching the equatorial Pacific during this time. SEM photos reveal evidence for minor dissolution and addition of secondary aragonite in the fossil corals, but our results suggest that coral D14C is only compromised after moderate to severe diagenesis for these relatively young fossil corals.

(Table 2) Chemical composition of gases in basalts from DSDP Leg 65 Holes

Basalts from different structural provinces in the ocean basins, such as mid-ocean ridges, island arcs, and oceanic plateaus, show marked differences in major and minor element composition stemming from differences in magma source. In addition, there are variations even within individual provinces, based on such processes as crystal fractionation, secondary alteration, and hydrothermal alteration. It is also known that hydrothermal processes can cause changes in the gas composition of submarine basalts. For example, Zolotarev et al. (1978) have established that hydrothermal alteration frequently causes an increase in the CO2 content of basalts. If the homogeneity in composition and concentration of organic gases in oceanic basalts is associated with degassing during epimagmatic alteration, it would be interesting to investigate the relative abundance of gas phases in young basalts from midoceanic ridges. This chapter deals with the distribution of organic gases and CO2 in young basalts recovered on Leg 65 from the Gulf of California. Our aim was to establish the relationship between gas composition and degree of alteration.