Mineral composition and major element oxides of gabbros from ODP Hole 179-1105A, southwest Indian Ridge

Hole 1105A penetrated 158 m of gabbros at a site offset 1.3 km east-northeast from Hole 735B on the Atlantis Bank near the Atlantis II Fracture Zone. A total of 118 m of dominantly medium- to coarse-grained intercalated Fe-Ti oxide gabbro and olivine gabbro was recovered from Hole 1105A that shows many petrographic features similar to those recovered from the upper part of Hole 735B. The main rock types are distinguished based on the constituent cumulus phases, with the most primitive gabbros consisting of olivine, plagioclase, and clinopyroxene. The inferred crystallization order is subsequently Fe-Ti oxides (ilmenite and titanomagnetite), followed by orthopyroxene, then apatite, and finally biotite. Orthopyroxene appears to replace olivine in a narrow middle interval. The magmatic evolution is likewise reflected in the mineral compositions. Plagioclase varies from An66 to An28. Olivine varies from Fo78 to Fo35. The gap in olivine crystallization occurs between Fo46 and Fo40 and coincides approximately with the appearance of orthopyroxene (~En50). The clinopyroxenes show large compositional variation in Mg/(Mg + Fe total) from 0.84 to 0.51. The nonquadrilateral cations of clinopyroxene similarly show large variations with Ti increasing for the olivine gabbros and decreasing for the Fe-Ti oxide gabbros with the decrease in Mg/(Mg + Fe total). The apatites are mainly flourapatites. The compositional variation in the gabbros is interpreted as a comagmatic suite resulting from fractional crystallization. Pyroxene geothermometry suggests equilibration temperatures from 1100°C and below. The coexisting Fe-Ti oxide minerals indicate subsolidus equilibration temperatures from 900°C for olivine gabbros to 700°C for the most evolved apatite-bearing gabbros. The cryptic variation in the olivine gabbros defines two or three lenses, 40 to 60 m thick, each characterized by a distinct convex zoning with a lower segment indicating upward reverse fractionation, a central maximum, and an upper segment showing normal fractionation. The Fe-Ti oxide gabbros show cryptic variations independent of the host olivine gabbros and reveal a systematic upward normal fractionation trend transgressing host olivine gabbro boundaries. Forward fractional crystallization modeling, using a likely parental magma composition from the Atlantis II Fracture Zone (MgO = 7.2 wt%; Mg/[Mg + Fe2+] = 0.62), closely matches the compositions of coexisting olivine, plagioclase, and clinopyroxene. This modeling suggests cosaturation of olivine, plagioclase, and clinopyroxene from 1155°C and the addition of Fe-Ti oxides from 1100°C. The liquid line of descent initially shows increasing FeO with moderately increasing SiO2. After saturation of Fe-Ti oxides, the liquid strongly decreases in FeO and TiO2 and increases in SiO2, reaching dacitic compositions at ~10% liquid remaining. The calculations indicate that formation of olivine gabbros can be accounted for by <65% fractionation and that only the residual 35% liquid was saturated in Fe-Ti oxides. The modeling of the solid fractionation products shows that both the olivine gabbro and the Fe-Ti oxide gabbros contain very small amounts of trapped liquid (<5%). The implications are that the gabbros represent crystal mush that originated in a recharging and tapping subaxial chamber. Compaction and upward melt migration in the crystal mush appear to have been terminated with relatively large amounts of interstitial liquid remaining in the upper parts of the cumulate mush. This termination may have been caused by tectonic disturbances, uplift, and associated withdrawal of magma into the subaxial dike and sill system. Prolonged compaction and cooling of the trapped melt in the mush formed small differentiated bodies and lenses by pressure release migration and crystallization along syntectonic channels. This resulted in differentiation products along lateral and vertical channelways in the host gabbro that vary from olivine gabbro, to Fe-Ti oxide gabbro, gabbronorite, and apatite gabbros and show large compositional variations independent of the host olivine gabbros.

Geochemistry of ODP Leg 129 igneous rocks

This report presents all the available major and trace elemental analyses and Sr, Nd, and Pb isotopic compositions of basaltic rocks recovered from Ocean Drilling Program Sites 800, 801, and 802 during Leg 129 (Table 1). Its main purpose is to provide other investigators a complete summary of geochemical data for Leg 129 basement basalts that they can use for later work. Detailed discussions of the data are presented elsewhere in the volume by Floyd and Castillo (Site 801 geochemistry and petrogenesis, dataset: doi:10.1594/PANGAEA.779154) Floyd et al. (Sites 800 and 802 geochemistry and petrography, dataset: doi:10.1594/PANGAEA.779129), Alt et al. (Site 801 alteration, dataset: doi:10.1594/PANGAEA.779207), and Castillo et al. (Sr, Nd, and Pb isotope geochemistry of Leg 129 basalts, dataset: doi:10.1594/PANGAEA.779191).

Strontium and neodymium concentrations and isotope compositions in fossil fish teeth and pore waters at ODP Sites 130-807 and 125-786

We analyzed Nd and Sr isotopic compositions of Neogene fossil fish teeth from two sites in the Pacific in order to determine the effect of cleaning protocols and burial diagenesis on the preservation of seawater isotopic values. Sr is incorporated into the teeth at the time of growth; thus Sr isotopes are potentially valuable for chemostratigraphy. Nd isotopes are potential conservative tracers of paleocirculation; however, Nd is incorporated post-mortem, and may record diagenetic pore waters rather than seawater. We evaluated samples from two sites (Site 807A, Ontong Java Plateau and Site 786A, Izu-Bonin Arc) that were exposed to similar bottom waters, but have distinct lithologies and pore water chemistries. The Sr isotopic values of the fish teeth appear to accurately reflect contemporaneous seawater at both sites. The excellent correlation between the Nd isotopic values of teeth from the two sites suggests that the Nd is incorporated while the teeth are in chemical equilibrium with seawater, and that the signal is preserved over geologic timescales and subsequent burial. These data also corroborate paleoseawater Nd isotopic compositions derived from Pacific ferromanganese crusts that were recovered from similar water depths (Ling et al., 1997; doi:10.1016/S0012-821X(96)00224-5). This corroboration strongly suggests that both materials preserve seawater Nd isotope values. Variations in Pacific deepwater e-Nd values are consistent with predictions for the shoaling of the Isthmus of Panama and the subsequent initiation of nonradiogenic North Atlantic Deep Water that entered the Pacific via the Antarctic Circumpolar Current.

Sedimentology and Lead and Strontium isotope ratios of Miocene sediments from the Kerguelen Plateau

Characterization of sediment from Ocean Drilling Program Site 745, representing the East Kerguelen Ridge sediment drift, addresses important issues surrounding the timing of Miocene to present East Antarctic ice sheet stability and oceanic environmental change. Our results show three periods of greatly enhanced accumulation of Antarctic-derived sediment, at 6.4-5.9 Ma, 4.9-4.4 Ma and 1.1-0.8 Ma, potentially indicative of warmer, less stable ice sheets at these times. Conversely, the accumulation of Antarctic-derived material is comparatively less during the middle of the Pliocene warm epoch (4.8-3.2 Ma). The deep flow forming the Kerguelen drift was stronger during the latest Miocene and earliest Pliocene and has decreased in intensity continuously since then.

Strontium and Oxygen isotope compositions from DSDP Holes 54-424A, 54-424B and 70-509B

Strontium and O isotope compositions of green clay minerals from sediment cores of three boreholes drilled into (sites 424A and 509B) and close to a hydrothermal mound (site 424B) near the Galapagos Spreading Center (DSDP Legs 54 and 70) were determined. The green clays consist mostly of a transition from Fesmectite (nontronite) to glauconite. 87Sr/86Sr ratios were measured on clay size-fractions after gentle acid leaching and on the recovered leachates from different samples. The 87Sr/86Sr ratios of the clay residues from both the 424A and B sites are well below the modern seawater value, which points consistently to precipitation from hydrothermal fluids that contained variable amounts of seawater, even away from mound. However, most of the clay residues from mound site 509B have 87Sr/86Sr ratios significantly above the seawater value, suggesting the occurrence of a detrital component together with the new authigenic particles. The clay minerals of the hydrothermal mound are mixed with detrital components, and that of the sample taken outside but near the mound as a reference for the surrounding oceanic environment, yields a hydrothermal signature. Crystallization temperatures of the clays range from 32 to 63 °C assuming a d18O value of +2.2 per mil for the mineralizing fluids. Hydrothermal fluids generated in the underlying oceanic crust, mixed in varied proportions with ambient seawater and migrated into beds of the mound in a sequence of recurrent processes that ultimately resulted in the formation of the observed clay minerals. No significant temperature differences were detected for crystallization of the K-rich glauconite and K-depleted nontronite. The 87Sr/86Sr ratios of the Sr leached off the clay particles are near the value of modern seawater, inferring a progressive replacement of the hydrothermal fluids by seawater in the pore space of the mound sediments.

Strontium isotopic composition of interstitial waters from DSDP sites 25-245 and 38-336

Measurements of 87Sr/86Sr ratios of interstitial waters from leg 25, site 245 and leg 38, site 336 of the Deep Sea Drilling Project show that the enrichment of Sr[2+] with depth is caused both by the alteration of volcanic material and by the introduction of strontium derived from calcium carbonate. 87Sr/86 Sr ratios range from 0.70913 to 0.70794 at site 245 and from 0.70916 to 0.70694 at site 336. The low ratios compared with contemporaneous seawater reflect the release of Sr from a volcanic source having, according to material-balance calculations, a 87Sr/86 Sr ratio of about 0.7034 at site 336. At this site the source appears to be volcanic ash and not basaltic basement which acts as a sink for Sr[2+] during in situ low-temperature weathering. The volcanic contribution to the strontium enrichment in the basal interstitial waters varies from <10% at site 245 to >50% at site 336. The remaining Sr[2+] is derived from Sr-rich biogenic carbonate during diagenetic recrystallization to form Sr-poor calcite.

Strontium chemistry of anhydrite from DSDP/ODP Hole 504B

A unique record of the chemical evolution of seawater during hydrothermal recharge into oceanic crust is preserved by anhydrite from the volcanic sequences and sheeted dike complex in ODP Hole 504B. Chemical and isotopic analyses 87Sr/86Sr, delta18O, delta34S of anhydrite constrain the changing composition of fluids due to reaction with basalt. There is a general trend of decreasing 87Sr/86Sr of anhydrite, corresponding to the minor incorporation of basaltic strontium with depth in the volcanic rocks. 87Sr/86Sr ratios decrease rapidly with depth in the dikes to values identical to host basalt (0.7029). Sr/Ca ratios (<0.1 mmol/mol) suggest that recharge fluids have very low Sr concentrations and fluids evolve by first precipitating Sr-bearing phases before extensive exchange of Sr with the host basalt. There is a background trend of decreasing sulfate delta18O with depth from +12-13? in the lower volcanics to +7? in the lower sheeted dikes recording an increase in recharge fluid temperature from c. 150° to c. 250°C, and confirming the presence of sulfate in hydrothermal fluids at elevated temperatures. From the amount of anhydrite recovered from Hole 504B and the amount of seawater sulfur that has been reduced to sulfide, a minimum seawater recharge flux can be calculated. This value is 4-25 times lower than estimates of high-temperature fluid fluxes based on either thermal constraints or global chemical budgets and suggests that there is significant deficit of seawater-derived sulfur in the oceanic crust. Only a minor proportion of the seawater that percolates into the crust near the axis is heated to high temperatures and exits as black smoker-type fluids. A significant proportion of the axial heat loss must be advected at 200-250°C by sulfate-bearing hydrothermal solutions that egress diffusely from the crust. These fluids penetrate into the dikes and exchange both heat and chemical tracers without the extensive clogging of porosity by anhydrite precipitation, which would halt hydrothermal circulation for any reasonable fluid flux. The heating of the major proportion of hydrothermal fluids to only moderate temperatures (c. 250°C) reconciles estimates of hydrothermal fluxes derived from thermal models and global geochemical budgets. The flux of hydrothermal sulfate would be of a magnitude similar to the riverine input, and oxygen-isotopic exchange at 200-250°C between dissolved sulfate and recharge fluids during hydrothermal circulation provides a mechanism to continuously buffer seawater sulfate oxygen to the light isotopic composition observed.

Strontium isotopes in pore waters of east equatorial Pacific sediments

Pore-water samples from the equatorial sedimentary bulge area show reversals in depth profiles of 87Sr/86Sr ratios at the sediment/basement interface. Results of this work support inferences made from previous pore-water data (from DSDP drilling in the area) that large-scale horizontal advection of seawater has occurred through the basement underlying the thick sedimentary sequence in this region. The area of apparent advection includes the eastern part of the equatorial high-productivity zone and part of the Guatemala Basin. We attempted to find links between the observed near-basement reversals in pore-water chemistry and sedimentary thickness, age, and topography of the area. Most of the sites that show horizontal advection have disturbed basement topography or outcrops within 10 to 20 km, suggesting that the cooling effects of outcrops may extend for at least 20 km horizontally. Heat-flow data from the area were compared to determine whether sites showing near-bottom chemistry reversals were consistent with areas of low conductive heat flow. This was generally true for the area of the sedimentary bulge and Guatemala Basin. Not enough pore-water data from the Nazca Plate were available to establish any reliable systematics. Because the high-productivity area is well-sealed from hydrothermal circulation, the missing heat must be lost by horizontal advective heat transport. From profiles of strontium isotopes and other elements that show departure from seawater values with increasing depth in the sediments, but return to seawater values near the basement, it appears that water flows relatively freely through much of the oceanic crust, even when sealed by considerable sedimentary cover.

Isotopic composition of strontium in planktonic foraminiferas from sediments of the DSDP Holes 90-588 and 94-607

Measurements of 87Sr/86Sr on samples of planktonic foraminifers were used to reconstruct changes in the Sr isotopic composition of seawater for the past 8 Ma. The late Neogene was marked by a general, but not regular, increase in 87S/86Sr with two breaks in slope at 5.5 and 2.5 Ma. These times mark the beginning of two periods of steep increase in 87Sr/86Sr values, relative to preceding periods characterized by essentially constant values. During the last 2.5 Ma, 87Sr/86Sr values increased at an average rate of 0.000054/Ma. This steep increase suggests that the modem ocean is not in Sr isotopic equilibrium relative to its major input fluxes. A non-equilibrium model for the modern Sr budget suggests that the residence time of Sr is ~2.5 Ma, which is significantly less than previously accepted estimates of 4-5 Ma. Modelling results suggest that the increase in 87Sr/86Sr over the past 8 Ma could have resulted from a 25% increase in the riverine flux of Sr or an increase in the average 87Sr/86Sr of this flux by 0.0006. The dominant cause of increasing 87Sr/86Sr values of seawater during the late Neogene is believed to be increased rates of uplift and chemical weathering of mountainous regions. Calculations suggest that uplift and weathering of the Himalayan-Tibetan region alone can account for the majority of the observed 87Sr/86Sr increase since the early Late Miocene. Exhumation of Precambrian shield areas by continental ice-sheets may have contributed secondarily to accelerated mechanical and chemical weathering of old crustal silicates with high 87Sr/86Sr values. In fact, the upturn in 87Sr/86Sr at 2.5 Ma coincides with increased glacial activity in the Northern Hemisphere. A variety of geochemical (87Sr/86Sr, Ge/Si, d13C, CCD, etc.) and sedimentologic data (accumulation rates) from the marine sedimentary record are compatible with a progressive increase in the chemical weathering rate of continents and dissolved riverine fluxes during the late Cenozoic. We hypothesize that chemical weathering of the continents and dissolved riverine fluxes to the oceans reached a maximum during the late Pleistocene because of repeated glaciations, increased continental exposure by lowered sea level, and increased continental relief resulting from high rates of tectonism.

Oligocene-Miocene strontium isotopes of ODP Hole 120-747A

This study tests and improves on previously published early and middle Miocene 87Sr/86Sr marine correlations, presents Sr isotopic age correlations for this interval using the new timescale of Cande and Kent [1992 doi:10.1029/92JB01202], and evaluates Sr isotopic changes against an inferred glacioeustatic proxy. We generated a latest Oligocene to early late Miocene 87Sr/86Sr isotope record from Ocean Drilling Program (ODP) Hole 747A; this site provides an excellent magnetostratigraphic record during most of this interval for independent age estimates, very good foraminiferal preservation, and excellent core recovery. Comparisons of new 87Sr/86Sr data from Hole 747A with previously published data from Deep Sea Drilling Project (DSDP) Sites 608 [Miller et al., 1991 doi:10.1029/90PA01941] and 588 [Hodell et al., 1991 doi:10.1130/0091-7613(1991)019<0024:VITSIC>2.3.CO;2] yield the following results: (1) confirmation and refinement of the early Miocene Sr isotope changes, (2) improved definition of the timing of the changes in slope of 87Sr/86Sr near 15.4 Ma and 22.8 Ma, (3) improved Sr isotopic age resolution for the middle Miocene with resolution as good as +/- 0.7 m.y., and (4) identification of an inflection in the Sr isotope record at 28.0 Ma based on the combined records from DSDP Site 522 [Miller et al., 1988 doi:10.1029/PA003i002p00223] and ODP Hole 747A. We have been unable to determine the cause of middle Miocene offset between Site 588 and Hole 747A data, although we believe it may be attributed to problems in the age assignments for Hole 588A for the interval ~14-11 Ma and Site 747 for the interval 11-8 Ma. Because Hole 747A results provide a better chronology than Site 588 for most of the Miocene and a better middle Miocene Sr isotope record than Site 608, we propose that Hole 747A serves as the best reference section for Miocene 87Sr/86Sr variations from ca. 23 to 11 Ma. Using 87Sr/86Sr data from Sites 522, 608, and 747A, we relate late Eocene to early Miocene inflections in the 87Sr/86Sr isotope record to oxygen isotope increases and decreases inferred to represent glacioeustatic events. The decreases (deglaciations) observed in the ?18O record apparently lead the 87Sr/86Sr inflections by 1 to 1.5 m.y.

Isotopic composition and Strontium/Calcium ratios of foraminifera of ODP Holes 113-689B and 113-690C

Oxygen and carbon isotopic ratios were measured from Maestrichtian benthic and planktonic foraminifer species and bulk carbonate samples from ODP Sites 689 and 690, drilled on the Maud Rise during Leg 113. Careful scanning electron microscope observations reveal that test calcite in some intervals was diagenetically altered, although Sr/Ca and isotopic ratios of these tests do not appear to have been modified significantly. Foraminifer d18O values at both sites document a cooling trend during early Maestrichtian time, a rapid drop in water temperatures at the time of the first appearance of Abathomphalus mayaroensis in the high southern latitude regions (about 69.9 Ma), and lower water temperatures during late Maestrichtian time. d13C values record a depletion in 13C in the latest early Maestrichtian time beginning at about 72.2 Ma, just prior to the sharp late Maestrichtian increase in d18O values. These trends are similar to those previously reported for well-preserved benthic foraminifer species from Seymour Island, in the Antarctic Peninsula. Paleotemperature estimates are also comparable to those at Seymour Island and suggest temperate climatic conditions in Antarctica and that bottom waters in the southern South Atlantic region were of Antarctic origin. Benthic and planktonic foraminifer 613C values fluctuate sympathetically and are higher in upper Maestrichtian sediments than in the lower Maestrichtian sequence.

Geochemistry of Lau Backarc Basin sediments

Major and minor (Mn, Sr, Ba, V, Cr, Ni, Co, Zn, Cu, Zr, Y, Sc) elements and mineralogic compositions were determined on bulk sediments collected during Ocean Drilling Program Leg 135. Three classes of sediment samples from holes drilled in the Lau Basin are discriminated by mineralogy and major element data. Samples labeled Class 1 are significantly enriched in biogenic calcite and occur predominantly in the northern part of the basin (Sites 834-835), whereas those of Class 3 are mostly enriched in volcanogenic material and are predominant in the central part of the basin (Sites 836-839). The minor element composition records the effects of the hydrothermal activity on the sediments. In the northern area of the basin (Sites 834-835), sedimentation is characterized by higher accumulation rates of the carbonate and hydrothermal fractions. These sediments are probably reworked predominantly, transported in the water column, and then settled locally. Thus, ponded sediments are probably responsible to this high accumulation rates. Diagenetic processes altered the volcanic material to a grade corresponding to the stability of phillipsite. In the central area of the basin (Sites 836-839), sedimentation is characterized by the action of bottom currents preferentially reworking the carbonate and hydrothermal fractions. Volcanogenic accumulation rates are greater at these sites than in the northern Lau Basin. Alteration of volcanic material is more important deeper in the holes and records authigenesis of clay rich in Fe-Mg, most likely smectite. Locally, clay minerals have apparently incorporated Cr and other ore-forming elements.

Major element oxides in ODP Site 164-997 sediments

Since being first discovered in the Blake-Bahama region of the west Atlantic in the 1970s (Hollister, Ewing, et al., 1972, doi:10.2973/dsdp.proc.11.1972), submarine gas hydrates have been identified in the continental margin worldwide. Ocean Drilling Program (ODP) Leg 164 was the first drilling designated to study the occurrence and distribution of natural gas hydrates in Blake Ridge where a well developed, distinct BSR (Bottom Simulating Reflector) has been identified (Paull, Matsumoto, Wallace, et al., 1996, doi:10.2973/odp.proc.ir.164.1996). It has been reported there is a prominent discrepancy between the BSR and the base of gas hydrate stability (Paull, Matsumoto, Wallace, et al., 1996, doi:10.2973/odp.proc.ir.164.1996; Ruppel, 1997, doi:10.1130/0091-7613(1997)025<0699:ACTOAT>2.3.CO;2), though theoretically they should be at the same depth. Natural gas hydrate in marine sediments coexists with sediment particles, so detailed delineation of sediment geochemistry will be of benefit to solve this apparent discrepancy. The main objectives of this study are to supply background data of the major chemical compositions of sediments from a hydrated sediment section.