Chemical and isotopic composition of interstitial waters and hydrocarbon composition at ODP Site 184-1146

Bottom-simulating reflectors were observed beneath the southeastern slope of the Dongsha Islands in the South China Sea, raising the potential for the presence of gas hydrate in the area. We have analyzed the chemical and isotopic compositions of interstitial water, headspace gas, and authigenic siderite concretions from Site 1146. Geochemical anomalies, including a slight decrease of chlorine concentration in interstitial water, substantial increase of methane concentration in headspace gas, and 18O enrichment in the authigenic siderite concretion below 400 meters below seafloor are probably caused by the decomposition of gas hydrate. The low-chlorine pore fluids contain higher molecular-weight hydrocarbons and probably migrate to Site 1146 along faults or bedded planes.

Age and isotopic and chemical compositions of volcanic rocks from the Japan and Okhotsk Seas

This paper reports results of petrographic and geochemical studies of Miocene-Pleistocene volcanic rocks that accompanied formation of deep-water basins of the Sea of Japan and Sea of Okhotsk. Geochemical types of these rocks, their geodynamic settings, and their derivation from different magmatic sources were determined. Marginal-sea basaltoids from the Sea of Japan are derivatives of fluid-enriched mantle (EMI), while volcanics from the Kuril basin were generated from mantle enriched in continental crust matter (EMU). In spite of different conditions of their genesis, they have some common geochemical features, in particular, their calc-alkaline signatures. These traces of influence of the sialic crust on magma generation confirm development of the basins of both these seas on the continental basement.

(Table 2) Oxygen, carbon, and strontium isotopic composition of carbonate-brucite material from the Lost City hydrothermal field

The isotopic (dD, d18O, d13C, and 87Sr/86Sr) and geochemical characteristics of hydrothermal solutions from the Mid-Atlantic Ridge and the material of brucite-carbonate chimneys at the Lost City hydrothermal field at 30°N, MAR, were examined to assay the role of the major factors controlling the genesis of the fluid and hydrothermal chimneys of the Lost City field. The values of dD and d18O in fluid samples indicates that solutions at the Lost City field were produced during the serpentinization of basement ultramafic rocks at temperatures higher than 200°C and at relatively low fluid/rock ratios (<1). The active role of serpentinization processes in the genesis of the Lost City fluid also follows from the results of the electron-microscopic studying of the material of hydrothermal chimneys at this field. The isotopic (d18O, d13C, and 87Sr/86Sr) and geochemical (Sr/Ca and REE) signatures indicate that, before its submarine discharging at the Lost City field, the fluid filtered through already cold altered outer zones of the Atlantis Massif and cooled via conductive heat loss. During this stage, the fluid could partly dissolve previously deposited carbonates in veins cutting serpentinite at the upper levels of the Atlantis Massif and the carbonate cement of sedimentary breccias underlying the hydrothermal chimneys. Because of this, the age of modern hydrothermal activity at the Lost City field can be much younger than 25 ka.

Isotopic and chemical compositions of lower crust rocks and minerals from ODP Hole 176-735B

The composition of gabbroic rocks from the drill core of Hole 735B (ODP Leg 176) at the 11 Ma Atlantis II bank close to the slow spreading Southwest Indian Ridge (SWIR) has been analyzed for major and trace elements and Sr, Nd and Pb isotopic composition. The samples are thought to represent much of the mineralogical and geochemical variation in a vertical 1-km section (500-1500 m below the sea floor) of the lower ocean crust. Primitive troctolitic gabbros, olivine gabbros and gabbros that have Mg#=84-70, Ca#>61 and low Na# (Na/(Na+Al)) (8-17) are intruded by patches or veins of more evolved FeTi-oxide rich gabbroic and dioritic rocks with Mg# to 20, Ca# to 32, Na#=14-23, TiO2<7 wt.% and FeOtotal<18 wt.%. All rocks are acdcumulates, and incompatible element concentrations are low, e.g. Pb=0.1-0.7 ppm and Uisotopic compositions of the unleached rocks is: 87Sr/86Sr=0.70280-0.70299, average 0.70287+/-0.00005 (1 S.D., N=30 samples) (except one felsic vein with 87Sr/86Sr=0.7045), 143Nd/144Nd=0.51304-0.51314, average 0.51310+/-0.00002 (1 S.D., N=28), 206Pb/204Pb=17.43-18.55, 207Pb/204Pb=15.40-15.61 and 208Pb/204Pb=37.19-38.28. The range of Sr and the almost constant Nd isotopic composition resemble that found in the upper 500 m of Hole 735B, while Pb ranges to more radiogenic compositions. In general, there is a decrease in isotopic variation of Sr and Pb as well as ? (238U/204Pb), U and Pb with depth, with a trend towards relatively unradiogenic compositions. This correlates with a decrease in alteration and frequency of evolved rock-types in the core. Leached samples generally have less radiogenic Pb with values trending towards 206Pb/204Pb=17.35, 207Pb/204Pb=15.35 and 208Pb/204Pb=37.0, while their 87Sr/86Sr ratios deviate less systematically from unleached rocks and reach both higher, 0.70307, and lower values, 0.70276. Separated clinopyroxene has elevated 87Sr/86Sr up to 0.7035, while plagioclase generally has close to whole rock Sr. Leaching reduced 87Sr/86Sr in clinopyroxene and in two (out of nine) cases leached separates and whole rock display isotopic equilibrium. Relatively minor hydrothermal seawater alteration is thought to have increased 87Sr/86Sr in the rocks, while a secondary high temperature percolation of a mantle-derived agent is thought to be the cause for the trend towards radiogenic Pb. This material had intermediate 87Sr/86Sr and may have originated from non-MORB off axis mantle. The main primary igneous isotopic variation of the gabbros is suggested to have been derived from the MORB-mantle and is defined mainly by leached samples from both ODP Leg 176 and Leg 118 and can be explained by two-component mixing of an end-member with composition like Central Indian Ridge basalts and an end-member with composition unlike any MORB. The latter is characterized by very unradiogenic Pb, in particular 207Pb/204Pb, and may have an origin with affinity to old depleted mantle (DM). The isotopic composition of the magmas parental to the FeTi-oxide rich rocks cannot be distinguished from the magmas parental to the primitive gabbros and an intimate relationship is indicated. The small-scale inhomogeneity indicated for the SWIR MORB-mantle at the Atlantis II Fracture Zone was probably inherited by the lower crustal rocks due to small-scale melting and monogenetic magma chambers at this slow spreading ridge.

Chemical and boron isotopic compositions of volcanics from ODP Sites 135-834 to 135-840

The influence of fluid flux on petrogenesis in the Tonga-Kermadec Arc was investigated using ion microprobe measurements of B/Be and boron isotope ratios (11B/10B) to document the source and relative volumes of the fluids released from the subducting oceanic plate. We analyzed young lavas from eight different islands along the Tonga-Kermadec Arc, as well as glass shards in volcanic sediments from Ocean Drilling Program (ODP) Site 840, which record the variations in the chemistry of Tonga magmatism since 7 Ma. B/Be is variable (5.8-122), in young Tonga-Kermadec Arc lavas. In contrast, glass shards from around 3 to 4 Ma old volcanic sediments at Site 840 have the highest B/Be values yet reported for arc lavas (18-607). These values are too high to be related simply to a sediment influence on petrogenesis. Together with very high d11B values (-11.6 to +37.5) for the same shards and lavas these data indicate that most of the B is derived from fluid escaped from the subducting altered Pacific oceanic crust, rather than from sediment. High d11B values also reflect large degrees of isotopic fractionation in this cold fast subduction zone. Lower d11B values noted in the Kermadec Arc (17 to -4.4) are related to the influence of sediment eroded from New Zealand and slower convergence. High fluid flux (B/Be) is synchronous in Tonga and the Marianas at 3 to 4 Ma and may be related to acceleration of the Pacific Plate just prior to this time. The timing of maximum B/Be at 3 to 4 Ma correlates with maximum light rare earth (LREE) and high field strength element depletion. This suggests maximum degrees of partial melting at this time. Although thinning of the arc lithosphere during rifting to form the Lau Basin is expected to influence the arc geochemistry, variable aqueous fluid flux from the subducting plate alone appears capable of explaining boron and other trace element systematics in the Tonga-Kermadec Arc with no indication of slab melting.

Sr/Ca ratios of Cenozoic benthic foraminifera

A Cenozoic multi-species record of benthic foraminiferal calcite Sr/Ca has been produced and is corrected for interspecific offsets (typically less than 0.3 mmol/mol) and for the linear relationship between decreasing benthic foraminiferal Sr/Ca and increasing water depth. The water depth correction, determined from Holocene, Late Glacial Maximum and Eocene paleowater-depth transects, is ~0.1 mmol/mol/km. The corrected Cenozoic benthic foraminiferal Sr/Ca record ranges from 1.2 to 2.0 mmol/mol, and has been interpreted in terms of long-term changes in seawater Sr/Ca, enabling issues related to higher-resolution variability in Sr/Ca to be ignored. We estimate that seawater Sr/Ca was ~1.5 times modern values in the late Cretaceous, but declined rapidly into the Paleogene. Following a minimum in the Eocene, seawater Sr/Ca increased gradually through to the present day with a minimum superimposed on this trend centered in the late Miocene. By assuming scenarios for changing seawater calcium concentration, and using published carbonate accumulation rate data combined with suitable values for Sr partition coefficients into carbonates, the seawater Sr/Ca record is used to estimate global average river Sr fluxes. These fluxes are used in conjunction with the seawater strontium isotope curve and estimates of hydrothermal activity/tectonic outgassing to calculate changes in global average river 87Sr/86Sr through the Cenozoic. The absolute magnitude of Sr fluxes and isotopic compositions calculated in this way are subject to relatively large uncertainties. Nevertheless, our results suggest that river Sr flux increased from 35 Ma to the present day (roughly two-fold) accompanied by an overall increase in 87Sr/86Sr (by ~0 to 0.001). Between 75 and 35 Ma, river 87Sr/86Sr also increased (by ~0.001 to 0.002) but was accompanied by a decrease (two- to three-fold) in river Sr flux.

Trace element abundances and Sr and Nd isotope compositions in bulk sediments from DSDP Legs 6 and 20

Rare earth element and Nd isotopic data for ten representative samples of Lower Cretaceous to Miocene pelagic sediments from the western Pacific indicate a wide range of compositions for sediments being subducted beneath the Mariana and Volcano arcs. All samples are enriched in light rare earth elements and show negative Eu and Ce anomalies. The values of e-Nd range from +0.6 to -7.3. These data are used to calculate the Bulk Western Pacific Sediment (BWPS), which is characterized by low Sr/Nd (10), Ba/La (13), and e-Nd (-5.2) and high 87Sr/86Sr (0.7078) compared to that of Mariana and Volcano arc lavas. This composite sediment is used to refine a mixing model for the origin of Mariana and Volcano arc melts. Some lavas from the northern Mariana Arc have Ba/La higher than that of BWPS, which indicates that a third component is required. The high Ba/La in the mantle source for these lavas is interpreted to result from multiple episodes of fluid fractionation. The mixing model indicates that a minor amount of sediment and a low proportion of metasomatic fluid fluxes the mantle source at a late stage when the subarc mantle is already highly metasomatized. This model also suggests that the mantle source for arc melts is affected more by metasomatic fluids than by melting or bulk mixing of sediments.

Isotopic composition of rocks from the Lau/Tonga back-arc basin, data of DSDP Leg 21 and ODP Legs 91 an 135

New trace element, Sr-, Nd-, Pb- and Hf isotope data provide insights into the evolution of the Tonga-Lau Basin subduction system. The involvement of two separate mantle domains, namely Pacific MORB mantle in the pre-rift and early stages of back-arc basin formation, and Indian MORB mantle in the later stages, is confirmed by these results. Contrary to models proposed in recent studies on the basis of Pb isotope and other compositional data, this change in mantle wedge character best explains the shift in the isotopic composition, particularly 143Nd/144Nd ratios, of modern Tofua Arc magmas relative to all other arc products from this region. Nevertheless, significant changes in the slab-derived flux during the evolution of the arc system are also required to explain second order variations in magma chemistry. In this region, the slab-derived flux is dominated by fluid; however, these fluids carry Pb with sediment-influenced isotopic signatures, indicating that their source is not restricted to the subducting altered mafic oceanic crust. This has been the case from the earliest magmatic activity in the arc (Eocene) until the present time, with the exception of two periods of magmatic activity recorded in samples from the Lau Islands. Both the Lau Volcanic Group, and Korobasaga Volcanic Group lavas preserve trace element and isotope evidence for a contribution from subducted sediment that was not transported as a fluid, but possibly in the form of a melt. This component shares similarities with that influencing the chemistry of the northern Tofua Arc magmas, suggesting some caution may be required in the adoption of constraints for the latter dependent upon the involvement of sediments from the Louisville Ridge. A key outcome of this study is to demonstrate that the models proposed to explain subduction zone magmatism cannot afford to ignore the small but important contributions made by the mantle wedge to the incompatible trace element inventory of arc magmas.

Isotopic composition of diagenetic silica and associated pore waters of Japan Sea sediments

Over a broad region of the eastern Japan Sea, Neogene opaline diatomaceous sediments alter with depth to hard porcellanites and cherts composed of opal-CT and quartz. We examined the oxygen isotopic compositions of these diagenetic silica minerals at four widely spaced sites occupied during ODP Leg 127 in order to investigate the thermal history of the region. Formation temperatures computed from these isotopic data range from 22° to 68°C for opal-CT and from 44° to 92°C for diagenetic quartz, quite similar to temperature ranges estimated from the extrapolated modern gradients, 36°-43°C and 49°-64°C, respectively. At each site the isotopic temperature values cluster near the extrapolated ambient sediment temperatures. As a first approximation, the similarities suggest that the positions of the silica transformations in the basin are controlled by the present thermal regime. In detail, isotopic and ambient temperatures differ. If these differences are real, then they reflect variations in the thermal histories at these sites. At Sites 794 and 797 in the Yamato Basin, isotopic temperatures and gradients computed from these data are lower than or comparable to ambient temperatures and gradients. We suggest that the silica zones have roughly equilibrated with the modern gradients at these localities. At Site 795 in the Japan Basin, isotopic temperatures are also lower than ambient sediment temperatures at comparable depths, but the gradient computed from the isotopic temperatures is higher than the present measured gradient. For both scenarios to hold, the silica zones must have formed under initially high gradients during the early post-rift period at this locality. These zones were then rapidly buried and have yet to equilibrate with the modern lower gradient. At Site 796 on Okushiri Ridge, isotopic temperatures exceed present temperatures as expected for an area of recent uplift. The gradient computed from our isotopic data and the thickness of the opal-CT zone indicate a higher gradient than at present at this site, apparently reflecting higher heat fluxes during the early post-rift period or recent frictional heating from nearby reverse fault activity.