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.

Mineralogy and isotopic composition of sulfur in ODP Hole 118-735B gabbros

Sulfide mineralogy, sulfur contents, and sulfur isotopic compositions were determined for samples from the 500-m gabbroic section of Ocean Drilling Program Hole 735B in the southwest Indian Ocean. Igneous sulfides (pyrrhotite, chalcopyrite, pentlandite, and troilite) formed by accumulation of immiscible sulfide droplets and crystallization from intercumulus liquids. Primary sulfur contents average around 600 ppm, with a mean sulfide d34S value near 0 per mil, similar to the isotopic composition of sulfur in mid-ocean ridge basalt glass. Rocks from a 48-m interval of oxide gabbros have much higher sulfur contents (1090-2530 ppm S) due to the increased solubility of sulfur in Fe-rich melts. Rocks that were locally affected by early dynamothermal metamorphism (e.g., the upper 40 m of the core) have lost sulfur, averaging only 90 ppm S. Samples from the upper 200 m of the core, which underwent subsequent hydrothermal alteration, also lost sulfur and contain an average of 300 ppm S. Monosulfide minerals in some of the latter have elevated d34S values (up to +6.9 per mil), suggesting local incorporation of seawater-derived sulfur. Secondary sulfides (pyrrhotite, chalcopyrite, pentlandite, troilite, and pyrite) are ubiquitous in trace amounts throughout the core, particularly in altered olivine and in green amphibole. Pyrite also locally replaces igneous pyrrhotite. Rocks containing secondary pyrite associated with late low-temperature smectitic alteration have low d34S values for pyrite sulfur (to - 16.6 per mil). These low values are attributed to isotopic fractionation produced during partial oxidation of igneous sulfides by cold seawater. The rocks contain small amounts of soluble sulfate (6% of total S), which is composed of variable proportions of seawater sulfate and oxidized igneous sulfur. The ultimate effect of secondary processes on layer 3 gabbros is a loss of sulfur to hydrothermal fluids, with little or no net change in d34S.

Chemical composition and age of metamorphic rocks from the Khavyven Highland, Eastern Kamchatka

Metamorphic rocks of the Khavyven Highland in eastern Kamchatka were determined to comprise two complexes of metavolcanic rocks that have different ages and are associated with subordinate amounts of metasediments. The complex composing the lower part of the visible vertical section of the highland is dominated by leucocratic amphibole-mica (+/-garnet) and epidote-mica (+/-garnet) crystalline schists, whose protoliths were andesites and dacites and their high-K varieties of island-arc calc-alkaline series. The other complex composing the upper part of the vertical section consists of spilitized basaltoids transformed into epidote-amphibole and phengite-epidote-amphibole green schists, which form (together with quartzites, serpentinized peridotites, serpentinites, and gabbroids) a sea-margin ophiolitic association. High LILE concentrations, high K/La, Ba/Th, Th/Ta, and La/Nb ratios, deep Ta-Nb minima, and low (La/Yb)_N and high 87Sr/86Sr ratios of the crystalline schists of the lower unit are demonstrated to testify to their subduction nature and suggest that their protolithic volcanics were produced in the suprasubduction environment of the Ozernoi-Valaginskii (Achaivayam-Valaginskii) island volcanic arc of Campanian-Paleogene age. The green schists of the upper unit show features of depleted MOR tholeiitic melts and subduction melts, which cause the deep Ta-Nb minima, and low K/La and 87Sr/86Sr ratios suggesting that the green schists formed in a marginal basin in front of the Ozernoi-Valaginskaya island arc. Recently obtained K-Ar ages in the Khavyven Highland vary from 32.4 to 39.3 Ma and indicate that metamorphism of the protolithic rocks occurred in Eocene under effect of collision and accretion processes of the arc complexes of the Ozernoi-Valaginskii and Kronotskii island arcs with the Asian continent and the closure of forearc oceanic basins in front of them. The modern position of the collision suture that marks the fossil subduction zone of the Ozernoi-Valaginskii arc and is spatially restricted to the buried Khavyven uplift in the Central Kamchatka Depression characterized by well-pronounced linear gravity anomalies.

Major and trace element composition of sepentine muds and metabasic rocks of ODP Leg 195 and Leg 125 sites

New geochemical data on serpentinite muds and metamorphic clasts recovered during Ocean Drilling Program Legs 195 (Holes 1200A-1200E) and 125 (Holes 778A and 779A) provide insights into the proportions of rock types of various sources that compose the serpentinite mudflows and the fluid-rock interactions that predominate in these muds. We interpret the metamorphic rock fragments as derivatives of mostly metamorphosed mafic rocks from the descending Pacific oceanic crust. Based on their mid-ocean-ridge basalt (MORB)-like Al2O3, TiO2, CaO, Si/Mg, and rare earth element (REE) systematics, these metamorphic rocks are classified as metabasalts/metagabbros and, therefore, ~30-km depths represent an active subduction zone setting. The serpentinite muds from Holes 1200A and 1200E have slightly lower REE when compared to Hole 1200D, but overall the REE abundance levels range between 0.1-1 x chondrite (CI) levels. The chondrite-normalized patterns have [La/Sm]N ~ 2.3 and [Sm/Yb]N ~ 2. With the exception of one sample, the analyzed metamorphic clasts show flat to slightly depleted light REE patterns with 1.0-15 x CI levels, resembling MORBs. Visually, ~6 vol% of the serpentinized muds are composed of 'exotic' materials (metamorphic clasts [schists]). Our mixing calculations confirm this result and show that the serpentinite muds are produced by additions of ~5% metamafic materials (with flat and up to 10 x CI REE levels) to serpentinized peridotite clast material (with very low REE abundances and U-shaped chondrite-normalized patterns). The preferential incorporation of B, Cs, Rb, Li, As, Sb, and Ba into the structure of H2O-bearing sheet silicates (different than serpentine) in the Leg 125 and Leg 195 metamorphic clasts (chlorite, amphibole, and micas) have little effect on the overall fluid-mobile element (FME) enrichments in the serpentinite muds (average B = ~13 ppm; average Cs = ~0.05 ppm; average As = ~1.25 ppm). The extent of FME enrichment in the serpentinized muds is similar to that described for the serpentinized peridotites, both recording interaction with fluids very rich in B, Cs, and As originating from the subducting Pacific slab.

Chemical and isotopic compositions of rocks and minerals from the Franz Josef Land Archipelago

Rb, Sr, Sm, Nd, U, and Pb contents and Sr, Nd, and Pb isotopic composition were determined in tholeiite and subalkaline basalts (in both whole-rock samples and individual minerals) from the Franz Josef Land Archipelago. Isotopic data obtained for the Arctic basin are similar to those for islands from the Pacific, Atlantic, and Indian oceans. The assimilation of crustal (sedimentary) rocks by primary depleted material makes isochron determination of basalt age difficult or impossible. The subalkaline basalts (basaltic andesites) were presumably formed by the metasomatic introduction of incompatible elements in tholeiitie basalts and, only partially, through crustal contamination and fractional crystallization.

Petrography and geochemistry of basement rocks from five DSDP Leg 60 Sites

Bulk chemistry and trace elements data were measured in 72 samples, selected from 5 basement sections, which have been recovered by Leg 60 drilling (Sites 453, 454, 456, 458, and 459). According to analytical results a metagabbro- metabasalt breccia, deposited about 5 Ma at the westernmost flank of the Mariana Trough (Site 453), was derived from an island arc source. Basalts from the Mariana Trough (Sites 454 and 456) are similar in many respects to midoceanic ridge basalts (MORB). Yet rocks of unusual geochemistry, reflecting the possible influence of arc volcanism, were found among the pillow lavas at the easternmost trough (Site 456). The acoustic basement in the Mariana fore-arc region was formed by submarine eruptions of arc tholeiites (Sites 458 and 459) and peculiar high-MgO andesites related to the boninite suite.

Chemical composition of Ninetyeast Ridge basalts

On Leg 121 of the Ocean Drilling Program, we recovered basaltic rocks from a total of three basement sites in the southern, central, and northern regions of Ninetyeast Ridge. These new sites complement the previous four basement holes drilled during Legs 22 and 26 of the Deep Sea Drilling Project, and confirm the predominantly tholeiitic, light rare earth element-enriched character of the basalts that cap the ridge. The basalts show marked iron enrichment; ferrobasalts occur at Sites 214 and 216 and oceanic andesites at Site 253. All of the basalts recovered during Leg 121 are altered, and range from aphyric olivine tholeiites (Site 756), to strongly plagioclase-phyric basalts (Site 757). Basalts from Site 758, which were clearly erupted in a submarine environment (pillow basalts are present in the section), are sparsely to strongly plagioclase-phyric. The basalts recovered at any one hole are isotopically homogeneous (except for the basalts from Site 758, which show a range of Pb isotopes), and it is possible to relate the magmas at any one site by high-level fractionation processes. However, there are significant variations in isotope ratios and highly incompatible element ratios between sites, which suggest that the mantle source for the ridge basalts was compositionally variable. Such variation, in view of the large volume of magmatic products that form the ridge system, is not surprising. There is not, however, a systematic variation in basalt composition along the ridge. We agree with previous models that relate Ninetyeast Ridge to a mantle plume in the southern Indian Ocean. The tholeiitic, iron-enriched, and voluminous character of the ridge basalts is typical of oceanic islands associated with plumes on or near a mid-ocean ridge (e.g., Iceland, Galapagos Islands, and St. Paul/Amsterdam islands). The absence of recovered alkalic suites is inconsistent with an intraplate setting, such as the Hawaiian Islands or Kerguelen Island. Thus, the major element data, like the gravity data, strongly suggest that the ridge was erupted on or very close to an active spreading center. Isotopically, the most likely plume that created the excess magmatism on the Ridge is the Kerguelen-Heard plume system, but the Ninetyeast Ridge basalts do not represent a simple mixing of the Kerguelen plume and mid-ocean Ninetyeast Ridge basalt mantle.

Petrography and geochemistry of lithic clasts in sediments obtained from ODP Leg 180 sites

This report includes the petrographic description and reviews the distribution of lithic clasts in sediments drilled during Leg 180 in the Woodlark Basin (southwest Pacific). The lithic clasts include (1) metamorphic rocks; (2) granites; (3) serpentinites, gabbros, dolerites, and basalts likely derived from the Papuan ophiolite belt; (4) rare alkaline volcanites reworked in middle Miocene sediments; (5) medium- to high-K calc-alkaline island arc volcanites, in part as reworked clasts, and explosive products deposited by fallout or reworked by turbiditic currents; and (6) rare sedimentary fragments. At the footwall sites the clast assemblage evidences the association of dolerites and evolved gabbroic rocks; the serpentinite likely pertaining to the same ophiolitic complex are likely derived from onland outcrops and transported by means of turbidity currents. On the whole, extensional tectonics active at least since the middle Pliocene can be inferred. The calc-alkaline volcanism is in continuity with the arc-related products from the Papua Peninsula and D'Entrecasteaux Islands and with the latest volcanics of the Miocene Trobrian arc. However, the medium- to high-K and shoshonitic products do not display a significant temporal evolution within the stratigraphic setting. Lava clasts, volcanogenic grains, and glass shards are associated with turbidity currents, whereas in the Pliocene of northern margin the increasing frequency of tephra (glass shards and vesicular silicic fragments) suggests more explosive activity and increasing contribution to the sediments from aerial fallout materials. Evidence of localized alkalic volcanism of presumable early to middle Miocene age is a new finding. It could represent a rift phase earlier than or coeval to the first opening of the Woodlark Basin or, less probably, could derive from depositional trajectories diverted from an adjacent basin.

Chemical and isotopic composition of rocks and minerals at ODP Site 209-1275

This paper reports results of an investigation of a representative collection of samples recovered by deep-sea drilling from the oceanic basement 10 miles west of the rift valley axis in the crest zone of the Mid- Atlantic Ridge at 15°44'N (Sites 1275B and 1275D). Drilling operations were carried out during Leg 209 of the Drilling Vessel JOIDES Resolution within the framework of the Ocean Drilling Program (ODP). The oceanic crust was penetrated to depth of 108.7 m at Site 1275B and 209 m at Site 1275D. We reconstructed the following sequence of magmatic and metamorphic events resulting in the formation of a typical oceanic core complex of slow-spreading ridges: (1) formation of strongly fractionated (enriched in iron and titanium) tholeiitic magmatic melt parental to gabbroids under investigation in a large magma chamber located in a shallow mantle and operating for a long time under steady-state conditions; (2) transfer of the parental magmatic melt of the gabbroids to the base of the oceanic crust, its interaction with host mantle peridotites, and formation of troctolites and plagioclase peridotites; (3) intrusion of enriched trondhjemite melts as veins and dikes in the early formed plutonic complex, contact recrystallization of the gabbro, and development in the peridotite-gabbro complex of enriched geochemical signatures owing to influence of trondhjemite injections; (4) emplacement of dolerite dikes (transformed to diabases); (5) metamorphism of upper epidoteamphibolite facies with participation of marine fluids; and (6) rapid exhumation of the plutonic complex to the seafloor accompanied by greenschist-facies metamorphism. Distribution patterns of Sr and Nd isotopes and strongly incompatible elements in the rocks suggest contributions from two melt sources to the magmatic evolution of the MAR crest at 15°44'N: a depleted reservoir responsible for formation of the gabbros and diabases and an enriched reservoir, from which trondhjemites (granophyres) were derived.

Geochemistry of ODP Site 125-786 volcanic rocks

Eocene-Oligocene volcanic rocks drilled at Site 786 in the Izu-Bonin forearc cover a wide range of compositions from primitive boninites to highly evolved rhyolites. K-Ar dating reveals at least two distinct episodes of magmatism; one at 41 Ma and a later one at 35 Ma. The early episode produced low-Ca boninites and bronzite andesites that form an oceanic basement of pillow lavas and composite intrusive sheets, overlain by flows and intrusive sheets of intermediate-Ca boninites and bronzite-andesites and a fractionated series of andesites, dacites, and rhyolites. The later episode produced high-Ca boninites and intermediate-Ca boninites, exclusively as intrusive sheets.

Physical properties and elastic constants of ODP Holes 137-504B and 140-504B upper crustal rocks

Seismic velocities have been measured at confining pressures of 100 MPa and 600 MPa for sheeted dike samples recovered during Ocean Drilling Program Legs 137 and 140. The compressional- and shear-wave velocities show an increase with depth at Hole 504B, which is in sharp contrast to the atmospheric pressure velocity measurements performed as part of the shipboard analyses. Rocks exposed to different types of alteration and fracture patterns show distinct changes in their physical properties. The seismic reflectors observed on the vertical seismic profile (VSP) experiment performed during Leg 111 may have been caused by low velocity zones resulting from alteration. The amount of fracturing and hydrothermal alteration in several zones also may have contributed to the acoustic impedance contrast necessary to produce the E5 reflector. Poisson's ratios calculated from laboratory velocity measurements show several low values at depths ranging from 1600 mbsf to 2000 mbsf, which tends to follow similar trends obtained from previous oceanic refraction experiments. A comparison of physical properties between samples recovered from Hole 504B and ophiolite studies in the Bay of Islands and Oman shows a good correlation with the Bay of Islands but significant differences from the measurements performed in the Oman complex.

Step-heating degassing data for argon-39 from volcanic rocks drilled in the Shikoku Basin and Mariana trench, DSDP Legs 58 and 60

From the experimental data on stepwise thermal release of neutron induced 39Ar (39K (n, p) 39Ar) from rocks and minerals, Arrhenius plots were constructed, which gave activation energies for the thermal release process. The activation energies for DSDP Leg 58 and Leg 60 submarine volcanic rocks range from 12 to 20 kcal/mol, whereas those for granodiorites and the K-feldspar separates have activation energies ranging from 37 to 48 kcal/mol. The smaller activation energies for the submarine volcanic rocks reflect the grain boundary diffusion process, while the thermal diffusion of 39Ar from granodiorites and K-feldspar is essentially controlled by a volume diffusion. The grain boundary diffusion for the submarine volcanic rocks suggests that K resides essentially in the grain boundaries.