Petrology and isotope characteristics of basalts from ODP Hole 111-504B

Petrography and isotope geochemical characteristics of H, O, S, Sr, and Nd have been described for basalts recovered from Hole 504B during Leg 111 of the Ocean Drilling Program. The petrographic and chemical features of the recovered basalts are similar to those obtained previously (DSDP Legs 69, 70, and 83); they can be divided into phyric (plagioclase-rich) and aphyric (Plagioclase- and clinopyroxene-rich) basalts and show low abundances of TiO2, Na2O, K2O, and Sr. This indicates that the basalts belong to Group D, comprising the majority of the upper section of the Hole 504B. The diopside-rich nature of the clinopyroxene phenocrysts and Ca-rich nature of the Plagioclase phenocrysts are also consistent with the preceding statement. The Sr and Nd isotope systematics (average 87Sr/86Sr = 0.70267 ± 0.00007 and average 143Nd/144Nd = 0.513157 ± 0.000041) indicate that the magma sources are isotopically heterogeneous, although the analyzed samples represent only the lowermost 200-m section of Hole 504B. The rocks were subjected to moderate hydrothermal alteration throughout the section recovered during Leg 111. Alteration is limited to interstices, microfractures, and grain boundaries of the primary minerals, forming chlorite, actinolite, talc, smectite, quartz, sphene, and pyrite. In harmony with the moderate alteration, the following alteration-sensitive parameters show rather limited ranges of variation: H2O = 1.1 ±0.2 wt%, dD = - 38 per mil ± 4 per mil, d180 = 5.4 per mil ± 0.3 per mil, total S = 562 ± 181 ppm, and d34S = 0.8 per mil ± 0.3 per mil. Based on these data, it was estimated that the hydrothermal fluids had dD and d180 values only slightly higher than those of seawater, the water/rock ratios were as low as 0.02-0.2, and the temperature of alteration was 300°-400°C. Sulfur exists predominantly as pyrite and in minor quantities as chalcopyrite. No primary monosulfide was detected. This and the d34S values of pyrite (d34S = 0.8 per mil) suggest that primary pyrrhotite was almost completely oxidized to pyrite by reaction with hydrothermal fluids containing very little sulfate.

Mineralogy and geochemistry of Mg-phyllosilicates from Middle Valley, northern Juan de Fuca Ridge

We present results of a detailed mineralogical and geochemical study of the progressive hydrothermal alteration of clastic sediments recovered at ODP Site 858 in an area of active hydrothermal venting at the sedimented, axial rift valley of Middle Valley (northern Juan de Fuca Ridge). These results allow a characterization of newly formed phyllosilicates and provide constraints on the mechanisms of clay formation and controls of mineral reactions on the chemical and isotopic composition of hydrothermal fluids. Hydrothermal alteration at Site 858 is characterized by a progressive change in phyllosilicate assemblages with depth. In the immediate vent area, at Hole 858B, detrital layers are intercalated with pure hydrothermal precipitates at the top of the section, with a predominance of hydrothermal phases at depth. Sequentially downhole in Hole 858B, the clay fraction of the pure hydrothermal layers changes from smectite to corrensite to swelling chlorite and finally to chlorite. In three pure hydrothermal layers in the deepest part of Hole 858B, the clay minerals coexist with neoformed quartz. Neoformed and detrital components are clearly distinguished on the basis of morphology, as seen by SEM and TEM, and by their chemical and stable isotope compositions. Corrensite is characterized by a 24 Å stacking sequence and high Si- and Mg-contents, with Fe/(Fe+Mg) ratio of = 0.08. We propose that corrensite is a unique, possibly metastable, mineralogical phase and was precipitated directly from seawater-dominated hydrothermal fluids. Hydrothermal chlorite in Hole 858B has a stacking sequence of 14 Å with Fe/(Fe+Mg) ratios of ? 0.35. The chemistry and structure of swelling chlorite suggest that it is a corrensiteychlorite mixed-layer phase. The mineralogical zonation in Hole 858B is accompanied by a systematic decrease in d18O, reflecting both the high thermal gradients that prevail at Site 858 and extensive sediment-fluid interaction. Precipitation of the Mg-phyllosilicates in the vent region directly controls the chemical and isotopic compositions of the pore fluids. This is particularly evident by decreases in Mg and enrichments in deuterium and salinity in the pore fluids at depths at which corrensite and chlorite are formed. Structural formulae calculated from TEM-EDX analyses were used to construct clay-H2O oxygen isotope fractionation curves based on oxygen bond models. Our results suggest isotopic disequilibrium conditions for corrensite-quartz and swelling chlorite-quartz precipitation, but yield an equilibrium temperature of 300° C ± 30° for chlorite-quartz at 32 m below the surface. This estimate is consistent with independent estimates and indicates steep thermal gradients of 10-11°/m in the vent region.

Chemistry of hydrothermal clasy and sulfides of ODP Site 106-649

Several meters of unconsolidated hydrothermal sediment were recovered from the Snake Pit hydrothermal field during ODP Leg 106. Polymetallic sulfides comprise most of the sediment with minor fragments of massive sulfide, organic debris, clay minerals, and fresh glass shards. Trace element and Sr-isotope contents of hydrothermal clays and sulfides from Holes 649B and 649G indicate that these minerals precipitated from a mixed hydrothermal fluid-seawater solution. Evaluation of the REE mineral data and the Snake Pit hydrothermal fluids shows that the REE distribution coefficients between the hydrothermal fluids and clay-sulfide mixes range from 100-500. This indicates that hydrothermal fluids originating in the root-zone of the Snake Pit hydrothermal system may be modified by the precipitation of hydrothermal minerals, either in the shallow subsurface or within chimney structures. Contrasting REE profiles of clay-sulfide aggregates and massive sulfides from Holes 649B and 649G may be accounted for by spatial and/or temporal variations in redox conditions in the plumbing system.

Geochemistry and mineralogy of ultramafic rocks from conical seamount

The Mariana arc-trench system, the easternmost of a series of backarc basins and intervening remnant arcs that form the eastern edge of the Philippine Sea Plate, is a well-known example of an intraoceanic convergence zone. Its evolution has been studied by numerous investigators over nearly two decades (e.g., Kang, 1971; Uyeda and Kanamori, 1979; LaTraille and Hussong, 1980; Fryer and Hussong, 1981; Mrosowski et al., 1982; Hussong and Uyeda, 1981; Bloomer and Hawkins, 1983; Karig and Ranken, 1983; McCabe and Uyeda, 1983; Hsui and Youngquist, 1985; Fryer and Fryer, 1987; Johnson and Fryer, 1988; Johnson and Fryer, 1989; Johnson et al., 1991). The Mariana forearc has undergone extensive vertical uplift and subsidence in response to seamount collision, to tensional and rotational fracturing associated with adjustments to plate subduction, and to changes in the configuration of the arc (Hussong and Uyeda, 1981; Fryer et al., 1985). Serpentine seamounts, up to 2500 m high and 30 km in diameter, occur in a broad zone along the outer-arc high (Fryer et al., 1985; Fryer and Fryer, 1987). These seamounts may be horsts of serpentinized ultramafic rocks or may have been formed by the extrusion of serpentine muds. Conical Seamount, one of these serpentine seamounts, is located within this broad zone of forearc seamounts, about 80 km from the trench axis, at about 19°30'N. The seamount is approximately 20 km in diameter and rises 1500 m above the surrounding seafloor. Alvin submersible, R/V Sonne bottom photography, seismic reflection, and SeaMARC II studies indicate that the surface of this seamount is composed of unconsolidated serpentine muds that contain clasts of serpentinized ultramafic and metamorphosed mafic rocks, and authigenic carbonate and silicate minerals (Saboda et al., 1987; Haggerty, 1987; Fryer et al., 1990; Saboda, 1991). During Leg 125, three sites were drilled (two flank sites and one summit site) on Conical Seamount to investigate the origin and evolution of the seamount. Site 778 (19°29.93'N, 146°39.94'E) is located in the midflank region of the southern quadrant of Conical Seamount at a depth of 3913.7 meters below sea level (mbsl) (Fig. 2). This site is located in the center of a major region of serpentine flows (Fryer et al., 1985, 1990). Site 779 (19°30.75'N, 146°41.75'E), about 3.5 km northeast of Site 778, is located approximately in the midflank region of the southeast quadrant of Conical Seamount, at a depth of 3947.2 mbsl. This area is mantled by a pelagic sediment cover, overlying exposures of unconsolidated serpentine muds that contain serpentinized clasts of mafic and ultramafic rocks (Fryer et al., 1985, 1990). Site 780 (19°32.5'N, 146°39.2'E) is located on the western side of Conical Seamount near the summit, at a depth of 3083.4 mbsl. This area is only partly sediment covered and lies near active venting fields where chimney structures are forming (Fryer et al., 1990).

Mineral composition, major element oxides and trace element concentration of sediments from ODP Leg 180 sites

Middle Miocene to Holocene fine-grained argillaceous sediments (clays, claystones/muds, and mudstones), which volumetrically dominated the sediment recovery in the Woodlark Basin during Leg 180, were chemically analyzed for major elements, trace elements, and some rare earth elements by X-ray fluorescence. Selected samples also underwent X-ray diffraction (XRD) analysis for mineral determination. The results shed light on sediment provenance when combined with shipboard sediment descriptions, smear slide study, and XRD. The oldest sediments recovered (Site 1108) of middle-late Miocene age include volcanogenic muds with distinctive high MgO and K2O, indicative of a relatively basic calc-alkaline source related to an inferred Miocene forearc succession. The forearc basement, composed of diabase and basalt, was locally exposed (Site 1109) and eroded in the late Miocene (<5.4-9.93 Ma), giving rise to fluvial conglomerates (Sites 1109, 1115, and 1118). Chemically distinctive fine-grained claystones and siltstones (with relatively high Ti, low K) are compatible with derivation from tropically weathered basic igneous rocks, correlated with the Paleogene Papuan ophiolite. Overlying latest Miocene-Pleistocene fine-grained sediments throughout the Woodlark Basin were partly derived from calc-alkaline volcanic sources. However, relatively high abundances of Al2O3 and related element oxides (K2O and Na2O) and trace elements (e.g., Rb and Y) reflect an additional terrigenous input throughout the basin, correlated with pelitic metamorphic rocks exposed on Papua New Guinea and adjacent areas. In addition, sporadic high abundances of Cr and Ni, some other trace metals, and related minerals (talc, crysotile, and chlorite) reflect input from an ophiolitic terrain dominated by ultramafic rocks, correlated with the Paleogene Papuan ophiolite. The source areas possibly included serpentinized ultramafic ophiolitic rocks exposed in the Papua New Guinea interior highlands. Chemical evidence further indicates that fine-grained terrigenous sediment reached the Woodlark Basin throughout its entire late Miocene-Holocene history. Distinctive high-K volcanogenic muds rich in tephra and volcanic ash layers that appear at <2.3 Ma (Sites 1109 and 1115) are indicative of high-K calc-alkaline volcanic centers, possibly located in the Dawson Strait, Moresby Strait, or Dobu Seamount area. Chemical diagenesis of fine-grained sediments within the Woodlark Basin is reflected in clay neomorphism and localized formation of minerals including dolomite, ankerite, and zeolite but has had little effect on the bulk chemical composition of most samples.

Geochemistry of ocean floor and forearc serpentinites

We provide new insights into the geochemistry of serpentinites from mid-ocean ridges (Mid-Atlantic Ridge and Hess Deep), passive margins (Iberia Abyssal Plain and Newfoundland) and fore-arcs (Mariana and Guatemala) based on bulk-rock and in situ mineral major and trace element compositional data collected on drill cores from the Deep Sea Drilling Project and Ocean Drilling Program. These data are important for constraining the serpentinite-hosted trace element inventory of subduction zones. Bulk serpentinites show up to several orders of magnitude enrichments in Cl, B, Sr, U, Sb, Pb, Rb, Cs and Li relative to elements of similar compatibility during mantle melting, which correspond to the highest primitive mantle-normalized B/Nb, B/Th, U/Th, Sb/Ce, Sr/Nd and Li/Y among subducted lithologies of the oceanic lithosphere (serpentinites, sediments and altered igneous oceanic crust). Among the elements showing relative enrichment, Cl and B are by far the most abundant with bulk concentrations mostly above 1000 µg/g and 30 µg/g, respectively. All other trace elements showing relative enrichments are generally present in low concentrations (µg/g level), except Sr in carbonate-bearing serpentinites (thousands of µg/g). In situ data indicate that concentrations of Cl, B, Sr, U, Sb, Rb and Cs are, and that of Li can be, increased by serpentinization. These elements are largely hosted in serpentine (lizardite and chrysotile, but not antigorite). Aragonite precipitation leads to significant enrichments in Sr, U and B, whereas calcite is important only as an Sr host. Commonly observed brucite is trace element-poor. The overall enrichment patterns are comparable among serpentinites from mid-ocean ridges, passive margins and fore-arcs, whereas the extents of enrichments are often specific to the geodynamic setting. Variability in relative trace element enrichments within a specific setting (and locality) can be several orders of magnitude. Mid-ocean ridge serpentinites often show pronounced bulk-rock U enrichment in addition to ubiquitous Cl, B and Sr enrichment. They also exhibit positive Eu anomalies on chondrite-normalized rare earth element plots. Passive margin serpentinites tend to have higher overall incompatible trace element contents than mid-ocean ridge and fore-arc serpentinites and show the highest B enrichment among all the studied serpentinites. Fore-arc serpentinites are characterized by low overall trace element contents and show the lowest Cl, but the highest Rb, Cs and Sr enrichments. Based on our data, subducted dehydrating serpentinites are likely to release fluids with high B/Nb, B/Th, U/Th, Sb/Ce and Sr/Nd, rendering them one of the potential sources of some of the characteristic trace element fingerprints of arc magmas (e.g. high B/Nb, high Sr/Nd, high Sb/Ce). However, although serpentinites are a substantial part of global subduction zone chemical cycling, owing to their low overall trace element contents (except for B and Cl) their geochemical imprint on arc magma sources (apart from addition of H2O, B and Cl) can be masked considerably by the trace element signal from subducted crustal components.

Petrology of basalts from DSDP Hole 83-504B

Basalts from Hole 504B, Leg 83, exhibit remarkable uniformity in major and trace element composition throughout the 1075.5 m of basement drilled. The majority of the basalts, Group D', have unusual compositions relative to normal (Type I) mid-ocean ridge basalts (MORB). These basalts have relatively high mg values (0.60-0.70) and CaO abundances (11.7-13.7%; Ca/Al = 0.78-0.89), but exhibit a marked depletion in compatible trace elements (Cr and Ni); moderately incompatible trace elements (Zr, Y, Ti, etc.); and highly incompatible trace elements (Nb, LREE, etc.). Petrographic and compositional data indicate that most of these basalts are evolved, having fractionated significant amounts of plagioclase, olivine, and clinopyroxene. Melting experiments on similar basalt compositions from the upper portion of Hole 504B (Leg 70; Autio and Rhodes, 1983) indicate that the basalts are co-saturated with olivine and plagioclase and often clinopyroxene on the 1-atm. liquidus. Two rarely occurring groups, M' and T, are compositionally distinct from Group D' basalts. Group T is strongly depleted in all magmaphile elements except the highly incompatible ones (Nb, La, etc.), while Group M' has moderate concentrations of both moderately and highly incompatible trace elements and is similar to Type I MORB. Groups M' and T cannot be related to Group D' nor to each other by crystal fractionation, crystal accumulation, or magma mixing. The large differences in magmaphile element ratios (Zr/Nb, La/Yb) among these three chemical groups may be accounted for by complex melting models and/or local heterogeneity of the mantle beneath the Costa Rica Ridge. Xenocrysts and xenoliths of plagioclase and clinopyroxene similar in texture and mineral composition to crystals in coarse-grained basalts from the lower portion of the hole are common in Hole 504B basalts. These suggest that addition of solid components either from conduit or magma chamber walls has occurred and may be a common source of disequilibrium crystals in these basalts. However, mixing of plagioclase-laden depleted melts (similar to the Costa Rica Ridge Zone basalts) with normal MORB magmas could provide an alternate source for some refractory plagioclase crystals found out of equilibrium in many phyric MORB. The uniformity of major element compositions in Hole 504B basalts affords an ideal situation for investigating the effects of alteration on some major and trace elements in oceanic basalts. Alteration observed in whole-rock samples records primarily two events - a high-temperature and a low-temperature phase. High-temperature phases include: chlorite, talc, albite, actinolite, sphene, quartz, and pyrite. The low-temperature phases include smectite (saponite), epistilbite or laumontite, and minor calcite. Laumontite may actually straddle the gap between the low- and high-temperature mineral assemblages. Alteration is restricted primarily to partial replacement of primary phases. Metamorphic grade, in general, increases from the top to the bottom of Hole 504B (Legs 69, 70, and 83) as seen in the change from a smectiteto- chlorite-dominated secondary mineral assemblage. However, a systematic progression for the interval recovered during Leg 83 is not apparent. Rather, the extent of alteration appears to be a function of the initial texture and fracture density. Variations in whole-rock major and trace element concentrations cannot be attributed convincingly to any differences in alteration observed. Compositional characteristics of the secondary minerals indicated that extensive remobilization of elements has not occurred; local redistribution is suggested in most cases. Thus, the major and trace element signature of these basalts remains effectively the same as the original composition prior to alteration.

Petrology and relict mineralogy of serpentinites at DSDP Leg 84 Holes

Eleven serpentine samples from DSDP Leg 84 and four serpentinized ultramafic samples from Costa Rica and Guatemala were described and their relict mineral compositions measured by electron microprobe to try to determine the origin of the Leg 84 serpentinites and their relationship to the ultramafic rocks of the onshore ophiolites. The Leg 84 samples comprise more than 90% secondary minerals, principally serpentine, with hematitic and opaque oxides, and minor talc and smectites. Four distinct textural types can be identified according to the distribution of opaque phases and smectite. Remnants of spinel, olivine, orthopyroxene, and clinopyroxene occur variously in the samples; spinal occurs in all the samples. Textural evidence suggests that the serpentinites were originally clinopyroxene-bearing harzburgites. Relict mineral compositions are refractory and relatively uniform: olivine, Fo90.6-90.9; orthopyroxene, En90-91; clinopyroxene, Wo47 En50 Fs3; spinels, Cr/Cr + Al = 0.4-0.6. 567A-29-2, 30-35 cm has slightly more magnesian olivines (Fo92) and orthopyroxene, and more aluminous spinels (Cr/Cr + Al = 0.3). These compositions are similar to those inferred for refractory upper-mantle materials and also fall within the range of compositions for relict minerals in abyssal peridotites. They could be of oceanic origin. The onshore samples include serpentinites, a clinopyroxene-bearing harzburgite, and a clinopyroxenite. They too have magnesium-rich silicate assemblages, but relative to the drilled samples have more iron-rich olivines (Fogo) and more aluminous and sodic pyroxenes; spinels which are clearly relicts are very aluminum-rich (Cr/Cr + Al = 0.1-0.25). These samples are most likely mantle materials, but significantly less depleted. Their relationship to the drilled samples is unclear. Serpentinites were the most common basement materials recovered during Leg 84, and there appears to be a bimodal assemblage (basalt/diabase and serpentine) of igneous rocks sampled from the trench slope. Diapirism of serpentine throughout the trench slope and forearc is suggested as an explanation for this distribution of samples.

(Appendix 1-4) Geochemistry, desorption methods, TOC, TC, and mineral content of different settings

Sorption of volatile hydrocarbon gases (VHCs) to marine sediments is a recognized phenomenon that has been investigated in the context of petroleum exploration. However, little is known about the biogeochemistry of sorbed methane and higher VHCs in environments that are not influenced by thermogenic processes. This study evaluated two different extraction protocols for sorbed VHCs, used high pressure equipment to investigate the sorption of methane to pure clay mineral phases, and conducted a geochemical and mineralogical survey of sediment samples from different oceanographic settings and geochemical regimes that are not significantly influenced by thermogenic gas. Extraction of sediments under alkaline conditions yielded higher concentrations of sorbed methane than the established protocol for acidic extraction. Application of alkaline extraction in the environmental survey revealed the presence of substantial amounts of sorbed methane in 374 out of 411 samples (91%). Particularly high amounts, up to 2.1 mmol kg**-1 dry sediment, were recovered from methanogenic sediments. Carbon isotopic compositions of sorbed methane suggested substantial contributions from biogenic sources, both in sulfate-depleted and sulfate-reducing sediments. Carbon isotopic relationships between sorbed and dissolved methane indicate a coupling of the two pools. While our sorption experiments and extraction conditions point to an important role for clay minerals as sorbents, mineralogical analyses of marine sediments suggest that variations in mineral composition are not controlling variations in quantities of sorbed methane. We conclude that the distribution of sorbed methane in sediments is strongly influenced by in situ production.

Mineral and chemical compositions of clay sediments from the Pacific Ocean, DSDP data

Mineral and chemical compositions, as well as conditions of formation of clay sediments in major structural elements of the Pacific Ocean floor with different ages are under consideration in the monograph. Depending on evolution of the region two ways of clay sediment formation are identified: terrigenous and authigenic. It is shown that terrigenous clay sediments predominate in marginal parts of the Pacific Ocean. Authigenic mineral formation occurring in the basal part of the sedimentary cover primarily results from removal of material from underlying basalts. This material is released during secondary alteration of the basalts due to their interaction with sea water, as well as with deep solutions.

Petrology and geochemistry of altered ocenaic crust of ODP Hole 140-504B

Altered basalt dikes from Hole 504B were partially melted at 1150°C and 1180°C to determine the composition of the first melts as oceanic Layer 2C is assimilated by a magma chamber. The partial melts are chemically similar to actinolite, the most abundant secondary mineral, but the melts are not simply melted actinolite. High TiO2, P2O5, and K2O abundances of the melts indicate that minor secondary minerals that are enriched in these elements also contribute to the melt. The incorporation of partial melts into a ridge-crest magma chamber may explain the local variability that is sometimes found in ocean ridge basalts that are not readily explained fractional crystallization or partial melting.

Minerals and geochemistry abundance and occurance, as well as K-Ar determinations for DSDP Site 92-597 basalts

Preliminary studies of hydrothermally altered massive basalts formed at the fast-spreading Mendoza Rise and recovered from DSDP Holes 597B and 597C indicate the presence of three secondary mineral assemblages which formed in the following order: (1) trioctahedral chlorite and talc, (2) goethite and smectite, and (3) calcite and celadonite. The sequential precipitation of these mineral assemblages denotes high water:rock ratios and time-varying conditions of temperature (early >200°C to late <30°C) and state of oxidation (early nonoxidative to late oxidative). A decrease in the relative proportion of oxidative mineral assemblages with depth to 70 m in Site 597 basement indicates a zone of oxidative alteration that became shallower with time as the deeper, more constricted fracture systems were filled by secondary mineralization. In this report we present the first results of the K-Ar dating of celadonite formation age; celadonite formation reflects end-stage hydrothermal alteration in Site 597 basement. Three celadonite dates obtained from Site 597 samples include 13.1 ± 0.3 m.y. from 17 m basement depth (Hole 597B), 19.9 ± 0.4 m.y. from 18 m basement depth (Hole 597C), and 19.3 ± 1.6 m.y. from 60 m basement depth (Hole 597C). The age of host rock crystallization (28.6 m.y.) and the K-Ar dates of celadonite formation establish that hydrothermal alteration in the upper 70 m of Site 597 basement continued for at least 10 m.y. and possibly as long as 16 m.y. after basalt crystallization at the ridge crest. Assuming a half-spreading rate of 55 km/m.y., we calculate that hydrothermal circulation was active in shallow basement at a distance of at least 550 km off ridge crest and possibly as far as 1000 km off ridge crest.

Chemistry of serpentinized peridotites from ODP Hole 109-670A

In this paper we describe textural relationships in hydrated upper mantle peridotites emplaced at a nonconstructive ridge segment. Development of serpentinites and partially serpentinized peridotites takes place in four main stages: (1) pervasive serpentinization forming mainly lizardite, (2) a tensional stage forming chrysotile + talc + chlorite, (3) a deformational stage forming antigorite + tremolite, and (4) a late local tensional stage forming another generation of chrysotile veinlets. Mineral chemistry of serpentine pseudomorphs reflects in part primary mineral compositions. Olivine pseudomorphs are typically nickeliferous and depleted in aluminum and chromium. Orthopyroxene pseudomorphs have lower nickel contents and relatively high iron, aluminum, and chromium contents. Clinopyroxene pseudomorphs have very low nickel contents and relatively high aluminum and chromium contents. These chemical patterns in the serpentinites can be used to help discriminate between harzburgitic and lherzolitic protoliths. Oxygen isotopes and mineral parageneses suggest serpentine is derived from circulation of hydrothermal (200?C) fluids through the peridotite body. Crystallization of tremolite, talc, and chlorite may have occurred at temperatures up to 525?C if C02/H20 ratios were less than 0.25. Open fissures developing in aging upper mantle provide paths for important seawater circulation through a thin basaltic carapace down to shallow mantle rocks.

Strontium, oxygen and hydrogen isotope ratios of basalts from DSDP Hole 504B

DSDP Hole 504B was drilled into 6 Ma crust, about 200 km south of the Costa Rica Rift, Galapagos Spreading Center, penetrating 1.35 km into a section that can be divided into four zones-Zone I: oxic submarine weathering; Zone II: anoxic alteration; Zones III and IV: hydrothermal alteration to greenschist facies. In Zone III there is intense veining of pillow basalts. Zone IV consists of altered sheeted dikes. Isotopic geochemical signatures in relation to the alteration zones are recorded in Hole 504B, as follows: Zone Depth(m) Average87Sr/86Sr Average delta18O (?) Average deltaD (?) I 275-550 0.7032 7.3 -63 II 550-890 0.7029 6.5 -45 III 890-1050 0.7035 5.6 -31 IV 1050-1350 0.7032 5.5 -36 Alteration temperatures are as low as 10°C in Zones I and II based on oxygen isotope fractionation. Strontium isotopic data indicate that a circulation of seawater is much more restricted in Zone II than in Zone I. Fluid inclusion measurements of vein quartz indicate the alteration temperature was mainly 300 +/- 20°C in Zones III and IV, which is consistent with secondary mineral assemblages. The strontium, oxygen, and hydrogen isotopic compositions of hydrothermal fluids which were responsible for the greenschist facies alteration in Zones III and IV are estimated to be 0.7037, 2?, and 3?, respectively. Strontium and oxygen isotope data indicate that completely altered portions of greenstones and vein minerals were in equilibrium with modified seawater under low water/rock ratios (in weight) of about 1.6. This value is close to that of the end-member hydrothermal fluids issuing at 21°N EPR. Basement rocks are not completely hydrothermally altered. About 32% of the greenstones in Zones III and IV have escaped alteration. Thus 1 g of fresh basalt including the 32% unaltered portion are required in order to make 1 g of end-member solution from fresh seawater in water-rock reactions.

Geochemistry of basal dolomitic and Fe-Mn sediments from the Tyrrhenian Sea

In the Tyrrhenian Sea (Western Mediterranean), unusual reddish, soft to lithified, dolomitic sediments up to 45 m thick overlie igneous crust at the base of thick Pliocene-Quaternary deep-sea sediment successions in the Marsili (Site 650) and Vavilov (Site 651) basins. These sediments also overlie the Gortani Ridge, a basaltic Seamount near the base of the Sardinian continental margin (Site 655). At both basinal sites (650, 651), the lowest sediments are dolomitic, with manganese oxide (MnO) segregations. Whole-rock X-ray diffraction indicates abundant dolomite and quartz, with subordinate calcite, illite (authigenic), feldspar and minor kaolinite, chlorite, and anhydrite. Chemical analyses show strong enrichment in magnesium oxide (MgO) and MnO relative to shale or deep-sea clay. Mg and Mn correlate positively and exhibit decreasing concentrations up the succession in the Marsili Basin (Site 650). The following scenario is proposed: peridotites were exposed on the seafloor in the Vavilov Basin (Site 651) and then eroded, depositing talc in local fine-grained dolomitic sediments within the igneous basement. After local magmatism ended, the igneous basement at each site subsided rapidly (about 800 m/m.y.) and was blanketed with calcareous and clay-rich oozes. During early diagenesis (from isotopic evidence; McKenzie et al., this volume) tepid fluids, of modified seawater composition, reacted with and dolomitized the overlying deep-sea sediments. At Site 651 additional Mg may have been extracted from asthenosphere peridotite cored at shallow depths (about 100 m). One can hypothesize that fluids rich in Mg and Mn were flushed from the igneous basement, triggered by extensional faulting and local tilting during subsidence of the basement, and that these fluids then dolomitized the base of the overlying sediment succession. Late tectonic movements in the Vavilov Basin (Site 651) fractured already lithified dolomitic sediments and more reducing (? hydrothermal) fluids locally remobilized Fe and Mn and corroded dolomite crystals.