(Table 7) Fe**3+/Fe**2+ ratios in selected nontronite samples at DSDP Leg 70 Holes

Since its discovery in 1974 (Klitgord and Mudie, 1974), the Galapagos mounds hydrothermal field has received much attention. Sediment samples were taken during Leg 54 of the Deep Sea Drilling Project (DSDP) and by other expeditions to the area (e.g., Corliss et al., 1978). While a hydrothermal origin for the mounds sediments has been generally accepted, several different theories of origin for the mounds themselves have been proposed (e.g., Corliss et al., 1978; Natland et al., 1979; Williams et al., 1979). One of the aims of DSDP Leg 70 was to return to the mounds field and, using the new hydraulic piston cor er described elsewhere in this volume, to obtain more complete recovery of mounds sediments than had previously been possible. It was our hope that this would help in our understanding of the nature and origin of these deposits. In this chapter, we describe the results of chemical analysis of over 250 sediment samples taken during the course of Leg 70.

(Table 3) Major element content of whole-rock samples of DSDP Leg 30 holes

All norms were calculated with an atomic ratio of Fe+3/Fe+2 = 0.2, except analysis 7 which was calculated directly from the analysis.

Mineralogy and chemistry of basalts and secondary minerals from DSDP Site 417, Atlantic Ocean

Basalts from DSDP Site 417 (109 Ma) exhibit the effects of several stages of alteration reflecting the evolution of seawater-derived solution compositions and control by the structure and permeability of the crust. Characteristic secondary mineral assemblages occur in often superimposed alteration zones within individual basalt fragments. By combining bulk rock and single phase chemical analyses with detailed mineralogic and petrographic studies, chemical changes have been determined for most of the alteration stages identified in the basalts. 1) Minor amounts of saponite, chlorite, and pyrite formed locally in coarse grained portions of massive units, possibly at high temperatures during initial cooling of the basalts. No chemical changes could be determined for this stage. 2) Possible mixing of cooled hydrothermal fluids with seawater resulted in the formation of celadonite-nontronite and Fe-hydroxide-rich black halos around cracks and pillow rims. Gains of K, Rb, H20, increase of Fe 3 +/FeT and possibly some losses of Ca and Mg occurred during this stage. 3a) Extensive circulation of oxygenated seawater resulted in the formation of various smectites, K-feldspar, and Fe-hydroxides in brown and light grey alteration zones around formerly exposed surfaces. K, Rb, H20, and occasionally P were added to the rocks, Fe3+/FeT increased, and Ca, Mg, Si and occasionally Al and Na were lost. 3 b) Anoxic alteration occurred during reaction of basalt with seawater at low water-rock ratios, or with seawater that had previously reacted with basalt. Saponite-rich dark grey alteration zones formed which exhibit very little chemical change: generally only slight increases in Fe 3 +/FeT and H20 occurred. 4) Zeolites and calcite formed from seawater-derived fluids modified by previous reactions with basalt. Chemical changes involved increases of Ca, Na, H20 , and CO2 in the rocks. 5) A late stage of anoxic conditions resulted in the formation of minor amounts of Mn-calcites and secondary sulfides in previously oxidized rocks. No chemical changes were determined for this stage. Recognition of such alteration sequences is important in understanding the evolution of submarine hydrothermal systems and in interpreting chemical exchange due to seawater-basalt reactions.

Mineral chemistry of primary and secondary phases in basaltic rocks

Primary magmatic phases (spinel, olivine, plagioclase, clinopyroxene, amphibole, and biotite) and secondary phyllosilicates (smectite, chlorite-smectite, and celadonite) were analyzed by electron microprobe in alkalic and tholeiitic dolerites and basalts from Ocean Drilling Program Sites 800, 801, and 802. Aphyric alkalic dolerite sills (Hole 800A) and basalt flows (Holes 801B and 801C) share common mineralogical features: matrix feldspars are strongly zoned from labradorite cores to discrete sodic rims of alkali feldspar with a high Or component, which overlaps that of quench microlites in glassy mesostasis; little fractionated clinopyroxenes are Ti-rich diopsides and augites (with marked aegirine-augite rims at Site 801); rare, brown, Fe**3+-rich amphibole is winchite; and late biotites exhibit variable Ti contents. Alkalic rims to feldspars probably developed at the same time as quenched mesostasis feldspars and late-stage magmatic biotite, and represent the buildup of K-rich hydrous fluids during crystallization. Phenocryst phases in primitive mid-ocean ridge tholeiites from Hole 801C (Mg numbers about 70) have extreme compositions with chrome spinel (Cr/Cr + Al ratios about 0.2-0.4), Ni-rich olivine (Fo90), and highly calcic plagioclase (An90). Later glomerophyric clumps of plagioclase (An75-80) and clinopyroxene (diopside-augite) are strongly zoned and probably reflect rapidly changing melt conditions during upward transport, prior to seafloor quenching. In contrast, phenocryst phases (olivine, plagioclase, and clinopyroxene) in the Hole 802A tholeiites show limited variation and do not have such primitive compositions, reflecting the uniform and different chemical composition of all the bulk rocks. Replacive phyllosilicates in both alkalic and tholeiitic basalts include various colored smectites (Fe-, Mg-, and Al-saponites), chlorite-smectite and celadonite. Smectite compositions typically reflect the replaced host composition; glass is replaced by brown Fe-saponites (variable Fe/Mg ratios) and olivine by greenish Mg-saponites (or Al-rich chlorite-smectite).

Chemical and mineral composition of rocks and sediments from the Amirante Arc

New geological and geophysical data on the Amirante Arc, which locates to the south of the Seychelles Islands, are presented. These data were obtained by Pacific Oceanological Institute during the 33-rd cruise of R/V Professor Bogorov in 1990. The Amirante Arc represents a seamount chain, which has submeridional strike and total length about 400 km. To the west of the Amirante Arc there are a deep sea trench and a back-arc basin, i.e. this area is characterized by structural elements associated with the subduction zone of Western Pacific type. According to our data the Amirante Arc is composed by tholeiites of ocean plateau type. This facts are evidences that the Amirante Arc differs from typical Pacific island arcs. This gives an opportunity to distinguish a special type of oceanic structures, i.e. non-volcanic (amagmatic) ridges. The Amirante Ridge has been probably formed as a result of oceanic crust heaping due to horizontal displacements of its blocks in the process of spreding ridge formation in the Indian Ocean during Cretaceous-Paleogene.

Zeolite and silica diagenesis and sandstone petrography at DSDP Sites 57-438 and 57-439

We detected authigenic clinoptilolites in two core samples of tuffaceous, siliceous mudstone in the lower Miocene section of Hole 439. They occur as prismatic and tabular crystals as long as 0.03 mm in various voids of dissolved glass shards, radiolarian shells, calcareous foraminifers, and calcareous algae. They are high in alkalies, especially Na, and in silica varieties. There is a slight difference in composition among them. The Si : (Al+ Fe3+) ratio is highest (4.65) in radiolarian voids, intermediate (4.34) in dissolved glass voids, and lowest (4.26) in voids of calcareous organisms. This difference corresponds to the association of authigenic silica minerals revealed by the scanning electron microscope: There are abundant opal-CT lepispheres in radiolarian voids, low cristobalite and some lepispheres in dissolved glass voids, and a lack of silica minerals in the voids of calcareous organisms. Although it contains some silica from biogenic opal and alkalies from trapped sea water, clinoptilolite derives principally from dissolved glass. Although they are scattered in core samples of Quaternary through lower Miocene diatomaceous and siliceous deposits, acidic glass fragments react with interstitial water to form clinoptilolite only at a sub-bottom depth of 935 meters at approximately 25°C. Analcimes occur in sand-sized clasts of altered acidic vitric tuff in the uppermost Oligocene sandstones. The analcimic tuff clasts were probably reworked from the Upper Cretaceous terrain adjacent to Site 439. Low cristobalite and opal-CT are found in tuffaceous, siliceous mudstone of the middle and lower Miocene sections at Sites 438 and 439. Low cristobalite derives from acidic volcanic glass and opal-CT from biogenic silica. Both siliceous organic remains and acidic glass fragments occur in sediments from the Quaternary through lower Miocene sections. However, the shallowest occurrence is at 700 meters subbottom in Hole 438A, where temperature is estimated to be 21°C. The d(101) spacing of opal-CT varies from 4.09 to 4.11 Å and that of low cristobalite from 4.04 to 4.06 Å. Some opal-CT lepispheres are precipitated onto clinoptilolites in the voids of radiolarian shells at a sub-bottom depth of 950 meters in Hole 439. Sandstone interlaminated with Upper Cretaceous shale is chlorite- calcite cemented and feldspathic. Sandstones in the uppermost Oligocene section are lithic graywacke and consist of large amounts of lithic clasts grouped into older sedimentary and weakly metamorphosed rocks, younger sedimentary rocks, and acidic volcanic rocks. The acidic volcanic clasts probably originated from the volcanic high, which supplied the basal conglomerate with dacite gravels. The older sedimentary and weakly metamorphosed rocks and green rock correspond to the lithologies of the lower Mesozoic to upper Paleozoic Sorachi Group, including the chert, limestone, and slate in south-central Hokkaido. However, the angular shape and coarseness of the clasts and the abundance of carbonate rock fragments indicate a nearby provenance, which is probably the southern offshore extension of the Sorachi Group. The younger sedimentary rocks, including mudstone, carbonaceous shale, and analcime-bearing tuff, correspond to the lithologies of the Upper Cretaceous strata in south-central Hokkaido. Their clasts were reworked from the southern offshore extension of the strata. Because of the discontinuity of the zeolite zoning due to burial diagenesis, an overburden several kilometers thick must have been denuded before the deposition of sediments in the early Oligocene.

Chemical and mineral compositions of altered peridotites from ODP Leg 209

Abyssal peridotite from the 15°20'N area of the Mid-Atlantic Ridge show complex geochemical variations among the different sites drilled during ODP Leg 209. Major element compositions indicate variable degrees of melt depletion and refertilization as well as local hydrothermal metasomatism. Strongest evidence for melt-rock interactions are correlated Light Rare Earth Element (LREE) and High Field Strength Element (HFSE) additions at Sites 1270 and 1271. In contrast, hydrothermal alteration at Sites 1274, 1272, and 1268 causes LREE mobility associated with minor HFSE variability, reflecting the low solubility of HFSE in aqueous solutions. Site 1274 contains the least-altered, highly refractory, peridotite with strong depletion in LREE and shows a gradual increase in the intensity of isochemical serpentinization; except for the addition of H2O which causes a mass gain of up to 20 g/100 g. The formation of magnetite is reflected in decreasing Fe(2+)/Fe(3+) ratios. This style of alteration is referred to as rock-dominated serpentinization. In contrast, fluid-dominated serpentinization at Site 1268 is characterized by gains in sulfur and development of U-shaped REE pattern with strong positive Eu anomalies which are also characteristic for hot (350 to 400°C) vent-type fluids discharging from black smoker fields. Serpentinites at Site 1268 were overprinted by talc alteration under static conditions due to interaction with high a_SiO2 fluids causing the development of smooth, LREE enriched patterns with pronounced negative Eu anomalies. These results show that hydrothermal fluid-peridotite and fluid-serpentinite interaction processes are an important factor regarding the budget of exchange processes between the lithosphere and the hydrosphere in slow spreading environments.

Chemical composition of rocks and minerals from the ophiolite complex in the Hunter Fracture Zone

A collection of dredge samples from the Hunter Fracture Zone includes holocrystalline massive and cumulose basic and ultrabasic rocks and volcanites of the ophiolite complex: from basalts to rhyolites. The ultrabasic rocks are largely serpentinized harzburgites and lherzolites; their relict mineralogy is typical of peridotite considered to be the refractory residue of partial melting of the mantle. Cumulate textured ultramafic rocks probably are related to the cumulate gabbro and granodiorite rather than to the residual mantle material. The gabbroic rocks are dominantly cumulate textured Pl-Opx-Cpx±Ol gabbronorite and Pl-Cpx±Ol gabbros; the mineral features of these rocks are the result of their crystallization at moderate pressure (in a moderate level magma chamber). The massive Pl-Cpx±Ol gabbros are less common. Green and brown-green Ca-amphibole has partially or totally replaced the clinopyroxene in many samples. There is an overlap in mineral chemistry between the cumulate rocks and the Opx-Cpx-Pl volcanic rocks and boninites. It is interpreted as an indication that the cumulate rocks were co-genetic with Opx-Cpx-Pl volcanic rocks and that they both constitute remnants of an island arc volcanic-plutonic series. The petrologic evidence indicates that ophiolite gabbroic rocks were derived from an island-arc rather than from a mid-ocean ridge.

Rock magnetic records and geochemical methods of sediment cores off NW Africa

Two gravity cores retrieved off NW Africa at the border of arid and subtropical environments (GeoB 13602-1 and GeoB 13601-4) were analyzed to extract records of Late Quaternary climate change and sediment export. We apply End Member (EM) unmixing to 350 acquisition curves of isothermal remanent magnetization (IRM). Our approach enables to discriminate rock magnetic signatures of aeolian and fluvial material, to determine biomineralization and reductive diagenesis. Based on the occurrence of pedogenically formed magnetic minerals in the fluvial and aeolian EMs, we can infer that goethite formed in favor to hematite in more humid climate zones. The diagenetic EM dominates in the lower parts of the cores and within a thin near-surface layer probably representing the modern Fe**2+/Fe**3+ redox boundary. Up to 60% of the IRM signal is allocated to a biogenic EM underlining the importance of bacterial magnetite even in siliciclastic sediments. Magnetosomes are found well preserved over most of the record, indicating suboxic conditions. Temporal variations of the aeolian and fluvial EMs appear to faithfully reproduce and support trends of dry and humid conditions on the continent. The proportion of aeolian to fluvial material was dramatically higher during Heinrich Stadials, especially during Heinrich Stadial 1. Dust export from the Arabian-Asian corridor appears to vary contemporaneous to increased dust fluxes on the continental margin of NW Africa emphasizing that melt-water discharge in the North Atlantic had an enormous impact on atmospheric dynamics.

Sample descriptions, d-spacing and geochemistry at DSDP Holes 68-501 and 69-504B

Mössbauer analyses were conducted on a sample of saponite selected from DSDP Leg 69 basalt core. The sample was initially placed within a nitrogen-purged container on-board Glomar Challenger approximately three hours after recovery, where it remained until analysis. The Mössbauer data revealed an original, in situ Fe2O3/FeO ratio of 0.46, with both Fe**2+ and Fe**3+ in octahedral coordination. With controlled exposure to air under ambient laboratory storage conditions, the proportion of Fe**3+ increased from an original 30% to 51% over a period of about 11.5 months. The Fe**3+ thus produced remained in octahedral coordination, and no observable changes occurred in the physical appearance of the sample.

Iron isotope and chemical compositions of sediments and basalts drilled seaward of the Mariana Trench

The purpose of this work is to study the mobility and budget of Fe isotopes in the oceanic crust and in particular during low-temperature interaction of seawater with oceanic basalt. We carried out this investigation using samples from Ocean Drilling Program (ODP) Site 801C drilled during Leg 129 and Leg 185 in Jurassic Pacific oceanic crust seaward of the Mariana Trench. The site comprises approximately 450 m of sediment overlying a section of 500 m of basalt, which includes intercalated pelagic and chemical sediments in the upper basaltic units and two low-temperature (10-30°C) ocherous Si-Fe hydrothermal deposits. Fe was chemically separated from 70 selected samples, and 57Fe/54Fe ratios were measured by MC-ICP-MS Isoprobe. The isotopic ratios were measured relative to an internal standard solution and are reported relative to the international Fe-standard IRMM-14. Based on duplicate measurements of natural samples, an external precision of 0.2? (2 sigma) has been obtained. The results indicate that the deep-sea sediment section has a restricted range of d57Fe, which is close to the igneous rock value. In contrast, large variations are observed in the basaltic section with positive d57Fe values (up to 2.05?) for highly altered basalts and negative values (down to ?2.49?) for the associated alteration products and hydrothermal deposits. Secondary Fe-minerals, such as Fe-oxyhydroxides or Fe-bearing clays (celadonite and saponite), have highly variable d57Fe values that have been interpreted as resulting from the partial oxidation of Fe(2+) leached during basalt alteration and precipitated as Fe(3+)-rich minerals. In contrast, altered basalts at Site 801C, which are depleted in Fe (up to 80%), display an increase in d57Fe values relative to fresh values, which suggest a preferential leaching of light iron during alteration. The apparent fractionation factor between dissolved Fe(2+) and Fe remaining in the mineral is from 0.5? to 1.3? and may be consistent with a kinetic isotope fractionation where light Fe is stripped from the minerals. Alternatively, the formation of secondary clays minerals, such as celadonite during basalt alteration may incorporate preferentially the heavy Fe isotopes, resulting in the loss of light Fe isotopes in the fluids. Because microbial processes within the oceanic crust are of potential importance in controlling rates of chemical reactions, Fe redox state and Fe-isotope fractionation, we evaluated the possible effect of this deep biosphere on Fe-isotope signatures. The Fe-isotope systematics presented in this study suggest that, even though iron behavior during seafloor weathering may be mediated by microbes, such as iron-oxidizers, d57Fe variations of more than 4? may also be explained by abiotic processes. Further laboratory experiments are now required to distinguish between various processes of Fe-isotope fractionation during seafloor weathering.

Annotated record of the detailed examination of Mn deposits from the QUEBRADA (1969) and SIQUEIROS (1974) expeditions around the East Pacific Rise

Basalt samples obtained from the Siqueiros transform fault/fracture zone and the adjacent East Pacific Rise are mostly very fresh oceanic tholeiite and fractionated oceanic tholeiite with Fe+3/ Fe+2 ? 0.25; however, alkali basalts occur in the area as well. The rocks of the tholeiitic suite are ol + pl phyric and ol + pl + cpx phyric basalts, while the alkali basalts are ol and ol + pl phyric. Microprobe analyses of the tholeiitic suite phenocrysts indicate that they are Fo68-Fo86, An58-An75, and augite (Ca34Mg50Fe16). The range of olivine and plagioclase compositions represents the chemical variation of the phenocryst compositions with fractionation. The phenocyrsts in the alkali basalts are Fo81 and An69. The suite of tholeiites comprises a fractionation series characterized by relative enrichment of Fe, Ti, Mn, V, Na, K, and P and depletion of Ca, Al, Mg, Ni, and Cr. The fractionated tholeiites occur on the median ridge (which is a sliver of normal oceanic crust) of the double Siqueiros transform fault, on the western Siqueiros fracture zone, and on the adjoining East Pacific Rise, while the two transform fault troughs contain mostly unfractionated or only slightly fractionated tholeiite. We suggest that the fractionated tholeiites are produced by fractional crystallization of more 'primitive' tholeiitic liquid in a crustal magma chamber below the crest of the East Pacific Rise. This magma chamber may be disrupted by the transform fault troughs, thus explaining the paucity of fractionated tholeiites in the troughs. The alkali basalts are found only on the flanks of a topographic high near the intersection of the northern transform trough with the East Pacific Rise.

Chemical composition of igneous rocks and origin of the sill and pillow-basalt complex at DSDP Site 61-462

The sill and pillow complex cored on Deep Sea Drilling Project Leg 61 (Site 462) is divided into two groups, A and B types, on the basis of chemical composition and volcanostratigraphy. The A-type basalt is characterized by a higher FeO*/MgO ratio and abundant TiO2, whereas the B-type basalt is characterized by a lower FeO*/MgO ratio and scarcity of TiO2. The A type is composed of sills interbedded with hyaloclastic sediments, and the B type consists of basalt sills and pillow basalt with minor amounts of sediment. However, the structure of pillow basalts in the B type is atypical; they might be eruptive. From paleontological study of the interbedded sediments and radiometric age determination of the basalt, the volcanic event of A type is assumed to be Cenomanian to Aptian, and that of B type somewhat older. The oceanic crust in the Nauru Basin was assumed to be Oxfordian, based on the Mesozoic magnetic anomaly. Consequently, two events of intraplate volcanism are recognized. It is thus assumed that the sill-pillow complex did not come from a normal oceanic ridge, and that normal oceanic basement could therefore underlie the complex. The Site 462 basalts are quartz-normative, and strongly hypersthene-normative, and have a higher FeO*/MgO ratio and lower TiO2 content. Olivine from the Nauru Basin basalts has a lower Mg/(Mg + Fe**2+) ratio (0.83-0.84) and coexists with spinel of lower Mg/(Mg + Fe**2+) ratio when compared to olivine-spinel pairs from mid-ocean ridge (MAR) basalt. The glass of spinel-bearing basalts has a higher FeO*/(FeO* + MgO) ratio (0.58-0.60) than that of MAR (<0.575). Therefore, the Nauru Basin basalts are chemically and mineralogically distinct from ocean-ridge tholeiite. That the Nauru Basin basalts are quartz-normative and strongly hypersthene-normative and have a lower TiO2 content suggests that the basaltic liquids of Site 462 were generated at shallower depths (<5 kbar) than ocean-ridge tholeiite: Site 462 basalts are similar to basalts from the Manihiki Plateau and the Ontong-Java Plateau, but different from Hawaiian tholeiite of hot-spot type, with lower K2O and TiO2 content. We propose a new type of basalt, ocean-plateau tholeiite, a product of intraplate volcanism.