Geochemistry of low-temperatuer altered basalts of ODP Hole 136-843B

The mineralogy and chemistry of altered basalts and the stable isotopic compositions of secondary vein carbonates were studied in cores from Ocean Drilling Program Hole 843B, located in 95-Ma crust of the Hawaiian Arch. Millimeter- to centimeter-sized dark alteration halos around veins are 5%-15% altered to celadonite and Fe-oxyhydroxides, plus minor saponite and calcite. Adjacent gray host rocks are about 15% altered to saponite and calcite. The dark halos are enriched in H2O+, CO2, FeT, K2O, MnO, and Fe3+/FeT and depleted in SiO2, Al2O3, MgO, and TiO2 relative to gray host rocks. Brown alteration halos occur around veins where veins are more abundant, and are similar to dark halos, but contain more Fe-oxyhydroxides and exhibit greater Fe2O3T contents and higher Fe3+/FeT. Stable isotopic compositions of vein carbonates are consistent with their precipitation from seawater at temperatures of 5°-40°C. Crosscutting relationships of veins and zoned vein and vesicle fillings reveal a sequence of secondary mineral formation and alteration conditions. Celadonite and Fe-oxyhydroxides formed and dark alteration halos developed relatively early, under oxidizing conditions at low temperatures (<50°C). Saponite formed later at lower seawater/rock ratios and under more reducing conditions. Calcite and pyrite formed last in veins and vesicles from more evolved, seawaterderived fluids at temperatures of 5°-40°C. A second stage of celadonite, with compositions distinct from the early celadonite, also occurred relatively late (within the "calcite stage"), and may be related to refracturing of the crust and introduction of less-evolved seawater solutions into the rocks. Trends to higher K2O contents are attributed to alteration, but high K/Ti, Ba, and Zr contents indicate the presence of enriched or transitional MORB. CO2 contents of Pacific ODP cores exhibit a general increase with age suggesting progressive fixation of CO2 as calcite in the crust, but this could be complicated by local heterogeneities in fracturing and calcite formation in the crust.

Geochemistry of the volcanic basement of ODP Hole 134-831B

The basement of Bougainville Guyot drilled at Site 831 consists of andesitic hyalobreccias derived from a submarine arc volcano. The volcanic sequence has been dated by K/Ar at approximately 37 Ma. The 121 m of andesitic hyalobreccias drilled in Hole 831B have been divided into five subunits of two types: one appears to be primary, and the other contains evidence of reworking and a subaerial clastic input. Variations are attributed to fluctuations in water depth. The distinctive hyalobreccias consist of andesitic blebs with chilled margins and peripheral fractures set in a chaotic greenish matrix that is mainly altered glass, with crystals similar to those in the blebs or clasts. Their formation is attributed to violent reaction of andesitic magma discharged into seawater, in perhaps the submarine equivalent of fire-fountaining. There was limited reworking by currents and debris flows on the flanks of the submarine volcano. The andesite shows no significant compositional variation in phenocryst phases throughout the drilled sequence and contains phenocrysts of plagioclase (An88-43), clinopyroxene (Ca44Mg46Fe10-Ca41Mg40Fe19), orthopyroxene (Ca4Mg79Fe17-Ca3Mg58Fe39), and titanomagnetite. There is a systematic change in volcanic composition with height in the section, from more mafic andesites at the base, to overlying more acid andesites, and strong evidence exists that magma mixing may have played a significant role in the genesis of these lavas. The andesites have affinities with the low-K arc tholeiite series. Trace element and isotopic systematics for these rocks indicate very minor involvement of a LILE- and 87Sr-enriched slab-derived fluid in their petrogenesis. This accords with the previous suggestion that Bougainville Guyot forms part of an Eocene proto-island arc developed along the southern side of the d'Entrecasteaux Zone, above a southward-dipping subduction zone.

Magnetic properties, grain sizes and minerals at DSDP Site 83-504B

Twenty-seven samples from the Leg 83 section of Hole 504B have been investigated using magnetic, optical, and electron optical methods. The primary magnetic mineral to crystallize was titanomagnetite of approximate composition Fe2.4Ti0.6O4 (TM60), but none survives, nor is there evidence of titanomaghemite produced by oxidation of TM60. The average measured magnetic properties can be interpreted in terms of magnetite, Fe3O4, having average grain size of <1 µm and present in average volume concentration of - 0.5%. The intensity of the natural remanent magnetization (NRM) of the rocks could also be accounted for as being a thermoremanence carried by this mineral. Although the heterogeneity of the titanomagnetite grains could be detected optically, the texture of the intergrown phases is poorly developed. In some samples from the massive units of the lower part of the section, trellis patterns were visible. The Fe3O4 present in the intergrowths is too intimately mixed with the other intergrown phases to be revealed by electron microprobe analysis that simply returns the bulk composition of the intergrowth (oxidized TM60). The path by which the mineral assemblage evolved from TM60 to an Fe304-containing intergrowth, under the temperature and pressure conditions obtaining in the Leg 83 section, makes interesting speculation. Deuteric oxidation, maghemitization/inversion, or some hypothetical low-temperature/high-pressure oxidation by a leaching-of-iron process may all play roles.

Sulfur and iron speciations in bottom sediments from the southwest Caspian Sea

Speciations of sulfur (sulfide S, pyrite S, sulfate S) and of reactive iron (Fe3+, Fe2+, sulfide Fe) in bottom sediments have been studied in gravity cores and drill cores collected on the shelf of the southwest Caspian Sea. It has been shown that intensity of reduction processes, in particular sulfate reduction, as well as speciations of S and reactive Fe reflect the change of transgressive and regressive stages of the Caspian basin. Characteristic features for the investigated area are high sedimentation rate and high reactivity of organic matter entering bottom sediments.

Pore water and sediment geochemistry of the Bothian Sea

Methane is a powerful greenhouse gas and its biological conversion in marine sediments, largely controlled by anaerobic oxidation of methane (AOM), is a crucial part of the global carbon cycle. However, little is known about the role of iron oxides as an oxidant for AOM. Here we provide the first field evidence for iron-dependent AOM in brackish coastal surface sediments and show that methane produced in Bothnian Sea sediments is oxidized in distinct zones of iron- and sulfate-dependent AOM. At our study site, anthropogenic eutrophication over recent decades has led to an upward migration of the sulfate/methane transition zone in the sediment. Abundant iron oxides and high dissolved ferrous iron indicate iron reduction in the methanogenic sediments below the newly established sulfate/methane transition. Laboratory incubation studies of these sediments strongly suggest that the in situ microbial community is capable of linking methane oxidation to iron oxide reduction. Eutrophication of coastal environments may therefore create geochemical conditions favorable for iron-mediated AOM and thus increase the relevance of iron-dependent methane oxidation in the future. Besides its role in mitigating methane emissions, iron-dependent AOM strongly impacts sedimentary iron cycling and related biogeochemical processes through the reduction of large quantities of iron oxides.

Petrology and geochemistry of volcanic rocks from ODP Sites 134-827, 134-829 and 134-830

Igneous rocks recovered from Ocean Drilling Program (ODP) Leg 134 Sites 827, 829, and 830 at the toe of the forearc slope of New Hebrides Island Arc were investigated, using petrography, mineral chemistry, major and trace element, and Sr, Nd, and Pb isotopic analyses. Basaltic and andesitic clasts, together with detrital crystals of plagioclase, pyroxenes, and amphiboles embedded in sed-lithic conglomerate or volcanic siltstone and sandstone of Pleistocene age, were recovered from Sites 827 and 830. Petrological features of these lava clasts suggest a provenance from the Western Belt of New Hebrides Island Arc; igneous constituents were incorporated into breccias and sandstones, which were in turn reworked into a second generation breccia. Drilling at Site 829 recovered a variety of igneous rocks including basalts and probably comagmatic dolerites and gabbros, plus rare ultramafic rocks. Geochemical features, including Pb isotopic ratios, of the mafic rocks are intermediate between midocean ridge basalts and island arc tholeiites, and these rocks are interpreted to be backarc basin basalts. No correlates of these mafic rocks are known from Espiritu Santo and Malakula islands, nor do they occur in the Pleistocene volcanic breccias at Sites 827 and 830. However, basalts with very similar trace element and isotopic compositions have been recovered from the northern flank of North d'Entrecasteaux Ridge at Site 828. It is proposed that igneous rocks drilled at Site 829 represent material from the North d'Entrecasteaux Ridge accreted onto the over-riding Pacific Plate during collision. An original depleted mantle harzburgitic composition is inferred for a serpentinite clast recovered at 407 meters below seafloor (mbsf) in Hole 829A. Its provenance is a matter of speculation. It could have been brought up along a deep thrust fault affecting the Pacific Plate at the colliding margin, or analogous to the Site 829 basaltic lavas, it may represent material accreted from the North d'Entrecasteaux Ridge.

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

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

Mössbauer characterisation of sediments from ODP Sites 128-798 and 128-799

57Fe Mössbauer spectra for 26 sediment and 6 carbonate concretion samples from Sites 798 and 799 were recorded at 293 K. Most spectra were deconvolved to two quadrupole doublets without magnetic hyperfine structure. Typical Mössbauer parameters were: isomer shift (I.S.) = 0.34 mm/s and quadrupole splitting (Q.S.) = 0.64 mm/s for the paramagnetic Fe3+ component (partly, pyrite); I.S. = 1.13 mm/s and Q.S. = 2.64 mm/s for the high-spin Fe2+ component derived from iron-bearing aluminosilicates. A few spectra included other high-spin Fe2+ components ascribed to iron-bearing carbonate minerals (e.g., ferroan magnesite), according to the Mössbauer parameters for Fe2+ in the carbonate concretions. We present the distribution of iron among different chemical forms as a function of depth. These data might indicate changes of depositional and diagenetic conditions.

Petrology and geochemistry of basalts from the Vavilov Basin

During ODP Leg 107, two holes were drilled in the basement of Vavilov Basin, a central oceanic area of the Tyrrhenian sea. Hole 655B is located near the Gortani ridge in off-axis position at the western rim of the basin; Hole 651A is located on a basement swell at the axis of the basin. This paper deals with mineral chemistry, major and trace element geochemistry, and petrogenesis of the basalts recovered in the two holes. The mineralogy of the basalts is broadly homogeneous, but all of them have suffered important seawater alteration. Their major-element compositions are similar to both normal-mid-ocean-ridge-basalts (N-MORB) and back-arc-basalts (BAB) except for Na2O contents (BAB-like), and K2O which is somewhat enriched in upper unit of Hole 651 A. Their affinity with N-MORB and BAB is confirmed by using immobile trace elements such as Zr, Y, and Nb. However, basalts from the two sites present contrasting geochemical characteristics on spidergrams using incompatible elements. Hole 655B basalts are homogeneous enriched tholeiites, similar to those from DSDP Hole 373 (located on the opposite side of the basin near the eastern rim), and show affinities with enriched MORB (E-MORB). At Hole 651 A, the two basalt units are chemically distinct. One sample recovered in lower unit is rather similar to those from Hole 655B, but basalts from upper unit display calc-alkaline characteristic evidenced by the increase of light-ion-lithophile-element (LILE)/high-field-strength-element (HFSE) ratio, and appearance of a negative Nb-anomaly, making them comparable with orogenic lavas from the adjacent Eolian arc. The observed chemical compositions of the basalts are consistent with a derivation of the magmas from a N-MORB type source progressively contaminated by LILE-enriched fluids released from dehydration of the bordering subducted plate. Implications for evolution of the Tyrrhenian basin are tentatively proposed taking into consideration geochemical and chronological relationships between basalts from Leg 107 Holes 655B and 651 A, together with data from Leg 42 Site 373 and Vavilov Seamount. These data illustrate back-arc spreading in ensialic basin closely associated with the maturation of the adjacent subduction, followed by the growth of late off-axis central volcano, whereas the active subduction retreats southeastward.

Minerals and geochemistry at DSDP Hole 62-466

Alkali-basalt clasts in Upper Cretaceous sediments from Site 466 on southern Hess Rise suggest that parts of Hess Rise were constructed by off-ridge volcanic activity. Apparently, tectonic adjustments at Hess Rise occurred during the Late Cretaceous (Campanian-Maastrichtian), when parts of the original volcanic pedestal were uplifted and provided source rocks for the clasts. Synchronous volcanism may have occurred. Causes for the Late Cretaceous tectonic adjustments (and volcanism?) are not known, but they may be related to intraplate movement along the Mendocino Fracture Zone.

Composition of sediments and cores from DSDP Legs 54 and 61-63

The monograph gives results of studies of sediments and rocks collected from D/S Glomar Challenger in the Pacific Ocean. These studies have been based on the lithological facial analysis applied for the first time for identificating genesis of ocean sediments. These results include new ideas on formation of the Earth's sedimentary cover and can be used for constructing regional and global schemes of ocean paleogeography, reconstructing some structures, correlating sedimentation on continents and in oceans, estimating perspectives of oil- and gas-bearing deposits and ore formation. The monograph also gives the first petrographic classification of organic matter in black shales.

High-resolution in situ oxygen microprofiles, porewater and solid phase geochemistry from the Crimean shelf (Black Sea) from Maria S. Merian cruise MSM15/1

The outer western Crimean shelf of the Black Sea is a natural laboratory to investigate effects of stable oxic versus varying hypoxic conditions on seafloor biogeochemical processes and benthic community structure. Bottom-water oxygen concentrations ranged from normoxic (175 µmol O2/L) and hypoxic (< 63 µmol O2/L) or even anoxic/sulfidic conditions within a few kilometers' distance. Variations in oxygen concentrations between 160 and 10 µmol/L even occurred within hours close to the chemocline at 134 m water depth. Total oxygen uptake, including diffusive as well as fauna-mediated oxygen consumption, decreased from 15 mmol/m**2/d on average in the oxic zone, to 7 mmol/m**2/d on average in the hypoxic zone, correlating with changes in macrobenthos composition. Benthic diffusive oxygen uptake rates, comprising respiration of microorganisms and small meiofauna, were similar in oxic and hypoxic zones (on average 4.5 mmol/m**2/d), but declined to 1.3 mmol/m**2/d in bottom waters with oxygen concentrations below 20 µmol/L. Measurements and modeling of porewater profiles indicated that reoxidation of reduced compounds played only a minor role in diffusive oxygen uptake under the different oxygen conditions, leaving the major fraction to aerobic degradation of organic carbon. Remineralization efficiency decreased from nearly 100 % in the oxic zone, to 50 % in the oxic-hypoxic zone, to 10 % in the hypoxic-anoxic zone. Overall, the faunal remineralization rate was more important, but also more influenced by fluctuating oxygen concentrations, than microbial and geochemical oxidation processes.