Mineralogy and chemical composition of ODP Sites 129-800 and 129-801

Sites 800 and 801 in the Pigafetta Basin allow the sedimentary history over the oldest remaining Pacific oceanic crust to be established. Six major deposition stages and events are defined by the main lithologic units from both sites. Mineralogical and chemical investigations were run on a large set of samples from these units. The data enable the evolution of the sediments and their depositional environments to be characterized in relation to the paleolatitudinal motion of the sites. The upper part of the basaltic crust at Site 801 displays a complex hydrothermal and alteration evolution expressed particularly by an ochre siliceous deposit comparable to that found in the Cyprus ophiolite. The oldest sedimentary cover at Site 801 was formed during the Callovian-Bathonian (stage 1) with red basal siliceous and metalliferous sediments similar to those found in supraophiolite sequences, and formed near an active ridge axis in an open ocean. Biosiliceous sedimentation prevailed throughout the Oxfordian to Campanian, with rare incursions of calcareous input during the middle Cretaceous (stages 2, 4, and 5). The biosiliceous sedimentation was drastically interrupted during the Aptian-Albian by thick volcaniclastic turbidite deposits (stage 3). The volcanogenic phases are pervasively altered and the successive secondary mineral parageneses (with smectites, celadonite, clinoptilolite, phillipsite, analcime, calcite, and quartz) define a "mineral stratigraphy" within these deposits. From this mineral stratigraphy, a similar lithologic layer is defined at the top of the Site 800 turbidite unit and the bottom of the Site 801 turbidite unit. Then, the two sites appear to have been located at the same distal distance from a volcanic source (hotspot). They crossed this locality, at about 10°S, at different times (latest Aptian for Site 800, middle Albian for Site 801). The Cretaceous siliceous sedimentation stopped during the late Campanian and was followed by deposition of Cenozoic pelagic red clay (stage 6). This deep-sea facies, which formed below the carbonate compensation depth, contains variable zeolite authigenesis in relation to the age of deposition, and records the global middle Cenozoic hiatus events. At the surface, the red clay from this part of the Pacific shows a greater detrital component than its equivalents from the central Pacific deep basins.

Chemical composition of altered volcanic rocks from ODP Sites 193-1188 and 193-1189

The conventional model of leaching volcanic rocks as a source of metals in a seafloor hydrothermal systems has been tested by examining the behavior of Pb and other trace elements during hydrothermal alteration. ODP Leg 193 drill sites 1188 (Snowcap) and 1189 (Roman Ruins) on Pual Ridge in the eastern Manus Basin offshore eastern Papua New Guinea provide a unique three-dimensional window into an active back-arc hydrothermal system. We investigate by means of a LA-ICP-MS microbeam technique the capacity of Pb to be leached from a host volcanic rock exposed to various types and intensities of alteration. Our results are in general agreement with previous studies that utilized bulk analytical techniques but provide a more detailed explanation of the processes. Fresh representative dacitic lavas from the Pual Ridge have an average whole rock Pb content of 5.2 ppm, an average interstitial glass Pb content of 5.6 ppm and an average plagioclase Pb content of 1.0 ppm. Altered matrix samples have highly variable Pb values ranging from 0 to 52.4 ppm. High Pb values in altered samples are associated with a low temperature chlorite and clay mineral assemblage, in some cases overprinted by a high temperature (up to 350°C) silica-rich "bleaching" alteration. Only the most highly altered matrix samples have REE patterns that differ from the fresh Pual Ridge dacite. This may represent either different lava histories or alteration characteristics that have affected normally immobile REEs. Altered samples with the highest Pb values have similar REE patterns to those of the local unaltered lavas. They are compositionally similar to typical Pual Ridge dacites indicating a genetic relationship between the main regional volcanic suite and the subseafloor hydrothermally altered, Pb-enriched material. Relative loss/gain for Pb between the analyzed altered samples and a calculated precursor show a maximum relative gain of 901%. Samples with relative Pb gain from both drill sites are associated with lower temperature alteration mineral assemblages characterized by pervasive chloritization. The related lower temperature (220-250°C) neutral to slightly acidic fluids have been ascribed by others to return circulation of hydrothermal fluids that did not interact with seawater. Because altered samples have a higher Pb content than the fresh precursor, leaching of fresh volcanic rocks cannot be the source of Pb in the hydrothermal systems.

Chemical composition of siderites and clay minerals from DSDP Holes 70-506G and 70-507B

As soon as they are emplaced on the sea floor, oceanic basalts go through a low-temperature alteration process which produces black halos concentrical with exposed surfaces and cracks, whereas the grey internal parts of the basaltic pieces apparently remain unaltered. This paper reports for the first time the occurrence of authigenic siderite and ankerite in oceanic basalts and more particularly in the grey internal parts of the latter. Small (8-50 µm) crystals of zoned siderite and ankerite have been observed in ten vesicles of two samples recovered from DSDP Holes 506G and 507B drilled south of the Galápagos Spreading Center (GSC). These Fe-carbonates show a large range of chemical composition (FeCO3 = 47-88%; CaCO3 = 5-40%; MgCO3 = 1-20%; MnCO3 = 0-11%). Most of them are Ca-richer than siderite reported in the literature. The chemical composition of the carbonate clearly reflects the fluctuation of the fluid chemical composition during crystallization. Mn and at least part of the Fe are thought to be hydrothermal in origin, whereas Mg and probably Ca were provided by seawater. It is proposed that siderite and ankerite formed at relatively low temperature (<85°C) and is metastable. The alteration of the GSC basalts seems to have proceeded in two stages: during the first, reducing stage, pyrite precipitated from hydrothermal fluids. A little further in the rock, siderite precipitated from the fluid which had already been modified by the formation of pyrite, and thus in a microenvironment where particular conditions prevailed (high P_CO2, increasing p_S**2- or increasing pH or increasing or decreasing pe). During the second, oxidizing, stage of alteration, a seawater-dominated fluid allowed crystallization of mixtures of Fe-rich smectites and micas, and Fe-hydroxides forming the black halos in the external portion of the basalt pieces and locally oxidizing pyrite and siderite in their innermost part. It is shown in this paper that, even at its earliest stage, and at low temperature, alteration of the upper oceanic crust (lavas) involves fluids enriched in Fe and Mn, interpreted to be of hydrothermal origin.

Chemical composition of bottom sediments and interstitial waters from DSDP Sites 252, 285, 315, 317, 336, and 386

Six Deep Sea Drilling Project (DSDP) Sites (252, 285, 315, 317, 336, 386) were examined for the chemical composition of the dissolved salts in interstitial waters, the oxygen isotopic composition of the interstitial waters, and the major ion composition of the bulk solid sediments. An examination of the concentration-depth profiles of dissolved calcium, magnesium, potassium, and H218O in conjunction with oxygen isotope mass balance calculations confirms the hypothesis that in DSDP pelagic drill sites concentration gradients in Ca. Mg. K, and H218O are largely due to alteration reactions occurring in the basalts of Layer 2 and to alteration reactions involving volcanic matter dispersed in the sediment column. Oxygen isotope mass balance calculations require substantial alteration of Layer 2 (up to 25% of the upper 1000 m). but only minor exchange of Ca, Mg, and K occurs with the overlying ocean. This implies that alteration reactions in Layer 2 are almost isochemical.

Chemical composition of interstitial solutions from sediments of DSDP Legs 6-8, 11, 12, 14, 15, and 22

Through the Deep Sea Drilling Project samples of interstitial solutions of deeply buried marine sediments throughout the World Ocean have been obtained and analyzed. The studies have shown that in all but the most slowly deposited sediments pore fluids exhibit changes in composition upon burial. These changes can be grouped into a few consistent patterns that facilitate identification of the diagenetic reactions occurring in the sediments. Pelagic clays and slowly deposited (<1 cm/1000 yr) biogenic sediments are the only types that exhibit little evidence of reaction in the pore waters. In most biogenic sediments sea water undergoes considerable alteration. In sediments deposited at rates up to a few cm/1000 yr the changes chiefly involve gains of Ca(2+) and Sr(2+) and losses of Mg(2+) which balance the Ca(2+) enrichment. The Ca-Mg substitution may often reach 30 mM/kg while Sr(2+) may be enriched 15-fold over sea water. These changes reflect recrystallization of biogenic calcite and the substitution of Mg(2+) for Ca(2+) during this reaction. The Ca-Mg-carbonate formed is most likely a dolomitic phase. A related but more complex pattern is found in carbonate sediments deposited at somewhat greater rates. Ca(2+) and Sr(2+) enrichment is again characteristic, but Mg(2+) losses exceed Ca(2+) gains with the excess being balanced by SO4(post staggered 2-) losses. The data indicate that the reactions are similar to those noted above, except that the Ca(2+) released is not kept in solution but is precipitated by the HCO3(post staggered -) produced in SO4(post staggered 2-) reduction. In both these types of pore waters Na(+) is usually conservative, but K(+) depletions are frequent. In several partly consolidated sediment sections approaching igneous basement contact, very marked interstitial calcium enrichment has been found (to 5.5 g/kg). These phenomena are marked by pronounced depletion in Na(+), Si and CO2, and slight enhancement in Cl(-). The changes are attributed to exchange of Na(+) for Ca(2+) in silicate minerals forming from submarine weathering of igneous rocks such as basalts. Water is also consumed in these reactions, accounting for minor increases in total interstitial salinity. Terrigenous, organic-rich sediments deposited rapidly along continental margins also exhibit significant evidences of alteration. Microbial reactions involving organic matter lead to complete removal of SO4(post staggered 2-), strong HCO3(post staggered -) enrichment, formation of NH4(post staggered +), and methane synthesis from H2 and CO2 once SO4(post staggered 2-) is eliminated. K+ and often Na+ (slightly) are depleted in the interstitial waters. Ca(2+) depletion may occur owing to precipitation of CaCO3. In most cases interstitial Cl- remains relatively constant, but increases are noted over evaporitic strata, and decreases in interstitial Cl- are observed in some sediments adjacent to continents.

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

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

Chemical composition of secondary minerals from ODP Site 206-1256

Two basement holes were drilled during Ocean Drilling Program (ODP) Leg 206. Hole 1256C penetrates 88.5 m into basement and Hole 1256D, ~30 m to the south, penetrates 502 m into basement (Wilson, Teagle, Acton, et al., 2003, doi:10.2973/odp.proc.ir.206.2003). Recovered cores consist of basalts exhibiting the effects of low-temperature alteration by seawater. As part of a larger study of alteration effects, a study of the secondary mineralogy was undertaken. This data report presents the major and some minor element compositions of secondary minerals. Analyses focus on the major secondary phases, phyllosilicates, and less abundant feldspars, but also include limited analyses of carbonates and apatite. Different occurrences of secondary minerals are included (e.g., veins and vesicles replacing olivine and plagioclase) as well as variations with depth.