Chemistry of altered basalts from ODP Hole 123-765D

Volcanic basement recovered at Hole 765D is characterized by nonpervasive, oxidative alteration, typical of seafloor weathering. Chilled margins and the mesostasis of the lavas are variably altered to assemblages of celadonite, Fe-oxyhydroxides, zeolites, and calcite with trace saponite. Plagioclase is partially altered to Ca-Na zeolites and/or albite. Well-developed alteration halos parallel fracture surfaces and extend several centimeters into the surrounding rock. These clay-rich halos are enriched in K2O and Fe2O3 relative to the adjacent clay-poor rock. The halos and adjacent rock are characterized by d18O values 2 per mil-3 per mil higher than those of fresh MORB. The "freshness" of the samples and the scarcity of saponite suggest that the duration of seawater circulation was short-lived. Albitization of plagioclase indicates that the volcanic rocks were altered initially at low temperatures and were subsequently reheated off-axis in a closed environment. Reheating did not result in significant modification of the bulk composition of the crust.

Mineral chemistry of basalts from DSDP Holes 65-483 and 65-483B

During DSDP Leg 65, a series of holes was drilled into the oceanic basement across the mouth of the Gulf of California to study the composition of the crust and the nature of its construction at a young spreading center. In Holes 483 and 483B, two of the deepest basement holes drilled on this leg, the basement is characterized by an upper sequence of interlayered massive basalts and sediments underlain by a lower sequence of interlayered pillow and massive basalts. Electron microprobe analyses were performed on pyroxene, plagioclase, olivine, spinel, and glass from 14 representative samples of 10 of the 16 major lithologic units. These analyses along with petrographic results can be used to interpret the detailed crystallization history of the basalts. We believe from the results of this study that the basalts were formed by at least a three-stage cooling process, followed by eruption and formation of quench phases. Our data do not support magma mixing.

Chemical composition of clinopyroxenes and melt inclusions in clinopyroxenes from rocks of the Malaita Island, Ontong Java Plateau (Pacific Ocean)

The paper is based on new results of melt inclusion studies in minerals. Physicochemical and geochemical parameters of plateau basalt magmatic systems of the Siberian Platform and Ontong Java Plateau (Pacific Ocean) have been established. The studied melts are enriched in Fe. That differs them from magmatic melts of mid-ocean ridges (MOR). A comparative analysis of data on inclusions has shown a similarity of continental and oceanic plateau basalt magmatic systems. They considerably differ from those of MOR and intraplate oceanic islands. Crystallization of oceanic plateau basalts took place at lower temperatures and pressures as compared with similar rocks of the Siberian Platform. The data on inclusions evidence that the melts of the Siberian Platform and the Malaita Island underwent a serious evolution in contrast to magmas of the Nauru Basin that have more stable geochemical parameters. The most fractionated low-temperature high-Fe magmas with elevated contents of trace and rare-earth elements occur in the Malaita Island (Ontong Java Plateau) magmatic system.

Chemical and isotopic compositions of basalts and glasses from lavas of the Sierra Leone fault site

According to detailed petrological, geochemical, and isotope-geochemical study, fragments of fresh pillow lavas with chilled glass margins dredged at the Sierra-Leone test site in the axial rift zone of the MAR between 5° and 7°N correspond to MORB tholeiites, which are not primitive mantle melts, but were differentiated in intermediate magmatic (intrusive) chambers. Small-scale geochemical and Sr-Nd isotope heterogeneities were established for the first time in basalts and their glasses. It was shown that some samples have significant nonsystematic differences in the 87Sr/86Sr ratio between basalts and their chilled glasses and less significant difference in e-Nd; higher Sr ratios can be observed both in glasses and basalts of the same lava fragments. No significant correlation is observed between isotope characteristics of samples and their geochemistry; it was also shown that seawater did not affect Sr and Nd isotope compositions of the chilled glasses from the studied pillow lavas. It is suggested that such differences in isotope ratios are related to small-scale heterogeneity of melts owing to incomplete homogenization during their rapid ascent to the surface. Heterogeneity of basaltic melts is explained by their partial contamination by older plutonic rocks (especially gabbroids) of the lower oceanic crust, through which they ascended to the surface of the ocean floor. The wider scatter of the Sr isotopic ratios relative to Nd ones is related to presence of xenocrysts of calcic plagioclase; correspondingly, absence of a Nd mineral carrier in the rocks results in less distinct Nd isotope variations. It was shown that all studied basalts define a single trend along the mantle correlation array in the Sr-Nd isotope diagram. Causes of this phenomenon remain unclear.

Geochemical composition of gabbroic rocks from ODP Hole 179-1105A, southwest Indian Ridge

Oxide-free olivine gabbro and gabbro, and oxide olivine gabbro and gabbro make up the bulk of the gabbroic suite recovered from Ocean Drilling Program (ODP) Leg 179 Hole 1105A, which lies 1.2 km away from Hole 735B on the eastern transverse ridge of the Atlantis II Fracture Zone, Southwest Indian Ridge. The rocks recovered during Leg 179 show striking similarities to rocks recovered from the uppermost 500 m of Hole 735B during ODP Leg 118. The rocks of the Atlantis platform were likely unroofed as part of the footwall block of a large detachment fault on the inside corner of the intersection of the Southwest Indian Ridge and the Atlantis II Transform at ~11.5 Ma. We analyzed the lithologic, geochemical, and structural stratigraphy of the section. Downhole lithologic variation allowed division of the core into 141 lithologic intervals and 4 main units subdivided on the basis of predominance of oxide gabbroic vs. oxide-free gabbroic rocks. Detailed analyses of whole-rock chemistry, mineral chemistry, microstructure, and modes of 147 samples are presented and clearly show that the gabbroic rocks are of cumulate origin. These studies also indicate that geochemistry results correlate well with downhole magnetic susceptibility and Formation MicroScanner (FMS) resistivity measurements and images. FMS images show rocks with a well-layered structure and significant numbers of mappable layer contacts or compositional contrasts. Downhole cryptic mineral and whole-rock chemical variations depict both "normal" and inverse fine-scale variations on a scale of 10 m to <2 m with significant compositional variation over a short distance within the 143-m section sampled. A Mg# shift in whole-rock or Fo contents of olivine of as much as 20-30 units over a few meters of section is not atypical of the extreme variation in downhole plots. The products of the earliest stages of basaltic differentiation are not represented by any cumulates, as the maximum Fo content was Fo78. Similarly, the extent of fractionation represented by the gabbroic rocks and scarce granophyres in the section is much greater than that represented in the Atlantis II basalts. The abundance of oxide gabbros is similar to that in Hole 735B, Unit IV, which is tentatively correlated as a similar unit or facies with the oxide gabbroic units of Hole 1105A. Oxide phases are generally present in the most fractionated gabbroic rocks and lacking in more primitive gabbroic rocks, and there is a definite progression of oxide abundance as, for example, the Mg# of clinopyroxene falls below 73-75. Coprecipitation of oxide at such early Mg#s cannot be modeled by perfect fractional crystallization. In situ boundary layer fractionation may offer a more plausible explanation for the complex juxtaposition of oxide- and nonoxide-bearing more primitive gabbroic rocks. The geochemical signal may, in part, be disrupted by the presence of mylonitic shear zones, which strike east-west and dip both to the south and north, but predominantly to the south away from the northern rift valley where they formed. Downhole deformation textures indicate increasing average strain and crystal-plastic deformation in units that contain oxides. Oxide-rich zones may represent zones of rheologic weakness in the cumulate section along which mylonitic and foliated gabbroic shear zones nucleate in the solid state at high temperature, or the oxide may be a symptom of former melt-rich zones and hypersolidus flow, as predicted during study of Hole 735B.

Composition and alteration of volcanic rocks of ODP Hole 119-738C

During ODP Leg 119 one basement hole was drilled at Site 738, on the Southern Kerguelen Plateau. The 38.2 m of basement rocks drilled comprises three basaltic aa-lava flows with basal and top breccias, overlain by Turanian marine carbonates. Site 738 basalts probably erupted near a fracture zone, and were emplaced during the plateau-forming stage of Kerguelen Plateau evolution under quiet, subaerial to shallow water conditions. The basalts are T-MORB, chemically resembling Mesozoic continental flood basalts of the southern hemisphere. Two slightly different magma batches are distinguished by Fe, Ti, Al, Zr, and REE concentrations. Prior to eruption, the magmas had undergone significant olivine and some clinopyroxene fractionation. Incompatible and immobile trace element concentrations and ratios point to a veined upper mantle source, where a refractory mineral assemblage retains Nb, Ta, and the HREE. The basaltic melts derived from this regionally veined, enriched upper mantle have high LREE, and especially Ba and Th concentrations and bear the DUPAL isotopic signature gained from deep- seated, recycled, old oceanic(?) crust. A saponite-celadonite secondary mineral assemblage confines the alteration temperature to <170°C. Alteration is accompanied by net gains of H2O, CO2, K2O, and Rb, higher oxidation, minor Na2O, SiO2 gains, and losses of V and CaO. Released Ca, together with Ca from seawater, precipitated as calcite in veins and vesicles, plumbed the circulation system and terminated the rock/open seawater interaction.

Electrical properties of basalts of ODP Sites 124-768 and 124-770

Conductivity of 54 basalt samples from ODP Sites 768 and 770 was measured as a function of temperature and fluid salinity. Porosity was also measured for all samples, and cation exchange capacity was measured for 46 of the samples. Porosity measurements indicated that porosity is underestimated for basalts like these, unless one uses extensive drying at high vacuum. At salinities greater than 29 ppt, and throughout the range of salinity and temperatures likely in situ, sample conductivity (Co) is controlled by porosity (phi) according to the Archie relation Co = 0.22*Cw phi*1-3 (orFF = 4.5/f1.3), where Cw is conductivity of the pore fluids and FF = Cw/CO is the formation factor. At lower salinity, clay-surface conduction or microcrack conduction may dominate. We are unable to distinguish reliably between the two mechanisms, but we do detect their effects subtly at high salinity and strongly at low salinity.

Geochemistry at DSDP Site 60-456

Basalts in two holes spaced 200 meters apart at DSDP Site 456 in the Mariana Trough both show a downward sequence of nonoxidative and oxidative zones of alteration, each 10 to 15 meters thick, overlying fresh basalts. Basalts in the nonoxidative zone have been extensively chloritized and have vein and vesicle fillings of quartz, opal, chlorite, calcite, and pyrite. Minor sulfides are chalcopyrite and digenite. Basalts in the oxidative zone have abundant smectites and iron hydroxides and are variably enriched in K, Rb, and Ba, unlike the nonoxidative basalts above them. We propose that the oxidative zone was a zone of mixing between high-temperature, reduced hydrothermal fluids moving horizontally beneath impermeable sediments at the top of the pillowed basement lavas and cold, oxygenated seawater in interpillow voids deeper in the basement. Recrystallized vitric tuffs immediately above the basalts containing authigenic quartz and wairakite, as well as occurrence of chlorite, epidote, and chalcopyrite in the basalts, suggest temperatures of alteration in excess of 200°C.

Chemical and isotopic compositions of lavas from the Broken Ridge and Southern Kerguelen Plateau

Lavas from several major bathymetric highs in the eastern Indian Ocean that are likely to have formed as Early to Middle Cretaceous manifestations of the Kerguelen hotspot are predominantly tholeiitic; so too are glass shards from Eocene to Paleocene volcanic ash layers on Broken Ridge, which are believed to have come from eruptions on the Ninetyeast Ridge. The early dominance of tholeiitic compositions contrasts with the more recent intraplate, alkalic volcanism of the Kerguelen Archipelago. Isotopic and incompatible-element ratios of the plateau lavas are distinct from those of Indian mid-ocean ridge basalts; their Nd, Sr, 207Pb/204Pb and 2078b/204Pb isotopic ratios overlap with but cover a much wider range than measured for more recent oceanic products of the Kerguelen hotspot (including the Ninetyeast Ridge) or, indeed, oceanic lavas from any other hotspot in the world. Samples from the Naturaliste Plateau and ODP Site 738 on the southern tip of the Kerguelen Plateau are particularly noteworthy, with e-Nd(T) = -13 to -7, (87Sr/86Sr)T=0.7090 to 0.7130 and high 207Pb/204Pb relative to 206Pb/204Pb. In addition, the low-e-Nd(T) Naturaliste Plateau samples are elevated in SiO2 (>54 wt%). In contrast to "DUPAL" oceanic islands such as the Kerguelen Archipelago, Pitcairn and Tristan da Cunha, the plateau lavas with extreme isotopic characteristics also have relative depletions in Nb and Ta (e.g., Th/Ta, La Nb > primitive mantle values); the lowest e-Nd(T) and highest Th/Ta and La Nb values occur at sites located closest to rifted continental margins. Accepting a Kerguelen plume origin for the plateau lavas, these characteristics probably reflect the shallow-level incorporation of continental lithosphere in either the head of the early Kerguelen plume or in plume-derived magmas, and suggest that the influence of such material diminished after the period of plateau construction. Contamination of asthenosphere with the type of material affecting Naturaliste Plateau and Site 738 magmatism appears unlikely to be the cause of low-206Pb/204Pb Indian mid-ocean ridge basalts. Finally, because isotopic data for the plateaus do not cluster or form converging arrays in isotope-ratio plots, they provide no evidence for either a quickly evolving, positive ?Nd, relatively high-206Pb/204Pb plume composition, or a plume source dominated by mantle with e-Nd of -3 to ~0.

Chemical, isotope and mineral composition of hydrothermally altered upper oceanic crust drilled at ODP Site 129-801C

ODP Hole 801C penetrates >400 m into 170-Ma oceanic basement formed at a fast-spreading ridge. Most basalts are slightly (10-20%) recrystallized to saponite, calcite, minor celadonite and iron oxyhydroxides, and trace pyrite. Temperatures estimated from oxygen isotope data for secondary minerals are 5-100°C, increasing downward. At the earliest stage, dark celadonitic alteration halos formed along fractures and celadonite, and quartz and chalcedony formed in veins from low-temperature (<100°C) hydrothermal fluids. Iron oxyhydroxides subsequently formed in alteration halos along fractures where seawater circulated, and saponite and pyrite developed in the host rock and in zones of restricted seawater flow under more reducing conditions. Chemical changes include variably elevated K, Rb, Cs, and H2O; local increases in FeT, Ba, Th, and U; and local losses of Mg and Ni. Secondary carbonate veins have 87Sr/86Sr = 0.706337 - 0.707046, and a negative correlation with d18O results from seawater-basalt interaction. Carbonates could have formed at any time since the formation of Site 801 crust. Variable d13C values (-11.2? to 2.9?) reflect the incorporation of oxidized organic carbon from intercalated sediments and changes in the d13C of seawater over time. Compared to other oceanic basements, a major difference at Site 801 is the presence of two hydrothermal silica-iron deposits that formed from low-temperature hydrothermal fluids at the spreading axis. Basalts associated with these horizons are intensely altered (60-100%) to phyllosilicates, calcite, K-feldspar, and titanite; and exhibit large increases in K, Rb, Cs, Ba, H2O, and CO2, and losses of FeT, Mn, Mg, Ca, Na, and Sr. These effects may be common in crust formed at fast-spreading rates, but are not ubiquitous. A second important difference is that the abundance of brown oxidation halos along fractures at Site 801 is an order of magnitude less than at some other sites (2% vs. 20-30%). Relatively smooth basement topography (<100 m) and high sedimentation rate (8 m/Ma) probably restricted the access of oxygenated seawater. Basement lithostratigraphy and early low-temperature hydrothermal alteration and mineral precipitation in fractures at the spreading axis controlled permeability and limited later flow of oxygenated seawater to restricted depth intervals.

Chemical composition of bottom sediments at DSDP Sites 91-595 and 91-596 and ODP Sites 114-701 and 129-801

Subducted sediments play an important role in arc magmatism and crust-mantle recycling. Models of continental growth, continental composition, convergent margin magmatism and mantle heterogeneity all require a better understanding of the mass and chemical fluxes associated with subducting sediments. We have evaluated subducting sediments on a global basis in order to better define their chemical systematics and to determine both regional and global average compositions. We then use these compositions to assess the importance of sediments to arc volcanism and crust-mantle recycling, and to re-evaluate the chemical composition of the continental crust. The large variations in the chemical composition of marine sediments are for the most part linked to the main lithological constituents. The alkali elements (K, Rb and Cs) and high field strength elements (Ti, Nb, Hf, Zr) are closely linked to the detrital phase in marine sediments; Th is largely detrital but may be enriched in the hydrogenous Fe-Mn component of sediments; REE patterns are largely continental, but abundances are closely linked to fish debris phosphate; U is mostly detrital, but also dependent on the supply and burial rate of organic matter; Ba is linked to both biogenic barite and hydrothermal components; Sr is linked to carbonate phases. Thus, the important geochemical tracers follow the lithology of the sediments. Sediment lithologies are controlled in turn by a small number of factors: proximity of detrital sources (volcanic and continental); biological productivity and preservation of carbonate and opal; and sedimentation rate. Because of the link with lithology and the wealth of lithological data routinely collected for ODP and DSDP drill cores, bulk geochemical averages can be calculated to better than 30% for most elements from fewer than ten chemical analyses for a typical drill core (100-1000 m). Combining the geochemical systematics with convergence rate and other parameters permits calculation of regional compositional fluxes for subducting sediment. These regional fluxes can be compared to the compositions of arc volcanics to asses the importance of sediment subduction to arc volcanism. For the 70% of the trenches worldwide where estimates can be made, the regional fluxes also provide the basis for a global subducting sediment (GLOSS) composition and flux. GLOSS is dominated by terrigenous material (76 wt% terrigenous, 7 wt% calcium carbonate, 10 wt% opal, 7 wt% mineral-bound H2O+), and therefore similar to upper continental crust (UCC) in composition. Exceptions include enrichment in Ba, Mn and the middle and heavy REE, and depletions in detrital elements diluted by biogenic material (alkalis, Th, Zr, Hf). Sr and Pb are identical in GLOSS and UCC as a result of a balance between dilution and enrichment by marine phases. GLOSS and the systematics of marine sediments provide an independent approach to the composition of the upper continental crust for detrital elements. Significant discrepancies of up to a factor of two exist between the marine sediment data and current upper crustal estimates for Cs, Nb, Ta and Ti. Suggested revisions to UCC include Cs (7.3 ppm), Nb (13.7 ppm), Ta (0.96 ppm) and TiO2 (0.76 wt%). These revisions affect recent bulk continental crust estimates for La/Nb and U/Nb, and lead to an even greater contrast between the continents and mantle for these important trace element ratios. GLOSS and the regional sediment data also provide new insights into the mantle sources of oceanic basalts. The classical geochemical distinction between 'pelagic' and 'terrigenous' sediment sources is not valid and needs to be replaced by a more comprehensive understanding of the compositional variations in complete sedimentary columns. In addition, isotopic arguments based on surface sediments alone can lead to erroneous conclusions. Specifically, the Nd/Hf ratio of GLOSS relaxes considerably the severe constraints on the amount of sediment recycling into the mantle based on earlier estimates from surface sediment compositions.

Geochemistry of Ninetyeast Ridge basaltic glasses

The Ninetyeast Ridge (NER), a north-south striking, 5,000 km long, 77 to 43 Ma chain of basaltic submarine volcanoes in the eastern Indian Ocean formed as a hotspot track created by rapid northward migration of the Indian Plate over the Kerguelen hotspot. Based on the major and trace element contents of unaltered basaltic glasses from six locations along the NER, we show that the NER was constructed by basaltic magma derived from at least three geochemically distinct mantle sources: (1) a source enriched in highly incompatible elements relative to primitive mantle like the source of the 29-24 Ma flood basalts in the Kerguelen Archipelago; (2) an incompatible element-depleted source similar to the source of Mid-Ocean Ridge Basalt (MORB) erupted along the currently active Southeast Indian Ridge (SEIR); and (3) an incompatible element-depleted source that is compositionally and mineralogically distinct from the source of SEIR MORB. Specifically, this depleted mantle source was garnet-bearing and had higher Y/Dy and Nb/Zr, but lower Zr/Sm, than the SEIR MORB source. We infer that this third source formed as a garnet-bearing residue created during a previous melting event, perhaps an initial partial melting of the mantle hotspot. Subsequently, this residue partially melted over a large pressure range, from slightly over 3 GPa to less than 1 GPa, and to a high extent (~ 30%) thereby creating relatively high SiO2 and FeO contents in some NER basalts relative to SEIR MORB.

Petrology and geochemistry of basalts at DSDP Hole 86-581

Approximately 5 m of aphyric to sparsely phyric basalt was recovered from Hole 581, the only hole on Leg 86 where basement was cored. The occurrence of samples with altered glassy rinds indicates that at least three cooling units (pillows or thin flows) were sampled. The samples were moderately to intensely altered; groundmass crystals are generally fresh, but all glass is altered. Alteration is greatest in vesicular samples, but most of the samples have fractures filled with iron oxyhydroxide, clay, and/or calcite. All 13 samples analyzed are moderately fractionated aluminous N-type mid-ocean ridge basalts. The samples can be divided into two groups based on TiO2 and FeO contents. The least-evolved group may be derived from a more primitive mid-ocean ridge basalt by the crystallization of 18% plagioclase, 24% clinopyroxene, and 3% olivine. The more evolved group may be derived from the first group by the fractionation of 18% plagioclase, 11% clinopyroxene, and 3% olivine. However, higher Ce/Yb ratios in the more evolved group cannot be produced by fractionation and thus we must invoke a more complex process such as dynamic melting to relate the two groups to a common source.

(Table 1) Physical properties of basalts from DSDP Legs 69 and 70

Physical properties of basalts from Deep Sea Drilling Project Sites 504 and 505, south of the Costa Rica Rift, including wet-bulk density, water content, sonic velocity, and thermal conductivity, were measured on board D/V Glomar Challenger during Legs 69 and 70. The mean wet-bulk density is 2.90±0.06 g/cm**3, porosity 5.0±2.2%, sonic velocity 5.75±0.30 km/s, and thermal conductivity 1.67±0.09 W/m°K. Basalts from this young ocean crust (5.9 m.y.) have relatively low porosity and consequently high density and sonic velocity, as compared to average DSDP basalts. Some systematic trends in depth variation of physical properties were found: down to Core 40 in Hole 504B, grain densities were lower than those deeper in the hole, whereas porosity in the upper section was higher. This can be attributed either to differences in the flow type or in the nature of alteration of basalts at the different levels in the hole.

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).