(Table 1) Composition of DSDP Hole 37-334 clinopyroxenes

Recent studies of abyssal peridotites (Johnson et al., 1990, doi:10.1029/JB095iB03p02661), mid-ocean-ridge basalts (MORBs) (McKenzie, 1985, doi:10.1016/0012-821X(85)90001-9) and their entrained melt inclusions (Sobolev and Shimizu, 1993, doi:10.1038/363151a0; Humler and Whitechurch, 1988, doi:10.1016/0012-821X(88)90055-6) have shown that fractional melting of the upwelling sub-oceanic mantle produces magmas with a much wider range of compositions than erupted MORBs. In particular, it seems that strongly depleted primary magmas are routinely produced by melting beneath ridges (Johnson et al., 1990, doi:10.1029/JB095iB03p02661). The absence of strongly depleted melts as erupted lavas prompts the question of how long such magmas survive beneath ridges, before their distinctive compositions are concealed by mixing with more enriched magmas. Here we report mineral compositions from a unique suite of oceanic cumulates recovered from DSDP Site 334 (Aumento et al., doi:10.2973/dsdp.proc.37.1977), which indicate that the rocks crystallized from basaltic liquids that were strongly depleted in Na, Ti, Zr, Y, Sr and rare-earth elements relative to any erupted MORB. It thus appears that the magmatic plumbing system beneath the Mid-Atlantic Ridge permitted strongly depleted magmas to accumulate in a magma chamber and remain sufficiently isolated to produce cumulate rocks. Even so, spatial heterogeneity in the compositions of high-calcium pyroxenes suggests that in the later stages of solidification these rocks reacted with infiltrating enriched basaltic liquids.

Composition of chromian diopside megacryst in DSDP Leg 37 basalts (Table 2, 3)

Refractory megacrysts of olivine, plagioclase, chromian diopside and Cr-Al spinel, which were not in equilibrium with the host oceanic tholeiite on eruption, are present in samples from several dredge sites and DSDP drill sites in the Atlantic and Pacific Oceans. They have multiple origins: (1) cognate or accidental mantle fragments; (2) relict fragments from fractional crystallization of parental liquids considerably more primitive than oceanic tholeiite; and most commonly (3) the fractional crystallization products of such liquids mixed with oceanic tholeiite magma. Melt inclusions in chrome-spinel phenocrysts provide evidence for this postulated Mg- and Ca-rich magma which has counterparts in the Scottish Tertiary Province and in west Greenland.

Nd and Sr isotopic composition of Cretaceous MORB

Chemical and isotopic (Nd and Sr) compositions have been determined for 12 Cretaceous basaltic samples (108 Ma old) from Holes 417D and 418A of Legs 51,52 and 53. We have found that: (1) The chemical compositions are typical of MORB. They do not vary systematically with the stratigraphic positions of the analyzed samples; thus, the chemical evolution is independent of the eruption sequence that occurred at this Cretaceous ridge. (2) REE patterns for all rocks are characterized by a strong LREE depletion with (La/Sm)N = 0.38-0.50; no significant Eu anomalies are found; HREE are nearly flat or slightly depleted towards Yb-Lu and have 12-18 * chondritic abundances. Combining the results of previous studies, it suggests that no significant temporal and spatial variation in magma chemistry (especially for LIL elements) has occurred in the 'normal' ridge segments over the last 150 Ma. (3) lsotopically, 143Nd/144Nd ratios vary from 0.513026 to 0.513154, corresponding to epsilon-Nd(0) = +7.5 to +10, and they fall in the typical range of MORB. However, these rocks have unexpectedly high 87Sr/86Sr ratios (0.70355-0.70470) which are attributed to the result of seawater-rock interaction. (4) The Nd model ages (Tin), ranging from 1.53 to 2.47 (average 2.06) AE, suggest that the upper mantle source(s) underwent a large scale chemical differentiation leading to LREE and other LIL element depletion about 2 AE ago, assuming a simple two-stage model. More realistically, the variation in Tm(Nd) or epsilon-Nd could be derived from mixing of heterogeneous mantle sources that were a consequence of continuous mantle differentiation and continental formation. (5) Because of the low mg values (0.52-0.63), the analyzed basaltic rocks do not represent primary liquids of mantle melting. The variation in La/Sm ratios and TiO2 are not compatible with a model in which all rocks are genetically related by a simple fractional crystallization. Rather, it is proposed that the basaltic rocks might have been derived from some heterogeneous upper mantle source with or without later magmatic mixing, and followed by some shallow-level fraetionations.

Chemistry of gabbroic rocks of ODP Hole 118-735B

We present results of a microprobe investigation of fresh and least-deformed and metamorphosed gabbroic rocks from Leg 118, Hole 735B, drilled on the east side of the Atlantis II Fracture Zone, Southwest Indian Ridge. This rock collection comprises cumulates ranging from troctolites to olivine-gabbro and olivine-gabbronorite to ilmenite-rich ferrogabbros and ferrogabbronorites. As expected, the mineral chemistry is variable and considerably expands the usual oceanic reference spectrum. Olivine, plagioclase, and clinopyroxene are present in all the studied samples. Orthopyroxene and ilmenite, although not rare, are not ubiquitous. Olivine compositions range from Fo85 to Fo30, while plagioclase compositions vary from An70 to An27. Mg/(Mg + Fe2+) of clinopyroxene (mostly diopside to augite) varies from 0.88 to 0.54. Mg/(Mg + Fe2+) of orthopyroxene varies from 0.84 to 0.50. These minerals are not significantly zoned. All mineralogical data indicate that fractional crystallization is an important factor for the formation of cumulates. However, sharp contacts, interpreted as layering boundaries or intrusion margins, suggest polycyclic fractionation of several magma batches of limited volumes. Calculated compositions of magmas in equilibrium with the most magnesian mineral samples at the bottom of the hole represent fractionated liquids through separation of olivine, plagioclase, and clinopyroxene at moderate to low pressures (less than 9 kb). Crystallization of orthopyroxene and ilmenite occurs in the most differentiated liquids. Mixing of magmas having various compositions before entering the cumulate zone is another mechanism necessary to explain extremely differentiated iron-rich gabbros formed in this slow-spreading ridge environment.

Estimation of the normal boiling point of organic compounds via group contributions

The normal boiling point is a fundamental thermo-physical property, which is important in describing the transition between the vapor and liquid phases. Reliable method which can predict it is of great importance, especially for compounds where there are no experimental data available. In this work, an improved group contribution method, which is second order method, for determination of the normal boiling point of organic compounds based on the Joback functional first order groups with some changes and added some other functional groups was developed by using experimental data for 632 organic components. It could distinguish most of structural isomerism and stereoisomerism, which including the structural, cis- and trans- isomers of organic compounds. First and second order contributions for hydrocarbons and hydrocarbon derivatives containing carbon, hydrogen, oxygen, nitrogen, sulfur, fluorine, chlorine and bromine atoms, are given. The fminsearch mathematical approach from MATLAB software is used in this study to select an optimal collection of functional groups (65 functional groups) and subsequently to develop the model. This is a direct search method that uses the simplex search method of Lagarias et al. The results of the new method are compared to the several currently used methods and are shown to be far more accurate and reliable. The average absolute deviation of normal boiling point predictions for 632 organic compounds is 4.4350 K; and the average absolute relative deviation is 1.1047 %, which is of adequate accuracy for many practical applications.

Major and trace element abundances of igneous rocks from DSDP Site 37-334

REE abundances in gabbros and peridotites from Site 334 of DSDP Leg 37 show that these rocks are cumulates produced by fractional crystallization of a primitive oceanic tholeiite magma. They may be part of a layered oceanic complex. The REE distributions in the residual liquids left after such a fractionation are similar to those of incompatible element-depleted oceanic tholeiites. The REE data indicate that the basalts which overlie the gabbro-peridotite complex, are not genetically related to plutonic rocks.

Mineralogy and isotopic composition of sulfur in ODP Hole 118-735B gabbros

Sulfide mineralogy, sulfur contents, and sulfur isotopic compositions were determined for samples from the 500-m gabbroic section of Ocean Drilling Program Hole 735B in the southwest Indian Ocean. Igneous sulfides (pyrrhotite, chalcopyrite, pentlandite, and troilite) formed by accumulation of immiscible sulfide droplets and crystallization from intercumulus liquids. Primary sulfur contents average around 600 ppm, with a mean sulfide d34S value near 0 per mil, similar to the isotopic composition of sulfur in mid-ocean ridge basalt glass. Rocks from a 48-m interval of oxide gabbros have much higher sulfur contents (1090-2530 ppm S) due to the increased solubility of sulfur in Fe-rich melts. Rocks that were locally affected by early dynamothermal metamorphism (e.g., the upper 40 m of the core) have lost sulfur, averaging only 90 ppm S. Samples from the upper 200 m of the core, which underwent subsequent hydrothermal alteration, also lost sulfur and contain an average of 300 ppm S. Monosulfide minerals in some of the latter have elevated d34S values (up to +6.9 per mil), suggesting local incorporation of seawater-derived sulfur. Secondary sulfides (pyrrhotite, chalcopyrite, pentlandite, troilite, and pyrite) are ubiquitous in trace amounts throughout the core, particularly in altered olivine and in green amphibole. Pyrite also locally replaces igneous pyrrhotite. Rocks containing secondary pyrite associated with late low-temperature smectitic alteration have low d34S values for pyrite sulfur (to - 16.6 per mil). These low values are attributed to isotopic fractionation produced during partial oxidation of igneous sulfides by cold seawater. The rocks contain small amounts of soluble sulfate (6% of total S), which is composed of variable proportions of seawater sulfate and oxidized igneous sulfur. The ultimate effect of secondary processes on layer 3 gabbros is a loss of sulfur to hydrothermal fluids, with little or no net change in d34S.

Mineralogy and geochemistry of ODP Hole 176-735B minerals

We present a synthesis of some 20,504 mineral analyses of ~500 Hole 735B gabbros, including 10,236 new analyses conducted for this paper. These are used to construct a mineral stratigraphy for 1.5-km-deep Hole 735B, the only long section of the lower crust drilled in situ in the oceans. At long wavelengths, generally >200 m, there is a good chemical correlation among the principal silicate phases, consistent with the in situ crystallization of three or four distinct olivine gabbro bodies, representing at least two major cycles of intrusion. Initial cooling and crystallization of these bodies must have been fairly rapid to form a crystal mush, followed by subsequent compaction and migration of late iron-titanium-rich liquids into shear zones and fractures through which they were emplaced to higher levels in the lower crust where they crystallized and reacted with the olivine gabbro host rock to form a wide variety of ferrogabbros. At the wave lengths of the individual intrusions, as represented by the several olivine gabbro sequences, there is a general upward trend of iron and sodium enrichment but a poor correlation between the compositions of the major silicate phases. This, together with a wide range in minor incompatible and compatible element concentrations in olivine and pyroxene at a given Mg#, is consistent with widespread permeable flow of late melt through these intrusions, in contrast to what has been documented for a 600-m section of reputedly fast-spreading ocean crust in the Oman Ophiolite. This unexpected finding could be related to enhanced compaction and deformation-controlled late-stage melt migration at the scale of intrusion at a slow-spreading ocean ridge, compared to the relatively static environment in the lower crust at fast-spreading ridges.

Compositions of Ni-rich magnesiowüstite and coexisting magnesioferrite spinel from sediments of DSDP Holes 86-577 and 91-596

We have found trace inclusions of Ni-rich magnesiowüstite within grains of magnesioferrite spinel recovered from Cretaceous/Tertiary boundary sediments from DSDP Site 596, South Pacific (23°51.20'S, 169°39.27'W) and DSDP Site 577, North Pacific (3°6.51'N, 157°43.40'E). Measured compositions of these inclusions range from (Mg_0.85Ni_0.74Fe_0.17)O to (Mg_0.74Ni_0.09Fe_0.17)O. Coexisting magnesioferrite and magnesiowüstite can only crystallize from ultramafic, refractory, Mg-rich liquids with Mg/Si > 2 (atom ratio). Such liquid compositions cannot form as a result of fractional crystallization and are unknown to occur as a result of terrestrial igneous processes or meteoroid ablation. We infer that these minerals crystallized from liquid droplets that equilibrated with silicate vapor at high temperatures (probably >2300°C), resulting in fractionation of volatile SiO2 from more refractory MgO. The most plausible source of this high-temperature vapor is in the fireball of the major impact event that terminated the Cretaceous.

Experimental petrology of basement basaltic rocks from ODP Leg 127/128 samples

The relatively fresh basement basaltic rocks cored at Sites 794 and 797 during ODP Legs 127 and 128 show compositional variations suggesting the following: (1) the aphyric rocks might be differentiated from compositional equivalents of the aphyric sample with the lowest FeO*/MgO (Sample 127-797C-12R-4, 35-37 cm); and (2) the plagioclase-phyric rocks (i.e., another constituent of the basement basaltic rocks from the sites) may be derivatives from the same parents; in this case, however, crystallized plagioclase was not effectively removed. Melting experiments were conducted for Sample 127-797C-12R-4, 35-37 cm, and the differentiation processes for the basement basaltic rocks were assessed. The high-pressure melting-phase relation can not account for the compositional variation of the aphyric rocks, suggesting that the variation was developed at relatively low pressure where olivine and plagioclase fractionation was followed by Ca-rich clinopyroxene fractionation. The density of Sample 127-797C-12R-4,35-37 cm, is comparable to that of plagioclase at some depth, but at still relatively low pressure, making it possible that the liquidus plagioclase was retained in the successive liquids to produce the plagioclase-phyric rocks. According to backtrack calculation assuming the olivine maximum fractionation, Sample 127-797C-12R-4, 35-37 cm, was differentiated from primary picritic high-Al basalt magma. The estimated primary magma composition was experimentally proved to coexist with harzburgite mantle at about 14 kbar, suggesting relatively shallow production (approximately 40-50 km below surface) of the rifting-related primary magma.

Geochemistry and isotopic composition of gabbros from ODP Hole 118-375B

Gabbros drilled from the shallow (720 m) east wall of the Atlantis II transform on the Southwest Indian Ridge (SWIR; 32°43.40', 57°16.00') provide the most complete record of the stratigraphy and composition of the oceanic lower crust recovered from the ocean basins to date. Lithologies recovered include gabbro, olivine gabbro, troctolite, trondhjemite, and unusual iron-titanium (FeTi) oxide-rich gabbro containing up to 30% FeTi oxides. The plutonic rock sequence represents a tholeiitic fractionation trend ranging from primitive magmas having Mg numbers of 67 to 69 that fractionated troctolites, to highly evolved liquids that crystallized two-pyroxene, FeTi oxide-rich gabbros and, ultimately, trondhjemite. Isotopic compositions of unaltered Leg 118 gabbros are distinct from Indian Ocean mid-ocean ridge basalts (MORB) in having higher 143Nd/144Nd (0.51301-0.51319) and lower 206Pb/204Pb values (17.35-17.67); 87Sr/86Sr values (0.7025-0.7030) overlap those of SWIR basalts, but are generally lower than MORBs from the Southeast Indian Ridge or the Rodrigues Triple Junction. More than one magma composition may have been introduced into the magma chamber during its crystallization history, as suggested by the higher 87Sr/86Sr, 206Pb/204Pb, and lower 143Nd/144Nd values of chromium-rich olivine gabbros from the bottom of Hole 735B. Whole-rock gabbro and plagioclase mineral separate 87Sr/86Sr values are uniformly low (0.7027-0.7030), irrespective of alteration and deformation. By contrast, 87Sr/86Sr values for clinopyroxene (0.7025-0.7039) in the upper half of Hole 735B are higher than coexisting plagioclase and reflect extensive replacement of clinopyroxene by amphibole. Hydrothermal veins and breccias have elevated 87Sr/86Sr values (0.7029-0.7035) and indicate enhanced local introduction of seawater strontium. Oxygen- and hydrogen-isotope results show that secondary amphiboles have uniform dD values of -49 to -54 per mil and felsic hydrothermal veins range from -46 to - 77 per mil. Oxygen-isotope data for secondary amphibole and visibly altered gabbros range to low values (+1.0-+5.5 per mil), and O-isotope disequilibrium between coexisting pyroxene and plagioclase pairs from throughout the stratigraphic column indicates that seawater interacted with much of the gabbro section, but at relatively low water/rock ratios. This is consistent with the persistence of low 87Sr/86Sr values, even in gabbros that were extensively deformed and altered.

Partial melting experiments on oceanic cumulated gabbros

We performed hydrous partial melting experiments at shallow pressures (0.2 GPa) under slightly oxidizing conditions (NNO oxygen buffer) on oceanic cumulate gabbros drilled by ODP (Ocean Drilling Program) cruises to evaluate whether the partial melting of oceanic gabbro can generate SiO2-rich melts with compositions typical of oceanic plagiogranites. The experimental melts of the low-temperature runs broadly overlap those of natural plagiogranites. At 940 °C, the normalized SiO2 contents of the experimental melts of all systems range between 60 and 61 wt%, and at 900 °C between 63 and 68 wt%. These liquids are characterized by low TiO2 and FeOtot contents, similar to those of natural plagiogranites from the plutonic section of the oceanic crust, but in contrast to Fe and Ti-rich low-temperature experimental melts obtained in MORB systems at ~950 °C. The ~1,500-m-long drilled gabbroic section of ODP Hole 735B (Legs 118 and 176) at the Southwest Indian Ridge contains numerous small plagiogranitic veins often associated with zones which are characterized by high-temperature shearing. The compositions of the experimental melts obtained at low temperatures match those of the natural plagiogranitic veins, while the compositions of the crystals of low-temperature runs correspond to those of minerals from high-temperature microscopic veins occurring in the gabbroic section of the Hole 735B. This suggests that the observed plagiogranitic veins are products of a partial melting process triggered by a water-rich fluid phase. If the temperature estimations for hightemperature shear zones are correct (up to 1,000 °C), and a water-rich fluid phase is present, the formation of plagiogranites by partial melting of gabbros is probably a widespread phenomenon in the genesis of the ocean crust.