Geochemistry and radiogenic isotopes of ODP Hole 157-953C lavas

The Canary Island primitive basaltic magmas are thought to be derived from an HIMU-type upwelling mantle containing isotopically depleted (NMORB)-type component having interacted with an enriched (EM)-type component, the origin of which is still a subject of debate. We studied the relationships between Ni, Mn and Ca concentrations in olivine phenocrysts (85.6-90.0 mol.% Fo, 1,722-3,915 ppm Ni, 1,085-1,552 ppm Mn, 1,222-3,002 ppm Ca) from the most primitive subaerial and ODP Leg 157 high-silica (picritic to olivine basaltic) lavas with their bulk rock Sr-Nd-Pb isotope compositions (87Sr/86Sr = 0.70315-0.70331, 143Nd/144Nd = 0.51288-0.51292, 206Pb/204Pb = 19.55-19.93, 207Pb/204Pb = 15.60-15.63, 208Pb/204Pb = 39.31-39.69). Our data point toward the presence of both a peridotitic and a pyroxenitic component in the magma source. Using the model (Sobolev et al., 2007, Science Vol 316) in which the reaction of Si-rich melts originated during partial melting of eclogite (a high pressure product of subducted oceanic crust) with ambient peridotitic mantle forms olivine-free reaction pyroxenite, we obtain an end member composition for peridotite with 87Sr/86Sr = 0.70337, 143Nd/144Nd = 0.51291, 206Pb/204Pb = 19.36, 207Pb/204Pb = 15.61 and 208Pb/204Pb = 39.07 (EM-type end member), and pyroxenite with 87Sr/86Sr = 0.70309, 143Nd/144Nd = 0.51289, 206Pb/204Pb = 20.03, 207Pb/204Pb = 15.62 and 208Pb/204Pb = 39.84 (HIMU-type end member). Mixing of melts from these end members in proportions ranging from 70% peridotite and 30% pyroxenite to 28% peridotite and 72% pyroxenite derived melt fractions can generate the compositions of the most primitive Gran Canaria shield stage lavas. Combining our results with those from the low-silica rocks from the western Canary Islands (Gurenko et al., 2009, doi:10.1016/j.epsl.2008.11.013), at least four distinct components are required. We propose that they are (1) HIMU-type pyroxenitic component (representing recycled ocean crust of intermediate age) from the plume center, (2) HIMU-type peridotitic component (ancient recycled ocean crust stirred into the ambient mantle) from the plume margin, (3) depleted, MORB-type pyroxenitic component (young recycled oceanic crust) in the upper mantle entrained by the plume, and (4) EM-type peridotitic component from the asthenosphere or lithosphere above the plume center.

Chemical analysis of ODP Hole 104-642E

During Ocean Drilling Program Leg 104 a 900-m-thick sequence of volcanic rocks was drilled at Hole 642E on the Vøring Plateau, Norwegian Sea. This sequence erupted in two series (upper and lower series) upon continental basement. The upper series corresponds to the seaward-dipping seismic reflectors and comprises a succession of about 122 flows of transitional oceanic tholeiite composition. They have been subdivided into several formations consisting of flows related to each other by crystal fractionation processes, magma mixing, or both. Major- and trace-element chemistry indicates affinities to Tertiary plateau lavas of northeast Greenland and to Holocene lavas from shallow transitional segments of the Mid-Atlantic Ridge, such as Reykjanes Ridge. The tholeiitic magmas have been derived from a slightly LREE-depleted mantle source. Two tholeiitic dikes that intruded the lower series derive from an extremely depleted mantle source. Interlayered volcaniclastic sediments are dominantly ferrobasaltic and more differentiated. They appear to come from a LREE-enriched mantle source, and may have been erupted in close vicinity of the Vøring Plateau during hydroclastic eruptions. The two tholeiitic dikes that intruded the lower series as well as some flows at the base of the upper series show evidence of assimilation of continental upper crustal material.

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.

Chemistry of gabbroic rocks from ODP Hole 118-735B

Gabbroic rocks and their late differentiates recovered at Site 735 represent 500 m of oceanic layer 3. The original cooling of a mid-ocean ridge magma chamber, its penetration by ductile shear zones and late intrusives, and the subsequent penetration of seawater through a network of cracks and into highly permeable magmatic hydrofracture horizons are recorded in the metamorphic stratigraphy of the core. Ductile shear zones are characterized by extensive dynamic recrystallization of primary phases, beginning in the granulite facies and continuing into the lower amphibolite facies. Increasing availability of seawater during dynamic recrystallization is reflected in depletions in 18O, increasing abundance of amphibole of variable composition and metamorphic plagioclase of intermediate composition, and more complete coronitic or pseudomorphous static replacement of magmatic minerals. Downcore correlation of synkinematic assemblages, bulk-rock oxygen isotopic compositions, and vein abundance suggest that seawater is introduced into the crust by way of small cracks and veins that mark the end of the ductile phase of deformation. This "deformation-enhanced" metamorphism dominates the upper 180 and the lower 100 m of the core. In the lower 300 m of the core, mineral assemblages of greenschist and zeolite facies are abundant within or adjacent to brecciated zones. Leucocratic veins found in these zones and adjacent host rock contain diopside, sodic plagioclase, epidote, chlorite, analcime, thomsonite, natrolite, albite, quartz, actinolite, sphene, brookite, and sulfides. The presence of zircon, Cl-apatite, sodic plagioclase, sulfides, and diopside in leucocratic veins having local magmatic textures suggests that some of the veins originated from late magmas or from hydrothermal fluids exsolved from such magmas that were subsequently replaced by (seawater-derived) hydrothermal assemblages. The frequent association of these late magmatic intrusive rocks within the brecciated zones suggests that they are both artifacts of magmatic hydrofracture. Such catastrophic fracture and hydrothermal circulation could produce episodic venting of hydrothermal fluids as well as the incorporation of a magmatically derived hydrothermal component. The enhanced permeability of the brecciated zones produced lower temperature assemblages because of larger volumes of seawater that penetrated the crust. The last fractures were sealed either by these hydrothermal minerals or by late carbonate-smectite veins, resulting in the observed low permeability of the core.

Lithologic and geochemical composition of samples from the Circum Superior Belt, North America

The ca. 1880 Ma Circum-Superior Large Igneous Province (LIP) consists of a number of discontinuous segments known to cover a significant portion of the margin of the Superior Province craton in North America. New geochemical and isotopic data from western segments of this LIP support a common origin for the these segments and suggest that magmatism in the Lake Superior region may have been fed through the ~ 600 km long Pickle Crow dyke from a source north of the Fox River Belt in northeastern Manitoba. The Fox River Belt, Pickle Crow dyke and sections of the Hemlock Formation in the Lake Superior region possess trace element signatures which are similar to those of more recent oceanic plateaux. The Hemlock Formation displays a heterogeneous geochemical signature. This chemical heterogeneity can in part be explained by lithospheric contamination and possibly by source heterogeneity. The tectonomagmatic setting in which these igneous rocks were formed could have involved a mantle plume. Evidence supporting a plume origin includes high MgO volcanic rocks, high calculated degrees of partial melting and geochemical signatures similar to those of oceanic plateaux.

Major elements oxides and mineralogy of primary minerals in ODP Hole 195-1201D basalts

The basement cored at Site 1201 (west Philippine Basin) during Ocean Drilling Program Leg 195 consists of a 91-m-thick sequence of basalts, mostly pillow lavas and perhaps one sheet lava flow, with a few intercalations of hyaloclastite and interpillow sedimentary material. Hydrothermal alteration pervasively affected the basalt sequence, giving rise to a variety of secondary minerals such as K-Fe-Mg-clay minerals, oxyhydroxides and clay minerals mixtures, natrolite group zeolites, analcite, alkali feldspar, and carbonate. The primary minerals of pillow and sheet basalts that survived the intense hydrothermal alteration were investigated by electron microprobe with the aim of characterizing their chemical composition and variability. The primary minerals are mostly plagioclase, ranging in composition from bytownite through labradorite to andesine, chromian-magnesian-diopside, and spinels, both Ti magnetite (partially maghemitized) and chromian spinel. Overall, the chemical features of the primary minerals of Site 1201 basalts correspond to the primitive character of the bulk rocks, suggesting that the parent magma of these basalts was a mafic tholeiitic magma that most likely only suffered limited fractional crystallization and crystallized at high temperatures (slightly below 1200°C) and under increasing fO2 conditions. The major element composition of clinopyroxene suggests a backarc affinity of the mantle source of Site 1201 basement.

Geochemistry of Pliocene-Pleistocene volcanic rocks from the Izu Arc

The igneous geochemistry of lavas and breccias from the basement of Sites 790 and 791, and pumice clasts from the Pliocene-Pleistocene sedimentary section of Sites 788, 790, 791, and 793 were studied. Arc volcanism became silicic about 1.5 m.y. before the inception of rifting in the Sumisu Rift at 2 Ma, but eruption of these silicic magmas reflects changes in stress regime, especially during the last 130,000 yr, rather than crustal anatexis. Arc magmas have had a larger proportion of slab-derived components since the inception of rifting than before, but are otherwise similar. Rift basalts and rhyolites are derived from a different source than are arc andesites to rhyolites. The rift source has less slab-derived material and is an E-MORB-like source, in contrast to an N-MORB-type source overprinted with more slab-derived material beneath the arc. Rift magma types, in the form of rare pumice and lithic clasts, preceded the rift, and the earliest magmas that erupted in the rift already differed from those of the arc. The earliest large rift eruption produced an exotic explosion breccia ("mousse") despite eruption at >1800 mbsl. Although this rock type is attributed primarily to high magmatic water content, the clasts are more MORB-like in trace element and isotopic composition than are modern Mariana Trough basalts. After rifting began, arc volcanism continued to be predominantly silicic, with individual pumice deposits containing clasts that vary in composition by about 5 wt% SiO2, or about as much as in historical eruptions of submarine Izu Arc volcanoes. The overall variations in magma composition with time during the inception of arc rifting are broadly similar in the Sumisu Rift and Lau Basin, though newly tapped OIB-type mantle seems to be present earlier during basin formation in the Sumisu than Lau case.

Chemical analysis of various geological samples from Northern Victoria Land, Antarctica

This paper reports the results of a preliminary palaeomagnetic investigation of the Admiralty Intrusives complex of northern Victoria Land, Antarctica. The samples were collected at Mt. Supernal and Inferno Peak, two pinions mainly formed of granodiorite and minor tonalite and emplaced at ab. 350 Ma at a high crustal level, as shown by amphibole geobarometric data and occurrence of miarolitic cavities. Microprobe and isothermal remanence analyses showed that magnetite. characterized by low coercivity and Curic point in the range 550-570 °C is the only primary ferromagnetic mineral. Stepwise thermaldemagnetization succeeded in isolatingamagnetization component. stable up to 530 °C. The virtual geomagnetic poles (VGPs) of the two plutons are different. That of Inferno Peak is consistent with the Australian palaeopoles of late Devonian-early Carboniferous age, whereas the location of the Mt. Supernal VGP probably results from the tectonic activity which affected the Ross Sea region during the Cenozoic.

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.

Petrology of mafic and ultramafic intrusions from the Portneuf-Mauricie Domain, Grenville Province, Canada

The Portneuf-Mauricie Domain (PMD), located in the south-central part of the Grenville Province, comprises several mafic and ultramafic intrusions hosting Ni-Cu ± platinum-group element (PGE) prospects and a former small mining operation (Lac Édouard mine). These meter- to kilometer-scale, sulfide-bearing intrusions display diverse forms, such as layered and tabular bodies with no particular internal structure, and zoned plutons. They were injected ~ 1.40 Ga into a mature oceanic arc, before and during accretion of the arc to the Laurentian margin. The pressure-temperature conditions of the magmas at the beginning of their emplacement were 3 kbar and 1319-1200 °C (according to the petrologic modeling results from this study). The PMD mineralized intrusions are interpreted to represent former magma chambers or magma conduits in the roots of the oceanic arc. The parent magmas of the mineralized intrusions resulted mainly from the partial melting of a mantle source composed of spinel-bearing lherzolite. Petrologic modeling and the occurrence of primary amphibole in the plutonic rocks indicate that these parent melts were basaltic and hydrous. In addition, fractional crystallization modeling and Mg/Fe ratios suggest that most of the intrusions may have formed from evolved magmas, with Mg# = 60, resulting from the fractionation of more primitive magmas (primary magmas, with Mg# = 68). Petrologic modeling demonstrates that 30% fractional crystallization resulted in the primitive to evolved characteristics of the studied intrusive rocks (as indicated by the crystallization sequences and mineral chemistry). Exceptions are the Réservoir Blanc, Boivin, and Rochette West parent magmas, which may have undergone more extensive fractional crystallization, since these intrusions contain pyroxenes that are more iron rich and have lower Mg numbers than pyroxenes in the other PMD intrusions. The PMD mafic and ultramafic intrusions were intruded into an island arc located offshore from the Laurentian continent. Thus, their presence confirms the existence of a well-developed magmatic network (responsible of the fractionation processes) beneath the Proterozoic arc, which resulted in the wide range of compositions observed in the various plutons.

Silicate mineralogy of basalts at DSDP Leg 54 Holes

Basalts drilled from the East Pacific Rise, OCP Ridge, and Siqueiros fracture zone during Leg 54 are texturally diverse. Dolerites are equigranular at Sites 422 and 428 and porphyritic, with phenocrysts of plagioclase (An69.73) and Ca-rich clinopyroxene (Ca42Mg48Fe10) at Site 427. The East Pacific Rise lavas and some of those from the OCP Ridge are fine-grained and porphyritic. The majority of the large crystals are clustered skeletal glomerocrysts of plagioclase An64-77), together with olivine (Fo80-87), Ca-rich clinopyroxene, or both. Euhedral phenocrysts of plagioclase, together with olivine, Carich clinopyroxene, and Cr-Al spinel in some cases, occur in most of the fine-grained lavas. These phenocrysts are small (maximum dimension <1 mm in all but one sample), sparse (combined modal amount <1% in all samples), and distinctive from the megacrysts which characterize many ocean-floor lavas. In two East Pacific Rise lavas, zoned plagioclase (An83 cores) is the sole phenocryst phase. In other porphyritic lavas from all the main East Pacific Rise and OCP Ridge units drilled during Leg 54, the plagioclase phenocrysts contain cores of bytownite (An79-87) surrounded by more-sodic feldspar (An67-77). Core/rim relationships vary from continuous normal zoning, through discontinuous zoning, to extensive resorption of the calcic cores in some samples. The compositions of the plagioclase calcic cores are systematically related to those of the glomerophyric plagioclase and olivine in the lavas containing them. Furthermore, only one compositional population of calcic cores occurs in each rock. The possible causes of these relationships are far from clear. Magma mixing, although superficially applicable, is inconsistent with important aspects of the phenocryst mineralogy of these particular lavas. A more satisfactory model to explain both phenocryst zoning and rapid glomerocryst growth immediately before extrusion may be constructed by postulating influx of water into the upwelling magmas within Layer 3 of the oceanic crust beneath the East Pacific Rise, and subsequent loss of part of this water during effervescence within feeder dykes between Layer 3 and the ocean floor. It is shown that this model is fully consistent with published data on water and carbon dioxide contents and ratios in the pillow-margin glasses, vesicles, and phenocryst inclusions of ocean-floor basalts. The evidence for the precipitation of plagioclase- dominated crystalline assemblages from these magmas in the upper part of Layer 3 is concordant with recent geophysically based modeling of the structure of the East Pacific Rise. Calcium-rich clinopyroxenes in dolerites from the OCP Ridge and Siqueiros fracture zone show radial, oscillatory, and sector-zoning. In Sample 428A-5-2 (Piece 5a), the compositional trends resulting from this zoning closely resemble those of the pyroxenes in some lunar lavas. The controls on crystallization of interstitial pigeonite - epitaxial upon augite - in this rock are discussed. Both sector-zoning of the augite and nucleation of pigeonite within microvolumes of magma with a low Ca(Mg + Fe) ratio appear to be important factors.

Composition of melts and minerals from volcanic rocks of the Kuril-Kamchatka Arc

In this paper allivalites, coarse- and giant-textured olivine-anorthite rocks occurring as separate blocks in the eruption products of many volcanoes from the frontal part of the Kuril-Kamchatka Arc are under consideration. New data are reported on petrography, mineralogy, and composition of melt inclusions in minerals from ten allivalite samples collected at Ksudach, Ilinsky, Zavaritsky, Kudryavy, and Golovnin Volcanoes. Crystallization temperatures of allivalite minerals were estimated as 970-1080°C at melt water content of 3.0-3.5 wt % and oxygen fugacity NNO=1-2. Genetic connection was established between compositions of melt inclusions and interstitial glasses in allivalites and volcanic rocks. Cumulate nature of allivalites was demonstrated. Using mass balance calculations, degree of fractionation of primary melts during formation of cumulate layers was estimated for various volcanoes as 22-46%.

Geochemistry of Pleistocene volcanic rocks in the Mariana Forearc

Geophysical surveys of the Mariana forearc, in an area equidistant from the Mariana Trench and the active Mariana Island Arc, revealed a 40-m-deep graben about 13 km northwest of Conical Seamount, a serpentine mud volcano. The graben and its bounding horst blocks are part of a fault zone that strikes northwest-southeast beneath Conical Seamount. One horst block was drilled during Leg 125 of the Ocean Drilling Program (Site 781). Three lithologic units were recovered at Site 781: an upper sedimentary unit, a middle basalt unit, and a lower sedimentary unit. The upper unit, between 0 and 72 mbsf, consists of upper Pliocene to Holocene diatomaceous and radiolarian-bearing silty clay that grades down into vitric silty clay and vitric clayey silt. The middle unit is a Pleistocene vesicular, porphyritic basalt, the top of which corresponds to a high-amplitude reflection on the reflection profiles. The lower unit is a middle to upper (and possibly some lower) Pliocene vitric silty clay and vitric clayey silt similar to the lower part of the upper unit. The thickness of the basalt unit can only be estimated to be between 13 and 25 m because of poor core recovery (28% to 55%). The absence of internal flow structures and the presence of an upper glassy chilled zone and a lower, fine-grained margin suggest that the basalt unit is either a single lava flow or a near-surface sill. The basalt consists of plagioclase phenocrysts with subordinate augite and olivine phenocrysts and of plagioclase-augite-olivine glomerocrysts in a groundmass of plagioclase, augite, olivine, and glass. The basalt is an island arc tholeiite enriched in large-ion-lithophile elements relative to high-field-strength elements, similar to the submarine lavas of the southern arc seamounts. In contrast, volcanic rocks from the active volcanoes on Pagan and Agrigan islands, 100 km to the west of the drill site, are calc-alkaline. The basalt layer, the youngest in-situ igneous layer reported from the Izu-Bonin and Mariana forearcs, is enigmatic because of its location more than 100 km from the active volcanic arc. The sediment layers above and below the basalt unit are late Pliocene in age (about 2.5 Ma) and normally magnetized. The basalt has schlierenlike structures, reverse magnetization, and a K-Ar age of 1.68±0.37 Ma. Thus, the basalt layer is probably a sill fed by magma intruded along a fault zone bounding the horst and graben in the forearc. The geochemistry of the basalt is consistent with a magma source similar to that of the active island arc and from a mantle source above the subducting Pacific plate.

Geochemistry of selected minerals at DSDP Leg 65 Holes

The majority of the basalts drilled on Leg 65 in the Gulf of California are aphyric to sparsely phyric massive flows ranging in average thickness between 5 meters in the upper part of the sections in Holes 483 and 483B, where they are interlayered with sediment, and 14 meters in Hole 485A, where interlayered sediments constitute more than half of the section. Massive flows interlayered with pillows are generally less than 4 meters thick. The pillow lavas recovered are more phyric (up to 15 modal%) and contain two to three generations of plagioclase and olivine ± clinopyroxene. Plagioclase generally exceeds 60% of any given phenocryst assemblage. Resorbed olivine, clinopyroxene, and plagioclase megacrysts may reflect a high-pressure stage, the phenocrysts crystallizing in the main magma chamber and the skeletal microphenocrysts in dikes. Precise measurements of length/width ratios of different phenocryst types and compositions show low aspect ratios and large crystal volumes for early crystals and high ratios and low volumes for late crystals grown under strong undercooling conditions. The minerals examined show wide ranges in composition: in particular, plagioclase ranges from An92 to An36; clinopyroxene ranges from Ca41Mg51Fe8 in the cores of phenocrysts to Ca40**36 Mg45**49Fe15**20 in the groundmass; and olivine ranges from Fo86 to Fo81. The wide range in mineral compositions, together with evidence of disequilibrium based on textures and comparisons of glass and mineral compositions, indicate complex crystallization histories involving both polybaric crystal fractionation and magma mixing.

Petrology and isotope characteristics of basalts from ODP Hole 111-504B

Petrography and isotope geochemical characteristics of H, O, S, Sr, and Nd have been described for basalts recovered from Hole 504B during Leg 111 of the Ocean Drilling Program. The petrographic and chemical features of the recovered basalts are similar to those obtained previously (DSDP Legs 69, 70, and 83); they can be divided into phyric (plagioclase-rich) and aphyric (Plagioclase- and clinopyroxene-rich) basalts and show low abundances of TiO2, Na2O, K2O, and Sr. This indicates that the basalts belong to Group D, comprising the majority of the upper section of the Hole 504B. The diopside-rich nature of the clinopyroxene phenocrysts and Ca-rich nature of the Plagioclase phenocrysts are also consistent with the preceding statement. The Sr and Nd isotope systematics (average 87Sr/86Sr = 0.70267 ± 0.00007 and average 143Nd/144Nd = 0.513157 ± 0.000041) indicate that the magma sources are isotopically heterogeneous, although the analyzed samples represent only the lowermost 200-m section of Hole 504B. The rocks were subjected to moderate hydrothermal alteration throughout the section recovered during Leg 111. Alteration is limited to interstices, microfractures, and grain boundaries of the primary minerals, forming chlorite, actinolite, talc, smectite, quartz, sphene, and pyrite. In harmony with the moderate alteration, the following alteration-sensitive parameters show rather limited ranges of variation: H2O = 1.1 ±0.2 wt%, dD = - 38 per mil ± 4 per mil, d180 = 5.4 per mil ± 0.3 per mil, total S = 562 ± 181 ppm, and d34S = 0.8 per mil ± 0.3 per mil. Based on these data, it was estimated that the hydrothermal fluids had dD and d180 values only slightly higher than those of seawater, the water/rock ratios were as low as 0.02-0.2, and the temperature of alteration was 300°-400°C. Sulfur exists predominantly as pyrite and in minor quantities as chalcopyrite. No primary monosulfide was detected. This and the d34S values of pyrite (d34S = 0.8 per mil) suggest that primary pyrrhotite was almost completely oxidized to pyrite by reaction with hydrothermal fluids containing very little sulfate.