Solubility of tin,tungsten and molybdenum oxides in felsic magmas

Saturation versus undersaturation of granitic melts in tin, tungsten and molybdenum oxides is discussed on the basis of experimental data. Results of dry and hydrothermal experiments are evaluated under the assumption of ideal solubility of Sn, W and Mo oxides in granitic melts. A conservative interpretation arrives at concentration levels of 1000 ppm SnO₂, WO₃ and MoO₃ respectively, considered as the maximum solubility of these components in granitic melts at 750°C-800 °C. Such values are never reached in natural granites unaffected by hydrothermal alteration and therefore even highly evolved granites are expected to be undersaturated in these metals. Consequently cassiterite and scheelite are neither common liquidus minerals of ore-bearing granites nor restite minerals from partial melting events.     

Origin of some magmas in oceanic and circum-oceanic regions

Partial melting experiments on spinel-lherzolite, a rock which probably occurs in relatively shallow parts of the oceanic upper mantle, demonstrate that alkali basaltic melt is formed at depths of at least 20 kbar whereas tholeiitic melt is formed at lower pressures (< 15 kbar) under anhydrous conditions. The specimen studied was a relatively iron-rich natural spinel-lherzolite (Fe/Mg+Fe=0.15) and the melts produced have ratios comparable to those obtained in basalts. Slight increase of degree of partial melting produces picritic melt over a wide pressure range. Under hydrous (water-excess) conditions, andesitic melt is produced by partial melting of the same natural spinel-lherzolite and a synthetic lherzolite. The melting experiments on two different abyssal tholeiites from the Mid-Atlantic Ridge suggest that the derivation of olivine tholeiite from a more mafic magma or a mantle peridotite (lherzolite) is possible, but is limited to depths shallower than 25 km under essentially anhydrous conditions, whereas plagioclase tholeiite may have been formed by fractional crystallization at depths of about 20 km in the presence of a small amount (～ 2 wt.%) of water.It is suggested that under mid-ocean ridges, partial melting of spinel-lherzolite at depths shallower than 60 km would produce olivine-tholeiitic magma, which differentiates at shallower levels (20–25 km) under either essentially anhydrous or hydrous (but vapor-absent) conditions to produce abyssal tholeiites of olivine-tholeiite type or plagioclase-tholeiite type. It may be also possible that the former olivine-tholeiite is generated by direct partial melting of plagioclase-lherzolite. Alkali basalts in the oceanic region may be generated at depths greater than 50 km by relatively small degree of partial melting. Along island arcs and continental margins, where the subduction zones probably exist, partial melting of lherzolite would take place in the presence of water that may be supplied by breakdown of hydrous minerals in the subducted oceanic crust, thereby producing andesitic magmas. High-alumina basalt magma could be produced by partial melting of the dehydrated oceanic crust in the subduction zone at depths between 40 and 60 km, where garnet is unstable above the solidus.     

Solubility of hydrogen and carbon in reduced magmas of the early Earth’s mantle

The solubility of volatile compounds in magmas and the redox state of their mantle source are the main factors that control the transfer of volatile components from the planet’s interior to its surface. In theories of the formation of the Earth, the composition of gases extracted by primary planetary magmas is accounted for by the large-scale melting of the early mantle in the presence of the metallic Fe phase [1, 2]. The fused metallic Fe phase and the melted silicate material experienced gravitational migration that exerted influence upon the formation of the metallic core of the planet. The large-scale melting of the early Earth should have been accompanied by the formation of volatile compounds, whose composition was controlled by the interaction of H and C with silicate and metallic melts, a process that remains largely unknown as of yet.     

Geochemical aspects of some accumulation models for primary magmas

The compositions of primary magmas depend to some degree on the dynamic processes occurring in the partially molten region of the mantle. The compositional dependence is estimated for three models which assume either accumulation from a migmatized source region or accumulation entirely by the interstitial flow of magma. Accumulation from a migmatised region results in magmas with higher concentrations of incompatible elements than does batch melting, whereas accumulation by interstitial flow results in magmas with lower concentrations of these elements. The concentrations of refractory elements are almost independent of both the accumulation process and the degree of partial melting and are therefore usefull for the identification of primary magmas.     

Empirical equations to predict the sulfur content of mafic magmas at sulfide saturation and applications to magmatic sulfide deposits

Empirical equations to predict the sulfur content of a mafic magma at the time of sulfide saturation have been developed based on several sets of published experimental data. The S content at sulfide saturation (SCSS) can be expressed as:

Buoyancy-controlled eruption of magmas at Mt Etna

Buoyancy controls the ability of magma to rise, its ascent rate and the style of the eruptions. Geophysical, geological and petrological data have been integrated to evaluate the buoyancy of magmas at Mt Etna. The density difference between host rocks and magmas is mainly related to the amount of H₂O dissolved in the magma and to the bubble‐liquid separation processes. In the depth interval 22–2 km b.s.l. highly hydrated (H₂O ～ 3%) basaltic magmas or mixtures of bubbles + liquid have positive buoyancy and rise rapidly. Conversely, bubble‐depleted liquids, with an intermediate H₂O content (～ 1.5%), having neutral buoyancy, will spread out and form magmatic reservoirs at different depths until cooling/crystallization further modify composition and density. These different processes account for the magma compositions, location of magmatic reservoirs as determined by geophysical methods, and the complex eruptive cycles (slow effusions, fire fountains and Plinian eruptions) that have been observed in the history of the volcano.     

Solubility of rare earth elements in carbonatite magmas,indicated by the liquidus surface in CaCO3Ca(OH)2La(OH)3 at 1 kbar pressure

The system CaCO₃Ca(OH)₂(CCCH) represents a synthetic analog to a carbonatite magma. Addition of a light rare earth (RE) component La(OH)₃ (LH) gives a simple analog of a rare earth carbonatite. Liquidus relations for two joins were studied at 1 kbar pressure; CHLH and (CC₅₅CH₄₅)LH. CHLH is binary with a eutectic at CH₇₉LH₂₁ and 710°C. Thejoin CC₅₅ + CH₄₅)LH has a liquidus piercing point between CC and LH, at (CC₅₅CH₄₅)₆₀LH₄₀ and 700°C. Combining the new results with known results for CCCH allows construction of a liquidus diagram for part of the join CCCHLH. A ternary eutectic between the primary liquidus fields for CH, CC and LH occurs near 610°C with estimated composition CC= 33%,CH= 47%,LH= 20%. The solubility of La(OH)₃ in the synthetic carbonatite magma increases with increase of CO₂/H₂O from 20% at the eutectic to 40% at the piercing point on the join (CC₅₅CH₄₅)LH. The solubility of La in synthetic carbonatite is high compared with that of silicates. P₂O₅, and S. The results show that REE can become concentrated to high levels by fractionation of carbonatites, as long as they are not removed by high temperature crystallization of apatite and monazite.     

Phase relations governing the derivation of alkaline basaltic magmas from primary magmas at high pressures

A comparison between the variation trend of alkaline basaltic magmas within the CaO-MgO-Al₂O₃-SiO₂ system and experimentally estimated phase relations for this system at high pressures, suggests an olivine reaction relationship, which may explain the transition from primary magmas in equilibrium with olivine to alkaline basaltic magmas in which olivine does not form at high pressures. This reaction relationship is considered to be due to a transition from positive to negative crystallization with respect to olivine along the four phase curve where olivine, diopside, pyrope garnet and liquid are initially in equilibrium. The bimineralic, eclogitic character of alkaline basaltic compositions at high pressures is interpreted as being due to the presence of a thermal minimum on the three phase surface, where dioside and pyrope garnet are in equilibrium with liquid.     

Precious metals in magnesian low-Ti lavas: Implications for metallogenesis and sulfur saturation in primary magmas

Boninites and related magnesian low-Ti magmas are generally regarded as partial melts of a moderately to severely depleted peridotite source. Incompatible lithophile element abundances indicate that this source was variably enriched in LREE, Zr, Sr, Ba and alkalis by some mantle metasomatic process. Low-Ti lavas from the Bonin-Mariana arc system, Cape Vogel, New Caledonia, Cyprus, Newfoundland and SE Australia have been analysed for Pd, Ir, Au, Cu, S and Se. Comparison of fresh glassy material with variably altered samples suggests sporadic loss of Au and Cu and essentially inert behaviour for Pd, Ir and Se during seawater and subsequent alteration. They are uniformly enriched in Pd (mean 15 ppb) and depleted in Cu (mean 20 ppm), S (mean < 54 ppm) and Se (mean 53 ppb) compared to average MORB (<0.8 ppb Pd, 72 ppm Cu, 800 ppm S and 196 ppb Se) and exhibit incompatible-like behaviour for these elements and Au.The data are compatible with fractionation of the chalcophile elements during multi-stage mantle melting. Primary MORB liquids are S-saturated in their mantle source and an immiscible sulfide component is retained in the mantle residue. This results in the preferential removal of metals having low D^S/L- values (base metals) and concentration of those metals with high D^S/L values (precious metals) in the residual mantle sulfide fraction. Subsequent remelting of this refractory source produces S-deficient precious metal-enriched magmas, as exemplified by boninites. The absence of correlation between incompatible lithophile element enrichment and chalcophile element abundances suggests that the latter were not added to the source during mantle metasomatism.The constraints imposed by the nature of the source region result in two fundamentally contrasting patterns of behaviour for exclusively chalcophile elements. Magmas generated in mildly depleted to undepleted source regions by low to moderate degrees of partial melting (e.g. MORB) are S-saturated and become rapidly impoverished in precious metals during the early stages of silicate fractionation, owing to the co-precipitation of an immiscible sulfide component. Magmas generated from a strongly depleted source are initially S-undersaturated and concentrate chalcophile metals in their liquid residua.The contrasting behaviour of chalcophile metals during the early crystallisation stage of MORB and low-Ti magmas lead to divergent predictions concerning the primary distribution of these metals in oceanic crust generated by these magmas. The similarity in composition of early Bushveld magmas and boninites suggests that these S-deficient, PGE-enriched magmas may be essential to the formation of platiniferous horizons in layered intrusions.     

On stereoimages of some structures in the solar atmosphere

Three-dimensional structures in the solar chromosphere and corona are considered. It is demonstrated that two photoheliograms separated by ～1 day can be used (using computer-graphics methods) to construct a stereo image of the Sun. The algorithm for this is presented and carried out for H_α images of the total disk. A bulge in the equatorial region resulting from the differential rotation of the Sun can be seen in the stereo image. Structures called Whitney pleats in catastrophe theory are observed in the solar corona. Such structures are encountered in prominences. The well-known helmets (or streamers) are pleats of heliospheric plasma sheets. Isophotes for such a sheet and the degree of polarization of the radiation in the pleat are calculated and compared with observational data.     

Solubility and speciation of sulfur in silicate melts: The Conjugated Toop-Samis-Flood-Grjotheim (CTSFG) model

A Conjugated Toop-Samis-Flood-Grjotheim (CTSFG) model is developed by combining the framework of the Toop-Samis polymeric approach with the Flood-Grjotheim theoretical treatment of silicate melts and slags. Electrically equivalent ion fractions are computed over the appropriate matrixes (anionic and cationic) in a Temkin notation for fused salts, and are used to weigh the contribution of the various disproportionation reactions of type:

     

The microbial sulfur cycle and some of its implications for the geochemistry of sulfur isotopes

Qualitatively most microbial processes of the sulfur cycle are well known, but the extent to which specific groups of microbes take part in sulfate reduction and sulfide oxidation is at present difficult to estimate and the same holds for the role played by purely chemical sulfide oxidation.The capacity of an organism to differentiate between sulfur isotopes is genetically determined and probably strain-specific; whether or not, and to what extent, fractionation actually occurs is codetermined by physiological conditions inside the cell and by ecological conditions, i.e. the parameters of the environment.For conclusive interpretation of sulfur fractionation data of natural deposits further microbiological studies on the enzymatic, cellular and ecological level are necessary; such studies would be technically feasible today. The study of isotope effects of relevant, purely chemical reactions should not be neglected.

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Zusammenfassung In qualitativer Hinsicht sind die meisten mikrobiellen Vorgänge des Schwefelkreislaufs gut bekannt. Jedoch ist es gegenwärtig noch schwierig zu sagen, in welchem Ausmaß die verschiedenen Mikroorganismengruppen an der Reduktion der Sulfate und an der Oxidation der Sulfide teilnehmen. In wieweit die Oxidation der Sulfide rein chemisch erfolgt, ist ebenso schwer einzuschätzen.Die Fähigkeit einer Mikrobe zwischen verschiedenen Schwefelisotopen zu unterscheiden, ist genetisch festgelegt und ist wahrscheinlich stammspezifisch. Ob überhaupt und, wenn ja, in welchem Ausmaß eine Fraktionierung tatsächlich stattfindet, wird von den physiologischen Verhältnissen innerhalb der Zelle und von ökologischen Verhältnissen, d. h. den Parametern der Umwelt, mitbestimmt.Um eine endgültige Interpretation der Fraktionierungsdata in der Natur abgelagerter Schwefelverbindungen zu ermöglichen, sind weitere mikrobiologische Forschungen auf enzymatischer, zellularer und ökologischer Stufe erforderlich, die heute ohne weiteres durchgeführt werden könnten. Isotopeneffekte bei rein chemischen Reaktionen sollten dabei ebenfalls untersucht werden.

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Résumé La plupart des processus microbiologiques du cycle du soufre est qualitativement assez connue mais il est encore difficile de déterminer quantitativement dans quelle mesure des microbes spécifiques contribuent à la réduction des sulfates et à l'oxidation des sulfides. La même difficulté se présente quant à l'oxidation des sulfides purement chimique.Le pouvoir d'un organisme de distinguer entre les isotopes de soufre est déterminé par voie génétique et probablement est spécifique pour la souche individuelle. Dans quelle mesure un fractionnement des isotopes est vraiment réalisé sous les conditions expérimentales ou. naturelles est déterminé par des conditions physiologiques dans les cellules et des conditions écologiques, c'est à dire par les paramètres du milieu.Pour une interprétation conclusive des dates de fractionnement du soufre des dépôts naturels, il est nécessaire d'étudier les processus microbiens relevants au niveau enzymatique, cellulaire et écologique, des études qui sont aujourd'hui tout à fait réalisables. D'autre part, l'étude des effets isotopiques des réactions purement chimiques ne devrait pas être négligée.

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Edited version of a lecture held at the Colloquium on the Geochemistry of Sulfur Isotopes, Bad Sooden-Allendorf, 1964; the references given provide entrances to the literature of the topics discussed rather than exhaustive documentation.     

The volatile component of some pumice-forming alkaline magmas from the Azores and Canary Islands

The abundances of pre-eruptive magmatic volatile species in the system H-O-S may be determined by application of thermodynamic methods to phenocryst assemblages commonly found in volcanic rocks, as demonstrated by Rutherford and Heming (1978). These methods are applied to alkaline pumice deposits, of airfall and ignimbrite type, from Tenerife (Canary Islands), Sao Miguel and Faial (Azores). It is argued that reliable temperature and fO₂ buffering mechanisms found in rhyolitic magmas appear not to operate in more alkaline liquids. fH₂O is estimated using biotite; the high values found are shown to be compatible with the violently explosive nature of the magmas concerned. fS₂ is estimated from pyrrhotite composition. fH₂, fH₂S, fSO₂, fSO₃ are calculated from gas equilibria. Water fugacity may be very roughly estimated for non-biotite bearing samples from data on the sulphur species. Abundances of these species are similar in alkaline and calc-alkaline salic magmas. Volcanological implications, relating to the release of volatiles during explosive eruptions, are considered.     

On the isotopic sulfur composition of some Precambrian strata

A study of minerals from Proterozoic and Archean series of various regions has been carried out. Sulfate and sulfide sulfur, having doubtlessly passed through the cycle of isotopic fractionation, has been determined in Archean rocks of the Baikal region. In the lazurite deposit of Malaya Bystraya, the country rocks are Precambrian stinking (fetid) dolomites which contain ancient hydrogen sulfide with ³⁴S from +19.0 to +33.4, and sulfate with ³⁴S=+44.9. Carbonate rocks have served as sources of sulfide and sulfate sulfur for a number of minerals (lazurite, scapolites, apatite, pyrrhotite, pyrite, a. o.). A connection between the enrichment of sulfides of metamorphic strata in the ³²S isotope or the ³⁴S isotope and the presence in rocks of increased amounts of graphite — the product of metamorphism of the organic matter of ancient sediments — is established. A conclusion has been drawn regarding the isotopic fractionation about 3·10⁹ y. ago.

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Zusammenfassung Schwefelisotopenfraktionierung durch den Sulfid-Sulfat-Zyklus findet nur dort statt, wo freier Sauerstoff vorhanden ist. Diese Tatsache wird benutzt, um das Eintreten von freiem Sauerstoff und den Beginn organischen Lebens im Präkambrium festzusetzen. Fraktionierter Sulfid- und Sulfatschwefel in archäischen Gesteinen vom Baikalsee wurde gemessen und ein Zusammenhang zwischen dem Schwefelisotopenverhältnis und einem zunehmenden Gehalt an Graphit festgestellt, der dem Gehalt an organischer Substanz entstammt. Diese Isotopenfraktionierung datiert ungefä hr 3:10⁹ M.J. her.

     

Primary magmas at Oldoinyo Lengai: The role of olivine melilitites

The paper describes olivine melilitites at Oldoinyo Lengai, Tanzania, and from tuff cones from the Tanzanian rift valley in the vicinity of Oldoinyo Lengai. Oldoinyo Lengai is the only active carbonatite volcano and is distinguished by its alkali-rich natrocarbonatites. Lengai is also unique for its extreme peralkaline silicate lavas related directly to the natrocarbonatites. Primitive olivine melilitites are, according to their Mg# and Ni, Cr contents, the only candidates in the Lengai area for primary melt compositions. Incompatible trace elements, including REE, constrain the melting process in their sub-lithospheric sources to very low degrees of partial melting in the garnet stability field. The strong peralkaline trend at Oldoinyo Lengai is already recognisable in these primary or near-primary melts. More evolved olivine melilitites, with Mg# < 60 allow the fractionation line in its major and trace element expressions to be followed. Nevertheless, a large compositional gap separates the olivine melilitites and olivine-poorer melilitites from the phonolites and nephelinites that form the bulk of the Lengai cone. These silicate lavas show a high degree of peralkalinity and are highly evolved with very low Mg, Ni and Cr. Prominent examples of the recent evolution are the combeite–wollastonite nephelinites that are unique for Lengai. In their Sr, Nd, and Pb isotope relationships the olivine melilitites define a distinct group with the most depleted Sr and Nd ratios and the most radiogenic Pb isotopes. They are closest to a supposed HIMU end member of the Lengai evolution, which is characterised by an extreme spread in isotopic ratios, explained as a mixing line between HIMU and EM1-like mantle components.     

The system CaO-MgO-SiO2-CO2 at 1 GPa, metasomatic wehrlites, and primary carbonatite magmas

New experimental data in CaO-MgO-SiO₂-CO₂ at 1 GPa define the vapor-saturated silicate-carbonate liquidus field boundary involving primary minerals calcite, forsterite and diopside. The eutectic reaction for melting of model calcite (1% MC)-wehrlite at 1 GPa is at 1100 °C, with liquid composition (by weight) 72% CaCO₃ (CC), 9% MgCO₃ (MC), and 18% CaMgSi₂O₆ (Di). These data combined with previous results permit construction of the isotherm-contoured vapor-saturated liquidus surface for the calcite/dolomite field, and part of the adjacent forsterite and diopside fields. Nearly pure calcite crystals in mantle xenoliths cannot represent equilibrium liquids. We recently determined the complete vapor-saturated liquidus surface between carbonates and model peridotites at 2.7 GPa; the peritectic reaction for dolomite (25% MC)-wehrlite at 2.7 GPa occurs at 1300 °C, with liquid composition 60% CC, 29% MC, and 11% Di. The liquidus field boundaries on these two surfaces provide the road-map for interpretation of magmatic processes in various peridotite-CO₂ systems at depths between the Moho and about 100 km. Relationships among kimberlites, melilitites, carbonatites and the liquidus phase boundaries are discussed. Experimental data for carbonatite liquid protected by metasomatic wehrlite have been reported. The liquid trends directly from dolomitic towards CaCO₃ with decreasing pressure. The 1.5 GPa liquid contains 87% CC and 4% Di, much lower in silicate components than our phase boundary. However, the liquids contain approximately the same CaCO₃ (90 ± 1 wt%) in terms of only carbonate components. For CO₂-bearing mantle, all magmas at depth must pass through initial dolomitic compositions. Rising dolomitic carbonatite melt will vesiculate and may erupt as primary magmas through cracks from about ˜70 km. If it percolates through metasomatic wehrlite from 70 km toward the Moho at 35–40 km, primary calcic siliceous carbonatite magma can be generated with silicate content at least 11–18% (70–40 km) on the silicate-carbonate boundary. Received: 22 June 1998 / Accepted: 7 July 1999     

汇聚板块边缘岩浆中金属和氯的地球化学性质研究

总结了铜(Cu)、金(Au)、铼(Re)和氯(Cl)在汇聚板块边缘岩浆中的性质。在岛弧型的火山岩岩浆演化的早期,Cu、Au和Re均表现为中度不相容元素,含量随SiO2含量的增加而增加。在SiO2质量分数为58%时,多数岛弧型火山岩中Au、Cu的含量会突然大幅度下降。这一变化与铁和钛的变化是耦合的,铁和钛均由不相容元素变为相容元素,显示钛磁铁矿开始结晶了。进一步的研究表明,钛磁铁矿的结晶使硫酸根被还原为氢硫酸根,后者与Au、Cu形成氢硫酸根络合物,被萃取到流体相中,从而形成成矿流体。这一过程可以很好地解释Au、Cu矿床广泛分布于汇聚板块边缘的现象。与Au、Cu相反,Re的含量在SiO2质量分数为60%时才开始下降,而且是缓慢下降。这是因为Re通常比Au、Cu更亲石。此外,Re还具有强烈的挥发性。氯在东Manus岩浆中表现为高度不相容的特点。氯的性质主要受压力、初始水含量和岩浆演化分异程度的控制。计算结果显示,由于MORB和OIB含水量低,分异演化程度低,氯在上述岩浆中表现为高度不相容的特点。相比之下,氯在岛弧岩浆中的性质就复杂得多。随着水含量和岩浆房深度的不同,氯的性质可以从相容变到高度不相容。     

Fluorite stability in silicic magmas

Recent experimental evidence is used to assess the conditions under which fluorite forms an early crystallising phase in silicic magmas. Fluorite solubility primarily depends on the (Na + K)/Al balance in the coexisting silicic melt, reaching a minimum in metaluminous melts. It can display reaction relationships with topaz and titanite, depending on changes in melt composition during crystallisation. An empirical model of fluorite stability in Ca-poor peralkaline rhyolite melts is derived and applied to selected rocks:

Olivine xenocrysts in picritic magmas

Experimental partial melting of plagioclase lherzolite at 0.7 MPa confining pressure has produced euhedral olivine crystals by corrosion and overgrowth during cooling. The particular conditions of this experiment allow observation of both processes recorded in the crystal shape: corrosion boundaries are rounded, or straight when parallel to [001] intersection of {110} planes; (010) and {110} facets are developed by fast overgrowth during quenching. These observations support the contention that phenocrysts in basaltic or picritic magmas are, in part, xenocrysts. The possible mantle origin of olivine crystals in two natural occurrences of ultramafic magmas; the picritic pillow lavas of the Troodos, and a wehrlitic intrusion of the oman ophiolite, is investigated. In both cases discriminant characteristics are deduced from detailed microstructural study. The mantle origin of olivine megacrysts in the investigated picrites raises the question about the existence of picritic magmas in the mantle.