Oxygen deficient Ti oxides (natural magnéli phases) from mudstone xenoliths with native iron from Disko,central West Greenland

Mudstone xenoliths in a strongly reduced andesitic subaquatic breccia with native iron from the Asuk Member on Disko contain Ti oxides which are oxygen deficient relative to rutile. Ore microscopy reveals that the mudstone xenoliths contain former clastic oxide grains which have equilibrated to blue Ti oxides and grey aluminous Ti oxides. They also contain still immature coal fragments in a glassy matrix with native iron.The blue oxides are compositionally similar to magnéli phases Ti_nO_2n–1 within the range n=4 to 7, and several grains contain more than one natural magnéli phase. Two other phases found are 1) pale orange blebs in magnéli phases with a composition approaching Al₁Ti ₁ ³⁺ Ti ₂ ⁴⁺ O₇ (AlTi phase B) and 2) grey oxide rims on magnéli phases or independent grains of the compositional series Al_2–x(Ti _0.5 ⁴⁺ (Mg,Fe)_0.5)_xTi _n–2 ⁴⁺ O_2n–1 with n mostly between 7 and 10 (AlTi phase A). The natural magnéli phases equilibrated at oxygen fugacities 4 to 5 log units below the Fe-W oxygen buffer at igneous temperatures and represent the most reduced high-temperature environment yet recorded among native iron bearing rocks from Disko. The extremely reducing conditions were met in rocks where coal fragments were still in a state of degassing hydrocarbon components at the time of quenching. Field geology and carbon barometry indicate equilibration at pressures of less than 10 bars.     

Thermal and redox equilibrium conditions of the upper-mantle xenoliths from the Quaternary volcanoes of NW Spitsbergen,Svalbard Archipelago

Upper-mantle xenoliths in Cenozoic basalts of northwestern Spitsbergen are rocks of peridotite (spinel lherzolites) and pyroxenite (amphibole-containing garnet and garnet-free clinopyroxenites, garnet clinopyroxenites, and garnet and garnet-free websterites) series. The upper-mantle section in the depth range 50–100 km is composed of spinel peridotites; at depths of 80–100 km pyroxenites (probably, dikes or sills) appear. The equilibrium conditions of parageneses are as follows: in the peridotites—730–1180 °C, 13–27 kbar, and oxygen fugacity of − 1.5 to + 0.3 log. un.; in the pyroxenites—1100–1310 °C, 22–33 kbar. The pyroxenite minerals have been found to contain exsolved structures, such as orthopyroxene lamellae in clinopyroxene and, vice versa, clinopyroxene lamella in orthopyroxene. The formation temperatures of unexsolved phases in orthopyroxene and clinopyroxene are nearly 100–150 °C higher than the temperatures of the lamellae–matrix equilibrium and the equilibrium of minerals in the rock. The normal distribution of cations in the spinel structure and the equilibrium distribution of Fe^2 + between the M1 and M2 sublattices in the orthopyroxenes point to the high rate of xenolith ascent from the rock crystallization zone to the surface. All studied Spitsbergen rock-forming minerals from mantle xenoliths contain volatiles in their structure: OH⁻, crystal hydrate water H₂O_cryst, and molecules with characteristic CH and CO groups. The first two components are predominant, and the total content of water (OH– + H₂O_cryst) increases in the series olivine → garnet → orthopyroxene → clinopyroxene. The presence of these volatiles in the nominally anhydrous minerals (NAM) crystallized at high temperatures and pressures in the peridotites and pyroxenites testifies to the high strength of the volatile–mineral bond. The possibility of preservation of volatiles is confirmed by the results of comprehensive thermal and mass-spectral analyses of olivines and clinopyroxene, whose structures retain these components up to 1300 °C. The composition of hypothetic C–O–H fluid in equilibrium (in the presence of free carbon) with the underlying mantle rocks varies from aqueous (> 80% H₂O) to aqueous–carbonic (~ 60% H₂O). The fluid becomes essentially aqueous when the oxygen activity in the system decreases. However, there is no strict dependence of the redox conditions on the depth of formation of xenoliths.     

Crystal chemistry of amphiboles: implications for oxygen fugacity and water activity in lithospheric mantle beneath Victoria Land,Antarctica

Amphibole is the hydrous metasomatic phase in spinel-bearing mantle xenoliths from Baker Rocks, Northern Victoria Land, Antarctica. It occurs in veins or in disseminated form in spinel lherzolites. Both types derive from reaction between metasomatic melts and the pristine paragenesis of the continental lithospheric mantle beneath Northern Victoria Land. To determine the effective role of water circulation during the metasomatic process and amphibole formation, six amphibole samples were fully characterized. Accurate determination of the site population and the state of dehydrogenation in each of these amphiboles was carried out using single-crystal X-ray diffraction, electron microprobe and secondary ion mass spectroscopy on the same single crystal. The Fe³⁺/ΣFe ratio was determined by X-ray absorption near edge spectroscopy on amphibole powder. The degree of dehydrogenation determined by SIMS is 0.870–0.994 O3(O^2?) a.p.f.u., primary and ascribed to the Ti-oxy component of the amphibole, as indicated by atom site populations; post-crystallization H loss is negligible. Estimates of aH₂O (0.014–0.054) were determined from the dehydration equilibrium among end-member components assuming that amphiboles are in equilibrium with the anhydrous peridotitic phases. A difference up to 58 % in determination of aH₂O can be introduced if the chemical formula of the amphiboles is calculated based on 23 O a.p.f.u. without knowing the effective amount of dehydrogenation. The oxygen fugacity of the Baker Rocks amphibole-bearing mantle xenoliths calculated based upon the dissociation constant of water (by oxy-amphibole equilibrium) is between ?2.52 and ?1.32 log units below the fayalite–magnetite–quartz (FMQ) buffer. These results are systematically lower and in a narrow range of values relative to those obtained from anhydrous olivine–orthopyroxene–spinel equilibria (fO₂ between ?1.98 and ?0.30 log units). A comparative evaluation of the two methods suggests that when amphibole is present in mantle peridotites, the application of oxy-amphibole equilibrium is preferred, because ol–opx–sp oxy-calibrations are not “sensitive” enough in recording the effects (if any) of amphibole in the peridotite matrix. Amphibole acts as the main H acceptor among the peridotite minerals and may prevent fluid circulation and buffer oxygen fugacity. The important conclusion of this study is that amphibole within the lithospheric mantle does not always means high water activity and oxidizing conditions.     

Optical spectroscopy study of natural Fe, Ti-bearing calcic amphiboles

Over thirty samples of natural Ti-bearing amphiboles with Ti- and Fe-contents ranging from 0.111 to 0.729 atom per formula unit (a.p.f.u.) and from 0.479 to 2.045 a.p.f.u., respectively, were studied by means of optical absorption spectroscopy and microprobe analysis. Thirteen samples were also studied by Mössbauer spectroscopy. A strong pleochroic absorption edge, causing the dark brown colours of Ti-bearing amphiboles, is attributed to ligand-metal and metal-metal charge transfer transitions involving both iron and titanium ions (O^2?→ Fe³⁺, Fe²⁺, O^2?→ Ti⁴⁺ and Fe²⁺ + Ti⁴⁺→ Fe³⁺ + Ti³⁺). A broad intense Y-polarized band ～22?000?cm^?1 (ν_1/2?≈?3700?cm^?1) in spectra of two low iron amphiboles with a relatively low Fe³⁺/Fe_total ratio, both from eclogite-like rocks in kimberlite xenoliths, was attributed to electronic Fe²⁺(M3) + Ti⁴⁺(M2)→Fe³⁺(M3)+Ti³⁺(M2) IVCT transitions. The IVCT bands of other possible ion pairs, involving Ti⁴⁺ and Fe²⁺ in M2 and M1, M4 sites, respectively, are presumed to be at higher energies, being obscured by the absorption edge.     

Cation distribution in amphiboles synthesized along the Ga analogue of the tremolite–aluminotschermakite join

 Amphiboles were synthesized from bulk compositions prepared along the join Ca_1.8Mg_5.2Si₈O₂₂(OH)₂–Ca_1.8Mg₃Ga₄Si₆O₂₂(OH)₂ hydrothermally at 750–850 °C and 1.0–1.8 GPa, and along the join Ca₂Mg₅Si₈O₂₂F₂–Ca₂Mg₃Ga₄Si₆O₂₂F₂, anhydrously at 1000 °C and 0.7 GPa to document how closely the tschermak-type substitution is obeyed in these analogues of aluminous amphiboles. Electron-microprobe analyses and Rietveld X-ray diffraction structure refinements were performed to determine cation site occupancies. The extent of Ga substitution was found to be limited in both joins, but with the fluorine series having about twice the Ga content (0.6 atoms per formula unit, apfu) of the hydroxyl-series amphiboles (0.3 apfu). The tschermak-type substitution was followed very closely in the hydroxyl series with essentially equal partitioning of Ga between tetrahedral and octahedral sites. The fluorine-series amphiboles deviated significantly from the tschermak-type substitution and, instead, appeared to follow a substitution that is close to a Ca-pargasite substitution of the type: ^[6]Ga³⁺+2^[4]Ga³⁺+1/2^[A] Ca²⁺ = ^[6]Mg²⁺+2^[4]Si⁴⁺+1/2^[A]□. Infrared spectroscopy revealed an inverse correlation between the intensity of the OH-stretching bands and the Ga content for the hydroxyl- and fluorine-series amphiboles. The direct correlation between the Ga and F content and inverse relationship between the Ga and OH content may be a general phenomenon present in other minerals and suggests, for example, that high F contents in titanite are controlled by the Al content of the host rock and that there may be similar direct Al–F correlations in tschermakitic amphiboles. Evidence for the possibility that Al (Ga) might substitute onto only a subset of the tetrahedral sites in tschermakitic amphiboles was sought but not observed in this study. Received: 5 March 2001 / Accepted: 31 July 2001     

The oxidation state of subcontinental mantle: oxygen thermobarometry of mantle xenoliths from central Asia

The oxygen fugacities of 48 mantle xenoliths from 5 localities in southern Siberia (USSR) and Mongolia have been determined. Ferric iron contents of spinels were measured by ⁵⁷Fe Mössbauer spectroscopy and oxygen fugacities calculated from spinel-olivineorthopyroxene equilibrium. The samples studied represent the major types of upper mantle lithologies including spinel and garnet peridotites and pyroxenites, fertile and depleted peridotites and anhydrous and metasomatized samples which come from diverse tectonic settings. Extensive geochemical and isotope data are also available for these samples. Oxygen fugacity values for most central Asian xenoliths fall within the range observed in peridotite xenoliths from other continental regions at or slightly below the FMQ buffer. However, xenoliths from the Baikal rift zone are the most reduced among xenoliths for which Mössbauer data on spinels are available. They yield fO₂ values similar to those in oceanic peridotites and MORBs, while xenoliths in other occurrences have higher fO₂s. In general, the continental lithosperic mantle is more oxidized than MORB-like oceanic mantle. This difference seems to be due to incorporation of oxidized material into some parts of the subcontinental mantle as a result of subduction of oceanic crust. Garnet- and garnet-spinel lherzolites from the Baikal rift area have slightly higher oxygen fugacities than shallower spinel lherzolites. Oxygen fugacity does not appear to be correlated with the degree of depletion of peridotites, and its values in peridotites and pyroxenites are very much alike, suggesting that partial melting (at least at moderate degrees) takes place at essentially the same fO₂s that are now recorded by the residual material. Modally (amphibole- and phlogopitebearing) and cryptically metasomatized xenoliths from the Baikal rift zone give the same fO₂ values as depleted anhydrous peridotites, suggesting that solid-melt-fluid reactions in the continental rift mantle also take place without substantial change in redox state. This is in contrast to other tectonic environments where metasomatism appears to be associated with oxidation.     

The oxidation state of Ti in hornblende and biotite determined by electron energy-loss spectroscopy,with inferences regarding the Ti substitution

Structural formulae of many Ti-rich hornblendes and biotites exhibit cation deficiencies that increase with Ti content. These deficiencies may be caused by the presence of trivalent instead of tetravalent Ti, of oxygen replacing hydroxyl, or of vacancies on octahedral cation sites. In order to determine the oxidation state of their Ti, electron energy-loss spectra of natural, Ti-rich hornblende and biotites are compared with spectra of natural and synthetic Ti-bearing oxides and silicates. Spectra of Ti₂O₃ and TiO₂ demonstrate that the Ti L _2,3 edge for Ti³⁺ is shifted by ca. 2 eV to lower energy relative to the edge for Ti⁴⁺. Oxidation states of Ti determined by energy-loss spectroscopy for several minerals agree with data from other techniques: tetravalent for Ti-omphacite, perovskite, ilmenite and titanite; trivalent for NaTi³⁺Si₂O₆ pyroxene and fassaite from the Allende meteorite. The energy-loss spectra of the hornblende and biotite show that their Ti is tetravalent and cannot be the cause of the cation deficiencies. The relations between Ti contents and the number of deficiencies differ for hornblende and biotite. Hornblende shows a 2:1 relation between Ti content and deficiencies, suggesting Ti is coupled to an oxygen that is replacing hydroxyl (Ti-oxyhornblende substitution). Biotite shows a 1:1 relation, consistent with coupling of Ti to a vacant octahedral cation site (Ti-vacancy substitution) or to a variable combination of such vacancies and two oxygens replacing hydroxyls (Ti-oxybiotite substitution).     

The mineralogy of the glaucophane schists and associated rocks from Île de Groix,Brittany, France

Ninety-seven mineral phases consisting of ten chloritoids, fifteen epidotes, sixteen garnets, four sphenes, seven rutiles, seven pyroxenes, thirteen blue amphiboles, two green amphiboles, eleven phengites, two paragonites, a mariposite, seven chlorites, and two specimens of albite were obtained from the metamorphic rocks of Île de Groix, and their chemical, physical, optical and X-ray properties determined. The chloritoids are all optically positive, monoclinic polymorphs with large 2V, moderate refractive indices and characterized by high densities. Their fluorine contents have been used to propose a new upper limit for OHF substitution in the chloritoid structure, suggesting that partial pressure of fluorine might modify the stability of chloritoids from that determined in pure H₂O. The epidotes belong to the Al-Fe epidote series and are epidote sensu stricto. The almandine-rich garnets and the chloromelanites are metastable relics in the glaucophane schists. The grossular contents of the calcareous schist garnets are believed to have become depressed under high CO₂ pressure and the low Tschermak's contents of the pyroxenes are to be explained by equilibria involving epidote at high and low temperature when the Tschermak's components will break down to epidote group minerals. The sphenes contain appreciable amounts of combined water, fluorine substituting for oxygen and aluminium substituting for silicon and titanium. The presence of H₃O⁺ is suspected in a specimen of blue amphibole. The barroisite has a composition between glaucophane and hornblende. On account of its high Fe³⁺ content it is believed to have formed under higher P _{O 2} than the blue amphiboles. The paragonites which occur in the ohloritoid veins are unstable in the potassium-rich aluminous schists. The phengites show a tendency towards sericitic composition due to post-glaucophanisation readjustments under the lower pressure conditions of the greenschist facies. Some of the Fe³⁺ contents of the chlorites are interpreted as due to oxidation of ferrous iron, e.g. 2 [Fe(OH)₂]2FeOOH + H₂. The minerals show strong chemical control of the host rock and their Mn contents are directly related to those of the minerals from which they have evolved through retrogression.Chloritoids and epidotes that are not associated with garnets contain higher amounts of manganese; similarly, the two blue amphiboles with the highest FeMg ratios were obtained from rocks in which garnet has not appeared. It is therefore believed that ottrelite and piemontite would be stable only at the lowest subfacies of the greenschist facies. Also, the ironrich amphiboles must have evolved from low-grade iron-aluminium chlorites, since on the appearance of garnet in a schist iron-aluminium chlorites react with quartz to give almandine and Mg-rich chlorites. The Fe²⁺Mg ratios of the blue amphiboles therefore reflect the grade of the original schist in which the minerals formed.     

Non-Stoichiometric magnesian spinels in shale xenoliths from a native iron-bearing andesite at Asuk,Disko, central West Greenland

A strongly reduced native iron-bearing andesite breccia from Disko contains graphite-rich modified shale xenoliths with magnesian spinels. These spinels are free from or very poor in ferric iron and vary considerably within the MgO-FeO-Cr₂O₃-Al₂O₃ compositional space. Through a simple substitution of the type 3 (Mg, Fe)²⁺ ⇆ 2(Al, Cr)³⁺+□_vacancy, the spinels vary from stoichiometric (Mg, Fe)²⁺ (Al, Cr)³⁺ ₂O₄ towards (Al, Cr)₂O₃. The simple substitution of Cr for Al suggests that Cr was accepted into the spinel structure as Cr³⁺, despite the reduced nature of the enclosing andesite. The most magnesian spinels are cation deficient spinel_ss in the synthetic systems MgO-Al₂O₃ and MgO-Al₂O₃-Cr₂O₃. The absence of exolved (Al, Cr)₂O₃-component is probable due to rapid quenching.     

Melt and fluid inclusion evidence for a genetic relationship between magmatism in the Shuangliao volcanic field and inorganic CO2 gas reservoirs in the southern Songliao Basin,China

We have studied melt and fluid inclusions in minerals from alkali basalts, mantle xenoliths, and dawsonite-bearing sandstones from the Shuangliao volcanic field in southern Songliao Basin, Northeast China. The inclusions have been investigated using petrographic, geochemical, and laser Raman spectroscopic techniques. Volcanic rocks of the Shuangliao field are predominantly alkali olivine basalts that contain rare mantle xenoliths. Silicate melt and fluid inclusions are common in both olivine phenocrysts and the mantle xenoliths. The fluid inclusions are mainly composed of CO₂ with small amounts of CO, CH₄, N₂, and H₂O, which is consistent with an upper mantle origin. CO₂ gas reservoirs in the southern Songliao Basin are mostly derived from a mantle–magmatic source. Coeval fluid-inclusion homogenization temperatures, coupled with the thermal burial history, show that the CO₂ gas reservoirs in the southern Songliao Basin are Cenozoic (40–63 Ma) and coeval with the magmatism in the Shuangliao volcanic field. Despite the relatively small scale of this volcanic activity, it released large amounts of CO₂. Much of the magma was not erupted, and CO₂- and H₂O-rich magma was probably intruded into the basin along deep faults, acting as a major source of inorganic CO₂ gas in the southern Songliao Basin.     

Mineral chemistry and geochemistry of vanadian silicates in the Hemlo gold deposit,Ontario, Canada

Some of the most vanadium-rich silicate minerals known are present in green mica schist from the Hemlo gold deposit, Ontario, Canada. Vanadium-rich silicate minerals include green mica (up to 17.6 wt. % V₂O₃), phlogopite (10.1 wt. % V₂O₃), pumpellyite (25.7 wt. % V₂O₃), garnet (18.5 wt. % V₂O₃), epidote-group minerals (9.1 wt. % V₂O₃), antimonian vesuvianite (4.3 wt. % V₂O₃), and titanite (18.5 wt. % V₂O₅). In addition, minor amounts of V (<2 wt. % V₂O₃) are present in tourmaline, chlorite, talc and tremolite in other lithologies of the Hemlo deposit. The principal substitution that incorporates V into most of these silicate minerals is Al³⁺=V³⁺ in octahedral positions. Vanadium is incorporated into phlogopite mainly by the two substitutions: 3Mg²⁺ =2V³⁺+ and ^VIMg²⁺+^IVSi⁴⁺=^VIV³⁺ +^IVAl³⁺, and all of the three substitutions Ti⁴⁺+O^2- =V³⁺+(OH,F)^-, Ti⁴⁺=V⁴⁺, and 5Ti⁴⁺=4V⁵⁺ + may have operated in titanite.Vanadium-enriched green mica schist from the Hemlo gold deposit is characterized by uniform Ti/Zr ratios, systematically low Ti, Ni, Co and Sc abundances, and low levels of incompatible elements Th, U, Hf and Zr and is distinct in these respects from its Cr-enriched counterpart. These geochemical features, along with textural evidence (relict quartz and oligoclase phenocrysts), indicate that the V-enriched green mica schist from Hemlo was most likely derived mainly from quartz-oligoclase porphyry. However, its anomalously high V and Cr contents were probably introduced metasomatically from local maficultramafic sources and were fixed in green mica and oxides during the waning of a second regional metamorphism. Vanadium was further remobilized, and its concentration probably enhanced, during the late hydrothermal alteration, which resulted in the formation of the characteristic V-rich calc-silicate minerals.     

Contrasting types of metasomatism in dunite, wehrlite and websterite xenoliths from Kimberley, South Africa

Dunite, wehrlite and websterite are rare members of the mantle xenolith suite in the Kimberley kimberlites of the Kaapvaal Craton in southern Africa. All three types were originally residues of extensive melt extraction and experienced varying amounts and types of melt re-enrichment. The melt depletion event, dated by Re-Os isotope systematics at 2.9 Ga or older, is evidenced by the high Mg# (Mg/(Mg + Fe)) of silicate minerals (olivine (0.89-0.93); pyroxene (0.88-0.93); garnet (0.72-0.85)), high Cr# (Cr/(Cr + Al)) of spinel (0.53-0.84) and mostly low whole-rock SiO₂, CaO and Al₂O₃ contents. Shortly after melt depletion, websterites were formed by reaction between depleted peridotites and silica-rich melt (>60 wt% SiO₂) derived by partial melting of eclogite before or during cratonization. The melt-peridotite interaction converted olivine into orthopyroxene.All three xenolith types have secondary metasomatic clinopyroxene and garnet, which occur along olivine grain boundaries and have an amoeboid texture. As indicated by the preservation of oxygen isotope disequilibrium in the minerals and trace-element concentrations in clinopyroxene and garnet, this metasomatic event is probably of Mesozoic age and was caused by percolating alkaline basaltic melts. This melt metasomatism enriched the xenoliths in CaO, Al₂O₃, FeO and high-field-strength-elements, and might correspond to the Karoo magmatism at 200 Ma. The websterite xenoliths experienced both the orthoyproxene-enrichment and clinopyroxene-garnet metasomatic events, whereas dunite and wehrlite xenoliths only saw the later basaltic melt event, and may have been situated further away from the source of melt migration channels.     

The compositional variation of synthetic sodic amphiboles at high and ultra-high pressures

Sodic amphiboles in high pressure and ultra-high pressure (UHP) metamorphic rocks are complex solid solutions in the system Na₂O–MgO–Al₂O₃–SiO₂–H₂O (NMASH) whose compositions vary with pressure and temperature. We conducted piston-cylinder experiments at 20–30?kbar and 700–800?°C to investigate the stability and compositional variations of sodic amphiboles, based on the reaction glaucophane=2jadeite+talc, by using the starting assemblage of natural glaucophane, talc and quartz, with synthetic jadeite. A close approach to equilibrium was achieved by performing compositional reversals, by evaluating compositional changes with time, and by suppressing the formation of Na-phyllosilicates. STEM observations show that the abundance of wide-chain structures in the synthetic amphiboles is low. An important feature of sodic amphibole in the NMASH system is that the assemblage jadeite–talc?±?quartz does not fix its composition at glaucophane. This is because other amphibole species such as cummingtonite (Cm), nyböite (Nyb), Al–Na-cummingtonite (Al–Na-Cm) and sodium anthophyllite (Na-Anth) are also buffered via the model reactions: 3cummingtonite?+?4quartz?+?4H₂O=7talc, nyböite?+?3quartz=3jadeite?+?talc, 3Al–Na-cummingtonite + 11quartz + 2H₂O=6jadeite + 5talc, and 3 sodium anthophyllite?+?13quartz?+?4H₂O=3 jadeite + 7talc. We observed that at all pressures and temperatures investigated, the compositions of newly grown amphiboles deviate significantly from stoichiometric glaucophane due to varying substitutions of Al^IV for Si, Mg on the M(4) site, and Na on the A-site. The deviation can be described chiefly by two compositional vectors: [Na^AAl^IV]<=>[□^ASi] (edenite) toward nyböite, and [Na^(M4)Al^VI]<=>[Mg^(M4)Mg^VI] toward cummingtonite. The extent of nyböite and cummingtonite substitution increases with temperature and decreases with pressure in the experiments. Similar compositional variations occur in sodic amphiboles from UHP rocks. The experimentally calibrated compositional changes therefore may prove useful for thermobarometric applications.     

Volatile contents of phlogopite micas from South African kimberlite

Phlogopite micas from nodules in South African kimberlites were analyzed for major elements with the electron microprobe and for volatile contents by high temperature mass spectrometry. The micas are from primary- (deformed) and secondary- (undeformed) textured grains in perodotite xenoliths, glimmerites, MARID (mica-amphibole-rutile-ilmenite-diopside) suite nodules and a mica megacryst. The major element and volatile contents of micas exhibiting these modes of occurrence overlap to a greater extent than indicated in previous studies. Concentrations of volatile species occupying structurally defined crystallographic sites (H₂O, F, Cl) are greater for many of the micas than predicted on the basis of the mica formula, particularly for the glimmerite and MARID suite samples. A correlation exists between micas with tetrahedral and octahedral cation deficiencies and those with excess H₂O, F and Cl. Substitution of H⁺ for tetrahedral and possibly octahedral cations may be responsible for the excess H₂O in these micas. Except for one sample, the major element and volatile data for the peridotite, glimmerite and MARID suite micas indicate that they crystallized at oxygen fugacities below the quartz-fayalite-magnetite buffer. F and K₂O are in the correct proportion in the micas to provide the source for these elements in alkali basalts, but not in mid-ocean ridge basalts. Kaersutite amphibole is a more likely source of potassium and fluorine in mid-ocean ridge basalts.     

New Compositional and Structural Constraints on the Smithsonian Microanalytical Reference Materials: Amphiboles from Kakanui and Arenal

The amphiboles from Kakanui and Arenal are two natural minerals that have been used worldwide as microanalytical reference materials, but their compositions and crystal structures are still poorly constrained. In this paper, we report new data on H₂O and trace element mass fractions and single-crystal structural refinement of these two amphiboles. H₂O mass fractions of the Kakanui and Arenal amphiboles determined via Karl-Fischer titration are 0.92 ± 0.18 (2s) and 1.56 ± 0.22% m/m (2s), respectively; these values estimated based on crystal-structure refinement are 0.86 and 1.46% m/m, respectively. Trace element mass fractions measured via LA-ICP-MS in two laboratories are in good agreement, and spots from five fragments for both Kakanui and Arenal amphiboles are generally consistent within reproducibility precision (2s). Our measurements indicate a better homogeneity for the amphiboles from Kakanui than that from Arenal. According to the latest scheme for amphibole classification and nomenclature (Hawthorne et al. 2012), the sample from Arenal is a (partially dehydrogenated) pargasite, and that from Kakanui is a kaersutite. The significant amount of oxo-component and that ^CTi⁴⁺ content is strongly ordered at the M(1) site for both amphiboles indicate crystallisation under high fO₂ conditions.     

Mineralogic and sulfur isotopic effects accompanying oxidation of pyrite in millimolar solutions of hydrogen peroxide at temperatures from 4 to 150 °C

Oxidation of pyrite by hydrogen peroxide (H₂O₂) at millimolar levels has been studied from 4 to 150 °C in order to evaluate isotopic effects potentially associated with radiolytic oxidation of pyrite. Gaseous, aqueous, and solid phases were collected and measured following sealed-tube experiments that lasted from 1 to 14 days. The dominant gaseous product was molecular oxygen. No volatile sulfur species were recovered from any experiment. Sulfate was the only aqueous sulfur species detected in solution, with sulfite and thiosulfate below the detection limits. X-ray diffraction patterns and images from scanning electron microscopy reveal solid residues composed primarily of hydrated ferric iron sulfates and sporadic ferric-ferrous iron sulfates. Hematite was detected only in solid residue produced during high temperature experiments. Elemental sulfur and/or polysulfides are inferred to be form on reacting pyrite surface based on extraction with organic solvents. Pyrite oxidation by H₂O₂ increases in rate with increasing H₂O₂concentration, pyrite surface area, and temperature. Rates measured in sealed-tube experiments at 25°C, for H₂O₂ concentration of 2 × 10⁻³ M are 8.8 × 10⁻⁹ M/m²/sec, which are higher than previous estimates. A combination of reactive oxygen species from H₂O₂ decomposition products and reactive iron species from pyrite dissolution is inferred to aggressively oxidize the receding pyrite surface. Competing oxidants with temperature-dependent oxidation efficiencies results in multiple reaction mechanisms for different temperatures and surface conditions. Sulfur isotope values of remaining pyrite were unchanged during the experiments, but showed distinct enrichment of ³⁴S in produced sulfate and depletion in elemental sulfur. The Δ_{sulfate-pyrite} and Δ_{elemental sulfur-pyrite} was +0.5 to +1.5‰ and was −0.2 to −1‰, respectively. Isotope data from high-temperature experiments indicate an additional ³⁴S-depleted sulfur fraction, with up to 4‰ depletion of ³⁴S, in the hematite. Sulfur isotope trends were not influenced by H₂O₂ concentration, temperature, or reaction time. Results of this study indicate that radiolytically produced oxidants, such as hydrogen peroxide and hydroxyl radicals, could efficiently oxidize pyrite in an otherwise oxygen-limited environment. Although H₂O₂ is generally regarded as being of minor geochemical significance on Earth, the H₂O₂ molecule plays a pivotal role in Martian atmospheric and soil chemistry. Additional experimental and field studies are needed to characterize sulfur and oxygen isotope systematics during radiolytical oxidation of metallic sulfides and elemental sulfur.     

Oxygen fugacity regime in the upper mantle as a reflection of the chemical differentiation of planetary materials

Oxygen fugacity (fO₂) in the Earth’s mantle has a bearing on the problems of the chemical differentiation of the Earth’s materials and formation of the chemical and phase state of its shells. This paper addresses some problems concerning changes in the redox state of the upper mantle over geologic time and through its depth and the possible influence of fO₂ stratification in the interiors on geochemical processes. Among these problems are the formation of fluids enriched in H₂O, CO₂, CH₄,and H₂; the possible influence of reduced fluid migration from mantle zones with low fO₂ values on reactions in the lithosphere; and the formation of films of silicate liquids with high H₂O and CO₂ contents, which could be responsible for metasomatic transformations in rocks. The formation of a metallic core and accompanying large-scale melting of the silicate part of the Earth are the early mechanisms of the chemical differentiation of the mantle that must have had an effect on the redox state and the composition of volatile components in planetary materials. The molten metallic and silicate phases were prone to gravitational migration, which affected the formation of the metallic core. Volatile components had to be simultaneously formed in the zones of large-scale melting of the early Earth. The composition of these volatiles was largely controlled by the interaction of hydrogen and carbon, the two major gas-forming elements in the mantle, with melt under low fO₂ values. A remarkable feature is that, despite fairly low fO₂ values imposed by the presence of a metallic phase, both reduced (CH₄ and H₂) and oxidized species of hydrogen and carbon (H₂O, OH^? and CO ₃ ^?2 ) are stable in the melt. This peculiarity of carbon and hydrogen dissolution in reduced melts may be crucial for the elucidation of mechanisms for the formation of initial amounts of CO₂ and H₂O connected with incipient melting in the reduced mantle.     

Eh ph Diagrams for mn, fe, co, ni, cu and as Under Seawater Conditions: Application of two new Types of eh ph Diagrams to the Study of Specific Problems in Marine Geochemistry

E_H pH diagrams have been calculated using the PHREEQC programme in order to establish the predominance fields of Mn, Fe, Co, Ni, Cu and As in bottom waters from the Angola Basin. Predominance fields are presented separately for both aquatic species and solid mineral phases in order to simplify interpretation of the data. The diagrams show significant differences from standard E_H pH diagrams for these elements calculated for freshwater at 25 °C and 1 bar which assume an element concentration of 10^-6 M. In particular, our diagrams show that Mn²⁺ and NiCO ₃ ⁰ are the predominant aquatic species for Mn and Ni in bottom seawater and FeOOH, Fe₂O₃, Fe₃O₄, CoFe₂O₄, CuFe₂O₄, CuFeO₂, and Ba₃ (AsO₄)₂ the predominant solid phases for Fe, Co, Cu and As, respectively. Mn and Ni are therefore undersaturated and Fe, Co, Cu and As supersaturated in bottom seawater from the Angola Basin. Neither rhodochrosite (MnCO₃) nor siderite (FeCO₃) can form in this marine environment in equilibrium with seawater. A mixed Mn-Ca carbonate is therefore formed within the pore waters of reducing sediments. The high Ni/Cu ratios in cobalt-rich manganese crusts formed adjacent to the oxygen minimum zone may be explained by the change from Cu²⁺ to CuCl ₃ ^2- as the dominant aquatic species of Cu in seawater at an E_H of +0.48 V.     

Oxygen isotope partitioning during oxidation of pyrite by H2O2 and its dependence on temperature

A detailed experimental study was conducted to investigate mechanisms of pyrite oxidation by determining product yields and oxygen isotopic fractionation during reactions between powdered pyrite (FeS₂) with aqueous hydrogen peroxide (H₂O₂). Sealed silica-tube experiments utilized aliquots of pyrite that were reacted with 0.2 M H₂O₂ for 7 to 14 days at 4 to 150 °C. No volatile sulfur species were detected in any experiment. The only gaseous product recovered was elemental oxygen inferred to result from decomposition of H₂O₂. Aqueous sulfate (S_aq) was the only sulfur product recovered from solution. Solid hydrated ferric iron sulfates (i.e., water-soluble sulfate fraction, S_ws) were recovered from all experiments. Ferric oxide (hematite) was detected only in high temperature experiments.Reactants were selected with large differences in initial δ¹⁸O values. The oxygen isotopic compositions of oxygen-bearing reactants and products were analyzed for each experiment. Subsequent isotopic mass-balances were used to identify sources of oxygen for reaction products and to implicate specific chemical reaction mechanisms. δ¹⁸O of water did not show detectable change during any experiment. δ¹⁸O of sulfate was similar for S_aq and S_ws and indicated that both H₂O and H₂O₂ were sources of oxygen in sulfate. Low-temperature experiments suggest that H₂O-derived oxygen was incorporated into sulfate via Fe³⁺ oxidation, whereas H₂O₂-derived oxygen was incorporated into sulfate via oxidation by hydroxyl radicals (HO). These two competing mechanisms for oxygen incorporation into sulfate express comparable influences at 25 °C. With increasing reaction temperatures from 4 to 100 °C, it appears that accelerated thermal decomposition and diminished residence time of H₂O₂ limit the oxygen transfer from H₂O₂ into sulfate and enhance the relative importance of H₂O-derived oxygen for incorporation into sulfate. Notably, at temperatures between 100 and 150 °C there is a reversal in the lower temperature trend resulting in dominance of H₂O₂-derived oxygen over H₂O-derived oxygen. At such high temperatures, complete thermal decomposition of H₂O₂ to water and molecular oxygen (O₂) occurs within minutes in mineral-blank experiments and suggests little possibility for direct oxidation of pyrite by H₂O₂ above 100 °C. We hypothesize that a Fe-O₂ mechanism is responsible for oxygenating pyrite to sulfate using O₂ from the preceding thermal decomposition of H₂O₂.     

Significance of OH,F and Cl content in biotite during metamorphism of the Western Adamello contact aureole

The hydroxyl (O(4)) site composition of biotite can in principle be used to retrieve information about fluid composition during fluid–rock interaction; however, due to low F and Cl content, as well as difficulties involved with analyzing the H₂O content using in situ techniques, measuring these species in biotite has remained an elusive goal. Here we present high-precision secondary ion mass spectrometry (SIMS) OH–F–Cl measurements from biotite within metapelites from the Western Adamello Tonalite (WAT) contact aureole, Northern Italy. Fluorine, chlorine and hydrogen are analyzed on the SIMS sequentially by peak-hopping at the same biotite spot; H₂O, F and Cl content were measured with a precision (1σ) οφ 0.06 ωτ%, 50 ανδ 5 ππµ, ρεσπεχτι?ελψ. The compositions of isolated biotite crystals in andalusite are compared with that of biotite in the matrix, documenting that halogens and H₂O behave refractory in biotite during the time scale of contact metamorphism. The H₂O and halogen contents of biotite are mostly locked in during the prograde to peak formation of biotite, and are not reset during further heating or cooling, unless significant biotite recrystallization occurs. It also appears that both Ti content and X_Mg of the biotite from the Western Adamello contact aureole were not significantly reset during cooling. The concentration of F and Cl does not vary systematically with metamorphic grade, which indicates that these species reflect initial compositions. No significant Rayleigh fractionation behavior was observed for these elements. H₂O variations in the biotite from samples throughout the Western Adamello contact aureole suggest that Al-oxy substitution partially controls the variations in OH content through charge balance of the type R^2+,VI + OH^? = Al^3+,VI + O^2? + H₂, while the Ti-oxy substitution does not seem to influence the O(4) site occupation. The main titanium substitution appears to be the Ti-vacancy (\({\text{2}}{{\text{R}}^{{\text{2}}+}}~=~{\text{T}}{{\text{i}}^{{\text{4}}+}}~+\,{\square ^{{\text{VI}}}}\)) exchange. Variations in H₂O and halogen concentrations in biotite define sub mm-scale areas of localized equilibration, even for biotite recrystallized during dehydration reactions that produced large amounts of fluid (chlorite or muscovite breakdown). Similar systematics were observed for Ti⁴⁺ and Al³⁺. These findings further support the increasing number of observations that kinetics control much of the mineralogical reactions occurring in contact aureoles, and hence care is advised in using equilibrium thermodynamics in this environment.