Subduction metamorphism of serpentinite‐hosted carbonates beyond antigorite‐serpentinite dehydration (Nevado‐Filábride Complex,Spain)

At sub‐arc depths, the release of carbon from subducting slab lithologies is mostly controlled by fluid released by devolatilization reactions such as dehydration of antigorite (Atg‐) serpentinite to prograde peridotite. Here we investigate carbonate–silicate rocks hosted in Atg‐serpentinite and prograde chlorite (Chl‐) harzburgite in the Milagrosa and Almirez ultramafic massifs of the palaeo‐subducted Nevado‐Filábride Complex (NFC, Betic Cordillera, S. Spain). These massifs provide a unique opportunity to study the stability of carbonate during subduction metamorphism at P–T conditions before and after the dehydration of Atg‐serpentinite in a warm subduction setting. In the Milagrosa massif, carbonate–silicate rocks occur as lenses of Ti‐clinohumite–diopside–calcite marbles, diopside–dolomite marbles and antigorite–diopside–dolomite rocks hosted in clinopyroxene‐bearing Atg‐serpentinite. In Almirez, carbonate–silicate rocks are hosted in Chl‐harzburgite and show a high‐grade assemblage composed of olivine, Ti‐clinohumite, diopside, chlorite, dolomite, calcite, Cr‐bearing magnetite, pentlandite and rare aragonite inclusions. These NFC carbonate–silicate rocks have variable CaO and CO₂ contents at nearly constant Mg/Si ratio and high Ni and Cr contents, indicating that their protoliths were variable mixtures of serpentine and Ca‐carbonate (i.e., ophicarbonates). Thermodynamic modelling shows that the carbonate–silicate rocks attained peak metamorphic conditions similar to those of their host serpentinite (Milagrosa massif; 550–600°C and 1.0–1.4 GPa) and Chl‐harzburgite (Almirez massif; 1.7–1.9 GPa and 680°C). Microstructures, mineral chemistry and phase relations indicate that the hybrid carbonate–silicate bulk rock compositions formed before prograde metamorphism, likely during seawater hydrothermal alteration, and subsequently underwent subduction metamorphism. In the CaO–MgO–SiO₂ ternary, these processes resulted in a compositional variability of NFC serpentinite‐hosted carbonate–silicate rocks along the serpentine‐calcite mixing trend, similar to that observed in serpentinite‐hosted carbonate‐rocks in other palaeo‐subducted metamorphic terranes. Thermodynamic modelling using classical models of binary H₂O–CO₂ fluids shows that the compositional variability along this binary determines the temperature of the main devolatilization reactions, the fluid composition and the mineral assemblages of reaction products during prograde subduction metamorphism. Thermodynamic modelling considering electrolytic fluids reveals that H₂O and molecular CO₂ are the main fluid species and charged carbon‐bearing species occur only in minor amounts in equilibrium with carbonate–silicate rocks in warm subduction settings. Consequently, accounting for electrolytic fluids at these conditions slightly increases the solubility of carbon in the fluids compared with predictions by classical binary H₂O–CO₂ fluids, but does not affect the topology of phase relations in serpentinite‐hosted carbonate‐rocks. Phase relations, mineral composition and assemblages of Milagrosa and Almirez (meta)‐serpentinite‐hosted carbonate–silicate rocks are consistent with local equilibrium between an infiltrating fluid and the bulk rock composition and indicate a limited role of infiltration‐driven decarbonation. Our study shows natural evidence for the preservation of carbonates in serpentinite‐hosted carbonate–silicate rocks beyond the Atg‐serpentinite breakdown at sub‐arc depths, demonstrating that carbon can be recycled into the deep mantle.     

Atmospheric CO2 sink: Silicate weathering or carbonate weathering?

It is widely accepted that chemical weathering of Ca–silicate rocks could potentially control long-term climate change by providing feedback interaction with atmospheric CO₂ drawdown by means of precipitation of carbonate, and that in contrast weathering of carbonate rocks has not an equivalent impact because all of the CO₂ consumed in the weathering process is returned to the atmosphere by the comparatively rapid precipitation of carbonates in the oceans. Here, it is shown that the rapid kinetics of carbonate dissolution and the importance of small amounts of carbonate minerals in controlling the dissolved inorganic C (DIC) of silicate watersheds, coupled with aquatic photosynthetic uptake of the weathering-related DIC and burial of some of the resulting organic C, suggest that the atmospheric CO₂ sink from carbonate weathering may previously have been underestimated by a factor of about 3, amounting to 0.477 Pg C/a. This indicates that the contribution of silicate weathering to the atmospheric CO₂ sink may be only 6%, while the other 94% is by carbonate weathering. Therefore, the atmospheric CO₂ sink by carbonate weathering might be significant in controlling both the short-term and long-term climate changes. This questions the traditional point of view that only chemical weathering of Ca–silicate rocks potentially controls long-term climate change.     

Pressure-temperature Evolution of the Metapelites in the Motuo Area,the Eastern Himalayan Syntaxis

The Motuo area is located in the east of the Eastern Himalayan Syntaxis. There outcrops a sequence of high-grade metamorphic rocks, such as metapelites. Petrology and mineralogy data suggest that these rocks have experienced three stages of metamorphism. The prograde metamorphic mineral assemblages(M1) are mineral inclusions(biotite + plagioclase + quartz ± sillimanite ± Fe-Ti oxides) preserved in garnet porphyroblasts, and the peak metamorphic assemblages(M2) are represented by garnet with the lowest XSps values and the lowest XFe# ratios and the matrix minerals(plagioclase + quartz ± Kfeldspar + biotite + muscovite + kyanite ± sillimanite), whereas the retrograde assemblages(M3) are composed of biotite + plagioclase + quartz symplectites rimming the garnet porphyroblasts. Thermobarometric computation shows that the metamorphic conditions are 562–714°C at 7.3–7.4 kbar for the M1 stage, 661–800°C at 9.4–11.6 kbar for the M2 stage, and 579–713°C at 5.5–6.6 kbar for the M3 stage. These rocks are deciphered to have undergone metamorphism characterized by clockwise P-T paths involving nearly isothermal decompression(ITD) segments, which is inferred to be related to the collision of the India and Eurasia plates.     

A Comparative geochemical study of pelitic schists and metamorphosed carbonate rocks from south-central Maine,USA

Whole-rock major element chemical analyses of progressively metamorphosed impure carbonate rocks and pelitic schists, collected from the same metamorphic terrain, reveal similarities and differences in the chemical response of these rock types to the metamorphic event. Relative to a constant aluminum reference frame, both schist and carbonate exhibit no detectable change in their contents of Fe, Mg, Ti, Si, and Ca with change in metamorphic grade. Carbonate rocks become progressively depleted in K and Na with increasing grade of metamorphism, while schists exhibit no statistically significant change in their contents of K and Na. Both rock types become depleted in volatiles (principally CO₂ and H₂O) with increasing grade.Whole-rock chemical data permit two mechanisms for migration of K and Na from the carbonate rocks during metamorphism: (a) diffusion of alkalis from carbonate to adjacent schist; (b) transport of alkalis by through-flowing metamorphic fluid (infiltration). Mineral equilibria in schist and metacarbonate rock from the same outcrops allow calculation of the affinity for cation exchange between the two rock types during metamorphism. Measured affinities indicate that if mass transport of K and Na occurred by diffusion, chemical potential gradients would have driven the alkalis from schist into carbonate rock. Because diffusion cannot produce the observed chemical trends in the metacarbonates, K and Na are believed to have been removed during metamorphism by infiltration.The disparity in chemical behavior between the pelitic schists and metacarbonate rocks may be a result of enhanced fluid flow through the carbonates. The carbonate rocks may have acted as metamorphic aquifers; the greater flow of fluid through them would then have had a correspondingly greater effect on their whole-rock chemistry.     

Unique Clinkers and Paralavas from a New Nyalga Combustion Metamorphic Complex in Central Mongolia: Mineralogy,Geochemistry, and Genesis

The paper presents mineralogical and geochemical data on clinkers and paralavas and on conditions under which they were formed at the Nyalga combustion metamorphic complex, which was recently discovered in Central Mongolia. Mineral and phase assemblages of the CM rocks do not have analogues in the world. The clinkers contain pyrogenically modified mudstone relics, acid silicate glass, partly molten quartz and feldspar grains, and newly formed indialite microlites (phenocrysts) with a ferroindialite marginal zone. In the paralava melts, spinel microlites with broadly varying Fe concentrations and anorthite–bytownite were the first to crystallize, and were followed by phenocrysts of Al-clinopyroxene ± melilite and Mg–Fe olivine. The next minerals to crystallize were Ca-fayalite, kirschsteinite, pyrrhotite, minerals of the rhönite–kuratite series, K–Ba feldspars (celsian, hyalophane, and Ba-orthoclase, Fe³⁺-hercynite ± (native iron, wüstite, Al-magnetite, and fresnoite), nepheline ± (kalsilite), and later calcite, siderite, barite, celestine, and gypsum. The paralavas contain rare minerals of the rhönite–kuratite series, a new end-member of the rhönite subgroup Ca₄Fe ₈ ²⁺ Fe ₄ ³⁺ O₄ [Si₈Al₄O₃₆], a tobermorite-like mineral Ca₅Si₅(Al,Fe)(OH)O₁₆ · 5H₂O, and high- Ba F-rich mica (K,Ba)(Mg,Fe)₃(Al,Si)₄O₁₀F₂. The paralavas host quenched relics of microemulsions of immiscible residual silicate melts with broadly varying Si, Al, Fe, Ca, K, Ba, and Sr concentrations, sulfide and calcitic melts, and water-rich silicate–iron ± (Mn) fluid media. The clinkers were formed less than 2 Ma ago in various parts of the Choir–Nyalga basin by melting Early Cretaceous mudstones with bulk composition varies from dacitic to andesitic. The pyrogenic transformations of the mudstones were nearly isochemical, except only for volatile components. The CM melt rocks of basaltic andesitic composition were formed via melting carbonate–silicate sediments at temperatures above 1450°C. The Ca- and Fe-enriched and silicaundersaturated paralavas crystallized near the surface at temperatures higher than 900–1100°C and oxygen fugacity \(f_{O_2 }\) between the IW and QFM buffers. In local melting domains of the carbonate–silicate sedimentary rocks and in isolations of the residual melts among the paralava matrix the fluid pressure was higher than the atmospheric one. The bulk composition, mineral and phase assemblages of CM rocks of the Nyalga complex are very diverse (dacitic, andesitic, basaltic andesitic, basaltic, and silica-undersaturated mafic) because the melts crystallized under unequilibrated conditions and were derived by the complete or partial melting of clayey and carbonate–silicate sediments during natural coal fires.     

Petrological and Geochemical Constraints on the Protoliths of Serpentine‐Magnetite Ores in the Zhaoanzhuang Iron Deposit,Southern North China Craton

The uncommon Mg-rich and Ti-poor Zhaoanzhuang serpentine-magnetite ores within Taihua Group of the North China Craton(NCC) remain unclear whether the protolith was sourced from ultramafic rocks or chemical sedimentary sequences. Here we present integrated petrographic and geochemical studies to characterize the protoliths and to gain insights on the ore-forming processes. Iron ores mainly contain low-Ti magnetite(TiO_2 ~0.1 wt%) and serpentine(Mg#=92.42–96.55), as well as residual olivine(Fo=89–90), orthopyroxene(En=89–90) and hornblende. Magnetite in the iron ores shows lower Al, Sc, Ti, Cr, Zn relative to that from ultramafic Fe-Ti-V iron ores, but similar to that from metamorphic chemical sedimentary iron deposit. In addition, interstitial minerals of dolomite, calcite, apatite and anhydrite are intergrown with magnetite and serpentine, revealing they were metamorphic, but not magmatic or late hydrothermal minerals. Wall rocks principally contain magnesian silicates of olivine(Fo=83–87), orthopyroxene(En=82–86), humite(Mg#=82–84) and hornblende [XMg=0.87–0.96]. Dolomite, apatite and anhydrite together with minor magnetite, thorianite(Th-rich oxide) and monazite(LREE-rich phosphate) are often seen as relicts or inclusions within magnesian silicates in the wall rocks, revealing that they were primary or earlier metamorphic minerals than magnesian silicates. And olivine exists as subhedral interstitial texture between hornblende, which shows later formation of olivine than hornblende and does not conform with sequence of magmatic crystallization. All these mineralogical features thus bias towards their metamorphic, rather than magmatic origin. The dominant chemical components of the iron ores are SiO_2(4.77–25.23 wt%), Fe_2O_3 T(32.9–80.39 wt%) and MgO(5.72–27.17 wt%) and uniformly, those of the wall rocks are also SiO_2(16.34–48.72 wt%), Mg O(16.71–33.97 wt%) and Fe_2O_3 T(6.98–30.92 wt%). The striking high Fe-Mg-Si contents reveal that protolith of the Zhaoanzhuang iron deposit was more likely to be chemical sedimentary rocks. The distinct high-Mg feature and presence of abundant anhydrite possibly indicate it primarily precipitated in a confined seawater basin under an evaporitic environment. Besides, higher contents of Al, Ti, P, Th, U, Pb, REE relative to other Precambrian iron-rich chemical precipitates(BIF) suggest some clastic terrestrial materials were probably input. As a result, we think the Zhaoanzhuang iron deposit had experienced the initial Fe-Mg-Si marine precipitation, followed by further Mg enrichment through marine evaporated process, subsequent high-grade metamorphism and late-stage hydrothermal fluid modification.     

Composition of manganese nodules and manganese carbonates from Loch Fyne,Scotland

Manganese nodules and manganese carbonate concretions occur in the upper 10–15 cm of the Recent sediments of Loch Fyne, Argyllshire in water depths of 180–200 m. The nodules are spherical, a few mm to 3 cm in diameter, and consist of a black, Mn-rich core and a thin, red, Fe-rich rim. The carbonate occurs as irregular concretions, 0.5–8 cm in size, and as a cement in irregular nodule and shell fragment aggregates. It partially replaces some nodule material and clastic silicate inclusions, but does not affect aragonitic and calcitic shell fragments.The nodules are approximately 75% pure oxides and contain 30% Mn and 4% Fe. In the cores, the principal mineral phase is todorokite, with a Mn/Fe ratio of 17. The rim consists of X-ray amorphous Fe and Mn oxides with a Mn/Fe ratio of 0.66. The cores are enriched, relative to Al, in K, Ba, Co, Mo, Ni and Sr while the rims contain more P, Ti, As, Pb, Y and Zn.The manganese carbonate has the composition (Mn_47.7 Ca_45.1 Mg_7.2) CO₃. Apart from Cu, all minor elements are excluded from significant substitution in the carbonate lattice.Manganese nodules and carbonates form diagenetically within the Recent sediments of Loch Fyne. This accounts for the high Mn/Fe ratios in the oxide phases and the abundance of manganese carbonate concretions. Mn concentrations in the interstitial waters of sediment cores are high (ca. 10 ppm) as also, by inference, are the dissolved carbonate concentrations.     

Dissolution of altered tuffaceous rocks under conditions relevant for CO2 storage

We conducted CO₂–water–rock interaction experiments to elucidate the dissolution characteristics and geochemical trapping potential of three different altered andesitic to rhyolitic tuffaceous rocks (Tsugawa, Ushikiri and Daijima tuffaceous rock) relative to fresh mid-ocean ridge basalt. The experiments were performed under 1 MPa CO₂ pressure to reproduce the water–rock–CO₂ interactions in CO₂ storage situations. Basalt showed high acid neutralization potential and rapid dissolution of silicate minerals. Two of the tuffaceous rocks (Ushikiri and Daijima) showed relatively high solubility trapping potential, mainly due to the dissolution of carbonate minerals in the andesitic Ushikiri tuffaceous rock and the ion-exchange reaction with zeolite minerals in the rhyolitic Daijima tuffaceous rock. The mineral trapping potential of the Ushikiri tuffaceous rock was found to be relatively high, due to the rapid dissolution of Mg- and Ca-bearing silicate minerals. Our experimental results suggest that regions of porous and andesitic tuffaceous rock hold global promise as CO₂ storage sites.     

Chromite in Komatiites, II. Modification during Greenschist to Mid-Amphibolite Facies Metamorphism

Chromite compositions in komatiites are influenced by metamorphicprocesses, particularly above 500°C. Metamorphosed chromiteis substantially more iron rich than igneous precursors, asa result of Mg–Fe exchange with silicates and carbonates.Chromite metamorphosed to amphibolite facies is enriched inZn and Fe, and depleted in Ni, relative to lower metamorphicgrades. Relative proportions of the trivalent ions Cr³⁺, Al³⁺and Fe³⁺ are not greatly modified by metamorphism up to loweramphibolite facies, although minor Fe³⁺ depletion occurs duringtalc–carbonate alteration at low temperature. SignificantAl is lost from chromite cores above 550°C, as a resultof equilibration with fluids in equilibrium with chlorite. ElevatedZn content in chromite is restricted to rocks with low (metamorphic)Mg/Fe ratios, and is the result of introduction of Zn duringlow-temperature alteration, with further concentration and homogenizationduring prograde metamorphism. Cobalt and Mn also behave similarly,except where carbonate minerals are predominant in the metamorphicassemblage. Chromite at amphibolite facies is typically extensivelyreplaced by magnetite. This is the result of incomplete metamorphicreaction between chromite and chlorite-bearing silicate assemblages.Magnetite compositions at the inner chromite–magnetiteboundary are indicators of metamorphic grade. KEY WORDS: chromite; komatiite; spinel; metamorphism; Zn     

Fluid flow and Al transport during quartz-kyanite vein formation, Unst, Shetland Islands, Scotland

Quartz‐kyanite veins, adjacent alteration selvages and surrounding ‘precursor’ wall rocks in the Dalradian Saxa Vord Pelite of Unst in the Shetland Islands (Scotland) were investigated to constrain the geochemical alteration and mobility of Al associated with channelized metamorphic fluid infiltration during the Caledonian Orogeny. Thirty‐eight samples of veins, selvages and precursors were collected, examined using the petrographic microscope and electron microprobe, and geochemically analysed. With increasing grade, typical precursor mineral assemblages include, but are not limited to, chlorite+chloritoid, chlorite+chloritoid+kyanite, chlorite+chloritoid+staurolite and garnet+staurolite+kyanite+chloritoid. These assemblages coexist with quartz, white mica (muscovite, paragonite, margarite), and Fe‐Ti oxides. The mineral assemblage of the selvages does not change noticeably with metamorphic grade, and consists of chloritoid, kyanite, chlorite, quartz, white mica and Fe‐Ti oxides. Pseudosections for selvage and precursor bulk compositions indicate that the observed mineral assemblages were stable at regional metamorphic conditions of 550–600 °C and 0.8–1.1 GPa. A mass balance analysis was performed to assess the nature and magnitude of geochemical alteration that produced the selvages adjacent to the veins. On average, selvages lost about −26% mass relative to precursors. Mass losses of Na, K, Ca, Rb, Sr, Cs, Ba and volatiles were −30 to −60% and resulted from the destruction of white mica. Si was depleted from most selvages and transported locally to adjacent veins; average selvage Si losses were about −50%. Y and rare earth elements were added due to the growth of monazite in cracks cutting apatite. The mass balance analysis also suggests some addition of Ti occurred, consistent with the presence of rutile and hematite‐ilmenite solid solutions in veins. No major losses of Al from selvages were observed, but Al was added in some cases. Consequently, the Al needed to precipitate vein kyanite was not derived locally from the selvages. Veins more than an order of magnitude thicker than those typically observed in the field would be necessary to accommodate the Na and K lost from the selvages during alteration. Therefore, regional transport of Na and K out of the local rock system is inferred. In addition, to account for the observed abundances of kyanite in the veins, large fluid‐rock ratios (10²–10³ m³_fluid m⁻³_rock) and time‐integrated fluid fluxes in excess of ∼10⁴ m³_fluid m⁻²_rock are required owing to the small concentrations of Al in aqueous fluids. It is concluded that the quartz‐kyanite veins and their selvages were produced by regional‐scale advective mass transfer by means of focused fluid flow along a thrust fault zone. The results of this study provide field evidence for considerable Al mass transport at greenschist to amphibolite facies metamorphic conditions, possibly as a result of elevated concentrations of Al in metamorphic fluids due to alkali‐Al silicate complexing at high pressures.     

Calculated silica activities in carbonatite liquids

Carbonatite magmas precipitate silicates, in addition to the abundant carbonates, oxides, and phosphates. Calculated silica activities for equilibria involving silicates and a silica component in magmatic liquids predict specific assemblages for silicate and oxide phases in carbonatites. These assemblages provide tests of alternative sources (carbonatite magma, coeval silicate magma, or older rock) for silicate minerals in carbonatites. Quartz, feldspars, and orthopyroxene are unlikely to be primary magmatic phases in carbonatites, because the silica activity in carbonatite magmas is too low to stabilize these minerals. Zircon and titanite should be unstable relative to baddeleyite and perovskite, respectively, but they do occur in carbonatites. Liquids dominated by carbonate are strongly nonideal with respect to dissolved silica. Consequently, activity coefficients for a silica component in carbonatite liquids are >>1, so that small mole fractions of SiO₂ translate into silica activities sufficient to stabilize phlogopite, clinopyroxene, amphibole, monticellite, and forsterite, among other silicates. Examination of silicate mineral assemblages in carbonatites in the light of silica activity indicates that many carbonatites are contaminated by solid silicate phases from external sources but these xenocrysts can be discriminated from magmatic minerals.     

Interaction of Titanium Minerals and Their Melts with Diamond-Forming Media (Experiments at 7–8 GPa)

Melting relations in the multicomponent diamond-forming systems of the upper mantle with a boundary of K–Na–Mg–Fe–Ca carbonate, phases of the model peridotite and eclogite, carbon, and titanium minerals from kimberlite (ilmenite FeTiO₃, perovskite CaTiO₃, and rutile TiO₂) were studied experimentally at 7–8 GPa and 1600–1650°C. Perovskite reacts with the formation of rutile in the diamond-forming silicate–carbonate melts. We discovered liquid immiscibility between melts of titanium minerals, on the one hand, and carbonate–carbon, peridotite–carbonate–carbon, and eclogite–carbonate–carbon diamond-forming melts, on the other. The solubility of titanium mineral in diamond-forming melts is negligible independent of their concentration in the experimental systems. Growth melts retain high diamond-forming efficiency. In general, the experimental results are evident for the xenogenic nature of titanium minerals in inclusions in diamond and, therefore, in diamond-forming melts. It is shown that the physicochemical factors that may correlate the diamond content with the concentration of Ti in kimberlite do not occur during the diamond genesis in silicate–carbonate–carbon parental melts containing titanium minerals and their melts.     

Differentiation of nelsonitic magmas in the formation of the ~1.74 Ga Damiao Fe–Ti–P ore deposit, North China

The ~1.74 Ga Damiao anorthosite complex, North China, is composed of anorthosite and leuconorite with subordinate melanorite, mangerite, oxide-apatite gabbronorite, perthite noritic (i.e., jotunitic) and ferrodioritic dykes. The complex hosts abundant vein-, pod- and lens-like Fe–Ti–P ores containing variable amounts of apatite (10–60 modal%) and Fe–Ti oxides. In addition to Fe–Ti–P ores, there are also abundant Fe–Ti ores which are closely associated with Fe–Ti–P ores in the deposit. Most of Fe–Ti–P ores are dominated by Fe–Ti oxides and apatite, devoid of silicate minerals, mineralogically similar to the common nelsonites elsewhere. In contrast, Fe–Ti ores are dominated by Fe–Ti oxides with minor apatite (<5 modal %). The parental magma of these ores, estimated from olivine and apatite compositions using mineral-melt partition coefficients, has composition similar to the ferrodioritic dykes. Fe–Ti–P ores have variable Fe–Ti oxides and apatite proportions, indicating that they are cumulates. Their simple assemblage of Fe–Ti oxides and apatite and local net-texture suggest that the Fe–Ti–P ores in Damiao have formed from nelsonitic melts immiscibly separated from the ferrodioritic magma during late-stage differentiation. Fe–Ti ores are also cumulates and have mineral compositions similar to Fe–Ti–P ores. The close association between Fe–Ti and Fe–Ti–P ores indicates that the Fe–Ti ores may have also formed from the nelsonitic melts. We proposed that differentiation of nelsonitic melts accompanied by gravity settling is responsible for the formation of Fe–Ti and Fe–Ti–P ores. Such a differentiation process in nelsonitic melts is well supported by variations of Sr, Y, Th, U, REE and Eu/Eu* of apatite in Fe–Ti–P ores. Using oxides/apatite ratio of 2:1 and compositions of apatite and calculated primary oxides, we estimate the composition of the nelsonitic melt as ~52.0 wt% Fe₂O₃t, ~18.5 wt% CaO, ~14.2 wt% P₂O₅, ~8.7 wt% TiO₂, ~4.0 wt% Al₂O₃ and ~1.1 wt% MgO with minor SiO₂, K₂O, Na₂O and F. Such a nelsonitic melt is suggested to be possibly conjugated with Si-rich melts compositionally similar to the Damiao jotunitic dykes (~50 wt% SiO₂ and ~15 wt% Fe₂O₃t) which may subsequently evolve to mangeritic rocks in Damiao. Our modeling also indicates that the onset of immiscibility occurs at a time when the evolved melt has ~44 wt% SiO₂, ~21 wt% Fe₂O₃t, ~3.0 wt% TiO₂ and ~2.6 wt% P₂O₅. High oxygen fugacity and phosphorous content in magmas may play important roles in the immiscibility of nelsonitic magmas, including promoting iron enrichments and widening the two-liquid field.     

Accurate Measurement of Lithium Isotopes in Eleven Carbonate Reference Materials by MC‐ICP‐MS with Soft Extraction Mode and 1012 Ω Resistor High‐Gain Faraday Amplifiers

Lithium isotopes in carbonate rocks and minerals can serve as important tools for assessing palaeoclimates and palaeoenvironments. However, carbonate bulk rock samples are commonly mixtures of carbonate and silicate minerals, which require the complete digestion of the carbonate without digesting the silicate. Additionally, the low Li content (ng g^?1 level) in carbonates provides an additional challenge. Hence, despite their wide applications, few carbonates have had their δ⁷Li values characterised, particularly carbonate reference materials, which hinders comparisons of Li isotope measurement results obtained in different laboratories and the further application of Li isotopes in geological studies. This study aimed to provide precise and accurate δ⁷Li values for carbonate reference materials based on an evaluation of sample leaching and the Li purification method for carbonates, as well as the adoption of soft extraction and 10¹² Ω amplifiers to increase the intensity/blank ratio and matrix effect on Li isotope measurement. The precision and accuracy of the proposed procedure were verified by analysing synthetic carbonate samples and mono‐elemental Li solutions. With the developed method we provide δ⁷Li values for eleven carbonate reference materials with a precision of ~ 0.4‰. The accuracy of the δ⁷Li values was validated using the standard addition method.     

Origin of carbonatite magma during the evolution of ultrapotassic basite magma

Clinopyroxene phenocrysts in fergusite from a diatreme in the Dunkel’dyk potassic alkaline complex in the southeastern Pamirs, Tajikistan, and from carbonate veinlets cutting across this rock contain syngenetic carbonate, silicate, and complex melt inclusions. The homogenization of the silicate and carbonate material of the inclusions with the complete dissolution of daughter crystalline phases and fluid in each of them occur simultaneously at 1150?1180°C. The pressures estimated using fluid inclusions and mineral geobarometers were 0.5–0.7 GPa. The behavior of the inclusions during their heating and their geochemistry are in good agreement with the origin of carbonate melts via liquid immiscibility. Carbonatite magma was segregated at the preservation of volatile components (H₂O, CO₂, F, Cl, and S) in the melt, and this resulted in the crystallization of H₂O-rich minerals and carbonates and testifies that the magma was not intensely degassed during its ascent to the surface. The silicate melts are rich in alkalis (up to 4 wt % Na₂O and 12 wt % K₂O), H₂O, F, Cl, and REE (up to 1000 ppm), LREE, Ba, Th, U, Li, B, and Be. The diagrams of the concentrations of incompatible elements of these rocks typically show deep Nb, Ta, and Ti minima, a fact making them similar to the unusual type of ultrapotassic magmas: lamproites of the Mediterranean type. These magmas are thought to be generated in relation to subduction processes, first of all, the fluid transport of various components from a down-going continental crustal slab into overlying levels of the mantle wedge, from which ultrapotassic magmas are presumably derived.     

Devolatilization of metabasic rocks during greenschist–amphibolite facies metamorphism

The production of large volumes of fluid from metabasic rocks, particularly in greenstone terranes heated across the greenschist–amphibolite facies transition, is widely accepted yet poorly characterized. The presence of carbonate minerals in such rocks, commonly as a consequence of sea‐floor alteration, has a strong influence, via fluid‐rock buffering, on the mineral equilibria evolution and fluid composition. Mineral equilibria modelling of metabasic rocks in the system Na₂O‐CaO‐FeO‐MgO‐Al₂O₃‐SiO₂‐CO₂‐H₂O (NCaFMASCH) is used to constrain the stability of common metabasic assemblages. Calculated buffering paths on T–X_CO2 pseudosections, illustrate the evolution of greenstone terranes during heating across the greenschist‐amphibolite transition. The calculated paths constrain the volume and the composition of fluid produced by devolatilization and buffering. The calculated amount and composition of fluid produced are shown to vary depending on P–T conditions, the proportion of carbonate minerals and the X_CO2 of the rocks prior to prograde metamorphism. In rocks with an initially low proportion of carbonate minerals, the greenschist to amphibolite facies transition is the primary period of fluid production, producing fluid with a low X_CO2. Rocks with greater initial proportions of carbonate minerals experience a second fluid production event at temperatures above the greenschist to amphibolite facies transition, producing a more CO₂‐rich fluid (X_CO2 = 0.2–0.3). Rocks may achieve these higher proportions of carbonate minerals either via more extensive seafloor alteration or via infiltration of fluids. Fluid produced via devolatilization of rocks at deeper crustal levels may infiltrate and react with overlying lower temperature rocks, resulting in external buffering of those rocks to higher X_CO2 and proportions of carbonate minerals. Subsequent heating and devolatilization of these overlying rocks results in buffering paths that produce large proportions of fluid at X_CO2 = 0.2–0.3. The production of fluid of this composition is of importance to models of gold transport in Archean greenstone gold deposits occurring within extensive fluid alteration haloes, as these haloes represent the influx of fluid of X_CO2 = 0.2–0.3 into the upper crust.     

The Quantitative Mineral Composition of Sedimentary Rocks: Calculation from Chemical Analyses and Assessment of Adequacy (MINLITH Computer Program)

The MINLITH program provides for calculating the first approximation mineral composition of sedimentary rocks and their metamorphic counterparts from the bulk chemical compositions. The method is universal and can be applied to most types of clastic, pelitic, and carbonate sedimentary rocks based on a limited set of minerals and their simplified compositions. The program comprises a great number of arithmetic operations making up an algorithm. Each operation solves the equations allocating the major oxides to possible (expected) normative minerals. The operation sequence is determined from empirical relationships based on the study of numerous reference samples. The accuracy of MINLITH calculations was statistically estimated from comparison with results of the high-precision study of modal mineral compositions. Uncertainty is commonly within a range of 5–15 rel % and attains 60–70 rel % if the mineral content is below 5 wt %. It is evident that the program is a rather simple, convenient, and useful tool for the approximate estimation of mineral compositions of sedimentary rocks for lithological purposes.     

A Study of Phase Equilibria in a Metamorphic Iron Formation

The paper is based on a study of minerl assemblages in metamorphiciron formations in northere Quebec. Thirty-four mineral analyseshave been performed, using photometric methods of silicate analysis. Three facies of iron formation are represented, namely, quartz-speculariteiron formation, quartz-magnetite iron formation, and quartz-silicateiron formation. The silicate iron formation is made up mainlyof quartz, ferrohypersthene, ferroaugite, cummingtonite, andcalcite. Arfvedsonite and aegirine-hedenbergite occur in magnetite-richrocks. The analysed coexisting minerals are from the silicate ironformation and from overlying mafic rocks of igneous origin.The analysed assemblages include ferrohypersthene-ferro-augite-cummingtonite,ferrohypersthen-ferroaugite, cummingtonite-ferroaugite, diopside-hornblende,anthophyllite-hornblende, hypersthene-diopside-hornblende-garnet,and olivine-hypersthene-chlorite. The analyses show that (1) the minerals are nearly in equilibriumas shown by parallel tie lines, (2) cummingtonite generallyhas a higher MgO/FeO ratio than coexisting ferrohypersthene,(3) the phase higher in calcium has the higher MgO/FeO ratio,(4) the solubility gap between ferrohypersthene and ferroaugiteis 43 mole percent. The stability relationships of pyroxenes and amphiboles arediscussed in view of the new data. It is shown that FeO-CaO-SiO₂systems often behave differently from MgO-CaO-SiO₂ systems.Hedenbergite is probably not stable in the presence of excessCO₂ in the area. The low variance ferrohypersthene-ferroaugite-cummingtonite-calcite-quartzassemblage indicates that the rocks were closed to H₂O and CO₂.The behaviour of the volatile components is discussed in viewof this fact. The source of the silicate minerals is assumed to be hydrousiron silicates and carbonates. A model of the sequence of chemicalreactions taking place in carbonate-silicate iron formationsduring metamorphism is suggested. ¹Present address: Bolidens Gruvaktiebolag, Boliden, Sweden.     

Melt loss and the preservation of granulite facies mineral assemblages

The loss of a metamorphic fluid via the partitioning of H₂O into silicate melt at higher metamorphic grade implies that, in the absence of open system behaviour of melt, the amount of H₂O contained within rocks remains constant at temperatures above the solidus. Thus, granulite facies rocks, composed of predominantly anhydrous minerals and a hydrous silicate melt should undergo considerable retrogression to hydrous upper amphibolite facies assemblages on cooling as the melt crystallizes and releases its H₂O. The common occurrence of weakly retrogressed granulite facies assemblages is consistent with substantial melt loss from the majority of granulite facies rocks. Phase diagram modelling of the effects of melt loss in hypothetical aluminous and subaluminous metapelitic compositions shows that the amount of melt that has to be removed from a rock to preserve a granulite facies assemblage varies markedly with rock composition, the number of partial melt loss events and the P–T conditions at which melt loss occurs. In an aluminous metapelite, the removal of nearly all of the melt at temperatures above the breakdown of biotite is required for the preservation of the peak mineral assemblage. In contrast, the proportion of melt loss required to preserve peak assemblages in a subaluminous metapelite is close to half that required for the aluminous metapelite. Thus, if a given proportion of melt is removed from a sequence of metapelitic granulites of varying composition, the degree of preservation of the peak metamorphic assemblage may vary widely.     

http://www.sciencedirect.com/science/article/pii/S1674987113000315

The Panzhihua gabbroic intrusion,part of the plumbing system of the Emeishan large igneous province, intruded late-Proterozoic dolomites and marls about～263 Ma ago.The dolomites in the contact aureole were converted to brucite marbles and a diverse suite of forsterite,diopside and garnet skarns.The variation in mineralogy is explained in part by differences in the composition of the protolith,particularly the proportion of silica minerals and clay,and in part by transfer of elements from intruding magmas.The trace element compositions of most marbles and skarns are very similar to those of unmetamorphosed dolomites and marls,but some contain high Si,Ti,and Fe contents that are interpreted to have come from a magmatic source.Three brucite marbles sampled～10 m from the contact of the intrusion and named "enriched brucite marble" have trace element compositions very different from their dolomitic protolith:their rare earth elements are strongly enriched whereas levels of Nb-Ta,Zr-Hf and Ti are very low.These characteristics resemble those of carbonate liquid in equilibrium with silicate liquid or more probably with silicate minerals in the case of Panzhihua,a similarity we take to indicate that the sample underwent partial melting.Samples taken up to 300 m from the contact contain brucite indicating that high temperatures persisted well into the country rocks.However,other samples collected only tens of metres from the contact are only slightly recrystallized indicating that conditions in the aureole were highly variable.We suggest that temperatures within the aureole were controlled by conduction of heat from the main intrusion and by supply of additional heat from abundant small dykes within the aureole.Circulation of fluids derived from deeper levels in the aureole flushed the carbon dioxide from the dolomite,lowering temperature needed to partially melt carbonate to the temperatures attained near the intrusion.Irregular but extensive heating destabilized the carbonates of the aureole and decarbonation reactions associated with carbonate breakdown and melting emitted a large volume of CO₂,with potential impact on global climate.