A review and analysis of silicate mineral dissolution experiments in natural silicate melts

We present a database and a graphical analysis of published experimental results for dissolution rates of olivine, quartz plagioclase, clinopyroxene, orthopyroxene, spinel, and garnet in basaltic and andesitic melts covering a range of experimental temperatures (1100–1500°C) and pressures (10⁵ Pa-3.0 GPa). The published datasets of Donaldson (1985, 1990) and Brearly and Scarfe (1986) are the most complete. Experimental dissolution rates from all datasets are recalculated and normalized to a constant oxygen basis to allow for direct comparison of dissolution rates between different minerals. Dissolution rates (ν) range from 5·10⁻¹⁰ oxygen equivalent moles (o.e.m.) cm⁻² s⁻¹ for olivine in a basaltic melt to 1.3·10⁻⁵ o.e.m. cm⁻² s⁻¹ for garnet in a basaltic melt. Values of ln ν are Arthenian for the experiments examined and activation energies range from 118 to 1800 kJ/o.e.m. for quartz and clinopyroxene, respectively.

The relationship between calculated A/RT for the dissolution reactions, where A is the thermodynamic potential affinity, and values of ν is linear for olivine, plagioclase, and quartz. We interpret this as strong evidence in support of using calculated A as a predictor of ν for, at least, superliquidus melt conditions.     

The origin of medium-K ankaramitic arc magmas from Lombok (Sunda arc, Indonesia): Mineral and melt inclusion evidence

High-calcium, nepheline-normative ankaramitic basalts (MgO > 10 wt.%, CaO/Al₂O₃ > 1) from Rinjani volcano, Lombok (Sunda arc, Indonesia) contain phenocrysts of clinopyroxene and olivine (Fo_85–92) with inclusions of spinel (Cr# 58–77) and crystallised melt. Olivine crystals have variable but on average low NiO (0.10–0.23 wt.%) and high CaO (0.22–0.35 wt.%) contents for their forsterite number. The CaO content of Fo_89–91 olivine is negatively correlated with the Al₂O₃ content of enclosed spinel (9–15 wt.%) and positively correlated with the CaO/Al₂O₃ ratios of melt inclusions (0.9–1.5). Major and trace element patterns of melt inclusions are similar to that of the host rock, indicating that the magma could have formed by accumulation of small batches of melt, with compositions similar to the melt inclusions. The liquidus temperature of the magma was  1275 °C, and its oxygen fugacity ≤ FMQ + 2.5. Correlations between K₂O, Zr, Th and LREE in the melt inclusions are interpreted to reflect variable degrees of melting of the source; correlations between Al₂O₃, Na₂O, Y and HREE are influenced by variations in the mineralogy of the source. The melts probably formed from a water-poor, clinopyroxene-rich mantle source.     

Water content in natural eclogite and implication for water transport into the deep upper mantle

Infrared spectroscopy and ion micro-probe measurements showed that the major constituent minerals of eclogites from the Kokchetav massif, which have been subducted to 180 km depths, contain significant amounts of water up to 870 ppm H₂O (by weight) in omphacite, 130 ppm H₂O in garnet and 740 ppm H₂O in rutile. Omphacite shows three hydroxyl absorption bands at 3440–3460, 3500–3530 and 3600–3625 cm^− 1, garnet has a single band at 3580–3630 cm^− 1 and rutile has a single sharp band at 3280 cm^− 1. The hydroxyl absorbance at these wavenumbers changes with the crystal orientation in polarized infrared radiation, indicating that the water is structurally incorporated in these minerals. The water contents in omphacite and garnet increase systematically with the metamorphic pressure of the host eclogites. The partitioning coefficient of the water content between coexisting garnet and omphacite is similar in different eclogites, D^Grt/Omp0.1–0.2, but decreases slightly at high pressure. Based on the mineral proportions of the eclogites, we estimate bulk-rock water content in the eclogites ranging from 3070 to 300 ppm H₂O (by weight). Although hydrous minerals are absent in the diamond-grade eclogite (60 kbar and 1000 °C), trace amounts of water are incorporated in the nominally anhydrous minerals such as omphacite and garnet. The presence of significant water in these minerals implies that the subducting oceanic crust can transport considerable amounts of water into the deep upper mantle beyond the stability of hydrous minerals. Such water may be stored in the deep upper mantle and have an important influence on dynamics in the Earth's interior.     

Dissolution/precipitation kinetics of boehmite and gibbsite: Application of a pH-relaxation technique to study near-equilibrium rates

The dissolution and precipitation rates of boehmite, AlOOH, at 100.3 °C and limited precipitation kinetics of gibbsite, Al(OH)₃, at 50.0 °C were measured in neutral to basic solutions at 0.1 molal ionic strength (NaCl + NaOH + NaAl(OH)₄) near-equilibrium using a pH-jump technique with a hydrogen-electrode concentration cell. This approach allowed relatively rapid reactions to be studied from under- and over-saturation by continuous in situ pH monitoring after addition of basic or acidic titrant, respectively, to a pre-equilibrated, well-stirred suspension of the solid powder. The magnitude of each perturbation was kept small to maintain near-equilibrium conditions. For the case of boehmite, multiple pH-jumps at different starting pHs from over- and under-saturated solutions gave the same observed, first order rate constant consistent with the simple or elementary reaction: .

This relaxation technique allowed us to apply a steady-state approximation to the change in aluminum concentration within the overall principle of detailed balancing and gave a resulting mean rate constant, (2.2 ± 0.3) × 10⁻⁵ kg m⁻² s⁻¹, corresponding to a 1σ uncertainty of 15%, in good agreement with those obtained from the traditional approach of considering the rate of reaction as a function of saturation index. Using the more traditional treatment, all dissolution and precipitation data for boehmite at 100.3 °C were found to follow closely the simple rate expression:

R_net,boehmite=10^-5.485{m_OH^-}{1-exp(ΔG_r/RT)}, with R_net in units of mol m⁻² s⁻¹. This is consistent with Transition State Theory for a reversible elementary reaction that is first order in OH⁻ concentration involving a single critical activated complex. The relationship applies over the experimental ΔG_r range of 0.4–5.5 kJ mol⁻¹ for precipitation and −0.1 to −1.9 kJ mol⁻¹ for dissolution, and the pH_m ≡ −log(mH⁺) range of 6–9.6. The gibbsite precipitation data at 50 °C could also be treated adequately with the same model:R_net,gibbsite=10^-5.86{m_OH^-}{1-exp(ΔG_r/RT)}, over a more limited experimental range of ΔG_r (0.7–3.7 kJ mol⁻¹) and pH_m (8.2–9.7).     

Comprehensive chemical analyses of natural cordierites: implications for exchange mechanisms

Cordierite samples from pegmatites and metamorphic rocks have been analysed for major [electron microprobe analysis (EMPA)] and trace elements [inductively coupled plasma mass spectrometry (ICP-MS), secondary ion mass spectrometry analyses (SIMS)] as well as for H₂O and CO₂ (coulometric titration), and the results evaluated in conjunction with published data in order to determine which exchange mechanisms are significant. Apart from the homovalent substitutions FeMg₋₁ and MnMg₋₁ on the octahedral site, some minor KNa₋₁ on the Ch0 channel site, and Fe³⁺Al₋₁ on the T₁1 tetrahedral site, the three most important substitution mechanisms are those for the incorporation of Li on the octahedral sites (NaLi□₋₁Mg₋₁), and of Be and other divalent cations on the tetrahedral T₁1 site (NaBe□₋₁Al₋₁ and Na(Mg,Fe²⁺)□₋₁Al₋₁). The dominant role of the last vector is clearly demonstrated. We propose a new generalized formula for cordierite: ^Ch(Na,K)_0–1 ^VI(Mg,Fe²⁺,Mn,Li)₂ ^IVSi₅ ^IVAl₃ ^IV(Al, Be, Mg, Fe²⁺, Fe³⁺)O₁₈ *x^Ch(H₂O, CO₂…). Our results show that the population of (Mg, Fe²⁺) on the T₁1-site is limited to about 0.08 a.p.f.u. Other exchange mechanisms that were encountered in experiments operate only under P–T conditions or in bulk compositions that are rarely realized in nature. Routine analyses by electron microprobe in which Li and Be are not determined can be plotted as (Mg+Fe+Mn) versus (Si+Al) to assess whether significant amounts of Li and Be could be present. These amounts can be calculated as Li (a.p.f.u.)=Al+Na–4 and Be (a.p.f.u.)=10–2Al–M²⁺–Na.     

The Fedorivka layered intrusion (Korosten Pluton, Ukraine): An example of highly differentiated ferrobasaltic evolution

This study documents the petrography and whole-rock major and trace element geochemistry of 38 samples mainly from a drill core through the entire Fedorivka layered intrusion (Korosten Pluton), as well as mineral compositions (microprobe analyses and separated mineral fraction analyses of plagioclase, ilmenite, magnetite and apatite) of 10 samples. The Fedorivka layered intrusion can be divided into 4 lithostratigraphic units: a Lower Zone (LZ, 72 m thick), a Main Zone (MZ, 160 m thick), and an Upper Border Zone, itself subdivided into 2 sub-zones (UBZ₂, 40 m thick; UBZ₁, 50 m thick). Igneous lamination defines the cumulate texture, but primary cumulus minerals have been affected by trapped liquid crystallization and subsolidus recrystallization. The dominant cumulus assemblage in MZ and UBZ₂ is andesine (An_39–42), iron-rich olivine (Fo_32–42), augite (En_29–35Fs_24–29Wo_42–44), ilmenite (Hem_1–6), Ti-magnetite (Usp_52–78), and apatite. The data reveal a continuous evolution from the floor of the intrusion (LZ) to the top of MZ, due to fractional crystallization, and an inverse evolution in UBZ, resulting from crystallization downwards from the roof. The whole-rock Fe/Mg ratio and incompatible element contents (e.g. Rb, Nb, Zr, REE) increase in the fractionating magma, whereas compatible elements (e.g. V, Cr) steadily decrease. The intercumulus melt remained trapped in the UBZ cumulates due to rapid cooling and lack of compaction, and cumulus mineral compositions re-equilibrated (e.g. olivine, Fe–Ti oxides). In LZ, the intercumulus melt was able to partially or totally escape. The major element composition of the MZ cumulates can be approximated by a mixing (linear) relationship between a plagioclase pole and a mafic pole, the latter being made up of all mafic minerals in (nearly) constant relative proportions. By analogy with the ferrobasaltic/jotunitic liquid line of descent, defined in Rogaland, S. Norway, and its conjugated cumulates occurring in the Transition Zone of the Bjerkreim-Sokndal intrusion (Rogaland, a monzonitic (57% SiO₂) melt is inferred to be in equilibrium with the MZ cumulates. The conjugated cumulate composition falls (within error) on the locus of cotectic compositions fixed by the 2-pole linear relationship. Ulvöspinel is the only Ti phase in some magnetites that have been protected from oxidation. QUIlF equilibria in these samples show that magnetite and olivine in MZ have retained their liquidus compositions during subsolidus cooling. This permits calculation of liquidus fO₂ conditions, which vary during fractionation from ΔFMQ = 0.7 to − 1.4 log units. Low fO₂ values are also evidenced by the late appearance of cumulus magnetite (Fo₄₂) and the high V³⁺-content of the melt, reflected in the high V-content of the first liquidus magnetite (up to 1.85% V).     

Petrology of the Hopen mangerite-charnockite intrusion, Lofoten, north Norway

The Hopen massif, intrusive age 1900 m.y., exposed area 15 km², in the Lofoten-Vesterålen granulite facies province has the mineral assemblages: (1) mesoperthite+plagioclase (An_7–20)+quartz+clinopyroxene (Di_20–25)+orthopyroxene En_15–25+opaques±minor amphibole±minor biotite; (2) mesoperthite+plagioclase (An <2)+quartz+clinopyroxene (Di <10)+olivine Fe lt;5)+opaques. By using mineral and whole rock analyses, the crystallization conditions were estimated to be 1000°C, 12 kb load pressure and an oxygen fugacity approximately corresponding to the WM buffer. Rocks with the assemblage of type (2) contain secondary orthoferrosilite (Fe_0.90–0.95Mn_0.04–0.07Mg_0.01Ca_0.01)₂Si₂O₆, generated by reactions involving fayalite, magnetite and quartz at 800°C, 10kb load pressure and at oxygen fugacities approaching QFM buffer conditions. Subsequent to a crustal thickening, the mangeritic rocks in Lofoten-Vesterålen were emplaced in a tensional environment comparable with modern continental rifts. A ‘gabbro pillow’ magma chamber at the crustal base is proposed as parental magma for the mangeritic rocks, of which the Hopen massif represents a late differentiation.     

Early Cretaceous gabbroic rocks from the Taihang Mountains: Implications for a paleosubduction-related lithospheric mantle beneath the central North China Craton

SHRIMP zircon U–Pb ages and geochemical and Sr–Nd–Pb isotopic data are presented for the gabbroic intrusive from the southern Taihang Mountains to characterize the nature of the Mesozoic lithospheric mantle beneath the central North China Craton (NCC). The gabbroic rocks emplaced at 125 Ma and are composed of plagioclase (40–50%), amphibole (20–30%), clinopyroxene (10–15%), olivine (5–10%) and biotite (5–7%). Olivines have high MgO (Fo = 78–85) and NiO content. Clinopyroxenes are high in MgO and CaO with the dominant ones having the formula of En_42–46Wo_41–50Fs_8–13. Plagioclases are dominantly andesine–labradorite (An = 46–78%) and have normal zonation from bytownite in the core to andesine in the rim. Amphiboles are mainly magnesio and actinolitic hornblende, distinct from those in the Precambrian high-pressure granulites of the NCC. These gabbroic rocks are characterized by high MgO (9.0–11.04%) and SiO₂ (52.66–55.52%), and low Al₂O₃, FeOt and TiO₂, and could be classified as high-mg basaltic andesites. They are enriched in LILEs and LREEs, depleted in HFSEs and HREEs, and exhibit (⁸⁷Sr/⁸⁶Sr)_i = 0.70492–0.70539, ε_Nd(t) = − 12.47–15.07, (²⁰⁶Pb/²⁰⁴Pb)_i = 16.63–17.10, Δ8/4 = 70.1–107.2 and Δ7/4 = − 2.1 to − 9.4, i.e., an EMI-like isotopic signatures. Such geochemical features indicate that these early Cretaceous gabbroic rocks were originated from a refractory pyroxenitic veined-plus-peridotite source previously modified by an SiO₂-rich melt that may have been derived from Paleoproterozoic subducted crustal materials. Late Mesozoic lithospheric extension might have induced the melting of the metasomatised lithospheric mantle in response to the upwelling of the asthenosphere to generate these gabbroic rocks in the southern Taihang Mountains.     

Petrogenesis of picritic mare magmas: Constraints on the extent of early lunar differentiation

Calculations of isobaric batch, polybaric batch, and polybaric fractional melting have been carried out on a variety of proposed lunar and terrestrial source region compositions. Results show that magmas with a generally tholeiitic character—plagioclase and high-Ca pyroxene crystallize before low-Ca pyroxene reflecting relatively high Al₂O₃ concentrations (>12 wt%)—are the inevitable consequence of anhydrous partial melting of source regions composed primarily of olivine and two pyroxenes with an aluminous phase on the solidus. Low-Al₂O₃ magmas (<10 wt%), as typified by the green picritic glasses in the lunar maria require deep (700–1000 km), low-Al₂O₃ source regions without an aluminous phase. The difference between primitive and depleted mantle beneath mid-ocean ridges amounts to less than 0.1 wt% Al₂O₃, whereas formation of the green glass source region requires a net loss of between 1.5 and 2.5 wt% Al₂O₃. Basalt extraction cannot account for fractionations of this magnitude. Accumulation of olivine and pyroxene at the base of a crystallizing magma ocean is, however, an effective method for producing the necessary Al₂O₃ depletions. Both olivine-rich and pyroxene-rich source regions can produce the picritic magmas, but mixing calculations show that both types of source region are likely to be hybrids consisting of an early- to intermediate-stage cumulate (olivine plus enstatite) and a later stage cumulate assemblage. Mass balance calculations show that refractory element-enriched bulk Moon compositions contain too much Al₂O₃ to allow for the deep low-Al₂O₃ source regions even after extraction of an Al₂O₃-rich (26–30 wt%) crust between 50 and 70 km thick.     

塔里木东北缘坡十Ni矿化侵入体中橄榄石和铬尖晶石对成岩成矿及源区特征的约束

坡十Ni矿化超镁铁侵入体的矿化岩相主要为第二侵入期次的（斜长）单辉橄榄岩、（斜长）二辉橄榄岩、 纯橄岩等岩相。坡十超镁铁岩的橄榄石成分变化范围较大, 橄榄石的Fo值在76.8～89.6之间, Ni含量为767×10^-6～4 580×10^-6。铬尖晶石的Mg^#值和Cr^#值变化范围分别为19.4～41.9和49.8～64.8, 原生铬尖晶石中Cr₂O₃和Al₂O₃表现为负相关, 蚀变改造的铬尖晶石则表现为正相关。橄榄石成分剖面显示坡十母岩浆处于一个动态的岩浆系统中, 成分稳定的新鲜岩浆的补给、 持续向上的动力及浅部橄榄石快速分离结晶,造成了不同深度橄榄石成分的不同变化。坡十侵入体母岩浆估算结果为MgO=14.49％, FeO=10.01％,模拟结果显示橄榄石中Ni含量的变化主要受橄榄石结晶分异和硫化物不混溶作用共同控制,其中橄榄石与硫化物熔体发生明显的Fe-Ni交换反应。坡十母岩浆中橄榄石分离结晶造成的硫饱和,是坡十硫化物熔离的重要因素。橄榄石高Fo值、母岩浆高MgO、超镁铁岩中斜长石发育、矿物高结晶温度和铬尖晶石成分的弧岩浆特征显示,塔里木东北缘坡十侵入体是俯冲交代的岩石圈地幔部分熔融形成的母岩浆的产物,表现出低压高温的演化特征,其中源区熔融机制可能与塔里木二叠纪地幔柱提供的热源或该区大规模拆沉作用造成的软流圈上涌有关。     

Antimony in hydrothermal processes: solubility, conditions of transfer, and metal-bearing capacity of solutions

Based on data on the composition of ore-bearing hydrothermal solutions and parameters of ore-forming processes at various antimony and antimony-bearing deposits, which were obtained in studies of fluid inclusions in ore minerals, we investigated the behavior of Sb(III) in the system Sb–Cl–H₂S–H₂O describing the formation of these deposits.

We also performed thermodynamic modeling of native-antimony and stibnite dissolution in sulfide (m_HS⁻ = 0.0001−0.1) and chloride (m_Cl⁻ = 0.1−5) solutions and the joint dissolution of Sb_(s)⁰ and Sb₂S_3(s) in sulfide-chloride solution (m_HS⁻ = 0.01; m_Cl⁻ = 1) depending on Eh, pH, and temperature. All thermodynamic calculations were carried out using the Chiller computer program. Under the above conditions, stibnite precipitates in acid, weakly acid to neutral, and medium redox solutions, whereas native antimony precipitates before stibnite under more reducing conditions in neutral to alkaline solutions.

The metal-bearing capacity of hydrothermal solutions (200–250 °C) of different compositions and origins has been predicted. We have established that the highest capacity is specific for acid (pH = 2–3) high-chloride solutions poor in sulfide sulfur and alkaline (pH = 7–8) low-chloride low-sulfide solutions.     

The origin of basic rocks of the Korosten AMCG complex, Ukrainian shield: Implication of Nd and Sr isotope data

The Korosten complex is a Paleoproterozoic gabbro–anorthosite–rapakivi granite intrusion which was emplaced over a protracted time interval — 1800–1737 Ma. The complex occupies an area of about 12 000 km² in the north-western region of the Ukrainian shield. About 18% of this area is occupied by various mafic rocks (gabbro, leucogabbro, anorthosite) that comprise five rock suites: early anorthositic A₁ (1800–1780 Ma), main anorthositic A₂ (1760 Ma), early gabbroic G₃ (between 1760 and 1758 Ma), late gabbroic G₄ (1758 Ma), and a suite of dykes D₅ (before 1737 Ma). In order to examine the relationships between the various intrusions and to assess possible magmatic sources, Nd and Sr isotopic composition in mafic whole-rock samples were measured. New Sr and Nd isotope measurements combined with literature data for the mafic rocks of the Korosten complex are consistent and enable construction of Rb–Sr and Sm–Nd isochronous regressions that yield the following ages: 1870 ± 310 Ma (Rb–Sr) and 1721 ± 90 Ma (Sm–Nd). These ages are in agreement with those obtained by the U–Pb method on zircons and indicate that both Rb–Sr and Sm–Nd systems have remained closed since the time of crystallisation. In detail, however, measurable differences in isotopic composition of the Korosten mafic rock depending on their suite affiliation were revealed. The oldest, A₁ rocks have lower Sr (⁸⁷Sr/⁸⁶Sr₍₁₇₆₀₎ = 0.70233–0.70288) and higher Nd (εNd₍₁₇₆₀₎ = 1.6–0.9) isotopic composition. The most widespread A₂ anorthosite and leucogabbro display higher Sr and lower Nd isotopic composition: ⁸⁷Sr/⁸⁶Sr₍₁₇₆₀₎ = 0.70362, εNd₍₁₇₆₀₎ varies from 0.2 to − 0.7. The G₃ gabbro–norite has slightly lower εNd₍₁₇₆₀₎ varying from − 0.7 to − 0.9. Finally, G₄ gabbroic rocks show relatively high initial ⁸⁷Sr/⁸⁶Sr (0.70334–0.70336) and the lowest Nd isotopic composition (εNd₍₁₇₆₀₎ varies from − 0.8 to − 1.4) of any of the mafic rocks of the Korosten complex studied to date. On the basis of Sr and Nd isotopic composition we conclude that Korosten initial melts may have inherited their Nd and Sr isotopic characteristics from the lower crust created during the 2.05–1.95 Ga Osnitsk orogeny and 2.0 Ga continental flood basalt event. Indeed, εNd₍₁₇₆₀₎ values in Osnitsk rocks vary from 0.0 to − 1.9 and from 0.2 to 3.4 in flood basalts. We suggest that these rocks being drawn into the upper mantle might melt and give rise to the Korosten initial melts. ⁸⁷Sr/⁸⁶Sr₍₁₇₆₀₎ values also support this interpretation. We suggest that the Sr and Nd isotopic data currently available on mafic rocks of the Korosten complex are consistent with an origin of its primary melts by partial melting of lower crustal material due to downthrusting of the lower crust into upper mantle forced by Paleoproterozoic amalgamation of Sarmatia and Fennoscandia.     

Experimental study of the joins forsterite–diopside–leucite– and forsterite–leucite–åkermanite up to 2.3 GPa [P(H2O) = P(Total)] and variable temperatures: Its petrological significance

We conducted a series of melting experiments in the join forsterite–diopside–leucite under 0.1 and 2.3 GPa and in the join forsterite–leucite–åkermanite under 2.3 GPa to understand paragenetic relationships amongst different types of lamproitic and lamprophyric magmas with K-rich mafic and ultramafic volcanic (kamafugitic) rocks. Both the joins were studied in the presence of excess water. The experimental results of the join forsterite–diopside–leucite at 0.1 GPa show that the five-phase point of forsterite (Fo)_ss + diopside (Di)_ss + leucite (Lc)_ss + liquid (Liq) + vapour (V) (equivalent to ugandite lava) occurs at Fo₂Di₅₀Lc₄₈ at 880 ± 5 °C. Phlogopite appears as the last phase at 830 ± 15 °C. The final crystalline assemblage of forsterite_ss + diopside_ss + leucite_ss + phlogopite is similar to the phenocryst assemblage of missourite lava. Present study suggests that an olivine leucitite (ugandite) can be derived from an olivine italite, a slightly potassic peridotite and a leucitite magma.

A study of the join Fo–Di–Lc [P(H₂O) = P(Total)] at 2.3 GPa shows that liquid compositions penetrate the primary phase volumes of forsterite_ss, phlogopite_ss, kalsilitess, K-feldspar_ss and diopside_ss. It has the following three five-phase points: 1) one occurring at Fo₉Di₄₉Lc₄₂ and 1005 ± 5 °C, where liquid and vapour coexists with forsterite_ss, phlogopite_ss and diopside_ss (phlogopite-bearing madupite), 2) the second one at Fo₄Di₅₀Lc₄₆ and 990 ± 10 °C, where diopside_ss, K-feldspar_ss and phlogopite_ss coexist with liquid and vapour (pyroxene-bearing minette), and 3) the third one at Fo₃Di₂₁Lc₇₆ and 775 ± 5 °C, where phlogopite_ss, kalsilite_ss and K-feldspar_ss are in equilibrium with liquid plus vapour (kalsilite-bearing minette).

The experimental results of the join Fo–Lc–åkermanite (Ak) show that the join 40 penetrates the primary phase volumes of forsterite_ss, phlogopite_ss, kalsilite, K-feldspar_ss, diopside_ss and merwinite_ss. The data indicate the presence of four five-phase points: 1) one occurring at Fo₇Lc₄₂Ak₅₁ and 1165 ± 5 °C, where phlogopite_ss, forsterite_ss, diopside_ss coexists with liquid and vapour (olivine-bearing madupite), 2) the second one at Fo₃Lc₄₉Ak₄₈ and 1140 ± 10 °C, where a liquid is in equilibrium with phlogopite_ss, K-feldspar_ss, diopside_ss and vapour (pyroxene-bearing minette), 3) the third one at Fo₁₈Lc₂₁Ak₆₁ and 1255 ± 10 °C, where merwinite_ss, forsterite_ss and diopside_ss are in equilibrium with liquid and vapour (merwinite-bearing wherlite), and 4) the fourth one at Fo₅Lc_73.5Ak_21.5 and 770 ± 5 °C, where kalsilite_ss, phlogopite_ss and K-feldspar coexist with liquid and vapour (kalsilite-bearing minette). The present data suggest that high pressure heteromorphic equivalent of a katungite magma is represented by a kalsilite-bearing minette, a pyroxene-bearing minette, or an olivine-bearing madupite.     

Peralkaline syenite autoliths from Kilombe volcano, Kenya Rift Valley: Evidence for subvolcanic interaction with carbonatitic fluids

Mineral chemistry, textures and geochemistry of syenite autoliths from Kilombe volcano indicate that they crystallized in the upper parts of a magma chamber from peralkaline trachytic magmas that compositionally straddle the alkali feldspar join in the “residuum system” (ne = 0–1.03; qz = 0–0.77). Mineral reaction and/or overgrowth processes were responsible for the replacement of (i) Mg–hedenbergite by aegirine–augite, Ca–aegirine and/or aegirine, (ii) fayalite by amphiboles, and (iii) magnetite by aenigmatite. Ti–magnetite in silica-saturated syenites generally shows ilmenite exsolution, partly promoted by circulating fluids.

By contrast, the Fe–Ti oxides in the silica-undersaturated (sodalite-bearing) syenites show no signs of deuteric alteration. These syenites were ejected shortly after completion of crystallization. Ilmenite–magnetite equilibria indicate fO₂ between − 19.5 and − 23.1 log units (T 679–578 °C), slightly below the FMQ buffer. The subsequent crystallization of aenigmatite and Na-rich pyroxenes suggests an increase in the oxidation state of the late-magmatic liquids and implies the influence of post-magmatic fluids.

Irrespective of silica saturation, the syenites can be divided into (1) “normal” syenites, characterized by Ce/Ce ratios between 0.83 and 0.99 and (2) Ce-anomalous syenites, showing distinct negative Ce-anomalies (Ce/Ce 0.77–0.24). “Normal” silica-saturated syenites evolved towards pantelleritic trachyte. The Ce-anomalous syenites are relatively depleted in Zr, Hf, Th, Nb and Ta but, with the exception of Ce, are significantly enriched in REE.

The silica-saturated syenites contain REE–fluorcarbonates (synchysite-bastnaesite series) with negative Ce-anomalies (Ce/Ce 0.4–0.8, mean 0.6), corroded monazite group minerals with LREE-rich patches, and hydrated, Fe- and P-rich phyllosilicates. Each of these is inferred to be of non-magmatic origin. Fractures in feldspars and pyroxenes contain Pb-, REE- and Mn-rich cryptocrystalline or amorphous material. The monazite minerals are characterized by the most prominent negative Ce-anomalies (Ce/Ce_mean = 0.5), and in the most altered and Ca-rich areas (depleted in REE), Ce/Ce is less than 0.2.

It is inferred that carbonatitic fluids rich in F, Na and lanthanides but depleted in Ce by fractional crystallization of cerian pyrochlore, percolated into the subvolcanic system and interacted with the syenites at the thermal boundary layers of the magma chamber, during and shortly after their crystallization.

Chevkinite–(Ce), pyrochlore, monazite and synchysite-bastnaesite, occurring as accessory minerals, have been found for the first time at Kilombe together with eudialyte, nacareniobsite–(Ce) and thorite. These latter represent new mineral occurrences in Kenya.     

Perspectives on basaltic magma crystallization and differentiation: Lava-lake blocks erupted at Mauna Loa volcano summit, Hawaii

Explosive eruptions at Mauna Loa summit ejected coarse-grained blocks (free of lava coatings) from Moku'aweoweo caldera. Most are gabbronorites and gabbros that have 0–26 vol.% olivine and 1–29 vol.% oikocrystic orthopyroxene. Some blocks are ferrogabbros and diorites with micrographic matrices, and diorite veins (≤ 2 cm) cross-cut some gabbronorites and gabbros. One block is an open-textured dunite.

The MgO of the gabbronorites and gabbros ranges  7–21 wt.%. Those with MgO > 10 wt.% have some incompatible-element abundances (Zr, Y, REE; positive Eu anomalies) lower than those in Mauna Loa lavas of comparable MgO; gabbros (MgO < 10 wt.%) generally overlap lava compositions. Olivines range Fo_83–58, clinopyroxenes have Mg#s  83–62, and orthopyroxene Mg#s are 84–63 — all evolved beyond the mineral-Mg#s of Mauna Loa lavas. Plagioclase is An_75–50. Ferrogabbro and diorite blocks have  3–5 wt.% MgO (TiO₂ 3.2–5.4%; K₂O 0.8–1.3%; La 16–27 ppm), and a diorite vein is the most evolved (SiO₂ 59%, K₂O 1.5%, La 38 ppm). They have clinopyroxene Mg#s 67–46, and plagioclase An_57–40. The open-textured dunite has olivine  Fo_83.5. Seven isotope ratios are ⁸⁷Sr/⁸⁶Sr 0.70394–0.70374 and ¹⁴³Nd/¹⁴⁴Nd 0.51293–0.51286, and identify the suite as belonging to the Mauna Loa system.

Gabbronorites and gabbros originated in solidification zones of Moku'aweoweo lava lakes where they acquired orthocumulate textures and incompatible-element depletions. These features suggest deeper and slower cooling lakes than the lava lake paradigm, Kilauea Iki, which is basalt and picrite. Clinopyroxene geobarometry suggests crystallization at < 1 kbar P. Highly evolved mineral Mg#s, < 75, are largely explained by cumulus phases exposed to evolving intercumulus liquids causing compositional ‘shifts.’ Ferrogabbro and diorite represent segregation veins from differentiated intercumulus liquids filter pressed into rigid zones of cooling lakes. Clinopyroxene geobarometry suggests < 300 bar P. Open-textured dunite represents olivine-melt mush, precursor to vertical olivine-rich bodies (as in Kilauea Iki). Its Fo_83.5 identifies the most primitive lake magma as  8.3 wt.% MgO. Mass balancing and MELTS show that such a magma could have yielded both ferrogabbro and diorite by ≥ 50% fractional crystallization, but under different fO₂: < FMQ (250 bar) led to diorite, and FMQ (250 bar) yielded ferrogabbro. These segregation veins, documented as similar to those of Kilauea, testify to appreciable volumes of ‘rhyolitic’ liquid forming in oceanic environments. Namely, SiO₂-rich veins are intrinsic to all shields that reached caldera stage to accommodate various-sized cooling, differentiating lava lakes.     

Evidence of diverse depletion and metasomatic events in harzburgite–lherzolite mantle xenoliths from the Iberian plate (Olot, NE Spain): Implications for lithosphere accretionary processes

Mantle xenoliths from the Olot volcanic district (NE Spain) comprise a bi-modal suite consisting of protogranular spinel lherzolites (cpx 12–14%) sometimes with pargasitic amphibole, and highly refractory spinel harzburgites (cpx ≤ 1%) with coarse-grained granular textures. The lherzolites range from slightly depleted to moderately LREE-enriched with flat HREE patterns between 1.5 and 2.7 × chondrite (Ch). In contrast, the harzburgites are extremely depleted in HREE (down to 0.2 × Ch) and strongly LREE-enriched (La_N/Yb_N = 12.3–17.2). LA-ICP-MS analyses of clinopyroxene and amphibole of the lherzolites highlight variable degrees of LREE depletion (HREE up to 13 × Ch, La_N/Yb_N down to 0.01), with the exception of a single sample in which both clinopyroxene and amphibole are LREE-enriched (La_N/Yb_N up to 19). In the harzburgites, clinopyroxenes display totally different REE distributions, characterized by extreme HREE depletion (down to 0.4 × Ch) and upward convex positively fractionated middle-light REE patterns (Nd_N/Yb_N up to 20.7 × Ch; La_N/Yb_N up to 12 × Ch). Sr–Nd–Hf isotopic data for both whole-rocks and cpx separates, coherently indicate depleted mantle (DM) compositions for the lherzolites (εSr = − 15 to − 26, εNd = + 9 to + 17, εHf = + 18 to + 68) and enriched mantle (EM) compositions for the harzburgites (εSr = − 10 to + 36, εNd = − 1 to − 6, εHf = + 3 to + 8). Modelling of the clinopyroxene REE data and isotopic systematics suggest that some lherzolites were affected by pre-Paleozoic (0.6–1 By) low-degree partial melting processes, while others probably reflect some extent of refertilization of the mantle protolith by metasomatizing melts similar to the Triassic rift-related tholeiites reported from several Pyrenean localities. The harzburgites represent extreme refractory residua, resulting from a complex depletion history due to multistage melt extraction as often observed in the cratonic mantle. The distinctive REE patterns and isotopic systematics of their clinopyroxenes suggest that the harzburgites were formed by the interaction of an ultra-depleted peridotite matrix with highly alkaline basic melts similar in composition to the Permo-Triassic alkaline lamprophyres which are widespread within the Iberian plate. Lherzolites possibly represent younger lithosphere (accreted asthenosphere?) up-lifted and juxtaposed to the older subcontinental lithospheric mantle (harzburgites) during the post-Variscan rifting of the Iberian margin. These two genetically different, but adjoining, mantle domains intimately mingled along the northern Iberian margin during the subsequent plate convergence processes, leading to the close association of harzburgites and lherzolites observed in the Olot mantle xenoliths and in some Pyrenean peridotite massifs.     

Petrogenesis of Cretaceous adakitic and shoshonitic igneous rocks in the Luzong area, Anhui Province (eastern China): Implications for geodynamics and Cu–Au mineralization

Both adakitic and shoshonitic igneous rocks in the Luzong area, Anhui Province, eastern China are associated with Cretaceous Cu–Au mineralization. The Shaxi quartz diorite porphyrites exhibit adakite-like geochemical features, such as light rare earth element (LREE) enrichment, heavy REE (HREE) depletion, high Al₂O₃, MgO, Sr, Sr / Y and La / Yb values, and low Y and Yb contents. They have low ε_Nd(t) values (− 3.46 to − 6.28) and high (⁸⁷Sr / ⁸⁶Sr)_i ratios (0.7051–0.7057). Sensitive High-Resolution Ion Microprobe (SHRIMP) zircon analyses indicate a crystallization age of 136 ± 3 Ma for the adakitic rocks. Most volcanic rocks and the majority of monzonites and syenites in the Luzong area are K-rich (or shoshonitic) and were also produced during the Cretaceous (140–125 Ma). They are enriched in LREE and large-ion lithophile elements, and depleted in Ti, and Nb and Ba and exhibit relatively lower ε_Nd(t) values ranging from − 4.65 to − 7.03 and relatively higher (⁸⁷Sr / ⁸⁶Sr)_i ratios varying between 0.7057 and 0.7062. The shoshonitic and adakitic rocks in the Luzong area have similar Pb isotopic compositions (²⁰⁶Pb / ²⁰⁴Pb = 17.90–18.83, ²⁰⁷Pb / ²⁰⁴Pb = 15.45–15.62 and ²⁰⁸Pb / ²⁰⁴Pb = 38.07–38.80). Geological data from the Luzong area suggest that the Cretaceous igneous rocks are distributed along NE fault zones (e.g., Tanlu and Yangtze River fault zones) in eastern China and were likely formed in an extensional setting within the Yangtze Block. The Shaxi adakitic rocks were probably derived by the partial melting of delaminated lower crust at pressures equivalent to crustal thickness of > 50 km (i.e., 1.5 GPa), possibly leaving rutile-bearing eclogitic residue. The shoshonitic magmas, in contrast, originated mainly from an enriched mantle metasomatized by subducted oceanic sediments. They underwent early high-pressure (> 1.5 GPa) fractional crystallization at the boundary between thickened (> 50 km) lower crust and lithospheric mantle and late low-pressure (< 1.5 GPa) fractional crystallization in the shallow (< 50 km) crust. The adakitic and shoshonitic rocks appear to be linked to an intra-continental extensional setting where partial melting of enriched mantle and delaminated lower crust was probably controlled by lithospheric thinning and upwelling of hot asthenosphere along NE fault zones (e.g., Tanlu and Yangtze River fault zones) in eastern China. Both the shoshonitic and adakitic magmas were fertile with respect to Cu–Au mineralization.     

Compositional diversity among Late Devonian peraluminous granitoid intrusions in the Meguma Zone of Nova Scotia, Canada

Late Devonian (385−370 Ma) granitoid intrusions in the Meguma Zone of southwestern Nova Scotia represent two geographically separate magmatic suites that show subtly different lithological, geochemical and isotopic characteristics. “Central intrusions” crop out with satellite mafic-intermediate intrusions, range in composition from granodiorite to leucogranite, contain two micas, have exclusively peraluminous compositions (molar A/CNK 1.1-1.3), variably high values for FeO_T (0.4–6.0 wt.%), Ba (5–980 ppm), Y (6–50 ppm), Pb (2–50 ppm), Ga (11–53 ppm), ⁸⁷Sr/⁸⁶Sr_i (0.7081-0.7130), δ¹⁸O (9.8–13.0) and δ³⁴S (4.5–11.9), in conjunction with low values for εNd (−1 to −6.5). In contrast, “peripheral plutons” crop out with synplutonic mafic-intermediate intrusions, range in composition from tonalite to leucogranite, may contain minor hornblende, have dominantly peraluminous compositions (molar A/CNK 0.9-1.3), variably high concentrations of TiO₂ (0.1-1.1 wt.%), Al₂O₃ (12.0–19.7 wt.%), CaO (0.2–4.9 wt.%), Sr (7–720 ppm), Cr (3–111 ppm) and V (1–136 ppm), higher εNd values (−2.0 to 3.2), and lower values for ⁸⁷Sr/⁸⁶Sr_i (0.7040-0.7079), δ¹⁸⁸O (7.6–10.5) and δ³⁴S (0–4.6). Such regional diversity is explained by inferring that upper crustal contamination dominated the central granitoid compositions and mixing with mantle-derived mafic-intermediate magmas dominated peripheral granitoid compositions. However, additional contributions from heterogeneous lower crust cannot be excluded.     

Nd isotopic data reveal the material and tectonic nature of the Main Central Thrust zone in Nepal Himalaya

The Main Central Thrust (MCT) is a tectono-metamorphic boundary between the Higher Himalayan crystallines (HHC) and Lesser Himalayan metasediments (LHS), reactivated in the Tertiary, but which had already formed as a collisional boundary in the Early Paleozoic. To investigate the nature of the MCT, we analyzed whole-rock Nd isotopic ratios of rocks from the MCT and surrounding zones in the Taplejung–Ilam area of far-eastern Nepal, Annapurna–Galyang area of central Nepal, and Maikot–Barekot area of western Nepal. We define the MCT zone as a ductile–brittle shear zone between the upper MCT (UMCT) and lower MCT (LMCT). The protoliths of the MCT zone may provide critical constraints on the tectonic evolution of the Himalaya. The LHS is lithostratigraphically divided into the upper and lower units. In the Taplejung–Ilam area, different lithologic units and their ε_Nd (0) values are as follows; HHC (− 10.0 to − 18.1), MCT zone (− 18.5 to − 26.2), upper LHS unit (− 17.2), and lower LHS unit (− 22.0 to − 26.9). There is a distinct gap in the ε_Nd (0) values across the UMCT except for the southern frontal edge of the Ilam nappe. In the Annapurna–Galyang and Maikot–Barekot areas, different lithologic units and their ε_Nd (0) values are as follows; HHC (− 13.9 to − 17.7), MCT zone (− 23.8 to − 26.2 except for an outlier of − 12.4), upper LHS unit (− 15.6 to − 26.8), and lower LHS unit (− 24.9 to − 26.8). These isotopic data clearly distinguish the lower LHS unit from the HHC. Combining these data with the previously published data, the lowest ε_Nd (0) value in the HHC is − 19.9. We regard rocks with ε_Nd (0) values below − 20.0 as the LHS. In contrast, rocks with those above − 19.9 are not always the HHC, and some parts of them may belong to the LHS due to the overlapping Nd isotopic ratio between the HHC and LHS. Most rocks of the MCT zone have Nd isotopic ratios similar to those of the LHS, but very different from those of the HHC. The spatial patterns in the distribution of ε_Nd (0) value around the UMCT suggest no substantial structural mixing of the HHC and LHS during the UMCT activities in the Tertiary. A discontinuity in the spatial distribution of ε_Nd (0) values is laterally continuous along the UMCT throughout the Himalayas. These facts support the theory that the UMCT was originally a material boundary between the HHC and LHS, suggesting the MCT zone was mainly developed with undertaking a role of sliding planes during overthrusting of the HHC in the Tertiary.     

Implications of super dense carbonic and hypersaline fluid inclusions in granites from the Ranchi area, Chottanagpur Gneissic Complex, Eastern India

A combined fluid inclusion and mineral thermobarometric study in groups of synchronous inclusions in quartz within weakly foliated granites from the Chottanagpur Gneissic Complex, India, reveals super dense carbonic (CO₂ with minor CH₄ and H₂O) inclusions and hypersaline (H₂O–NaCl ± NaHCO₃) inclusions, with halite- and nahcolite daughter phases. This study documents the highest density (1.115 g cm^− 3) CO₂ fluids ever reported in granites. Fluid isochores, constructed from CO₂ (± CH₄) and halite-bearing inclusions, coupled with two-feldspar thermometry constrain the minimum P–T at 8 kbar/ 750 °C for fluid entrapment in granites. By contrast, the carbonic inclusions in quartz from granite-hosted metapelite enclaves contain substantial CH₄ (up to 30 mol%), and the entrapment pressure ( 4.3 kbar/600 °C) is considerably lower compared to those in the granites. By implication, the sillimanite-free granites were not derived from the metapelitic enclaves, and instead were formed by partial melting of fluid-heterogeneous lower crustal protoliths, with fluid entrapment at magmatic conditions.