Carbonate assimilation in magmas: A reappraisal based on experimental petrology

The main effect of magma–carbonate interaction on magma differentiation is the formation of a silica-undersaturated, alkali-rich residual melt. Such a desilication process was explained as the progressive dissolution of CaCO₃ in melt by consumption of SiO₂ and MgO to form diopside sensu stricto. Magma chambers emplaced in carbonate substrata, however, are generally associated with magmatic skarns containing clinopyroxene with a high Ca-Tschermak activity in their paragenesis. Data are presented from magma–carbonate interaction experiments, demonstrating that carbonate assimilation is a complex process involving more components than so far assumed. Experimental results show that, during carbonate assimilation, a diopside–hedenbergite–Ca-Tschermak clinopyroxene solid solution is formed and that Ca-Tschermak/diopside and hedenbergite/diopside ratios increase as a function of the progressive carbonate assimilation. Accordingly, carbonate assimilation reaction should be written as follows, taking into account all the involved magmatic components:CaCO₃^solid + SiO₂^melt + MgO^melt + FeO^melt + Al₂O₃^melt → (Di–Hd–CaTs)_ss^solid + CO₂^fluidThe texture of experimental products demonstrates that carbonate assimilation produces three-phases (solid, melt, and fluid) whose main products are: i) diopside–hedenbergite–Ca-Tschermak clinopyroxene solid solution; ii) silica-undersaturated CaO-rich melt; and iii) C–O–H fluid phase. The silica undersaturation of the melt and, more importantly, the occurrence of a CO₂-rich fluid phase, must be taken into account as they significantly affect partition coefficients and the redox state of carbonated systems, respectively.     

Coupled lithium- and iron isotope fractionation during magmatic differentiation

In this study, we investigated Fe and Li isotope fractionation between mineral separates of olivine pheno- and xenocrysts (including one clinopyroxyene phenocryst) and their basaltic hosts. Samples were collected from the Canary Islands (Teneriffa, La Palma) and some German volcanic regions (Vogelsberg, Westerwald and Hegau). All investigated bulk samples fall in a tight range of Li and Fe isotope compositions (δ⁵⁶Fe_wr = 0.06–0.17‰ and δ⁷Li_ma = 2.5–5.2‰, assuming δ⁷Li of the olivine-free matrix is virtually identical to that of the bulk sample for mass balance reasons). In contrast, olivine phenocrysts display highly variable, but generally light Fe and mostly light Li isotope compositions compared to their respective olivine-free basaltic matrix, which was considered to represent the melt (with δ⁵⁶Fe_ol = ? 0.24 to 0.14‰ and δ⁷Li_ol = ? 10.5 to + 6.5‰, respectively). Single olivine crystals from one sample display even a larger range of δ⁵⁶Fe_ol between ? 0.7 and + 0.1‰. One single clinopyroxene phenocryst displays the lightest Li isotope composition (δ⁷Li_cpx = ? 17.7‰), but no Fe isotope fractionation relative to melt. The olivine phenocrysts show variable Mg# and Ni (correlated in most cases) that range between 0.89 and 0.74 and between 300 and 3000 μg/g, respectively. These olivines likely grew by fractional crystallization in an evolving magma. One sample from the Vogelsberg volcano contained olivine xenocrysts (Mg# > 0.89 and Ni > 3000 μg/g), in addition to olivine phenocrysts. This sample displays the highest Li- and the second highest Fe-isotope fractionation between olivine and melt (Δ⁷Li_ol-melt = ? 13; Δ⁵⁶Fe_ol-melt = ? 0.29).Our data, i.e. the variable olivine- at constant whole rock and matrix isotope compositions, strongly indicate disequilibrium, i.e. kinetic Fe and Li isotope fractionation between olivine and melt (for Li also between cpx and melt) during fractional crystallization. Δ⁷Li_ol-melt is correlated with the Li partitioning between olivine and melt (i.e. with Li_ol/Li_melt), indicating Li isotope fractionation due to preferential (faster) diffusion of ⁶Li into olivine during fractional crystallization. Olivine with low Δ⁷Li_ol-melt, also have low Δ⁵⁶Fe_ol-melt, indicating that Fe isotope fractionation is also driven by diffusion of isotopically light Fe into olivine, potentially, as Fe–Mg inter-diffusion. The lowest Δ⁵⁶Fe_ol-melt (? 0.40) was observed in a sample from Westerwald (Germany) with abundant magnetite, indicating relatively oxidizing conditions during magma differentiation. This may have enhanced equilibrium Fe isotope fractionation between olivine and melt or fine dispersed magnetite in the basalt matrix may have shifted its Fe isotope composition towards higher δ⁵⁶Fe. The decoupling of Li- and Fe isotope fractionation in cpx is likely due to faster diffusion of Li relative to Fe in cpx, implying that the large investigated cpx phenocryst resided in the magma for only a short period of time which was sufficient for Li- but not for Fe diffusion. The absence of any equilibrium Fe isotope fractionation between the investigated cpx phenocryst and its basaltic host may be related to the similar Fe^3 +/Fe^2 + of cpx and melt. In contrast to cpx, the generally light Fe isotope composition of all investigated olivine separates implies the existence of equilibrium- (in addition to diffusion-driven) isotope fractionation between olivine and melt, on the order of 0.1‰.     

Peridotite-chromitite complexes in the Eastern Desert of Egypt: Insight into Neoproterozoic sub-arc mantle processes

The Neoproterozoic peridotite-chromitite complexes in the Central Eastern Desert of Egypt, being a part of the Arabian-Nubian Shield, are outcropped along the E–W trend from Wadi Sayfayn, Wadi Bardah, and Jabal Al-Faliq to Wadi Al-Barramiyah, from east to west. Their peridotites are completely serpentinized, and the abundance of bastite after orthopyroxene suggests harzburgite protoliths with subordinate dunites, confirmed by low contents of Al₂O₃, CaO and clinopyroxene (< 3 vol%) in bulk peridotites. The primary olivine is Fo89.3–Fo92.6, and the residual clinopyroxene (Cpx) in serpentinites contains, on average, 1.1 wt% Al₂O₃, 0.7 wt% Cr₂O₃, and 0.2 wt% Na₂O, similar in chemistry to that in Izu-Bonin-Marian forearc peridotites. The wide range of spinel Cr-number [Cr/(Cr + Al)], 0.41–0.80, with low TiO₂ (0.03 wt%), MnO (0. 3 wt%) and Y_Fe [(Fe^3 +/(Cr + Al + Fe^3 +) = 0.03 on average)] for the investigated harzburgites-dunites is similar to spinel compositions for arc-related peridotites. The partial melting degrees of Bardah and Sayfayn harzburgites range mainly from 20 to 25% and 25 to 30% melting, respectively; this is confirmed by whole-rock chemistry and Cpx HREE modelling (~ 20% melting). The Barramiyah peridotite protoliths are refractory residues after a wide range of partial melting, 25–40%, where more hydrous fluids are available from the subducting slab. The Neoproterozoic mantle heterogeneity is possibly ascribed mainly to the wide variations of partial melting degrees in small-scale areas, slab-derived inputs and primordial mantle compositions. The Sayfayn chromitites were possibly crystallized from island-arc basaltic melts, followed by crystallization of Barramiyah chromitites from boninitic melt in the late stage of subduction. The residual Cpx with a spoon-shape REE pattern is rich in both LREE and fluid-mobile elements (e.g., Pb, B, Li, Ba, Sr), but poor in HFSE (e.g., Ta, Nb, Zr, Th), similar to Cpx in supra-subduction zone (SSZ) settings, where slab-fluid metasomatism is a prevalent agent. The studied chromitites and their host peridotites represent a fragment of sub-arc mantle, and originated in an arc-related setting. The systematic increase in the volume of chromitite pods with the increasing of their host-peridotite thickness from Northern to Southern Eastern Desert suggests that the thickness of wall rocks is one factor controlling the chromitite size. The factors controlling the size of Neoproterozoic chromitite pods are the thickness, beside the composition, of the host refractory peridotites, compositions and volumes of the supplied magmas, the amount of slab-derived fluids, and possibly the partial melting degree of the host peridotites.     

Conditions for the origin of oxidized carbonate-silicate melts: Implications for mantle metasomatism and diamond formation

An experimental study on the origin of ferric and ferrous carbonate-silicate melts, which can be considered as the potential metasomatic oxidizing agents and diamond forming media, was performed in the (Ca,Mg)CO₃-SiO₂-Al₂O₃-(Mg,Fe)(Cr,Fe,Ti)O₃ system, at 6.3 GPa and 1350–1650 °C. At 1350–1450 °C and ?O₂ of FMQ + 2 log units, carbonate–silicate melt, coexisting with Fe^3 +-bearing ilmenite, pyrope-almandine and rutile, contained up to 13 wt.% of Fe₂O₃. An increase in the degree of partial melting was accompanied by decarbonation and melt enrichment with CO₂, up to 21 wt.%. At 1550–1650 °C excess CO₂ segregated as a separate fluid phase. The restricted solubility of CO₂ in the melt indicated that investigated system did not achieve the second critical point at 6.3 GPa. At 1350–1450 °C and ?O₂ close to CCO buffer, Fe^2 +-bearing carbonate–silicate melt was formed in association with pyrope-almandine and Fe^3 +-bearing rutile. It was experimentally shown that CO₂-rich ferrous carbonate-silicate melt can be an effective waterless medium for the diamond crystallization. It provides relatively high diamond growth rates (3–5 μm/h) at P,T-conditions, corresponding to the formation of most natural diamonds.     

Melt impregnation phases in the mantle section of the Ślęża ophiolite (SW Poland)

The ultramafic member of the Variscan Ślęża Ophiolite (SW Poland) consists of heavily serpentinised, refractory harzburgites. Those located down to 1.5 km below paleo-Moho contain scarce grains or aggregates of olivine, clinopyroxene and spinel. Non-serpentine phases occur in various assemblages: M1—olivine (Fo 90.2–91.0%, NiO 0.38–0.47 wt.%) and rounded or amaeboidal aluminous chromite, rimmed by Al poor chromite and magnetite; M2—olivine (Fo 90.5–91.5, NiO 0.32–0.44 wt.%), olivine with magnetite inclusions (Fo 87.1–92.5, NiO 0.01–0.68 wt.%), rounded, cleavaged clinopyroxene I (Mg# 91.1–93.2, Al₂O₃ 3.00–4.00 wt.%, Cr₂O₃ 1.00–1.40 wt.%) and elongated clinopyroxene II and clinopyroxene from symplectites with magnetite (Mg# = 92.2–94.1, Al₂O₃ 2.20–3.20 wt.% and Cr₂O₃ 0.80–1.20 wt.%). Clinopyroxene is depleted in REEs relative to chondrite. The M3 assemblage consists of intergrown olivine (Fo 90.8–92.7, NiO 0.20–0.38 wt.%) and clinopyroxene (Mg# = 96.0–98.1, Al₂O₃ 0.00–1.00 wt.% and Cr₂O₃ 0.20–0.60 wt.%).The M1 assemblage contains chromite which records greenschist-facies metamorphism. Textural relationships and chemical composition of clinopyroxene occurring in the M2 assemblage are similar to those formed in oceanic spreading centres by LREE depleted basaltic melt percolation. Olivine occurring in M1 assemblage and part of that from M2 have composition typical of residual olivine from the abyssal harzburgites and of olivine formed in those rocks by melt percolation. The olivine with magnetite inclusions (M2 assemblage) and that from M3 record later deserpentinization event, which supposedly produced also M3 clinopyroxene. The non-serpentine phases from the Ślęża ophiolite mantle member, albeit very poorly preserved, document depleted basaltic melt percolation in the Variscan oceanic spreading centre.     

Mineral chemistry and H–O–S–Pb isotopic compositions of skarn type copper deposits in the Jiurui district of the Middle-Lower Yangtze River metallogenic belt,Eastern China

The skarn type copper deposits are widespread in the Jiurui district in the Middle-Lower Yangtze River metallogenic belt. This paper reports a detailed study on mineral chemistry, and H, O, S and Pb isotopic compositions on skarn silicate and sulfide minerals in the three major skarn dominant deposits (Wushan, Dongleiwan and Dengjiashan). The Wushan skarn deposit is characterized with prograde garnet-dominated and clinopyroxene limited skarns with average andradite content of 83% and hedenbergite content of 10%, whereas the Dongleiwan and Dengjiashan deposits are featured with retrograde skarn alteration with abundant hydrous minerals such as epidote and chlorite. The garnet and clinopyroxene compositions show 59% andradite and 15% hedenbergite for the Dongleiwan skarns, and 43% and 22% for the Dengjiashan skarns respectively. The pistacite components (Ps value) defined as Fe^3 +/(Fe^3 ++ Al) and Fe^3 +/Fe^2 + value of epidote are 0.12 and 1.63 for the Wushan skarns, 0.30 and 32.73 for the Dongleiwan skarns, and 0.17 and 42.85 for the Dengjiashan skarns. It is suggested that the prograde skarn mineralization in the three deposits was all formed in a relatively oxidizing environment, with the Wushan showing the highest oxidation potential and the Dengjiashan having the least oxidation potential. However, in the retrograde skarns, the Dongleiwan and Dengjiashan deposits show higher oxidation potential than that of Wushan. The three deposits show similar sulfur isotopic compositions of − 2.9 to + 1.4‰ and similar lead isotopic compositions with ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios of 17.900 to 18.205, 15.538 to 15.649 and 38.170 to 39.025, respectively. All the three deposits should have similar magmatic origin for the ore-forming materials based on their S and Pb isotopes. The oxygen isotopic compositions of the prograde and retrograde fluids in the three deposits show some differences, with δ¹⁸O_Fluid values of + 8.13‰ and + 7.81‰ for the Wushan, + 6.47‰ and + 2.33‰ for the Dongleiwan, and + 8.27‰ and + 4.43‰ for the Dengjiashan. But the hydrogen isotopic compositions are similar for the prograde (− 65 to − 31‰) and retrograde (− 64 to − 33‰) fluids. Therefore, the fluid origins and evolution may be different in each deposit. The hydrothermal fluids for the prograde skarns in all three deposits were likely derived from magmatic–hydrothermal sources, but the Dongleiwan and Dengjiashan show a higher proportion of meteoric water input in the retrograde stage. Considering the similar average prograde temperatures (574 to 560 °C) as calculated from coexisting garnet–clinopyroxene pairs, and similar retrograde temperatures (281 to 246 °C) as calculated from chlorite chemistry for the three deposits, we suggest that the trigger for deposition of sulfide ores in the Wushan garnet-dominated skarn deposit was mainly caused by system cooling with temperature drop along with magmatic intrusion and crystallization process. The Dongleiwan and Dengjiashan skarn deposits constitute a well developed retrograde skarn system with abundant epidote, chlorite, quartz and calcite, which probably caused by fluid mixing of high-temperature saline magmatic–hydrothermal fluids with cooler, oxidizing and dilute meteoric water.     

Fe isotope systematics of coexisting amphibole and pyroxene in the alkaline igneous rock suite of the Ilímaussaq Complex,South Greenland

The Ilímaussaq intrusion, South Greenland, provides an exceptional test case for investigating the changes of stable Fe isotope fractionation of solidus phases with changes in the Fe³⁺/∑Fe ratio of an evolving melt. The intrusion comprises a sequence of four melt batches that were fed from the same parental alkali basaltic magma. Differentiation produced cumulate rocks that range from augite syenite (phase I) over peralkaline granite (phase II) to agpaitic syenites (phases IIIa and IIIb). Fe³⁺/∑Fe ratios in amphiboles increase substantially from phase I to phase II and III rocks and mark a major change in the parental magma composition from augite syenites to peralkaline granites and agpaitic syenites. Before this transition, olivine, clinopyroxene, and amphibole in augite syenite, the most primitive rock type in the Ilímaussaq Complex, have a uniform Fe isotope composition that is identical to that of the bulk of igneous crustal rocks and approximated by the average isotopic composition of basalts (δ^56/54Fe_IRMM-014 = 0.072 ± 0.046‰). After the transition, amphiboles in the peralkaline granites and agpaitic syenites yield significantly heavier Fe isotope compositions with δ^56/54Fe_IRMM-014 values ranging from 0.123 to 0.237‰. Contamination of the Ilímaussaq magma by ongoing crustal assimilation as cause for this increase can be excluded on the grounds of Nd isotope data. Large-scale metasomatic overprint with an external fluid can also be dismissed based on amphibole O and Li isotope systematics. Rather, the increase towards heavy Fe isotope compositions most likely reflects the change in chemical compositions of amphiboles (calcic in augite syenite to sodic in the agpaitic syenites) and their Fe³⁺/ΣFe ratios that mirror changes in the chemical composition of the melt and its oxygen fugacity. A sensitive adjustment of equilibrium Fe isotope fractionation factors to amphibole ferric/ferrous ratios is also supported by beta-factors calculated from Mössbauer spetroscopy data. Comparison of the measured isotope fractionation between clinopyroxene and amphibole with that predicted from Mössbauer data reveal Fe isotope systematics close to equilibrium in augite syenites but Fe isotopic disequilibrium between these two phases in phase IIIa agpaitic syenites. These results are in agreement with O and Li isotope systematics. While amphiboles in all Ilímaussaq lithologies crystallized at temperatures between 650 and 850 °C, textural evidence reveals later clinopyroxene crystallization at temperatures as low as 300–400 °C. Therefore, isotopic equilibrium at crystallization conditions between these two phases can not be expected, but importantly, subsolidus reequilibration can also be dismissed.     

Origins of non-equilibrium lithium isotopic fractionation in xenolithic peridotite minerals: Examples from Tanzania

Olivine, clinopyroxene and orthopyroxene in variably metasomatised peridotite xenoliths from three lithospheric mantle sections beneath the East African Rift in Tanzania (Lashaine, Olmani, Labait) show systematic differences in their average Li concentrations (2.4 ppm, 2.0 ppm and 1.5 ppm, respectively) and intermineral isotopic fractionations, with olivine being heaviest (δ⁷Li = + 2.3 to + 13.9‰, average + 5.0‰), followed by orthopyroxene (? 4.1 to + 6.5‰, average + 0.8‰) and clinopyroxene (? 6.7 to + 4.1‰, average ? 1.6‰). These features are ascribed to the effects of kinetic Li isotope fractionation combined with different Li diffusivities in mantle minerals.Two main mechanisms likely generate diffusion-driven kinetic Li isotope fractionation in mantle xenoliths (1) Li diffusion from grain boundary melt into minerals during recent metasomatism or entrainment in the host magma and (2) subsolidus intermineral Li-redistribution. The latter can produce both isotopically light (Li-addition) and heavy (Li-loss) minerals and may occur in response to changes in pressure and/or temperature.Modelling shows that non-mantle-like δ⁷Li in clinopyroxene (< + 2‰), combined with apparent equilibrium olivine-clinopyroxene elemental partitioning in most peridotite xenoliths from all three Tanzanian localities probably reflects incipient Li addition during interaction with the host magma. Low δ⁷Li (< ? 3‰), combined with high Li concentrations (> 3 ppm) in some clinopyroxene may require very recent (minutes) Li ingress from a Li-rich melt (100s of ppm) having mantle-like δ⁷Li. This might happen during late fragmentation of some mantle xenoliths caused by a volatile- (and Li-) rich component exsolved from the host basalt. In contrast, high Li concentrations (> 2 ppm) and δ⁷Li (> 4‰) in olivine from many Labait and Olmani samples are attributed to an older, pre-entrainment enrichment event during which isotopic equilibrium was attained and whose signature was not corrupted during xenolith entrainment. Low Li concentrations and mantle-like isotopic composition of olivine from most Lashaine xenoliths indicate limited metasomatic Li addition.Thus, Li concentrations and isotope compositions of mantle peridotites worldwide may reflect two processes, with olivine mainly preserving a signature of depletion in refractory samples (low Li contents and δ⁷Li) or of older (precursory) melt addition in metasomatised samples (high Li contents and δ⁷Li), while non mantle-like, low δ⁷Li in almost all clinopyroxene can be due to Li ingress during transport in the host magma and/or slow cooling, if the samples were erupted in lavas. In Tanzania, the peridotites experienced rift-related heating prior to entrainment and were quenched upon eruption, so Li ingress is the most likely process responsible for the isotopically light clinopyroxene here.     

Metasomatic alteration of chromite from parts of the late Archaean Sittampundi Layered Magmatic Complex (SLC), Tamil Nadu,India

Chromite deposits associated with layered anorthosite complexes in the Archaean high-grade terranes are rare in the world. The late Archaean Sittampundi Layered Magmatic Complex, Tamil Nadu, India is one of the few such deposits in the world where layers of Fe-Al rich chromites are associated with extremely calcic (An>95) anorthosite. ‘Frozen in’ magmatic mineralogy of the chromitite and the enclosing anorthosite suggest successive crystallization of chromite + clinopyroxene and chromite + clinopyroxene + anorthite from a hydrous Al-rich basaltic melt that was emplaced in a suprasubduction zone setting. Intense deformation and upper amphibolite facies metamorphism at ∼2.45 Ga converted the magmatic assemblages to hitherto unreported hornblende + gedrite + Mg-Al rich spinel ± chlorite bearing assemblages. During metamorphic reconstitution, chromite was pseudomorphically replaced by green spinel in the domains rich in secondary amphiboles. Mass-balance calculation and algebraic analyses of the observed mineralogy suggest that a number of chemical species including chromium became mobile during the formation of spinel pseudomorph in response to infiltration driven metamorphism. Aluminium became mobile in the length scale of chromite grain but remained immobile in the length scale of a thin section.     

Petrology and geochemistry of peridotite xenoliths from the Lianshan region: Nature and evolution of lithospheric mantle beneath the lower Yangtze block

Lithospheric thinning beneath the North China Craton is widely recognized, but whether the Yangtze block has undergone the same process is a controversial issue. Based on a detailed petrographic study, a suite of xenoliths from the Lianshan Cenozoic basalts have been analyzed for the compositions of minerals and whole rocks, and their Sr–Nd isotopes to probe the nature and evolution of the subcontinental lithospheric mantle beneath the lower Yangtze block. The Lianshan xenoliths can be subdivided into two Types: the main Type 1 xenoliths (9–15% clinopyroxene and olivine-Mg# < 90) and minor Type 2 peridotites (1.8–6.2% clinopyroxene and olivine-Mg# > 90). Type 1 peridotites are characterized by low MgO, high levels of basaltic components (i.e., Al₂O₃, CaO and TiO₂), LREE-depleted patterns in clinopyroxenes and whole rocks, and relatively high ¹⁴³Nd/¹⁴⁴Nd (0.513219–0.513331) and low ⁸⁶Sr/⁸⁷Sr (0.702279–0.702789). These features suggest that Type 1 peridotites represent fragments of the newly accreted fertile lithospheric mantle that have undergone ~ 1% of fractional partial melting and later weak silicate–melt metasomatism, similar to Phanerozoic lithospheric mantle beneath the eastern North China Craton. Type 2 peridotites may be shallow relics of the older lithospheric mantle depleted in basaltic components, with LREE-enriched and HREE-depleted patterns, relatively low ¹⁴³Nd/¹⁴⁴Nd (0.512499–0.512956) and high ⁸⁶Sr/⁸⁷Sr (0.703275–0.703997), which can be produced by 9–14% partial melting and subsequent carbonatite–melt metasomatism. Neither type shows a correlation between equilibration temperatures and Mg# in olivine, indicating that the lithospheric mantle is not compositionally stratified, but both types coexist at similar depths. This coexistence suggests that the residual refractory lithospheric mantle (i.e., Type 2 peridotites) may be irregularly eroded by upwelling asthenosphere materials along weak zones and eventually replaced to create a new and fertile lithosphere mantle (i.e., Type 1 xenoliths) as the asthenosphere cooled. Therefore, the subcontinental lithospheric mantle beneath the lower Yangtze block shared a common evolutional dynamic environment with that beneath the eastern North China Craton during late Mesozoic–Cenozoic time.     

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.     

The Cihai diabase in the Beishan region,NW China: Isotope geochronology,geochemistry and implications for Cornwall-style iron mineralization

Diabase dykes in Cihai, Beishan region, NW China are spatially and temporally associated with ‘Cornwall-type’ iron deposits. U–Pb dating of zircons from a diabase dyke using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) yields an age of 128.5 ± 0.3 Ma, indicating an Early Cretaceous crystallization age. Most of the diabases show low Mg-numbers, suggesting evolved magmas. The diabase dykes show typical ophitic or sub-ophitic textures, and are dominantly composed of phenocrysts of plagioclase (40–50%) and clinopyroxene (30–45%), with minor and varying amounts of biotite and hornblende (1–5%), and minor disseminated magnetite (∼5%). Their mineralogy reflects magma differentiation under relatively low oxygen fugacity conditions. The diabase dykes are characterized by minor variation in SiO₂ (44.67–49.76 wt.%) and MnO (0.14–0.26 wt.%), but show a marked range of Al₂O₃ (10.66–14.21 wt.%), total Fe₂O₃ (9.52–13.88 wt.%), TiO₂ (0.66–2.82 wt.%) and relatively high MgO (4.87–9.29 wt.%) with an Mg# value [atomic Mg/(Mg + Fe²⁺)] of up to 66. The Cihai diabases possibly experienced fractional crystallization of olivine + clinopyroxene and minor crustal contamination during the differentiation process. Prominent negative Nb, Ta and Ti anomalies suggest derivation from subduction-modified mantle. Furthermore, the rocks have relatively unradiogenic Sr- and Nd-isotopic ratios. These characteristics probably reflect partial melting of a subduction component in the source mantle lithosphere through heat input from an upwelling asthenospheric mantle. Such processes probably occurred within an extensional setting during the Early Cretaceous in the Beishan area. The iron-rich fluids were derived from deep sources, and the iron ores were concentrated through a convection cell driven by temperature gradients established by the intrusion of the diabase sills. The combined processes of subduction-related enrichment in the source, shallow depth of emplacement, and the involvement of large-scale circulation of basinal brines from an evaporitic source are inferred to have contributed to the formation of the ‘Cornwall-type’ mineralization in Cihai.     

Compositional signatures of SSZ-type peridotites from the northern Vourinos ultra-depleted upper mantle suite,NW Greece

The northern Vourinos massif, located in the Dinarides-Hellenides mountain belt in the Balkan Peninsula, forms a section of the so-called Neotethyan ophiolitic belt in the Alpine-Himalayan orogenic system. It is comprised mainly of a well-preserved mantle sequence, dominated by voluminous massive harzburgite with variable clinopyroxene and olivine modal abundances, accompanied by subordinate coarse- and fine-grained dunite. The harzburgite rock varieties are characterized by high Cr# [Cr/(Cr + Al)] values in Cr-spinel (0.47–0.74), elevated Mg# [Mg/(Mg + Fe²⁺)] in olivine (0.90–0.93), low Al₂O₃ content in clinopyroxene (≤1.82 wt.%) and low average bulk-rock concentrations of CaO (0.52 wt.%) and Al₂O₃ (0.40 wt.%), which are indicative of their refractory nature. In addition, dunite-type rocks display even more depleted compositions, containing Cr-spinel and olivine with higher Cr# (0.76–0.84) and Mg# (0.91–0.94), respectively. They also display extremely low average abundances of CaO (0.13 wt.%) and Al₂O₃ (0.15 wt.%). The vast majority of the studied peridotites are also strongly depleted in REE. Simple batch and fractional melting models are not sufficient to explain their ultra-depleted composition. Whole-rock trace element abundances of the northern Vourinos mantle rocks can be modeled by up to 22–31% closed-system non-modal dynamic melting of an assumed primitive mantle (PM) source having spinel lherzolite composition. The highly depleted compositional signatures of the investigated peridotites indicate that they have experienced hydrous melting in the fore-arc mantle region above a SSZ. This intense melting event was responsible for the release of arc-related melts from the mantle. These melts reacted with the studied peridotites causing incongruent melting of pyroxenes followed by considerable olivine and Cr-spinel addition in terms of cryptic metasomatism. This later metasomatic episode has obscured any geochemical fingerprints indicative of an early mantle melting event in a MOR setting. The lack of any MOR-type peridotites in the northern Vourinos depleted mantle suite is quite uncommon for SSZ-type Neotethyan ophiolites.     

Solubility of Fe2(OH)3Cl (pure-iron end-member of hibbingite) in NaCl and Na2SO4 brines

Pure-iron end-member hibbingite, Fe₂(OH)₃Cl(s), may be important to geological repositories in salt formations, as it may be a dominant corrosion product of steel waste canisters in an anoxic environment in Na–Cl- and Na–Mg–Cl-dominated brines. In this study, the solubility of Fe₂(OH)₃Cl(s), the pure-iron end-member of hibbingite (Fe^II, Mg)₂(OH)₃Cl(s), and Fe(OH)₂(s) in 0.04 m to 6 m NaCl brines has been determined. For the reactionFe₂(OH)₃Cl(s) + 3H⁺ ? 3 H₂O + 2 Fe²⁺ + Cl^?,the solubility constant of Fe₂(OH)₃Cl(s) at infinite dilution and 25 °C has been found to be log₁₀ K = 17.12 ± 0.15 (95% confidence interval using F statistics for 36 data points and 3 parameters). For the reactionFe(OH)₂(s) + 2H⁺ ? 2 H₂O + Fe²⁺,the solubility constant of Fe(OH)₂ at infinite dilution and 25 °C has been found to be log₁₀ K = 12.95 ± 0.13 (95 % confidence interval using F statistics for 36 data points and 3 parameters). For the combined set of solubility data for Fe₂(OH)₃Cl(s) and Fe(OH)₂(s), the Na⁺–Fe²⁺ pair Pitzer interaction parameter θ_{Na⁺/Fe²⁺} has been found to be 0.08 ± 0.03 (95% confidence interval using F statistics for 36 data points and 3 parameters). In nearly saturated NaCl brine we observed evidence for the conversion of Fe(OH)₂(s) to Fe₂(OH)₃Cl(s). Additionally, when Fe₂(OH)₃Cl(s) was added to sodium sulfate brines, the formation of green rust(II) sulfate was observed, along with the generation of hydrogen gas. The results presented here provide insight into understanding and modeling the geochemistry and performance assessment of nuclear waste repositories in salt formations.     

Mineralogy and petrogenesis of a Ba–Ti–Zr-rich peralkaline dyke from Šebkovice (Czech Republic): Recognition of the most lamproitic Variscan intrusion

A peralkaline, ultrapotassic dyke found at ?ebkovice (T?ebí? district, western Moravia) is a mineralogically extreme member of a dyke swarm occurring along the south-eastern border of the Moldanubian Region of the Bohemian Massif. The dyke shows a simple zoning, with a very fine-grained marginal zone grading into a medium-grained central zone. It has a primary mineral assemblage of microcline and potassic amphiboles, with accessory apatite and altered phlogopite. The microcline exhibits an unusual red luminescence colour and pronounced substitution of Fe³⁺ for Al, with measured contents of Fe₂O₃ up to 8.5 wt.% (0.31 apfu Fe³⁺). Amphiboles have very high K (up to 0.99 apfu) and Si contents; their compositions follow an alkaline fractionation trend from potassic-richterite to potassic-magnesio-arfvedsonite, characterized by an increase of Na/K and a decrease of Ca, Mg, Fe²⁺ and Ti via heterovalent substitutions ^[B]Ca + ^[C](Mg,Fe²⁺) → ^[B]Na + ^[C]Fe³⁺ and Ti + Mg → 2Fe³⁺. The most evolved apatite is significantly enriched in SrO (up to 9.7 wt.%; 0.49 apfu Sr). The core of the dyke and late veinlets contain unique late- to post-magmatic Ba–Ti–Zr-bearing mineral assemblages of baotite, henrymeyerite, titanite, rutile, benitoite and bazirite. Anhedral baotite fills interstices distributed inhomogeneously in the dyke centre; it is locally replaced by a Ba-bearing titanite + henrymeyerite + rutile + quartz assemblage. Henrymeyerite (the second record in a lamproite) shows variable Fe/Ti ratios and represents a solid solution of the hepta- and hexatitanate components. Euhedral crystals of benitoite and bazirite are enclosed in the late-stage quartz–titanite–apatite veinlets in the fine-grained margin of the intrusion. In terms of a mineralogical–genetic classification, the ?ebkovice dyke can be considered as a new high-silica (~ 57 wt.% SiO₂) variety of lamproite (variety ?ebkovice), and represents a unique expression of post-collisional potassic magmatism on the south-eastern border of the Bohemian Massif. The peralkaline dykes from this area show mineralogical and geochemical features similar to those of silica-rich orogenic lamproites emplaced at destructive plate margins. In terms of the modern classification of lamproites, the ?ebkovice dyke is the first lamproite recognised in the Variscan orogenic belt.     

Mineral chemistry and genesis of the Permian Cihai and Cinan magnetite deposits,Beishan, NW China

Cihai and Cinan are Permian magnetite deposits related to mafic-ultramafic intrusions in the Beishan region, Xinjiang, NW China. The Cihai mafic intrusion is dominantly composed of dolerite, gabbro and fine-grained massive magnetite ore, while gabbro, pyrrhotite + pyrite-bearing clinopyroxenite and magnetite ore comprise the major units in Cinan. Clinopyroxene occurs in both deposits as 0.1–2 mm in diameter subhedral to anhedral grains in dolerite, gabbro and clinopyroxenite. High FeO contents (11.7–28.9 wt%), low SiO₂ (43.6–54.3 wt%) and Al₂O₃ contents (0.15–6.08 wt%), and low total REE and trace element contents of clinopyroxene in the Cinan clinopyroxenite imply crystallization early, at high pressure. This clinopyroxene is FeO-rich and Si and Ti-poor, consistent with the clinopyroxene component of large-scale Cu-Ni sulfide deposits in the Eastern Tianshan and Panxi ares, as well as Tarim mafic intrusion and basalt, implying the Cinan mafic intrusion and sulfide is related to tectonic activity in the Tarim LIP. The similar mineral chemistry of clinopyroxene, apatite and magnetite in the Cihai and Cinan gabbros (e.g., depleted LREE, negative Zr, Hf, Nb and Ta anomalies in clinopyroxene, lack of Eu anomaly in apatite and similarity of oxygen fugacity as indicated by V in magnetite), indicate similar parental magmatic characteristics. Mineral compositions suggest a crystallization sequence of clinopyroxenite/with a small amount of sulfide – gabbro – magnetite ore in the Cinan deposit, and magnetite ore – gabbro – dolerite in Cihai. The basaltic magma was emplaced at depth, with magnetite segregation (and formation of the Cinan magnetite ores) occurring in relatively low fO₂ conditions, after clinopyroxenite and gabbro fractional crystallization. The evolved Fe-rich basaltic magma rapidly rose to intermediate or shallow depths, forming an immiscible Fe-Ti oxide magma as fO₂ increased and leaving a Fe-poor residual magma in the chamber. The residual magmas was emplaced at different levels in the crust, forming the Cihai gabbro and dolerite, respectively. Finally, the immiscible Fe-Ti oxide magma was emplaced into the earlier formed dolerite because of late magma pulse uplift, resulting in a distinct boundary between the magnetite ores and dolerite.     

Early Paleozoic tectonic evolution of the North Qinling orogenic belt: Evidence from geochemistry,phase equilibrium modeling and geochronology of metamorphosed mafic rocks from the Songshugou ophiolite

The Shangdan suture zone (SSZ) is the main collisional boundary between the North China Craton and the South China Craton, along which discontinuous Paleozoic ophiolites and subduction–accretion related volcanic arc assemblages occur. Here we report the petrology, geochemistry, geochronology and phase equilibria modeling of garnet amphibolite from the Songshugou ophiolite which is one of the largest ophiolite outcrops in the northern side of the SSZ. From petrological studies, we identify: (1) prograde stage, defined by garnet + clinopyroxene + calcic amphibole + ilmenite + rutile + epidote + plagioclase + quartz; (2) peak stage with garnet + clinopyroxene + ilmenite + rutile + quartz; and (3) retrograde stage with amphibole + plagioclase + titanite + ilmenite. Our pseudosection analysis defines stability of the peak assemblage at 750–850 °C, 15–19 kbar and traces a clockwise P–T path in the system Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–Fe₂O₃ (NCFMASHTO), suggesting high pressure (HP) metamorphism. Subsequently, the rocks experienced rapid decompression and cooling. LA-ICP-MS U-Pb analyses of zircons from the garnet amphibolite yield a weighted mean ²⁰⁶Pb/²³⁸U age of 515 ± 12 Ma. This Early Paleozoic metamorphic age represents the emplacement time of the Songshugou ophiolite, and suggests that the HP metamorphism is possibly related to the northward deep subduction of the Shangdan oceanic crust in Early Paleozoic.     

Iron and lithium isotope systematics of the Hekla volcano,Iceland — Evidence for Fe isotope fractionation during magma differentiation

In this study potential iron isotope fractionation by magmatic processes in the Earth's crust was systematically investigated. High precision iron isotope analyses by MC-ICP-MS were performed on a suite of rock samples representative for the volcanic evolution of the Hekla volcano, Iceland. The whole series of Hekla's rocks results from several processes. (i) Basaltic magmas rise and induce partial melting of meta-basalts in the lower part of the Icelandic crust. The resulting dacitic magma evolves to rhyolitic composition through crystal fractionation. During this differentiation the δ^56/54Fe_IRMM-014 values increase successively from 0.051 ± 0.021‰ for the primitive dacites to 0.168 ± 0.021‰ for the rhyolites. This increase can be described by a Rayleigh fractionation model using a constant bulk fractionation factor between all mineral phases (M) and the silicate liquid (L) of Δ^56/54Fe_M–L = ? 0.1‰. (ii) The basaltic magma itself differentiates by crystal fractionation to basaltic andesite composition. No Fe isotope fractionation was found in this series. All basalts and basaltic andesites have an average δ^56/54Fe_IRMM-014 value of 0.062 ± 0.042‰ (2SD, n = 9), identical to mean terrestrial basaltic values reported in previous studies. This observation is consistent with the limited removal of iron from the remaining silicate melt through crystal fractionation and small mineral-melt Fe isotope fractionation factors expected at temperatures in excess of 1050 °C. (iii) Andesites are produced by mixing of basaltic andesite with dacitic melts. The iron isotope composition of the andesites is matching that of the basaltic andesites and the less evolved dacites, in agreement with a mixing process. In the Hekla volcanic suite Li concentrations are positively correlated with indicators of magma differentiation. All Hekla rocks have δ⁷Li values typical for the upper mantle and demonstrate the absence of resolvable Li isotope fractionation during crystal fractionation. As a fluid-mobile trace element, Li concentrations and isotopes are a potential tracer of magma/fluid interaction. At Hekla, Li concentrations and isotope compositions do not indicate any extensive fluid exsolution. Hence, the heavy Fe isotope composition of the dacites and rhyolites can be predominately attributed to fractional crystallisation. Iron isotope analyses on single samples from other Icelandic volcanoes (Torfajökull, Vestmannaeyjar) confirm heavy Fe isotope enrichment in evolving magmas. Our results suggest that the iron isotope composition of highly evolved crust can be slightly modified by magmatic processes.     

Chromitites from the Luanga Complex,Carajás,Brazil: Stratigraphic distribution and clues to processes leading to post-magmatic alteration

The Neoarchean (ca. 2.75 Ga) Luanga Complex, located in the Carajás Mineral Province in Brazil, is a medium-size layered intrusion consisting, from base to top, of ultramafic cumulates (Ultramafic Zone), interlayered ultramafic and mafic cumulates (Transition Zone) and mafic cumulates (Mafic Zone). Chromitite layers in the Luanga Complex occur in the upper portion of interlayered harzburgite and orthopyroxenite of the Transition Zone and associated with the lowermost norites of the Mafic Zone. The stratigraphic interval that hosts chromitites (∼150 meters thick) consists of several cyclic units interpreted as the result of successive influxes of primitive parental magma. The compositions of chromite in chromitites from the Transition Zone (Lower Group Chromitites) have distinctively higher Cr# (100Cr/(Cr + Al + Fe³⁺)) compared with chromite in chromitites from the Mafic Zone (Upper Group Chromitites). Chromitites hosted by noritic rocks are preceded by a thin layer of harzburgite located 15–20 cm below each chromitite layer. Lower Cr# in chromitites hosted by noritic rocks are interpreted as the result of increased Al₂O₃ activity caused by new magma influxes. Electron microprobe analyses on line transverses through 35 chromite crystals indicate that they are rimmed and/or extensively zoned. The composition of chromite in chromitites changes abruptly in the outer rim, becoming enriched in Fe³⁺ and Fe²⁺ at the expense of Mg, Cr, Al, thus moving toward the magnetite apex on the spinel prism. This outer rim, characterized by higher reflectance, is probably related to the metamorphic replacement of the primary mineralogy of the Luanga Complex. Zoned chromite crystals indicate an extensive exchange between divalent (Mg, Fe²⁺) cations and minor to none exchange between trivalent cations (Cr³⁺, Al³⁺ and Fe³⁺). This Mg-Fe zoning is interpreted as the result of subsolidus exchange of Fe²⁺ and Mg between chromite and coexisting silicates during slow cooling of the intrusion. A remarkable feature of chromitites from Luanga Complex is the occurrence of abundant silicate inclusions within chromite crystals. These inclusions show an adjacent inner rim with higher Cr# and lower Mg# (100 Mg/(Mg + Fe²⁺)) and Al# (100Al/(Cr + Al + Fe³⁺)). This compositional shift is possibly due to crystallization from a progressively more fractionated liquid trapped in the chromite crystal. Significant modification of primary cumulus composition of chromite, as indicated in our study for the Luanga Complex, is likely to be common in non-massive chromitites and the rule for disseminated chromites in mafic intrusions.     

Reduction of buried oxidized oceanic crust during subduction

The relationship among subducted oxidized oceanic crust and oxidation state of the subarc mantle, and arc magmas is one of the important aspects to evaluate convergent margin tectonics. However details of the oxidized mass transferred from buried oceanic crust to the overlying subarc mantle wedge remain obscure. Here we investigate the Songduo eclogites from south Tibet formed by the subduction of the paleo-Tethyan oceanic crust, and identify an abrupt decrease in pyrope and increase in almandine contents from the mantle to rim of garnet grains. This is coupled with a decrease in the Fe^3 + content of epidote and Fe^3 +/(Fe^2 ++ Fe^3 +) ratios from garnet core to rim domains, as well as speciation of calcite, a new mineral phase, in the rock matrix. Minor sulfates occur only as inclusions in garnet core domains, whereas sulfides are confined to the matrix as an accessory mineral phase. Aegirine augite occurs as relics or inclusions in garnet and omphacite. These features clearly suggest that oxidized components, Fe^3 + and S^6 +, were reduced as Fe^2 + and S^2 −, respectively, at the subduction zone. Thermodynamic modeling in the P–T-log₁₀f_O2 space using updated Perplex_X programs further revealed that the Songduo eclogites experienced oxygen fugacity variation of up to 8 log₁₀ units, with decreasing pressure. Petrological observations further suggest that the strong redox processes took place, after breaking of garnet, during the initial exhumation of the eclogites. CO₂ and minor sulfur are subsequently transferred from the cold oceanic subduction zone to the overlying mantle wedge, partially released by arc volcanoes to atmosphere. Our study presents a case of C and S recycling between the Earth's exterior and interior.