Carbonatite melt inclusions in coexisting magnetite,apatite and monticellite in Kerimasi calciocarbonatite,Tanzania: melt evolution and petrogenesis

Kerimasi calciocarbonatite consists principally of calcite together with lesser apatite, magnetite, and monticellite. Calcite hosts fluid and S-bearing Na–K–Ca-carbonate inclusions. Carbonatite melt and fluid inclusions occur in apatite and magnetite, and silicate melt inclusions in magnetite. This study presents statistically significant compositional data for quenched S- and P-bearing, Ca-alkali-rich carbonatite melt inclusions in magnetite and apatite. Magnetite-hosted silicate melts are peralkaline with normative sodium-metasilicate. On the basis of our microthermometric results on apatite-hosted melt inclusions and forsterite–monticellite phase relationships, temperatures of the early stage of magma evolution are estimated to be 900–1,000°C. At this time three immiscible liquid phases coexisted: (1) a Ca-rich, P-, S- and alkali-bearing carbonatite melt, (2) a Mg- and Fe-rich, peralkaline silicate melt, and (3) a C–O–H–S-alkali fluid. During the development of coexisting carbonatite and silicate melts, the Si/Al and Mg/Fe ratio of the silicate melt decreased with contemporaneous increase in alkalis due to olivine fractionation, whereas the alkali content of the carbonatite melt increased with concomitant decrease in CaO resulting from calcite fractionation. Overall the peralkalinity of the bulk composition of the immiscible melts increased, resulting in a decrease in the size of the miscibility gap in the pseudoquaternary system studied. Inclusion data indicate the formation of a carbonatite magma that is extremely enriched in alkalis with a composition similar to that of Oldoinyo Lengai natrocarbonatite. In contrast to the bulk compositions of calciocarbonatite rocks, the melt inclusions investigated contain significant amount of alkalis (Na₂O + K₂O) that is at least 5–10 wt%. The compositions of carbonatite melt inclusions are considered as being better representatives of parental magma composition than those of any bulk rock.     

Chemical composition of nyerereite and gregoryite from natrocarbonatites of Oldoinyo Lengai volcano,Tanzania

Alkali carbonates nyerereite, ideally Na₂Ca(CO₃)₂ and gregoryite, ideally Na₂CO₃, are the major minerals in natrocarbonatite lavas from Oldoinyo Lengai volcano, northern Tanzania. They occur as pheno- and microphenocrysts in groundmass consisting of fluorite and sylvite; nyerereite typically forms prismatic crystals and gregoryite occurs as round, oval crystals. Both minerals are characterized by relatively high contents of various minor elements. Raman spectroscopy data indicate the presence of sulfur and phosphorous as (SO₄)²⁻ and (PO₄)³⁻ groups. Microprobe analyses show variable composition of both nyerereite and gregoryite. Nyerereite contains 6.1–8.7 wt % K₂O, with subordinate amounts of SrO (1.7–3.3 wt %), BaO (0.3–1.6 wt %), SO₃ (0.8–1.5 wt %), P₂O₅ (0.2–0.8 wt %) and Cl (0.1–0.35 wt %). Gregoryite contains 5.0–11.9 wt % CaO, 3.4–5.8 wt % SO₃, 1.3–4.6 wt % P₂O₅, 0.6–1.0 wt % SrO, 0.1–0.6 wt % BaO and 0.3–0.7 wt % Cl. The content of F is below detection limits in nyerereite and gregoryite. Laser ablation ICP-MS analyses show that REE, Mn, Mg, Rb and Li are typical trace elements in these minerals. Nyerereite is enriched in REE (up to 1080 ppm) and Rb (up to 140 ppm), while gregoryite contains more Mg (up to 367 ppm) and Li (up to 241 ppm) as compared with nyerereite.     

Nyerereite from carbonatite rocks at Vulture volcano: implications for mantle metasomatism and petrogenesis of alkali carbonate melts Research Article

Vulture volcano displays a wide range of mafic to alkaline, carbonate-, and/or CaO-rich volcanic rocks, with subvolcanic and plutonic rocks together with mantle xenoliths in pyroclastic ejecta. The roles of magmatic volatiles such as CO₂, S, and Cl have been determined from compositions and trapping temperatures of inclusions in phenocrysts, which include the Na-K-Ca-carbonate nyerereite within melilite. We surmise that this alkali carbonate crystallised from an appropriate carbonatitic melt at relatively high temperature. Carbonatitic metasomatic features are traceable throughout many of the mantle xenoliths, and various carbonatitic components are found in the late stage extrusive suite. There is no evidence that alkali carbonatite developed as a separate magma, but it may have been an important evolutionary stage. We compare the rare occurrence of nyerereite at Vulture with other carbonatites and with an unaltered kimberlite from the Udachnaya pipe. We review the evidence at Vulture for associated carbonatitic metasomatism in the mantle, and we suggest that low viscosity alkali carbonatitic melts may have a primary and much deeper origin than previously considered.     

Thermodynamic Analysis of Secondary Minerals Stability in Altered Carbonatites of the Oldoinyo Lengai Volcano,Northern Tanzania

Carbonatites from the Oldoinyo Lengai volcano, northern Tanzania, are unstable under normal atmospheric conditions. Owing to carbonatite interaction with water, the major minerals—gregoryite Na₂(CO₃), nyerereite Na₂Ca(CO₃)₂, and sylvite KCl—are dissolved and replaced with secondary low-temperature minerals: thermonatrite Na₂(CO₃) · H₂O, trona Na₃(CO₃)(HCO₃) · 2H₂O, nahcolite Na(HCO₃), pirssonite Na₂Ca(CO₃)₂ · 2H₂O, calcite Ca(CO₃), and shortite Na₂Ca₂(CO₃)₃. Thermodynamic calculations show that the formation of secondary minerals in Oldoinyo Lengai carbonatites are controlled by the pH of the pore solution, H₂O and CO₂ fugacity, and the ratio of Ca and Na activity in the Na₂O–CaO–CO₂–H₂O system.     

A Brine Evolution Model and Mineralogy of Chemical Sediments in a Volcanic Crater,Lake Kitagata,Uganda

Lake Kitagata, Uganda, is a hypersaline crater lake with Na–SO₄–Cl–HCO₃–CO₃ chemistry, high pH and relatively small amounts of SiO₂. EQL/EVP, a brine evaporation equilibrium model (Risacher and Clement 2001), was used to model the major ion chemistry of the evolving brine and the order and masses of chemically precipitated sediments. Chemical sediments in a 1.6-m-long sediment core from Lake Kitagata occur as primary chemical mud (calcite, magadiite [NaSi₇O₁₃(OH)₃·3H₂O], burkeite [Na₆(CO₃)(SO₄)₂]) and as diagenetic intrasediment growths (mirabilite (Na₂SO₄·10H₂O)). Predicted mineral assemblages formed by evaporative concentration were compared with those observed in salt crusts along the shoreline and in the core from the lake center. Most simulations match closely with observed natural assemblages. The dominant inflow water, groundwater, plays a significant role in driving the chemical evolution of Lake Kitagata water and mineral precipitation sequences. Simulated evaporation of Lake Kitagata waters cannot, however, explain the large masses of magadiite found in cores and the formation of burkeite earlier in the evaporation sequence than predicted. The masses and timing of formation of magadiite and burkeite may be explained by past groundwater inflow with higher alkalinity and SiO₂ concentrations than exist today.     

Petrology and genesis of natrocarbonatite

Microprobe analyses of phenocrysts and groundmass, and crystal-size distributions of phenocrysts of pahoehoe natrocarbonatite lavas of the 1963 eruption of Oldoinyo Lengai have been determined. Nyerereite phenocrysts are homogeneous, with average composition Nc₄₁Kc₉Cc₅₀ (neglecting F, Cl, P₂O₅, and SO₃) where Nc=Na₂CO₃, Kc=K₂CO₃, and Cc= (Ca,Sr)CO₃. Gregoryite phenocrysts have turbid, pale brown, oscillatorily zoned cores (average composition Nc₇₇Kc₅Cc₁₈) with 0–30% oriented inclusions of exsolved nyerereite. Overgrowths on gregoryites (30 m wide) are relatively sodic (Nc₈₁Kc₄Cc₁₅) and are free of inclusions. Cores and rims are rich in SO₃ (4%) and P₂O₅ (2%). Blebs of pyrite-alabandite mixtures (100 m) occur in the groundmass. The groundmass has the simplified composition Nc₆₅Kc₁₅Cc₂₀, less calcic than the composition of the 1-kbar nyerereite+gregoryite +liquid cotectic in the ternary system Nc-Kc-Cc. Groundmass quench growth of alkali halides + carbonate was followed by slower growth of coarse-grained and irregular gregoryite +KCl+BaCO₃. Crystal size distributions of gregoryite and nyerereite in one sample are linear, implying little loss or gain of phenocrysts by crystal settling. AverageG is 0.15 mm, compared toG=0.03 mm for combeite phenocrysts from consanguineous nephelinite. Assuming an equal residence time () for both lavas, the apparent crystal growth rate (G) in carbonate melt is 5 times greater than in peralkaline undersaturated silicate melt. Data from experiments with natrocarbonatite and related synthetic systems indicate that Na–K–Ca carbonatite magmas which crystallize calcite cannot fractionate to nyerereite+gregoryite +liquid assemblages. Natrocarbonatites plot in the liquidus field of nyerereite, and minor fractionation of nyerereite to produce the erupted lavas is indicated. The term natrocarbonatite has been inappropriately applied to other eruptive rocks with calcite phenocrysts, and the only known occurrence of gregoryite-bearing natrocarbonatite is Oldoinyo Lengai. Natrocarbonatite probably originates by liquid immiscibility from strongly peralkaline nephelinites, which have also been erupted at Oldoinyo Lengai.     

A modified iterative sandwich method for determination of near-solidus partial melt compositions. II. Application to determination of near-solidus melt compositions of carbonated peridotite

We performed modified iterative sandwich experiments (MISE) to determine the composition of carbonatitic melt generated near the solidus of natural, fertile peridotite + CO₂ at 1,200–1,245°C and 6.6 GPa. Six iterations were performed with natural peridotite (MixKLB-1: Mg# = 89.7) and ∼10 wt% added carbonate to achieve the equilibrium carbonatite composition. Compositions of melts and coexisting minerals converged to a constant composition after the fourth iteration, with the silicate mineral compositions matching those expected at the solidus of carbonated peridotite at 6.6 GPa and 1,230°C, as determined from a sub-solidus experiment with MixKLB-1 peridotite. Partial melts expected from a carbonated lherzolite at a melt fraction of 0.01–0.05% at 6.6 GPa have the composition of sodic iron-bearing dolomitic carbonatite, with molar Ca/(Ca + Mg) of 0.413 ± 0.001, Ca# [100 × molar Ca/(Ca + Mg + Fe*)] of 37.1 ± 0.1, and Mg# of 83.7 ± 0.6. SiO₂, TiO₂ and Al₂O₃ concentrations are 4.1 ± 0.1, 1.0 ± 0.1, and 0.30 ± 0.02 wt%, whereas the Na₂O concentration is 4.0 ± 0.2 wt%. Comparison of our results with other iterative sandwich experiments at lower pressures indicate that near-solidus carbonatite derived from mantle lherzolite become less calcic with increasing pressure. Thus carbonatitic melt percolating through the deep mantle must dissolve cpx from surrounding peridotite and precipitate opx. Significant FeO* and Na₂O concentrations in near solidus carbonatitic partial melt likely account for the ∼150°C lower solidus temperature of natural carbonated peridotite compared to the solidus of synthetic peridotite in the system CMAS + CO₂. The experiments demonstrate that the MISE method can determine the composition of partial melts at very low melt fraction after a small number of iterations.     

Parental melts of melilitolite and origin of alkaline carbonatite: evidence from crystallised melt inclusions, Gardiner complex

Perovskite and melilite crystals from melilitolites of the ultramafic alkaline Gardiner complex (East Greenland) contain crystallised melt inclusions derived from: (1) melilitite; (2) low-alkali carbonatite; (3) natrocarbonatite. The melilitite inclusion (1) homogenisation temperature of 1060 °C is similar to liquidus temperatures of experimentally investigated natural melilitites. The compositions are peralkaline, low in MgO (ca.␣5 wt%), Ni and Cr, and they are low-pressure fractionates of more magnesian larnite-normative ultramafic lamprophyre-type melts of primary mantle origin. Low-alkali carbonatite compositions (2) homogenise at 1060–1030 °C and are compositionally similar to immiscible calcite carbonatite dykes derived from the melilitolite magma. Natrocarbonatite inclusions (3) homogenise between 1030 and 900 °C and are compositionally similar to natrocarbonatite lava from Oldoinyo Lengai. Nephelinitic to phonolitic dykes which are related to the calcite carbonatite dykes, are very Zr-rich and agpaitic (molecular Na₂O + K₂O/Al₂O₃ > 1.2) and resemble nephelinites of Oldoinyo Lengai. The petrographic, geochemical and temporal relationships indicate unmixing of carbonatite compositions (ca. 10% alkalies) from evolving melilitite melt and continued fractionation of melilitite to nephelinite. It is suggested that the natrocarbonatite compositions represent degassed supercritical high temperature fluid formed in a cooling body of strongly larnite-normative nephelinite or evolved melilitite. The Gardiner complex and similar melilitolite and carbonatite-bearing ultramafic alkaline complexes are believed to represent subvolcanic complexes formed beneath volcanoes comparable to Oldoinyo Lengai and that the suggested origin of natrocarbonatite may be applied to natrocarbonatites of Oldoinyo Lengai. Received: 18 January 1996 / Accepted: 2 September 1996     

Dualite, Na30(Ca,Na,Ce,Sr)12(Na,Mn,Fe,Ti)6Zr3Ti3MnSi51O144(OH,H2O,Cl)9, a new zircono-titanosilicate with a modular eudialyte-like structure from the Lovozero alkaline Pluton, Kola Peninsula, Russia

Dualite has been found at Mount Alluaiv, the Lovozero Pluton, the Kola Peninsula in peralkaline pegmatoid as sporadic, irregularly shaped grains up to 0.3–0.5 mm across. K-Na feldspar, nepheline, sodalite, cancrinite, aegirine, alkaline amphibole, eudialyte, lovozerite, lomonosovite, vuonnemite, lamprophyllite, sphalerite, and villiaumite are associated minerals. Dualite is yellow, transparent or translucent, with conchoidal fracture. The new mineral is brittle, with vitreous luster and white streaks. The Mohs hardness is 5. The measured density is 2.84(3) g/cm₃ (volumetric method); the calculated density is 2.814 g/cm₃. Dualite dissolves and gelates in acid at room temperature. It is nonfluorescent. The new mineral is optically uniaxial and positive; ω = 1.610(1), ɛ = 1.613(1). Dualite is trigonal, space group R3m. The unit cell dimensions are a = 14.153(9), c = 60.72(5) ?, V = 10533(22) ?, Z = 3. The strongest reflections in the X-ray powder pattern [d, ? (I,%)(hkl)] are as follows: 7.11(40)(110), 4.31(50)(0.2.10), 2.964(100)(1.3.10), 2.839(90)(048), 2.159(60)(2.4.10, 0.4.20), 1.770(60)(2.4.22, 4.0.28, 440), 1362(50)(5.5.12, 3.0.42). The chemical composition (electron microprobe, H₂O calculated from X-ray diffraction data) is as follows, wt %: 17.74 Na₂O, 0.08 K₂O, 8.03 CaO, 1.37 SrO, 0.29 BaO, 2.58 MnO, 1.04 FeO, 0.79 La₂O₃, 1.84 C₂O₃, 0.88 Nd₂O₃, 0.20 Al₂O₃, 51.26 SiO₂, 4.40 TiO₂, 5.39 ZrO₂, 1.94 Nb₂O₅, 0.58 Cl, 1.39 H₂O,-O = 0.13 Cl₂; they total is 99.67. The empirical formula calculated on the basis of 106 cations as determined by crystal structure is (Na_29.79Ba_0.1K_0.10)_Σ30(Ca_8.55Na_1.39REE_1.27Sr_0.79)_Σ12 · (Na_3.01Mn_1.35Fe_0.87²⁺Ti_0.77)_Σ6(Zr_2.61Nb_0.39)_Σ3 (Ti_2.52Nb_0.48)_Σ3(Mn_0.82Si_0.18)_Σ1(Si_50.77Al_0.23)_Σ51 O₁₄₄[(OH)_6.54(H₂O)_1.34·Cl_0.98]_Σ8.86). The simplified formula is Na₃₀(Ca,Na,Ce,Sr)₁₂(Na,Mn,Fe,Ti)₆Zr₃Ti₃ MnSi₅₁O₁₄₄ (OH,H₂O,Cl)₉). The name dualite is derived from Latin dualis (dual) alluding to the dual taxonomic membership of this mineral, which is at the same time zirconosilicate and titanosilicate. The crystal structure is characterized by two module types (alluivite-like and eudialyte-like) alternating along a threefold axis with a doubled c period relative to eudialyte and close chemical affinity to rastsvetaevite (Khomyakov et al., 2006a) and labyrynthite (Khomyakov et al., 2006b). According to the authors’ crystal chemical taxonomy of the eudialyte group, the new mineral belongs to one of three subgroups characterized by a 24-layered structural framework. Dualite is a mineral formed during the final stages of peralkaline pegmatite formation. The type material of dualite is deposited at the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow. Original Russian Text ? A.P. Khomyakov, G.N. Nechelyustov, R.K. Rastsvetaeva, 2007, published in Zapiski Rossiiskogo Mineralogicheskogo Obshchestva, 2007, Pt CXXXVI, No. 4, pp. 68–73. Approved by the Commission on New Minerals and Mineral Names, International Mineralogical Association, July 8, 2005.     

Hydrogeochemical properties of CO2-rich thermal–mineral waters in Kayseri (Central Anatolia), Turkey

The present study highlights the hydrogeological and hydrogeochemical characteristics of the CO₂-rich thermal–mineral waters in Kayseri, Turkey. These waters of Dokuzpınar cold spring (DPS) (12–13°C), Yeşilhisar mineral spring (YMS) (13–16°C), Acısu mineral spring (ACMS) (20–22.5°C), Tekgöz thermal spring (TGS) (40–41°C), and Bayramhacı thermal-mineral spring (BTMS) (45–46.5°C) have different physical and chemical compositions. The waters are located within the Erciyes basin in the Central Anatolian Crystalline complex consisting of three main rock units. Metamorphic/crystalline rocks occur as the basement, sedimentary rocks of Upper Cretaceous-Quaternary age form the cover, and volcanosedimentary rocks Miocene-Quaternary in age represent the extrusive products of magmatism acting in that period. All these units are covered unconformably by terrace and alluvial deposits, and travertine occurrences have variable permeability. Dokuzpinar cold spring, YMS and ACMS localized mainly along the faults within the region have higher Na⁺ and Cl⁻ contents whereas TGS and BTMS have higher amounts of Ca²⁺ and HCO ₃ ⁻ . The high concentrations of Ca²⁺ and HCO ₃ ⁻ are mainly related to the high CO₂ contents resulting from interactions with carbonate rocks. Whereas the high Na⁺ content is derived from the alkaline rocks, such as syenite, tuff and basalts, the Cl⁻ is generally connected to the dissolution of the evaporitic sequences. These waters are of meteoric-type. BTMS deviates from meteoric water line. The content is related to the increases in the δ¹⁸O compositions due to mineral–water interaction (re-equilibrium) process. CO₂-dominated YMS and ACMS with low temperatures have higher mineralizations. Yeşilhisar mineral spring, ACMS, TGS and BTMS are oversaturated in terms of calcite, aragonite, dolomite, goethite and hematite, and undersaturated with respect to gypsum, halite and anhydrite. Yeşilhisar mineral spring, ACMS and BTMS are also characterized by recent travertine precipitation. Dokuzpınar cold spring is undersaturated in terms of the above minerals. The higher ratios of Ca/Mg and Cl/HCO₃, and lower ratios of SO₄/Cl in BTMS than TGS suggest that TGS has shallow circulation compared to BTMS, and/or has much more heat-loss enroute the surface. The sequence of hydrogeochemical and isotopic compositions of the waters is in an order of DPS>YMS>ACMS>TGS>BTMS and this suggests a transition period from a shallow circulation to a deep circulation path.     

The origin and evolution of the parental magmas of frontal volcanoes in Kamchatka: Evidence from magmatic inclusions in olivine from Zhupanovsky volcano

The paper presents data on naturally quenched melt inclusions in olivine (Fo 69–84) from Late Pleistocene pyroclastic rocks of Zhupanovsky volcano in the frontal zone of the Eastern Volcanic Belt of Kamchatka. The composition of the melt inclusions provides insight into the latest crystallization stages (∼70% crystallization) of the parental melt (∼46.4 wt % SiO₂, ∼2.5 wt % H₂O, ∼0.3 wt % S), which proceeded at decompression and started at a depth of approximately 10 km from the surface. The crystallization temperature was estimated at 1100 ± 20°C at an oxygen fugacity of ΔFMQ = 0.9–1.7. The melts evolved due to the simultaneous crystallization of olivine, plagioclase, pyroxene, chromite, and magnetite (Ol: Pl: Cpx: (Crt-Mt) ∼ 13: 54: 24: 4) along the tholeiite evolutionary trend and became progressively enriched in FeO, SiO₂, Na₂O, and K₂O and depleted in MgO, CaO, and Al₂O₃. Melt crystallization was associated with the segregation of fluid rich in S-bearing compounds and, to a lesser extent, in H₂O and Cl. The primary melt of Zhupanovsky volcano (whose composition was estimated from data on the most primitive melt inclusions) had a composition of low-Si (∼45 wt % SiO₂) picrobasalt (∼14 wt % MgO), as is typical of parental melts in Kamchatka and other island arcs, and was different from MORB. This primary melt could be derived by ∼8% melting of mantle peridotite of composition close to the MORB source, under pressures of 1.5 ± 0.2 GPa and temperatures 20–30°C lower than the solidus temperature of “dry” peridotite (1230–1240°C). Melting was induced by the interaction of the hot peridotite with a hydrous component that was brought to the mantle from the subducted slab and was also responsible for the enrichment of the Zhupanovsky magmas in LREE, LILE, B, Cl, Th, U, and Pb. The hydrous component in the magma source of Zhupanovsky volcano was produced by the partial slab melting under water-saturated conditions at temperatures of 760–810°C and pressures of ∼3.5 GPa. As the depth of the subducted slab beneath Kamchatkan volcanoes varies from 100 to 125 km, the composition of the hydrous component drastically changes from relatively low-temperature H₂O-rich fluid to higher temperature H₂O-bearing melt. The geothermal gradient at the surface of the slab within the depth range of 100–125 km beneath Kamchatka was estimated at 4°C/km.     

Origin of CO2-rich fluid inclusions in synorogenic veins from the Eastern Mount Isa Fold Belt, NW Queensland, and their implications for mineralization

Synorogenic veins from the Proterozoic Eastern Mount Isa Fold Belt contain three different types of fluid inclusions: CO₂-rich, aqueous two-phase and rare multiphase. Inclusions of CO₂ without a visible H₂O phase are particularly common. The close association of CO₂-rich inclusions with aqueous two-phase, and possibly multiphase inclusions suggests that phase separation of low- to -moderate salinity CO₂-rich hydrothermal fluids led to the selective entrapment of the CO₂. Microthermometric results indicate that CO₂-rich inclusions homogenize between –15.5 and +29.9 °C which corresponds to densities of 0.99 to 0.60 g.cm⁻³. The homogenization temperatures of the associated aqueous two-phase inclusions are 127–397 °C, with salinities of 0.5 to 18.1 wt.% NaCl equivalent. The rarely observed multiphase inclusions homogenize between 250 and 350 °C, and have salinities ranging from 34.6 to 41.5 wt.% NaCl equivalent. Evidence used to support the presence of fluid immiscibility in this study is mainly derived from observations of coexisting H₂O-rich and CO₂-rich inclusions in groups and along the same trail. In addition, these two presumably unmixed fluids are also found on adjacent fractures where monophase CO₂-rich inclusions are closely related to H₂O-rich inclusions. Similar CO₂-rich inclusions are widespread in mineral deposits in this region, which are simply metal-enriched synorogenic veins. Therefore, we argue that fluid immiscibility caused volatile species such as CO₂ and H₂S to be lost from liquid, thus triggering ore deposition by increasing the fluid pH and decreasing the availability of complexing ligands. Received: 28 April 1997 / Accepted: 4 January 1999     

Metamorphic reactions between fluid inclusions and mineral hosts. I. Progress of the reaction calcite+quartz=wollastonite+CO2 in natural wollastonite-hosted fluid inclusions

 At the Bufa del Diente contact-metamorphic aureole, brine infiltration through metachert layers embedded in limestones produced thick wollastonite rims, according to Cc+Qz=Wo+CO₂. Fluid inclusions trapped in recrystallized quartz hosts include: (1) high salinity four phase inclusions [Th(V-L)=460–573° C; Td(salts)=350–400° C; (Na+K)_Cleq=64–73 wt%; X _{CO 2}≤0.02]; (2) low density vapour-rich CO₂-bearing inclusions [Th(L-V)≈500±100° C; X _{CO 2}=0.22–0.44; X _NaCl≤0.01], corresponding to densities of 0.27± 0.05 gcm⁻³. Petrographical observations, phase compositions and densities show that the two fluids were simultaneously trapped in the solvus of the H₂O-CO₂-salts system at 500–600° C and 700±200 bars. The low density fluid was generated during brine infiltration at the solvus via the wollastonite producing reaction. Identical fluid types were also trapped as inclusion populations in wollastonite hosts 3 cm adjacent to quartz crystals. At room temperature, both fluid types additionally contain one quartz and one calcite crystal, generated by the back-reaction Wo+CO₂=Cc+Qz of the host with the CO₂-proportion of the fluid during retrogression. All of the CO₂ was removed from the fluid. On heating in the microstage, the reaction progress of the prograde reaction was estimated via volume loss of the calcites. In vapour-rich fluids, 50% progress is reached at 490–530° C; 80% at 520–560° C; and 100% at 540–590° C, the latter representing the trapping temperatures of the original fluid at the two fluid solvus. The progress is volume controlled. With knowledge of compositions and densities from unmodified inclusions in quartz and using the equation of state of Duan et al. (1995) for H₂O-CO₂-NaCl, along with f _{CO 2}-values extracted from it, the reaction progress curve was recalculated in the P-T-X-space. The calculated progress curve passes through the two fluid solvus up to 380° C/210 bars, continues in the one fluid field and meets the solvus again at trapping conditions. The P-T slope is steep, most of the reaction occurs above 450° C and there is high correspondence between calculated and measured reaction progress. We emphasize that with the exception of quartz, back-reactions between inclusion fluids and mineral hosts is a common process. For almost any prograde metamorphic mineral that was formed by a devolatilization reaction and that trapped the equilibrium fluid or any peak metamorphic fluid as an inclusion, a fluid-host back-reaction exists which must occur somewhere along the retrograde path. Such retrograde reactions may cause drastic changes in density and composition of the fluid. In most cases, however, evidence of the evolving mineral assemblages is not given for they might form submicroscopical layers at the inclusion walls. Received: 15 March 1995 / Accepted: 1 June 1995     

Fluid and gas migration in the North German Basin: fluid inclusion and stable isotope constraints

Fluid inclusions have been studied in minerals infilling fissures (quartz, calcite, fluorite, anhydrite) hosted by Carboniferous and Permian strata from wells in the central and eastern part of the North German Basin in order to decipher the fluid and gas migration related to basin tectonics. The microthermometric data and the results of laser Raman spectroscopy reveal compelling evidence for multiple events of fluid migration. The fluid systems evolved from a H₂O–NaCl±KCl type during early stage of basin subsidence to a H₂O–NaCl–CaCl₂ type during further burial. Locally, fluid inclusions are enriched in K, Cs, Li, B, Rb and other cations indicating intensive fluid–rock interaction of the saline brines with Lower Permian volcanic rocks or sediments. Fluid migration through Carboniferous sediments was often accompanied by the migration of gases. Aqueous fluid inclusions in quartz from fissures in Carboniferous sedimentary rocks are commonly associated with co-genetically trapped CH₄–CO₂ inclusions. P–T conditions estimated, via isochore construction, yield pressure conditions between 620 and 1,650 bar and temperatures between 170 and 300°C during fluid entrapment. The migration of CH₄-rich gases within the Carboniferous rocks can be related to the main stage of basin subsidence and stages of basin uplift. A different situation is recorded in fluid inclusions in fissure minerals hosted by Permian sandstones and carbonates: aqueous fluid inclusions in calcite, quartz, fluorite and anhydrite are always H₂O–NaCl–CaCl₂-rich and show homogenization temperatures between 120 and 180°C. Co-genetically trapped gas inclusions are generally less frequent. When present, they show variable N₂–CH₄ compositions but contain no CO₂. P–T reconstructions indicate low-pressure conditions during fluid entrapment, always below 500 bar. The entrapment of N₂–CH₄ inclusions seems to be related to phases of tectonic uplift during the Upper Cretaceous. A potential source for nitrogen in the inclusions and reservoirs is C_org-rich Carboniferous shales with high nitrogen content. Intensive interaction of brines with Carboniferous or even older shales is proposed from fluid inclusion data (enrichment in Li, Ba, Pb, Zn, Mg) and sulfur isotopic compositions of abundant anhydrite from fissures. The mainly light δ³⁴S values of the fissure anhydrites suggest that sulfate is either derived through oxidation and re-deposition of biogenic sulfur or through mixing of SO₄²⁻-rich formation waters with variable amounts of dissolved biogenic sulfide. An igneous source for nitrogen seems to be unlikely since these rocks have low total nitrogen content and, furthermore, even extremely altered volcanic rocks from the study area do not show a decrease in total nitrogen content.     

Genesis of itabirite-hosted Au–Pd–Pt-bearing hematite-(quartz) veins, Quadrilátero Ferrífero, Minas Gerais, Brazil: constraints from fluid inclusion infrared microthermometry, bulk crush-leach analysis and U–Pb systematics

Fluid inclusions hosted in quartz and specular hematite from auriferous (jacutinga) and barren veins in the Quadrilátero Ferrífero (QF) have been studied using conventional and near infrared microscopy, respectively. The mineralization consists of veins that cross-cut metamorphosed iron formation (itabirite) of the Paleoproterozoic Itabira Group. The sample suite comprises hematite from veins from the low-strain domain in the W and SW of the study area, as well as hematite samples from the eastern high-strain domain in the central and NE parts of the QF. Halogen ratios of fluid inclusions in quartz and hematite from all studied deposits are consistent with a fluid evolved from dissolving and reprecipitating halite that was subsequently diluted. Fluid inclusions hosted in quartz and hematite are characterized by consistent Na/K ratios and considerable SO₄ contents, and suggest similar formation conditions and, perhaps, fluid origin from a common source. Na/K and Na/Li fluid mineral geothermometers indicate water–rock interaction at approximately 340±40°C. Hematites from the high-strain domain contain fluid inclusion assemblages of high-temperature aqueous-carbonic and multiphase high-salinity, high-temperature aqueous inclusions probably due to fluid immiscibility in the system H₂O–NaCl–CO₂. Fluid inclusions hosted in hematite from barren veins in the low-strain domain, as well as in hematite from jacutinga-type mineralization from the central part of the QF, only host multiphase aqueous fluid inclusions all showing narrow ranges of salinity (7.2–11.7 wt.% NaCl equiv.) and homogenization temperatures (148 to 229°C). Lower homogenization temperatures and the absence of CO₂-rich inclusions in specular hematite from these occurrences are attributed to carbonate precipitation and/or CO₂ escape due to cooling during fluid migration from the high- to the low-strain domain. Pb–Pb and U–Pb systematics of gold, hematite and hematite-hosted fluid inclusions in combination with geochemical evidence indicate distinct sources for Pd, Au, and Pb. The formation of specular hematite veins may be related to retrograde metamorphic fluids being released during the Brazilian orogenic cycle (600–700 Ma). The Pb isotopic characteristics of all samples are readily reconciled in a simple model that involves two different Paleoproterozoic or Archean source lithologies for lead and reflects contrasting depths of fluid percolation during the Brasiliano orogeny.     

Partitioning of Mg, Ca, and Na between carbonatite melt and hydrous fluid at 0.1–0.2 GPa

Experimental studies of the element distribution between carbonatite melts and hydrous fluids are hampered by the fact that neither the fluid nor the melt can be isochemically quenched in conventional high-pressure vessels. In order to overcome this problem, we used a double-capsule technique to separate immiscible fluid and melt phases during and after the runs. The inner platinum capsules were charged with carbonate mixtures (CaCO₃, MgCO₃ and Na₂CO₃) and placed inside the outer capsules charged with distilled water and diamond powder. The latter was used as an inert trap for solids precipitating from the fluid on quenching. Carbonate melt and hydrous fluid equilibrated through a small hole left in the upper end of the inner capsule. The runs were performed in rapid-quench cold-seal pressure vessels at 0.1–0.2 GPa and 700–900 °C in the two-phase (fluid + melt) stability region. Both quenched melt and quenched fluid were dissolved in dilute HCl and analysed by inductively coupled plasma atomic emission spectroscopy. The results show that under all conditions investigated, fluid/melt partition coefficients for Ca and Mg are similar and several times smaller than those for Na. At 0.1 GPa and a water/carbonatite ratio of 1 (by weight), the partition coefficients are D_Na = 0.35 ± 0.02, D_Ca = 0.09 ± 0.02, and D_Mg = 0.13 ± 0.01. Between 700 and 900 °C, the effect of temperature on partitioning is negligible. However, D_Na increases significantly with decreasing water/carbonatite ratio in the system. Our data show that the release of a hydrous fluid enriched in sodium and simultaneous crystallisation of calcite can transform an alkaline, vapour-saturated carbonatite melt into a body of pure calcite surrounded by zones of sodium metasomatism. Thus, it is quite possible that carbonate magmas with substantial amounts of alkalies were common parental liquids of plutonic carbonatites. Received: 6 May 1999 / Accepted: 31 August 1999     

Kyanoxalite,a new cancrinite-group mineral species with extraframework oxalate anion from the Lovozero alkaline pluton,Kola Peninsula

Kyanoxalite, a new member of the cancrinite group, has been identified in hydrothermally altered hyperalkaline rocks and pegmatites of the Lovozero alkaline pluton, Kola Peninsula, Russia. It was found at Mount Karnasurt (holotype) in association with nepheline, aegirine, sodalite, nosean, albite, lomonosovite, murmanite, fluorapatite, loparite, and natrolite and at Mt. Alluaiv. Kyanoxalite is transparent, ranging in color from bright light blue, greenish light blue and grayish light blue to colorless. The new mineral is brittle, with a perfect cleavage parallel to (100). Mohs hardness is 5–5.5. The measured and calculated densitiesare 2.30(1) and 2.327 g/cm³, respectively. Kyanoxalite is uniaxial, negative, ω = 1.794(1), ɛ = 1.491(1). It is pleochroic from colorless along E to light blue along O. The IR spectrum indicates the presence of oxalate anions C₂O₄²⁻ and water molecules in the absence of CO₃²⁻ Oxalate ions are confirmed by anion chromatography. The chemical composition (electron microprobe; water was determined by a modified Penfield method and carbon was determined by selective sorption from annealing products) is as follows, wt %: 19.70 Na₂O, 1.92 K₂O, 0.17 CaO, 27.41 Al₂O₃, 38.68 SiO₂, 0.64 P₂O₅, 1.05 SO₃, 3.23 C₂O₃, 8.42 H₂O; the total is 101.18. The empirical formula (Z = 1) is (Na_6.45K_0.41Ca_0.03)_Σ6.89(Si_6.53Al_5.46O₂₄)[(C₂O₄)_0.455(SO₄)_0.13(PO₄)_0.09(OH)_0.01]_Σ0.68 · 4.74H₂O. The idealized formula is Na₇(Al₅₋₆Si₆₋₇O₂₄)(C₂O₄)_0.5−1 · 5H₂O. Kyanoxalite is hexagonal, the space group is P6₃, a = 12.744(8), c = 5.213(6) -ray powder diffraction pattern are as follows, [d, [A] (I, %)(hkl)]: 6.39(44) (110), 4.73 (92) (101), 3.679 (72) (300), 3.264 (100) (211, 121), 2.760 (29) (400), 2.618 (36) (002), 2.216, (29) (302, 330). According to the X-ray single crystal study (R = 0.033), two independent C₂O₄ groups statistically occupy the sites on the axis 6₃. The new mineral is the first natural silicate with an additional organic anion and is the most hydrated member of the cancrinite group. Its name reflects the color (κɛανgoΣς is light blue in Greek) and the species-forming role of oxalate anions. The holotype is deposited at the Fersman Mineralogical Museum of the Russian Academy of Sciences, Moscow, registration no. 3735/1.     

Genesis of the Khaluta alkaline-basic Ba-Sr carbonatite complex (West Transbaikala, Russia)

The Khaluta carbonatite complex comprizes fenites, alkaline syenites and shonkinites, and calcite and dolomite carbonatites. Textural and compositional criteria, melt inclusions, geochemical and isotopic data, and comparisons with relevant experimental systems show that the complex formed by liquid immiscibility of a carbonate-saturated parental silicate melt. Mineral and stable isotope geothermometers and melt inclusion measurements for the silicate rocks and carbonatite all give temperatures of crystallization of 915–1,000°C and 890–470°C, respectively. Melt inclusions containing sulphate minerals, and sulphate-rich minerals, most notably apatite and monazite, occur in all of the lithologies in the Khaluta complex. All lithologies, from fenites through shonkinites and syenites to calcite and dolomite carbonatites, and to hydrothermal mineralisation are further characterized by high Ba and Sr activity, as well as that of SO3 with formation of the sulphate minerals baryte, celestine and baryte-celestine. Thus, the characteristic features of the Khaluta parental melt were elevated concentrations of SO₃, Ba and Sr. In addition to the presence of SO₃, calculated fO₂ for magnetites indicate a high oxygen fugacity and that Fe⁺³>Fe⁺² in the Khaluta parental melt. Our findings suggest that the mantle source for Khaluta carbonatite and associated rocks, as well as for other carbonatites of the West Transbaikalia carbonatite province, were SO₃-rich and characterized by high oxygen fugacity.     

CO<Subscript>2</Subscript>-rich fluid inclusions with chalcopyrite daughter mineral from the Fenghuangshan Cu–Fe–Au deposit,China: implications for metal transport in vapor

CO₂-rich fluid inclusions containing opaque mineral crystals were found in the Fenghuangshan skarn-porphyry Cu–Fe–Au deposit in Tongling, Anhui, China. These inclusions show variable CO₂ contents and are accompanied by aqueous inclusions, both occurring as secondary inclusions in quartz and being locally associated with chalcopyrite mineralization. Laser Raman microspectroscopic analyses confirm the predominance of CO₂ in the vapor and the presence of H₂S as high as 8 mol%, and identify the opaque mineral with yellow reflectance color in the inclusions as chalcopyrite. More than half of the CO₂-bearing inclusions contains chalcopyrite, whereas few of the associated aqueous inclusions do so. The chalcopyrite, occupying less than 1% (volume) of the inclusions, is interpreted to be a daughter mineral, and calculated Cu concentrations in the inclusions range from 0.1 to 3.4 wt%. Copper is inferred to have been transported in CO₂-dominated fluids as HS⁻ complexes. The occurrence of chalcopyrite daughter crystals in CO₂-rich fluid inclusions indicates that CO₂-rich vapor has the capacity of transporting large amounts of Cu, and possibly Au. This finding has significant implications for metal transport and mineralization in hydrothermal systems enriched in CO₂, such as orogenic-type and granitic intrusion-related gold deposits.