Stability and phase equilibria of chloride and carbonate bearing scapolites at 750°C and 4000 bar

At 750°C and 4000 bar scapolite is stable relative to plagioclase + calcite over the range of plagioclase compositions An₅₃–An₈₃. The assemblage plagioclase + scapolite + calcite is stable relative to plagioclase + calcite over the ranges of plagioclase composition An₄₈-An₅₃ and An₈₃–An_91.5. When NaCl is present in the coexisting fluid the range of scapolite compositions stable relative to plagioclase increases. High mole fractions of NaCl in the fluid stabilize scapolite relative to plagioclases from An₂₅ to An₈₇ in the presence of excess calcite. Determination of the $\text{Cl}\text{(Cl + CO}{}_3\text{)}$ ratios of the synthetic scapolites shows that the range of stable scapolite compositions is significantly larger than heretofore proposed, and that even the chloride and carbonate bearing scapolites must be considered a four component solid solution. The K_D for the exchange of NaCl and CaCo₃ between coexisting scapolite, fluid and carbonate is given by the equation In $\text{K}{}_{\mathrm{D}}\text{= (?0.0028) [}\text{Al}\text{(Al + Si)}\text{]}{}^{\mathrm{?5.5580}}$. This equation implies that Cl-poor natural scapolites coexisted with fluids low in NaCl, and that regional occurrences of Cl-rich scapolites are likely to represent metamorphosed evaporite sequences.     

Scapolite stoichiometry

Over the range Ca/(Ca + Na) from zero to 0.75, scapolites vary linearly between Na₄Al₃Si₉O₂₄Cl and NaCa₃Al₅Si₇O₂₄CO₃, by means of a coupled replacement of Na₃Si₂Cl by Ca₃Al₂CO₃. Ca includes minor Sr, Na includes K, and CO₃ may include substantial SO₄. From Ca/(Ca + Na) = 0.75 to 1.00, variation is between NaCa₃Al₅Si₇O₂₄CO₃ and Ca₄Al₆Si₆O₂₄CO₃, by means of a coupled replacement of NaSi by CaAl, as in plagioclase. Anion substitution is complete at the 0.75 point. Recalculation of scapolite analyses on the basis of Al + Si atoms = 12.0, as suggested by computed unit cell contents, offers a reasonable basis for normalization of atomic proportions. On this basis, Ca + Sr + Na + K + Fe atoms total very close to 4.0. New limits on the minor element content of scapolite are proposed. In view of the inflection at 0.75, subdivision of the scapolites at Ca/(Ca + Na) ratios of 0.25, 0.5, and 0.75 seems more logical than the 0.2, 0.5, and 0.8 limits used hitherto for marialite, dipyre, mizzonite, and meionite.     

Stable isotopic and petrological constraints on scapolitization of the Whitestone meta-anorthosite,Grenville Province,Ontario*

The Whitestone Anorthosite (WSA), located in the Central Gneiss Belt of the south-western Grenville Province, Ontario, exhibits a nearly concentric metamorphic envelope characterized by an increase in modal scapolite, hornblende, epidote and garnet, developed around a core of granulite facies clinopyroxene ± orthopyroxene ± garnet meta-anorthosite. Scapolite- and hornblende-bearing assemblages develop mainly at the expense of plagioclase and pyroxene within the envelope. Stable isotopic and petrological data for scapolite-bearing mineral assemblages within meta-anorthosite constrain the source of carbon responsible for CO₃-scapolite formation and the extent of fluid/rock interaction between the anorthosite and adjacent lithologies. Stable isotopic data indicate increasing δ¹⁸O and δ¹³C from core to margin of the meta-anorthosite and for samples from the southern extension of the WSA, where it is ductilely deformed within the Parry Sound Shear Zone (PSSZ). The average δ¹⁸O_SMOW value (whole rock) for the WSA core is 6.9‰, increasing to 11.5‰ where the WSA is in tectonic contact with marble breccia. The average δ¹³C_PBD value of scapolite in meta-anorthosite from the centre of the WSA is -3.4‰, increasing to -0.5‰ at the eastern (marble) contact. Average values of δ¹³C for scapolite and whole-rock δ¹⁸O for samples from the shear zone are -1.0 and 8.0‰, respectively. Marbles have average δ¹⁸O and δ¹³C values of 19.2 and -0.4‰, respectively. The sulphate content of texturally primary scapolite decreases from the core of the WSA (X_SO4= 0.48) to the eastern contact (≤0.05). Texturally late scapolite after plagioclase and garnet tends to be CO₃-rich relative to texturally primary scapolite, and some scapolite grains show zoning in the anion site with CO₃-enriched rims. Scapolite composition may vary at any scale from a single grain to outcrop. The pattern of isotopic enrichment in ¹³C and ¹⁸O preserved in the eastern margin of the WSA is consistent with marble as the major source of fluid contributing to the formation of the metamorphic envelope. The decrease in X_SO4 and increase in X_CO3 in scapolite toward the margin of the WSA indicate that the volatile content was reset by, or developed from, a CO₂-bearing fluid. Assuming derivation of fluid from marble, minimum fluid/rock values at the margin of the WSA range from 0.03 for the least enriched, to 0.30 for the most isotopically enriched samples. Although marble is not found in immediate contact with samples of sheared meta-anorthosite from the PSSZ, a marble source is also consistent with the C and O isotope composition and anion chemistry of scapolite within these samples.     

Stability of scapolite in the system Ab-An-NaCl-CaCO3 at 4 kb and 750°C

Scapolite solid solution has been synthesized at 750°C and 4 kbar and is stable relative to plagioclase + calcite + halite over the range of plagioclase compositions from Ab₈₅An₁₅ to Ab₇₀An₃₀, although albite + halite is stable relative to marialite, Na₄Al₃Si₉O₂₄Cl, and anorthite + calcite is stable relative to meionite, Ca₄Al₆Si₆O₂₄CO₃. A chloride-free scapolite, mizzonite, has been synthesized at the approximate composition NaCa₃Al₅Si₇O₂₄CO₃ (Ab. 2An. CaCO₃). In the absence of chloride, a three-phase invariant assemblage, sodic plagioclase (~Ab₆₀An₄₀) + scapolite + calcite is stable relative to plagioclase + calcite over the approximate range of plagioclase composition Ab₆₀An₄₀-Ab₃₅An₆₅ and another three-phase invariant assemblage, calcic plagioclase (~Ab₁₅An₈₅) + scapolite + calcite is stable over the approximate range Ab₃₀An₇₀-An₁₅An₈₅.Unit-cell dimensions and refractive indices have been determined for the scapotite synthesized in these experiments and are compared with values for chemically analyzed natural scapolites.Scapolite must be regarded as a ternary solid solution in which, at a given equivalent An-content, the Cl/CO₃ ratio in the large anion site can vary as a function of NaCl and CaCO₃ activities.     

Some precambrian scapolite-bearing rocks evolved from evaporites

Scapolitic gneisses and schists and conformable layers and lenses of scapolite-bearing marbles and calciphyres with scapolites and parapyroxenites are well developed in metasedimentary series of the Aldan shield, south Yakutia, USSR. Here scapolite, either by itself or associated with plagioclase, quartz, diopside or hornblende, is believed to be a metamorphic derivative of Archean saliferous sediments. Discoveries of disseminations and interlayered beds of anhydrite along with S-isotope data, support the theory that the scapolite rocks owe their origin to the metamorphism of evaporites. Commonly, the metasediments alternate with magnetite-rich horizons that were possibly derived from siderite, chlorite or hydroxide ironstones, interstratified with the evaporites.Rather similar rocks in the Precambrian of the Vitim and Baikal regions in Siberia and in the Canadian, Scandinavian and Madagascar-Australian shields, were probably also generated through the metamorphism of evaporites.     

Stability of the scapolite meionite (3CaAl2Si2O2 · CaCO3) at high pressures and storage of CO2 in the deep crust

The stability field of the end-member scapolite meionite was determined in piston-cylinder apparatus. Meionite has very high thermal stability at high pressures, exceeding 1500° C at 20 kbar. Below 6 kbar and 1270 ° C scapolite breakdown is subsolidus, to an-orthite + gehlenite + wollastonite + CO₂, with a slope of 20 bars/degree. An extrapolation of existing thermodynamic data for CO₂ permits calculation of ΔG _F ^o =-2384.5 kcal/mol for meionite at 1270 ° C, very close to the value for 3 anorthite + calcite. Above 1270 ° C, scapolite begins to melt to An+Geh+Liq+CO₂, and as pressure increases the melting curve steepens, the Geh and An being progressively replaced by Liq+corundum with Al in 6-coordination. At pressures >25kbar dp/dt becomes negative, corundum is the only crystalline product, and CO₂ bubbles disappear from the quenched glass, indicating a solubility of CO₂ under these conditions of about 5 wt. percent in the liquid. The subsolidus breakdown of meionite at high pressures to grossularite + kyanite + quartz + calcite nearly coincides with the upper pressure limits of anorthite. Thus scapolite is essentially limited to crustal rocks. In view of its great thermal stability, meionite can play a role as a primary mineral in deep-seated basic or intermediate magmatic processes. It is also likely that CO₂ coming from the earth's interior will be captured by reaction with plagioclase and clinopyroxene. Scapolite has been noted in basic granulite inclusions from basaltic pipes in three continents. It seems probable that scapolite acts as a major storage site for CO₂ in the deep crust.     

Mode of formation of hibonite (CaAl12O19) within the U-Th skarns from the granulites of S-E Madagascar

 In Madagascar, hibonite occurs as a rather frequent mineral within thorianite-bearing skarns which are widespread in the Pan African granulitic formations constituting the S-E part of the Island (Tranomaro area). In these skarns, leucocratic segregations made up of CO₃-scapolite to meionite (An_equivalent=89–95% which implies T≥850° C), spinel and corundum were formed at stage 1 of metasomatism in a titanite-bearing matrix consisting of scapolite (An_eq=77–88) and aluminous diopside. During stage 2 of metasomatism, scapolite from the lenses were altered to anorthite+calcite while the less calcic scapolite remained stable which indicates T≈800° C. Hibonite crystallized at the expense of corundum and spinel. Expressed as mol% of the CaAl₁₂O₁₉/Ca(Al₁₀TiR²⁺)O₁₉/REE(Al₁₁R²⁺)O₁₉ [+Th (Al₁₀R²⁺ ₂)O₁₉] end-members (R ²⁺=Mg, Fe²⁺, Zn²⁺; Al=Al, Fe³⁺; Ti=Ti, Si), its composition varies from 26/72/2 to 50/23/27. The ideal activity of the CaAl₁₂O₁₉ component is about 0.25. Fluid inclusions in corundum, hibonite and anorthite are composed of nearly pure CO₂. In corundum, the isochores for primary inclusions are in agreement with the P-T estimates for regional metamorphism and stage 1 metasomatism (T≈850° C, P≈5 kbar). Inclusions with the highest density in hibonite and anorthite constrain P to about 3–3.5 kbar for T=800° C. Thermodynamic calculations indicate that, in addition to a low activity of CaAl₁₂O₁₉, stability of hibonite in equilibrium with anorthite and calcite implies an extremely low activity of silica (below the zircon-baddeleyite buffer). By contrast the activity of CO₂ may be high, in agreement with the observed fluid compositions. These results are corroborated by a short comparison with the other granulite occurrences of hibonite in Tanzania and South India. Received: 18 August 1994 / Accepted: 12 October 1995     

New constraints on the release of noble gases during in vacuo crushing and application to scapolite Br–Cl–I and Ar/Ar age determinations

The release of irradiation-produced noble gas isotopes (³⁸Ar_Cl, ⁸⁰Kr_Br, ¹²⁸Xe_I and ³⁹Ar_K) during in vacuo crushing scapolite has been investigated and is compared to quartz. Three thousand crushing strokes released 98% of fluid inclusion-hosted noble gas from quartz. In comparison, 3000 crushing strokes released only 4% of the lattice-hosted ³⁸Ar_Cl from a scapolite gem. In vacuo crushing released lattice Ar preferentially relative to lattice Kr or Xe and prolonged crushing released 88% of the lattice-hosted noble gas in 96,000 crushing strokes. We suggest fast diffusion pathways generated by crushing are an important noble gas release mechanism and we demonstrate two applications of prolonged in vacuo crushing on irradiated scapolite.Firstly, scapolite molar Br/Cl and I/Cl values are shown to vary over a similar range as crustal fluids. The Cl-rich scapolite gem from Hunza, Pakistan has Br/Cl of 0.5–0.6 × 10⁻³ and I/Cl values of 0.3–2 × 10⁻⁶, that are similar to fluids that have dissolved evaporites. In contrast, three out of four skarn-related scapolites from the Canadian Grenville Province have molar Br/Cl values of 1.5–2.4 × 10⁻³, and I/Cl values of 11–24 × 10⁻⁶, that are broadly consistent with skarn formation by magmatic fluids. The fourth Grenvillian scapolite, with only 0.02 wt% Cl, has an exceptionally elevated molar Br/Cl value of up to 54 × 10⁻³ and I/Cl of 284 × 10⁻⁶. It is unclear if these values reflect the composition of fluids formed during metamorphism or preferential incorporation of Br and I in Cl-poor meionitic scapolite.Secondly, the Grenvillian scapolites give plateau ages of between 830 Ma and 400 Ma. The oldest ages post-date regional skarn formation by 200 Myr, but are similar to feldspar cooling ages in the Province. The age variation in these samples is attributed to a combination of factors including variable thermal history and the presence of mineral sub-grains in some of the samples. These sub-grains control the release of ³⁹Ar_K, ³⁸Ar_Cl and ⁴⁰Ar* during in vacuo crushing as well as the samples ⁴⁰Ar* retentivity in nature. Scapolite is suggested as a possible analogue for K-feldspar in thermochronologic studies.     

T-XCO2 stability relations and phase equilibria of a calcic carbonate scapolite

At a total pressure of 5 kb, calcic, Cl-free scapolite (Me₈₃) is stable relative to plagioclase-bearing assemblages at $\text{T ≧ 625°C}$, . With decreasing temperature, scapolite breaks down to plagioclase + calcite. Scapolite is replaced by plagioclase + grossular + cancrinite + CO₂ in the presence of H₂O-rich fluids. The stable coexistence of scapolite and calcite, an assemblage typical of most natural occurrences of calcic scapolite, is limited by the reaction: scapolite + calcite → grossular + cancrinite + CO₂, which occurs at 750°C, X_CO2 = 0.46; 700°C, X_CO2 = 0.33; 650°C, X_CO2 = 0.18, for the chosen bulk composition.Generalization of the experimental results to encompass the complete range of fully carbonated scapolite compositions indicates that mizzonite (Me₇₅) has the largest T-X_CO2 stability field. For scapolite more calcic than mizzonite, stable growth is restricted to conditions of increasingly higher temperature and X_CO2.The experimental results are consistent with various petrologic features of scapolite-bearing rocks, particularly scapolite-clinopyroxene granulites, and indicate that such rocks were formed in the presence of CO₂-rich fluids.     

Occurrence and origin of marialitic scapolite in the Humboldt lopolith,N.W. Nevada

The occurrence and origin of marialitic scapolite in the Humboldt lopolith was investigated in the field and in the laboratory using petrographic and experimental techniques. Scapolite occurs in three modes: as a pervasive replacement of plagioclase and other minerals in gabbro, diorite and extrusive rocks; as a poikiloblastic mineral in scapolitite dikes; and as a fracture-filling mineral with analcime, albite and sphene in scapolite veins. Additional secondary minerals associated with scapolite include epidote, prehnite, hornblende and diopside-salite clinopyroxene. Relations with these minerals suggest that most marialitic scapolite grew at temperatures around 400° C. Scapolite composition varies from EqAn₁₂ to EqAn₃₇, containing from 72 to 96 atomic% Cl in the R position. Experiments on systems of similar compositions indicate that NaCl-H₂O fluid having more than 40 mol% NaCl is needed to stabilize the scapolite.Variation in scapolite compositions is due to thermal and fluid compositional gradients normal to conduits of hydrothermal fluids, and occurs on a scale up to 100 m. The likely source of Na and Cl is pre-existing evaporites or evaporitic brine derived from the wallrocks. Salinity could have been increased to a level sufficient to stabilize scapolite by hydration of an originally dry magma, possibly aided by hydrothermal boiling. Results may be applied to hydrothermal alteration in areas of rifting or back-arc spreading, and in mid-ocean ridge hydrothermal systems.     

Tungsten skarn mineralizations in a regional metamorphic terrain in northern Norway: a possible metamorphic ore deposit

Scheelite- and molybdenite-bearing scapolite skarn and plagioclase skarn occur as stratabound mineralizations in a terrain which has suffered regional metamorphism. Scapolite skarn formed as replacement skarns in plagioclase-bearing hornblendic gneiss whereas plagioclase skarn precipitated in fractures as vein skarn mineralizations. The genesis of these skarn deposits are closely connected to an episode of boudinage on the limbs of a large-scale dome-shaped fold. Fluid inclusion studies revealed that the ore-forming fluids were composed of CO₂ with 2 to 17 mole% CH₄, which formed due to decarbonation reactions during peak metamorphism at the end of the Caledonian orogenesis. Thermodynamic considerations indicate that scapolite and plagioclase formed above 550 °C and 2 Kbar pressure and were followed by precipitation of scheelite between 400 and 570 °C.     

Retrograde formation of NaCl-scapolite in high pressure metaevaporites from the Cordilleras Béticas (Spain)

A Permo-Triassic pelite-carbonate rock series (with interacalated metabasitic rocks) in the Cordilleras Béticas, Spain, was metamorphosed during the Alpine metamorphism at high pressures (P _min near 18 kbar). The rocks show well preserved sedimentary features of evaporites such as pseudomorphs of talc, of kyanite-phengitetalc-biotite, and of quartz after sulfate minerals, and relicts of baryte, anhydrite, NaCl, and KCl, indicating a salt-clay mixture of illite, chlorite, talc, and halite as the original rock. The evaporitic metapelites have a whole rock composition characterized by high Mg/(Mg+Ca) ratios>0.7, variable alkaline and Sr, Ba, contents, but are mostly K₂O rich (<8.8 wt%). The F (<2600 ppm), Cl (<3600 ppm), and P₂O₅ (<0.24 wt%) contents are also high. The pelitic member of this series is a fine grained biotite rock. Kyanite-phengite-talc-biotite aggregates in pseudomorphs developed in the high pressure stage. Albite-rich plagioclase was formed when the rocks crossed the albite stability curve in the early stages of the uplift. Scapolite, rich in NaCl (Ca/(Ca+Na) mol% 24–40) and poor in SO₄, with Cl/(Cl+CO₃) ratios between 0.6 and 0.8, formed as porphyroblasts, sometimes replacing up to 60% of the rock in a late stage of metamorphism (between 10 and 5 kbar, near 600°C). No reaction with albite is observed, and the scapolite formed from biotite by: $$\begin{gathered} Al - biotite + CaCO_3 + NaCl + SiO_2 \hfill \\ = Al - poor biotite + scapolite + MgCO_3 + KCl \hfill \\ + MgCl_2 + H_2 O \hfill \\ \end{gathered}$$ Calculated fluid composition in equilibrium with scapolite indicates varying salt concentrations in the fluid. Distribution of Cl and F in biotite and apatite also indicates varying fluid compositions.     

Polymerization of silicate and aluminate tetrahedra in glasses,melts, and aqueous solutions—IV. Aluminum coordination in glasses and aqueous solutions and comments on the aluminum avoidance principle

The coordination of aluminum with oxygen in crystalline and amorphous alumina, aluminates, and aluminosilicates has been determined with magic angle spinning ²⁷Al nuclear magnetic resonance. The ²⁷Al NMR spectra of crystalline materials show that ^VIAl and ^IVAl can readily be distinguished. The same is not the case for amorphous aluminosilicates due to the superposition of a narrow peak, characteristic of ^IVAl, on a broad band. Our spectroscopic results indicate that Al coordination is not the determining factor in explaining differences in devitrification behavior of albite and anorthite glasses. The coordination of Al in aqueous solutions seems to prevent precipitation of the three common Al(OH)₃ polymorphs (^VIAl) at pH above 10. There is clear evidence to suggest that, in solutions containing Si as well as Al, aluminum coordination is related to the type of precipitate formed in acid (clays, ^VIAl, ^IVAl), and basic (zeolites, ^IVAl) environments. Zeolites can be precipitated in near neutral pH environments at higher temperatures, reflecting an increase in ^IVAl under these conditions. The Al avoidance principle for aluminosilicates does not seem to be a hard principle. It is likely that the validity of this principle depends on the type of modifying cation present in the aluminosilicate framework.     

Empirical study of the infrared lattice vibrations (1100–350 cm−1) of phlogopite

A detailed evaluation of the assignments given to the infrared (IR) vibrations in the lattice stretching region is presented here based on observations of the effects of various chemical substitutions in synthetic analogues of phlogopite, KMg₃(AlSi₃)O₁₀(OH)₂. As in previous studies, this study has confirmed that the 995, 960, and 460 cm^?1 vibrations are influenced by Si, the 822 and 760 cm^?1 vibrations by Al, the 915 and 725 cm^?1 vibrations by Al and Si, and the 592 cm^?1 vibration by OH. Contrary to previous studies, it is shown here that the 690, 495, and 375 cm^?1 vibrations are strongly linked with Mg and not just Si. The 655 cm^?1 band in phlogopite is attributed to an in-plane Al-O vibration rather than an Al-O-Si vibration. As a check on the band assignments made here, IR spectra were obtained for synthetic clintonite, CaMg₂Al(Al₃Si)O₁₀(OH)₂, as well as its chemical analogues and compared with the IR spectrum of phlogopite. The band intensities for the Si-O, Al-O, and Si-O-Mg vibrations changed in accord with the composition of clintonite. The most intense band in clintonite at 660 cm^?1 appears to be associated only with Al and is assigned here to a tetrahedral Al-O-Al vibration which must be present, if not dominant, in this mineral. The near coincidence of an in-plane Al-O vibration at 655 cm^?1 (phlogopite) and an in-plane Al-O-Al vibration at 660 cm^?1 (clintonite) makes the identification of tetrahedral Al-Si order-disorder in trioctahedral layered silicates by IR spectroscopy very difficult. The ratio of the 822/995 cm^?1 bands may, however, prove to be very useful for discerning the amount of tetrahedrally coordinated Al in these types of minerals.     

Defects and short-range order in nepheline group minerals: a silicon-29 nuclear magnetic resonance study

²⁹Si magic-angle spinning nuclear magnetic resonance (NMR) spectra are presented for seven crystalline phases of the nepheline group: natural nephelines from a plutonic environment (Bancroft, Ontario) and a volcanic deposit (Mt. Somma, Italy), kalsilite, synthetic pure Na nepheline, carnegieite, and two samples of orthorhombic KAlSiO₄. In all phases, nearly all of the Si sites have four Al neighbors, indicating nearly complete Al-Si ordering. Excess Si over the 1:1 stoichiometric Si/Al ratio appears to substitute randomly for Al on an ordered lattice, adding Si sites with 3 and 0 Al neighbors in a 3:1 ratio. Various types of structural disorder, including Al-Si disorder, that are reported from some x-ray diffraction studies are probably long range in nature and are due to the presence of ordered domains. In naturally occurring nepheline, the relative abundance of T sites with three-fold local symmetry is maintained at the ideal stoichiometric value of 1/4, even when the K/(K+Na) ratio is substantially lower. This is in agreement with conclusions reached about the average structure from x-ray data. The distinction between the two sites, at least in terms of the local structure that is reflected in ²⁹Si NMR chemical shifts, is lost in a pure Na nepheline sample.     

Photoluminescence spectra of S<Subscript>2</Subscript><Superscript><Emphasis Type="Bold">−</Emphasis></Superscript> center in natural and heat-treated scapolites

The emission and excitation spectra of yellow luminescence due to S₂ ⁻ in scapolites (#1 from Canada and #2 from an unknown locality) were observed at 300, 80 and 10 K. Emission and excitation bands at 10 K showed vibronic structures with a series of maxima spaced 15–30 and 5–9 nm, respectively. The relative efficiency of yellow luminescence from scapolite #2 was increased up to 117 times by heat treatment at 1,000°C for 2 h in air. The enhancement of yellow luminescence by heat treatment was ascribed to the alteration of SO₃ ²⁻ and SO₄ ²⁻ to S₂ ⁻ in scapolite.     

Metasomatism of gabbro – mineral replacement and element mobilization during the Sveconorwegian metamorphic event

Widespread metasomatism affected the 100 km long and 25 km wide Proterozoic Bamble and Modum‐Kongsberg sectors, South Norway, resulting in the chemical and mineralogical transformation of wide segments of continental crust. Scapolitization was associated with veining, and was followed by albitization, transforming metagabbros pervasively over large areas. Fluids played an active role in these reactions, forming H₂O‐, CO₂‐ and Cl‐bearing phases at the expense of the primary volatile‐free minerals, causing depletion in Fe and infiltration of K, Mg, Na, B and P. The transformation of gabbro to scapolite metagabbro is observed as a fluid front replacing the primary magmatic mineral assemblage in three stages: during an incipient amphibolitization stage, the primary mafic minerals were replaced by anthophyllite or hastingsite, followed by pargasitic and edenitic Ca‐amphibole. Magnetite was dissolved, while rutile formed by the breakdown of ilmenite. Plagioclase was replaced by Cl‐rich scapolite (Me_19‐42) reflecting Cl‐saturation, while K‐ and Mg‐saturation produced phlogopite, enstatite, sapphirine and rare corundum. The high modal contents of chlorapatite and tourmaline in the scapolite metagabbro imply infiltration of B and P. The albitites consist dominantly of albite (Ab_95‐98) with varying, generally small, amounts of chlorite, calcite, rutile, epidote and pumpellyite. They formed from a H₂O–CO₂‐fluid rich in Na. The gabbro yields a zircon U–Pb age of 1149 ± 7 Ma and tonalite 1294 ± 38 Ma, whereas rutile from scapolite metagabbro and albitite has U–Pb ages of 1090–1084 Ma, and phlogopite produced during scapolitization Rb–Sr ages of 1070–1040 Ma. Temperature conditions for the scapolitization are inferred to have been 600–700 °C. The reported ages, combined with mineralogical and petrographic observations and inferred P–T conditions, indicate that the metasomatism was a part of the regional Sveconorwegian amphibolite facies metamorphic phase. Initial ⁸⁷Sr/⁸⁶Sr of the scapolite ranges from 0.704 to 0.709. The Sr‐signature, the Cl‐ and B‐rich environment and regional distribution of lithologies suggest that the fluid may have originated from evaporites that were mobilized during the regional metamorphism.     

Evidence for the nucleation and epitaxial growth of Zn phyllosilicate on montmorillonite

Zinc uptake in suspensions (?3.7 g L⁻¹) of MX80 montmorillonite was investigated at pH 4.0 and 7.3, a total Zn concentration ([Zn]_total) of 500 μM, and dissolved Si concentrations ([Si]_aq) of ∼70 and ∼500 μM in 0.5 M NaCl, by kinetics experiments and polarized extended X-ray absorption fine structure (P-EXAFS) spectroscopy. Differential thermogravimetric analysis verified the cis-vacant character of the montmorillonite. No Zn uptake occurred at pH 4.0, confirming that cation exchange was hampered by the high ionic strength of the suspension. At pH 7.3 and low [Si]_aq (∼70 μM), Zn uptake occurred rapidly during the first hour of reaction, and then leveled off to 50 μmol/g montmorillonite at 168 h. The uptake rate is consistent with Zn sorption on pH-dependent edge sites. At pH 7.3 and high [Si]_aq (∼500 μM), the initial sorption rate was similar, but Zn sorption continued, reaching 130 μmol/g at 168 h, and was paralleled by Si uptake with a Si/Zn uptake ratio of 1.51(10), suggesting formation of a Zn (hydrous) silicate. P-EXAFS data indicated that the first oxygen coordination shell of sorbed Zn is split into two subshells at 1.97(2) and 2.08(3)-2.12(2) Å for all EXAFS samples. These two distances are assigned to a mixture of tetrahedral (^IVZn) and octahedral (^VIZn) Zn complexes. The proportion of ^IVZn was lower in the high [Si]_aq samples and decreased with reaction time. Al low [Si]_aq and 216 h of reaction, nearest cationic shells of 0.6(4) Al in the film plane and 0.5(4) Si out of the film plane were detected at 3.00(2) and 3.21(2) Å, respectively, and were interpreted as the formation of ^IVZn and ^VIZn mononuclear complexes at the edges of montmorillonite platelets, in structural continuity to the (Al, Mg) octahedral sheets. At high [Si]_aq, in-plane Zn and Al and out-of-plane Si neighbors were detected at 4 h, indicating the formation of Zn phyllosilicate nuclei at the layer edges. At 313 h, Zn-Al pairs were no longer detected, and Zn atoms were surrounded on average by 3.4(5) in-plane Zn at 3.10(1) Å and 1.7(9) out-of-plane Si at 3.30(2) Å, supporting the precipitation of a Zn phyllosilicate. Thus, dioctahedral Al phyllosilicate may act as a nucleating surface for the heterogeneous formation of trioctahedral Zn phyllosilicate at [Si]_aq relevant to natural systems.     

Pedogenically degenerated illite and chlorite lattices aid to palaeoclimatic reconstruction for chronologically constrained(8-130 ka) loess-palaeosols of Dilpur Formation,Kashmir,India

Chronologically well-constrained loess-palaeosols(recorded glacial and inter-glacial climate) revealed pedogenesis induced ionic substitutions,caused end-member compositional deviations in illite and chlorite,linked to widespread climatic changes occurred during Late Pleistocene.Further,micro-level climatic resolution is yet to be resolved.Thus,layer-wise X-ray diffraction analyses of clay separates,followed by Rietveld refinement revealed varied cell parameters and interatomic distances.Obtained values for detrital and pedogenic illite and chlorite when plotted against stratigraphic succession show notable changes in the crystallographic axes.The illite lattices associated with inadequately pedogenized palaeosols have been altered into illite/smectite mixed layers,but,the chlorite lattices represent expansion of a-,b-and contraction of c-axes with much greater amount of distortions,suggestive of warm-humid and acidic environment.The detrital 48,44 and 83,74 bonded illite and chlorite with2 sub-types each,when pedogenized retained 48,44 and 34;and 83 and 74 bonds(in their neo-formed 3 and 2 sub-types),respectively.The Al-O bond shows expansion,but,unchanged Si-O and decreased Si-K and K-O bonds show loss of Al and retention of Si and K ions in the illite lattices.The illite with 32 atoms and 48 bonds represent contraction of K-O,Si-K,Al-O and Si-O bonds caused bond reinforcement;however,loss of Al~(3+)reflects all-out illite alteration.Owing to Al-O and K-O bond expansion,major K~+ and Al~(3+) ionic loss occurred during the LGM,however,further ionic loss depends upon the magnitude of the loess-palaeosol weathering that they have suffered.The clilate sensitive Fe,Mg and Al ionic losses for Fe-O,Mg-O and Al_(11)-O_9 bond length expansions were recognized in the chlorite lattices.Such ionic losses are common,but,complete distortion is attributed to Al,Si,Fe and Mg ionic losses,followed by weakening of Al-O,Si-O,Fe-O and Mg-O bonds.Though,Si-O_4 and Fe_1-O_4 bonds,and Si and Fe_(1 st) ions remain intact.Thus,three major glacial episodes of ～5 ka each occurred under alkaline environment,but,intervened by two successive cycles of 55 ka each,encompassing three alternate warm and cold climatic sub-cycles of 12-15 ka.But,the coldness increases with each warm-cold sub-cycle that attained the glacial maxima.Further,these events correlate well with the deep-sea records of the North Atlantic(MIS-1 to MIS-5 e) and CLP loess-palaeosols(～127 ka).     

Mineralogy of a scapolite-bearing rock from Rajasthan,northwest peninsular India

Electron-microprobe analyses of coexisting phases from a scapolite-garnet-epidote-calcite-plagioclase-hornblende-pyroxene (sphere-hematite-magnetite) rock of the Aravalli Group (Early Precambrian) at Karera, district Bhilwara, Rajasthan, reveal that chlorine is an important constituent of both scapolite (Me_71.3 and hornblende, making the latter a dashkesanite variety. The amphibole also contains an unusually high K₂O (3.7 wt.%), and is a chlor-potassium hastingsite. The epidote contains 41% pistacite and shows complete substitution of Al by Fe³⁺ in the Al-site and to some extent also in AIO and/or Al(OH) sites. The garnet is also rich in ferric iron and has a mol. composition Pyr₂₃Alm_8.5Gro₁₃And_54.5 Sp_1.0. The pyroxene is dominantly a hedenbergite. The phase relations and textural as well as geological criteria exclude metasomatic processes and favour equilibrium recrystallization of the scapolite-bearing assemblage; the chlorine presumably derived from an evaporite component of the Aravalli metasediments. The geothermometry based on the fractionation of Na and Ca between scapolite (EqAn 43.3) and plagioclase (An_85?90 yields metamorphic temperatures of around 700°C for the scapolite-bearing rock which are in agreement with those obtained by other mineral equilibria in the associated pelitic assemblages.