Carbonation of Cl-rich scapolite boudins in Skallen, East Antarctica: evidence for changing fluid condition in the continental crust

Spectacular reaction textures in poikiloblastic scapolitite boudins, within marbles in the continental crust exposed in the Lützow–Holm Complex, East Antarctica, provide insights into the changing fluid composition and movement of fluid along grain boundaries and fractures. Petrographic and geochemical features indicate scapolite formation under contrasting fluid compositions. Core composition of scapolite poikiloblasts (Scp_I) are marialitic (Cl = 0.7 apfu) whereas rims in contact with biotite or clinopyroxene are meionite rich. Fine‐grained recrystallized equigranular scapolite (Scp_II) shows prominent chemical zoning, with a marialitic core and a meionitic rim (Cl = 0.36 apfu). Scapolite poikiloblasts are traversed by Scp_III reaction zones along fractures with compositional gradients. Pure CO₂ fluid inclusions are observed in healed fractures in scapolite poikiloblasts. These negative crystal‐shaped fluid inclusions are moderately dense, and are believed to be coeval with Scp_III formation at temperatures >600 °C and a minimum pressure of c. 3.8 kbar. Grain‐scale LA‐ICPMS studies on trace and rare earth elements on different textural types of scaplolites and a traverse through scapolite reaction zone with compositional gradient suggest a multistage fluid evolution history. Scp_I developed in the presence of an internally buffered, brine‐rich fluid derived probably from an evaporite source during prograde to peak metamorphism. Recrystallization and grain size reduction occurred in the presence of an externally sourced carbonate (CaCO₃)‐bearing fluid, resulting in the leaching of Cl, K, Rb and Ba from Scp_I along fractures and grain boundaries. Movement of fluids was enhanced by micro‐fracturing during the transformation of Scp_I to Scp_III. Fractures in fluorapatite are altered to chlorapatite proving evidence for the pathways of escaping Cl‐bearing fluids released from Scp_I. The present study thus provides evidence for the usefulness of scapolite in fingerprinting changing volatile composition and trace element contents of fluids that percolate within the continental crust.     

The origin of scapolite in the regionally metamorphosed rocks of Mary Kathleen,Queensland, Australia

Scapolite at Mary Kathleen (North-Western Queensland) occurs in calcareous and non-calcareous metapelites, acid and basic metavolcanics and metadolerites. Graphical treatment of the relationship between scapolite composition (Me%) and the host rock oxide ratios CaO/Na₂O and Al₂O₃/(CaO + Na₂O) reveals the following points:

1. The calcareous metapelites are also very sodic.
2. Scapolite in calcareous metapelites is more marialitic than that in low-calcium equivalents.
3. In graphs of Me% against CaO/Na₂O and Al₂O₃/(CaO + Na₂O) the metasediments and the metaigneous rocks show markedly different trends.

It is concluded that scapolite in the metasediments originated by isochemical metamorphism of shales and marls containing evaporitic halite. The local abundance of halite was the main control on the composition and distribution of the scapolite, but the relative abundance of CaO and Na₂O was a modifying factor. In the metaigneous rocks scapolite formed metasomatically during regional metamorphism by the introduction of volatile-rich fluids derived from the adjacent evaporitic sediments. The relative availability of CO₂ and Cl₂ again appears to have been the primary control on scapolite composition and may in turn have been controlled by bulk rock composition.     

西昆仑南带斜长角闪岩中方柱石的形成与流体挥发分的作用

对西昆仑南带变基性岩矿物组合及矿物成分变化的研究结果表明，挥发分的种类和含量直接影响到变基性岩矿物组合和矿物成分，如角闪石、黑云母、方柱石、磷灰石和榍石；方柱石并非如有人总结的那洋没有出溶现象，实际上其自身亦可沿{100}析离出黄铁矿晶体，所含硫的赋存状态很可能是S^2-，而不是SO4^2-；方柱石是早期（高温）变质过程中部分挥发分（如Cl、CO3^2-、S^2-）的存储器，晚期剪切变形降温和/或降压时挥发分释出，伴随的流体作用可形成金属硫化物，并可能导致矿化。     

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.     

Unusual shape of pyrrhotite inclusions in scapolite of igneous rocks from the southernern Urals

The unique igneous rock (scapolite–diopside gabbro) from the Ilmeny Mountains in the southern Urals is described. Gabbro fills a segment of dike 1.3 m thick that cuts through calcite–dolomite carbonatite. Medium-grain pyroxenite with scapolite that occurs at selvages gradually passes to scapolite-bearing gabbro in the central part of the dike. Scapolite crystals display surfaces of concurrent growth, which are evidence of their magmatic origin. Scapolite (Me 63–70%) contains numerous pyrrhotite inclusions as platelets 0.001 mm thick oriented parallel to the cleavage plane {100}. The calculated pyrrhotite formula is consistent with its stoichiometry (Fe_1–xS). The morphology of the platelets (hexagonal sections) and their optical properties indicate a hexagonal symmetry of pyrrhotite. As follows from the insignificant difference between scapolite grains with and without pyrrhotite inclusions, scapolite and pyrrhotite should be regarded as products of synchronous magmatic melt crystallization.     

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.     

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.     

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.     

Metamorphic Conditions and Fluid Compositions of Scapolite-Bearing Rocks from the Lapis Lazuli Deposit at Sare Sang, Afghanistan

Scapolite and other halogen-rich minerals (phlogopite, amphibole,apatite, titanite and clinohumite) occur in some high-pressureamphibolite facies calc-silicates and orthopyroxene-bearingrocks at Sare Sang (Sar e Sang or Sar-e-Sang), NE Afghanistan.The calc-silicates are subdivided into two groups: garnet-bearingand garnet-free, phlogopite-bearing. Besides garnet and/or phlogopite,the amphibolite facies mineral assemblages in the calc-silicatesinclude clinopyroxene, calcite, quartz and one or more of theminerals scapolite, plagioclase, K-feldspar, titanite, apatiteand rarely olivine. Orthopyroxene-bearing rocks consist of clinopyroxene,garnet, plagioclase, scapolite, amphibole, quartz, calcite andaccessory dolomite and alumosilicate (kyanite?). Retrogradephases in the rocks are plagioclase, scapolite, calcite, amphibole,sodalite, haüyne, lazurite, biotite, apatite and dolomite.The clinopyroxene is mostly diopside and rarely also hedenbergite.Aegirine and omphacite with a maximum jadeite content of 29mol % were also found. Garnet from the calc-silicates is Grs_45–95Py_0–2and from the orthopyroxene-bearing rocks is Grs_10–15Py_36–43.Peak P–T metamorphic conditions, calculated using availableexchange thermobarometers and the TWQ program, are 750°Cand 1·3–1·4 GPa. Depending on the rock type,the scapolite exhibits a wide range of composition (from Eq_An= 0·07, X_Cl =0·99 to Eq_An = 0·61, X_Cl =0·07).Equilibria calculated for scapolite and coexisting phases atpeak metamorphic conditions yield X_CO2 = 0·03–0·15.X_NaCl (fluid), obtained for scapolite, ranges between 0·04and 0·99. Partitioning of F and Cl between coexistingphases was calculated for apatite–biotite and amphibole–biotite.Fluorapatite is present in calc-silicates, but orthopyroxene-bearingrocks contain chlorapatite. Cl preferentially partitions intoamphibole with respect to biotite. All these rocks have sufferedvarious degrees of retrogression, which resulted in removalof halogens, CO₂ and S. Halogen- and S-bearing minerals formedduring retrogression and metasomatism are fluorapatite, sodalite,amphibole, scapolite, clinohumite, haüyne, pyrite, andlazurite, which either form veins or replace earlier formedphases. KEY WORDS: scapolite; fluid composition; high-pressure; amphibolite facies; Western Hindukush; Afghanistan     

Cl/Br of scapolite as a fluid tracer in the earth's crust: insights into fluid sources in the Mary Kathleen Fold Belt,Mt. Isa Inlier,Australia

A combination of analytical methods, including trace element analysis of Br in scapolite by LA‐ICP‐MS, was employed to unravel the fluid–rock interaction history of the Mary Kathleen Fold Belt of northern Australia. Halogen ratios in the metamorphic and hydrothermally derived scapolite from a range of rock‐types record interaction between the host rocks and magmatic‐hydrothermal fluids derived from granite plutons and regional metamorphism. The results show that halite‐dissolution supplied at best only minor chlorine to fluids in the Fold Belt. Chlorine/bromine ratios in metamorphic scapolite indicate that fluids were dominantly derived from basinal brines formed from sub‐aerial evaporation of seawater beyond the point of halite saturation. This bittern fluid infiltrated the underlying sedimentary sequences prior to regional metamorphism. Zoned scapolite in a major late metamorphic mineralized shear‐zone records three discrete pulses of magmatic and metamorphic fluid, and it is suggested that fluid mixing may have assisted mineralization along and around this shear‐zone. As a crucial prerequisite for halogen fluid tracer studies using scapolite, we find in our samples that Cl and Br do not fractionate when incorporated in scapolite. Furthermore, unaltered rims of heavily retrogressed scapolite show indistinguishable Cl/Br signatures compared with fresh grains from the same sample indicating retrograde metamorphism did not significantly affect Cl and Br signatures in scapolite group minerals.     

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.     

Short-chain carboxylates in fluid inclusions in minerals

The carboxylate (formate, acetate, propionate and oxalate) and common inorganic anions (F⁻, Cl⁻ and SO²⁻₄) compositions for aqueous fluid inclusion leachates from 17 mineral samples collected from various deposits have been determined using ion chromatography in conjunction with microthermometric measurements on the fluid inclusions of their host minerals. The minerals, quartz, fluorite, barite, beryl and a few `ore' minerals (wolframite, pyrite and galena), came from hydrothermal vein-type deposits in felsic igneous rocks or Archean metamorphic rocks. The results indicate that short-chain carboxylates are common components in hydrothermal fluids and can be present in considerable amounts. Formic acid (as formate) is the dominant species over other carboxylic acids. The present study raises new questions about the origin and geochemical significance of carboxylates in hydrothermal ore-forming processes.     

大别-苏鲁高压、超高压变质带榴辉岩和脉体中磷灰石氯含量和流体盐度关系的研究

流体的盐度对含羟基变质矿物组合的稳定温压条件和岩石-流体的相互作用有重要影响.流体的盐度可从矿物中氯含量的角度加以研究.磷灰石是一个含氯矿物,作为副矿物广泛分布在各种岩石中,且能在较宽的温压范围内稳定存在.本文选择大别-苏鲁造山带中典型的高压、超高压岩石开展了磷灰石成分的研究,结合前人流体包裹体的研究结果,探讨了榴辉岩相条件下流体盐度和磷灰石中的氯含量之间的关系.榴辉岩和脉体中磷灰石的XClAp/XOHAp比值与已有的流体包裹体盐度呈很好的线性正相关.榴辉岩和脉体中磷灰石的XClAp/XoHAp比值范围为0.00～0.35时,对应的流体包裹体盐度约为0～40％ NaCleqv.     

流体的氯含量及其演化：来自岩石含氯矿物的记录

含氯流体是地质作用中重要的流体形式之一。通过含羟基矿物的氯含量来反演流体的组分及其演化是流体研究的一个重要方面。角闪石、黑云母、方柱石和磷灰石是主要的含氯矿物,可以揭示含氯流体与岩石的相互作用。这些矿物的氯含量受平衡流体的成分、温压条件以及自身的晶体化学结构等复杂因素制约。一方面,结合实验确定的热力学数据可以通过矿物氯含量在一定范围内定量计算流体的氯组分;另一方面,也可以根据矿物的氯含量变化特征来反演流体 岩石相互作用过程中流体成分的变化特征,这样的流体成分演化可能反映了特定的地质过程。     

Textures and compositions of cobalt pentlandite and cobaltian mackinawite from the Madan-Kudan copper deposit,Khetri Copper Belt,Rajasthan, India

The Khetri Copper Belt (KCB), a part of the Proterozoic Delhi–Aravalli fold belt in western India, hosts several Cu deposits, which are known to contain considerable Au, Ag, Co and Ni. Although many Co-bearing phases have been reported from the KCB and adjacent areas, detailed textural and geochemical data are either unavailable or scant except for mackinawite. In this study, we describe the textures and compositions (determined by EPMA) of two very rare Co-rich phases, namely cobaltian mackinawite (containing up to 12.68 wt.% Co, 1.90 wt.% Ni and 2.52 wt.% Cu) and cobalt-pentlandite (containing up to 49.30 wt.% Co and 10.19 wt.% Ni), identified based on composition, from the Madan-Kudan deposit. To the best of our knowledge, neither cobalt-pentlandite nor such highly Co-rich mackinawite have previously been reported from this area. The common sulphide minerals viz. chalcopyrite, pyrrhotite and rare pyrite occur in chalcopyrite-pyrrhotite ± pyrite-magnetite-chlorite-blue amphibole (Cl-rich hastingsite-pargasite-sadanagaite) ± marialitic scapolite ± allanite ± uraninite veins in amphibole-bearing feldspathic quartzite and garnetiferous chlorite schist. Cobaltian mackinawite is invariably associated with chalcopyrite and occurs as exsolution and inclusion within chalcopyrite or outside, but at the contact of chalcopyrite. On the other hand, cobalt-pentlandite is invariably associated with pyrrhotite and shows similar textural relation with pyrrhotite as that of mackinawite with chalcopyrite. Mineralogically diverse undeformed sulphide veins comprising Cl-rich amphibole and locally Cl-rich marialitic scapolite suggests epigenetic hydrothermal mineralization involving Cl-rich saline fluid in the Madan-Kudan deposit. Transport of metals, derived from a mafic source rock with high intrinsic Ni:Co ratio, by Cl-rich fluid can suitably explain the high Co:Ni ratio of the studied ore minerals. Presence of such highly Co-rich phases and other circumstantial evidences, enumerated in this work, are consistent with variants of Fe oxide (–Cu–Au) (IOCG) style mineralization, at least for some stages of mineralization in the Madan-Kudan deposit.     

Electron Probe Microanalysis of Bromine in Minerals and Glasses with Correction for Spectral Interference from Aluminium,and Comparison with Microbeam Synchrotron X‐Ray Fluorescence Spectrometry

The strong spectral interference between Br‐ and Al‐induced X‐ray lines hampers the utilisation of electron probe microanalysis (EPMA) for measuring Br mass fractions in Al‐bearing minerals and glasses. Through measuring Br‐free Al‐bearing materials, we established an EPMA method to quantify the overlap from AlKα on BrLβ, which can be expressed as a linear function of the Al₂O₃ content. The count rate of the BrLβ peak signal was enhanced by high beam currents and long measurement times. Application of this EPMA method to Al‐ and Br‐bearing materials, such as sodalite and scapolite, and to five experimental glasses yielded Br mass fractions (in the range of 250–4000 μg g^?1) that are consistent with those measured by microbeam synchrotron X‐ray fluorescence (μ‐SXRF) spectrometry. The EPMA method has an estimated detection limit of ~ 100–300 μg g^?1. We propose that this method is useful for measuring Br mass fractions (hundreds to thousands of μg g^?1) in Al‐bearing minerals and glasses, including those produced in Br‐doped experiments. In addition, the natural marialitic scapolite (ON70) from Mpwapwa (Tanzania) containing homogeneously distributed high mass fractions of Br (2058 ± 56 μg g^?1) and Cl (1.98 ± 0.03% m/m) is an ideal reference material for future in situ analyses.     

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.     

Garnet coronas in scapolite-wollastonite calc-silicates from East Antarctica: the application and limitations of activity-corrected grids

Calc-silicate boudins within Proterozoic granulite facies gneisses of the northern Prince Charles Mountains, East Antarctica, preserve a number of reaction textures including garnet coronas between calcite and scapolite; garnet-quartz coronas between scapolite and wollastonite and between plagioclase and wollastonite; calcite-quartz intergrowths in wollastonite; and calcite-plagioclase symplectites in scapolite. These textures have been modelled using petrogenetic grids for reactions in the CaO-Al₂,O₃-SiO₂-CO₂ system, but with reduced mineral activities to account for additional components in real mineral compositions. Such fixed-composition reduced-activity grids are strictly valid only at the point in P-T-a_CO2 space where an assemblage last equilibrated, and do not show the true positions of reactions away from this point because mineral compositions change with reaction progress. In this case, however, mineral compositions close to end-member values and low extents of reaction progress mean that compositional change was limited and the grids are good approximations to true pseudosections over the entire P-T-a_co2 range of interest. The grids show that the textures are consistent with near-isobaric cooling from about 850 to 700d? C at 7 kbar, a P-T path compatible with thermobarometric studies of other lithologies from the area. Phase relationships indicate that CO₂ activities were buffered by the local mineral assemblage during peak and retrograde metamorphism, either under fluid-absent conditions or within a non-pervasive fluid phase. Previous studies of garnet coronas in scapolite-wollastonite calc-silicates have used qualitative grids based on limited experimental data to invoke garnet growth during water infiltration at high temperature, but the grids used here show that garnet coronas can form on cooling, without any need for water influx.     

Formation of baotite - a Cl-rich silicate - together with fluorapatite and F-rich hydrous silicates in the Kval?ya lamproite dyke, North Norway

Baotite occurs as a late phase in the Kval?ya lamproite dyke and in the fenitized granite adjacent to the dyke, suggesting that baotite formed during reactions between rock and fluids derived from a volatile-rich lamproitic magma. Most of the analyzed grains of baotite from the Kval?ya lamproite show compositions close to the ideal Nb-free end-member Ba₄Ti₈Si₄O₂₈Cl. Compilation of all published baotite analyses suggests that the major compositional variations of baotite occur between the Nb-free end member Ba₄Ti₈Si₄O₂₈Cl, and a Nb-rich end member Ba₄Ti₂Fe2⁺ ₂Nb₄Si₄O₂₈Cl. However, a Pb-bearing baotite, showing significant concentrations of Ca, Sr, Pb and K, and approximately 3 Ba p.f.u., was also identified from the Kval?ya lamproite. Euhedral fluorapatite formed as an early phase during crystallization of the lamproite magma, while anhedral REE-rich fluorapatite overgrowths on the euhedral grains formed during reactions with the late magmatic fluid. Fluorapatite contains up to 1.2?F p.f.u., but only traces of Cl. Other F-rich, but Cl-poor minerals of the lamproite include fluoro-potassic-magnesio-arfvedsonite, fluoro-phlogopite, and yangzhumingite. The presence of baotite together with a range of high-F, but low-Cl mineral phases suggests that the minerals formed in equilibrium with a high-F, Cl-bearing hydrous fluid. The high Cl-content of baotite demonstrates that Cl is strongly partitioned into this mineral in the presence of a Cl-bearing F-rich hydrous fluid. We suggest that a combination of high a_Si, a_Ti, a_Ba, and f_O2, but low a_Ca of the fluid enabled baotite formation.     

Internal control of fluid compositions in amphibolite-facies scapolitic calc-silicates,Mary Kathleen,Australia

Unaltered metasediments of the Mary Kathleen Fold Belt are composed predominantly of layered amphibolite-facies scapolitic calc-silicate rocks in which minimal infiltration of externally derived fluids occurred during regional metamorphism. There were substantial differences in volatile activities between different layers in the layered sequences, in particular: a _CO2/a _{H 2 O} inferred from reaction progress estimates and analysis of biotite-clinopyroxene-fluid phase relations; a _NaCl/a _{H 2 O} inferred from scapolite compositions; and a _HCl/a _{H 2 O} inferred from biotite compositions. In one outcrop in which a clinopyroxene-producing reaction dominated, differences in approximate X _{CO 2}of up to 0.25 occurred between several samples collected over 50 metres. Variations in a _{H 2 O}/a _HCl of up to one order of magnitude are inferred at 1 to 50 m scales from biotite-Cl contents, and variations in NaCl contents of scapolite from 0.0 to up to 0.6 Cl atoms in the Cl–CO₃–SO₄ site reflect a large variation of a _NaCl in the coexisting fluid at similar scales. Most calcsilicate layers internally buffered fluid compositions in the H₂O–CO₂–NaCl–HCl system. Local occurrences of NaCl-rich scapolite suggest that some layers may have been in equilibrium with halite during early prograde metamorphism. At peak metamorphic temperatures, disolution of halite was complete but layers containing high-NaCl scapolite continued to buffer fluid at high values of a _NaCl. Fluid immiscibility does not appear to have affected the progress of the devolatilization reactions. Although fluid was predominantly internally buffered, moderate quantities of fluid were released by prograde mineral reactions in many layers, up to 30 cm³ fluid per 100 cm³ rock. Numerous episodes of fluid escape were required, probably via microfractures, such that the released fluid did not obviously influence reaction progress in the layers through which it passed. The anomaly of beautifully preserved internal buffering signatures and the requirement for produced fluid locally to pass across layers in a deforming rock sequence suggest that the escaping fluid did not leave any readily observable tracks. This is explained by rapid rates of fracture propogation and fluid migration therein. This internally buffered system contrasts strongly with adjacent calc-silicate rocks that show evidence for infiltration of externally derived fluids at high fluid/rock ratios, and highlights the broad range of fluid behaviour that can be expected in deforming, heterogeneous rock sequences.