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.     

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.     

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.     

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.     

The Geochemistry of Scapolite: Part II. Trace Elements, Petrology, and General Geochemistry

Fifty scapolites have been analysed spectrographically for numerouselements. Average concentrations (p.p.m.) were as follows: B25, Be 9–3, Ga 33, Ti 82, Li 56, Cu 4–4, Zr 59,Mn 57, Sr 1,800, Pb 45, Ba 120, Rb 20. The following were seldomor never detected: Cr, Ni, Co, Mo, Sn, V, Sc, Ag, Y, La. Themajor elements Ca, Na, K were also determined. The distributionof the trace elements can be explained by isomorphous substitution,but no detailed correlation of trace elements with each otheror with major elements was found. Refractive indices were determined and the relation betweenaverage index and per cent Me was examined: correlation waspoor, which may in part be attributed to analytical error. Examination of scapolite parageneses shows that scapolite characteristicallyoccurs in the upper amphibolite facies or the pyroxene hornfelsfacies: it is not restricted to these and may occur in any faciesfrom zeolitic to granulitic and in any hornfels facies. Theelements generally concentrated in scapolite include Ca, Na,C, Cl, S, H, B, Be, Li, Sr, Pb. The presence of C, Cl, S, Htestify to genesis in the presence of high partial pressureof CO₂, Cl₂, SO₃, H₂O (or related compounds), that is in pneumatolytic,pegmatitic, or hydrothermal environments. The concentrationof B, Be, Li can also be attributed to these conditions. The source of the elements concentrated in scapolite must inpart be common rocks. In a limited contact zone, the nearbymagma supplied some elements, but where regional scapolitizationhas taken place the presence of magma is less clear. Many commonrocks or rock series contain all the necessary constituents,but some particular conjunction of conditions is necessary forscapolite to form, or it would be more common.     

Ion exchange between tectosilicates with the nepheline-kalsilite framework and molten MNO3 or MO (M = Li,Na, K,Ag)

Natural nepheline, a synthetic Na-rich nepheline, and synthetic kalsilite were ion exchanged in molten MNO₃ or MCl (M = Li, Na, K, Ag) at 220–800° C. Crystalline products were characterized by wet chemical and electron microprobe analysis, single crystal and powder X-ray diffraction, and transmission electron microscopy and diffraction. Two new compounds were obtained: Li-exchanged nepheline with a formula near (Li,K_0.3,□)Li₃[Al₃(Al,Si)Si₄O₁₆] and a monoclinic unit cell with a = 951.0(6) b = 976.1(6) c = 822.9(5)pm γ = 119.15°, and Ag-exchanged nepheline with a formula near (K,Na,□)Ag₃[Al₃(Al,Si)Si₄O₁₆] and a hexagonal unit cell with a = 1007.4(8) c = 838.2(1.0) pm. Both compounds apparently retain the framework topology of the starting material. Ion exchange isotherms and structural data show that immiscibility between the end members is a general feature in the systems Na-Li, Na-Ag, and Na-K. For the system Na-K, a stepwise exchange is observed with (K,D)Na₃[Al₃(Al,Si)Si₄O₁₆] as an intermediate composition which has the nepheline structure and is miscible with the sodian end member (Na,□)Na₃[Al₃(Al,Si)Si₄O₁₆], but not with the potassian end member (K,□)₄[Al₃(Al,Si)Si₄O₁₆] which shows the kalsilite structure; there was no indication for the formation of trior tetrakalsilite (K/(K + Na)≈0.7) at the temperatures studied (350 and 800° C). The exact amount of vacancies □ on the alkali site depends upon the starting material and was found to be conserved during exchange, with ca 0–0.2 and 0.3–0.4 vacancies per 16 oxygen atoms for the synthetic and natural precursors, respectively. Thermodynamic interpretation of the Na-K exchange isotherms shows, as one important result, that the sodian end member is unstable with respect to the intermediate at K/(K+Na)≈0.25 by an amount of ca 45 kJ/mol Na in the large cavity at 800° C (52 kJ/mol at 350° C).     

The Geochemistry of Scapolite Part II. Trace Elements, Petrology, and General Geochemistry

Fifty scapolites have been analysed spectrographically for numerouselements. Average concentrations (p.p.m.) were as follows: B25, Be 9-3, Ga 33, Ti 82, Li 56, Cu 4-4, Zr 59, Mn 57, Sr 1,800,Pb 45, Ba 120, Rb 20. The following were seldom or never detected:Cr, Ni, Co, Mo, Sn, V, Sc, Ag, Y, La. The major elements Ca,Na, K were also determined. The distribution of the trace elementscan be explained by isomorphous substitution, but no detailedcorrelation of trace elements with each other or with majorelements was found. Refractive indices were determined and the relation betweenaverage index and per cent Me was examined: correlation waspoor, which may in part be attributed to analytical error. Examination of scapolite parageneses shows that scapolite characteristicallyoccurs in the upper amphibolite facies or the pyroxene hornfelsfacies: it is not restricted to these and may occur in any faciesfrom zeolitic to granulitic and in any hornfels facies. Theelements generally concentrated in scapolite include Ca, Na,C, Cl, S, H, B, Be, Li, Sr, Pb. The presence of C, Cl, S, Htestify to genesis in the presence of high partial pressureof CO₂, Cl₂, SO₃, H₂O (or related compounds), that is in pneumatolytic,pegmatitic, or hydrothermal environments. The concentrationof B, Be, Li can also be attributed to these conditions. The source of the elements concentrated in scapolite must inpart be common rocks. In a limited contact zone, the nearbymagma supplied some elements, but where regional scapolitizationhas taken place the presence of magma is less clear. Many commonrocks or rock series contain all the necessary constituents,but some particular conjunction of conditions is necessary forscapolite to form, or it would be more common.     

Ordering and composition of scapolite: Field observations and structural interpretations

Field observations, experimental and crystallographic data and thermodynamic considerations all suggest that Al-Si order-disorder is a crucial factor in explaining composition and stability of the mineral scapolite. Over the whole compositional range, scapolites have Al^IV-O-Al^IV bonds with the exception of one intermediate member with an Al/Si ratio of 1/2. Scapolites of this composition are the lowest temperature form and appear in areas with argillaceous carbonates and evaporites which have been subjected to progressive metamorphism. In similar areas without evaporites, the onset of the CO₃-scapolite stability field is approx. 150° C higher with an Al/Si ratio in the scapolite of about 5/7. This particular CO₃-scapolite is a compromise between the number of Al-O-Al bonds and the volume of the anion site occupied by CO₃. Based on field- and experimental data, temperature-composition diagrams for scapolite, plagioclase and calcite have been constructed. These diagrams may be explained in the light of contrasting Al-Si order-disorder in plagioclase and scapolite, i.e. at low temperature, plagioclase endmembers and intermediate scapolite members are stable, towards higher temperatures the ∩-shaped temperature-composition field of plagioclase and the V-shaped one of scapolite interfere in a complicated way. Electron microscopy of Al-rich scapolite, 632/n extinction rules. But these scapolites (with or without Cl-anion) show domain boundaries. We interpret them as APB's in the Al/Si ordering pattern on T₂-T₃ sites which reverses when a displacement R=1/2 [111] is applied.     

The Origin and Composition of Metasomatic Fluids and Amphiboles beneath Malaita, Solomon Islands

A suite of mantle peridotite xenoliths from the Malaitan alnoitedisplay both trace element enrichment and modal metasomatism.Pargasitic amphibole is present in both garnet- and spinelbearingxenoliths, formed by reaction of a metasomatic fluid (representedby H₂O and Na₂O) with the peridotite assemblage. Two pargasite-formingreactions are postulated, whereby spinel is totally consumed: 6MgAl₂O₄ + 8CaMgSi₂O₆ + 7Mg₂Si₂O₆ + 4H₂O + 2Na₂O = 4NaCa₂Mg₄Al₃Si₆O₁₂(OH)₂+ 6Mg₂SiO₄ or spinel is both a reactant (low Cr) and a product (high Cr): 24MgAlCrO₄ + 16CaMgSi₂O₆ + 14Mg₂Si₂O₆ + 8H₂O + 4Na₂O = 8NaCa₂Mg₄Al₃Si₆O₁₂(OH)₂+ 12MgCr₂O₄ + 12Mg₂SiO₄ Seven garnet—spinel-peridotites display cryptic metasomatismas demonstrated by the LREE enrichment in clinopyroxenes. TheLREE enrichment correlates positively with ¹⁴³ND/¹⁴⁴ND (0?512771–0?513093)which defines a mixing line between a mantle MORB source anda metasomatic fluid. Isotopic evidence (Sr and Nd) from garnet,clinopyroxene, and amphibole demonstrate this fluid has notoriginated in the alnoite sensu stricto. Calculated amphiboleequilibrium liquids show a range in La/Yb and Ce/Yb ratios similarto those calculated for the augite and subcalcic diopside megacrysts.Sr and Nd isotope analyses from amphibole are within error ofthe augite (PHN4074) and subcalcic diopside megacrysts (CRN2I6,PHN4069, and PHN4085). It is concluded that fluids emanatedfrom a proto-alnoite magma throughout megacryst fractionation,and the mixing line was generated during the crystallizationof the subcalcic diopsides. This study demonstrates that metasomatismrepresented in these xenoliths is not a prerequisite for alnoitemagmatism, but is a consequence of it.     

Tunisit: Kristallstruktur und Revision der chemischen Formel

Zusammenfassung Die Kristallstruktur des Tunisits wurde zunächst an Material vom Originalfundort prinzipiell bestimmt; in Übereinstimmung mit einer neuen Analyse ergab sich eine Änderung der chemischen Idealformel auf NaCa₂ Al₄(CO₃)₄(OH)₈Cl. Die Strukturverfeinerung erfolgte an dafür besser geeignetem Material aus Frankreich; mit 692 kristallographisch unabhängigen Röntgenreflexen wurde ein konventioneller ZuverlässigkeitsindexR=0,059 erreicht. Die Atomanordnung stellt einen neuen Strukturtyp mit [Al^[6](OH)₂ CO₃]^1–-Schichten parallel zu {001} dar. Die Na-Atome sind von vier O-Atomen und einem Cl-Atom koordiniert. Um die Ca-Atome wurde eine (4+2+4)-Koordination von Sauerstoffen gefunden; da sich für dieses Atom ein stark ausgelängtes Schwingungs-ellipsoid ergab, scheint eine Aufspaltung der Ca-Punktlage um ca. 0,4 Å möglich.

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Tunisite: Crystal structure and revision of chemical formula

Summary The crystal structure of tunisite was principally solved on material from the type locality; in agreement with a new analysis the ideal chemical formula was found to be NaCa₂Al₄ (CO₃)₄(OH)₈Cl. The structure refinement was carried out on better suited material from France; with 692 crystallographically independent X-ray reflections a conventional reliability indexR=0.059 was reached. The atomic arrangement represents a new structure type with [Al^[6](OH)₂CO₃]^1–-sheets parallel to {001}. The Na atoms are coordinated by four O atoms and one Cl atom. Around the Ca atoms a (4+2+4)-coordination of O atoms was obtained; as the ellipsoid of thermal vibration for this atom is strongly elongated, a splitting of the Ca position by ca. 0.4 Å seems to be possible.

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Mit 3 Abbildungen     

The effects of sulfur intercalation on the optical properties of artificial ‘hackmanite’, Na8[Al6Si6O24]Cl1.8S0.1; ‘sulfosodalite’, Na8[Al6Si6O24]S; and natural tugtupite, Na8[Be2Al2Si8O24](Cl,S)2?δ

The minerals ??hackmanite?? and tugtupite exhibit tenebrescence (reversible photochromism) and photoluminescence. These features are generally attributed to the presence of sulfide species within their structures. But how these optical properties might be affected by intercalating additional amounts of sulfur into their structures was until now unknown. Artificial ??hackmanite??, Na₈[Al₆Si₆O₂₄]Cl_1.8S_0.1, and ??sulfosodalite??, Na₈[Al₆Si₆O₂₄]S, were heated with sulfur in evacuated quartz-glass ampoules over the temperature range 450?C1,050°C. This work has shown that sulfur intercalation into Na₈[Al₆Si₆O₂₄]Cl_1.8S_0.1 destroys the tenebrescence and induces a permanently pale blue and, at higher temperature, a pale green coloration. The effect on Na₈[Al₆Si₆O₂₄]S induced similar colorations but of a deeper hue. Annealing tugtupite, Na₈[Be₂Al₂Si₈O₂₄](Cl,S)_2??? under a sulfur atmosphere over the range 600?C700°C, destroyed the tenebrescence and resulted in a colorless tugtupite; but did not effect the photoluminescence. This suggests that the chemical species responsible for the tenebrescence in tugtupite is unlikely to be the same as that for the luminescence.     

Thermodynamic study of calcic amphiboles

The paper reports original thermochemical data on six natural amphibole samples of different composition. The data were obtained by high-temperature melt solution calorimetry in a Tian–Calvet microcalorometer and include the enthalpies of formation from elements for actinolite Ca_1.95(Mg_4.4Fe _0.5 ²⁺ Al₀₁)[Si_8.0O₂₂](OH)₂(–12024 ± 13 kJ/mol) and Ca_2.0(Mg_2.9Fe _1.9 ²⁺ Fe _0.2 ³⁺ )[Si_7.8Al_0.2O₂₂](OH)₂, (–11462 ± 18 kJ/mol), and Na_0.1Ca_2.0(Mg_3.2Fe _1.6 ²⁺ Fe _0.2 ³⁺ )[Si_7.7Al_0.3O₂₂](OH)₂ (–11588 ± 14 kJ/mol); for pargasite Na_0.5K_0.5Ca_2.0-(Mg_3.4Fe _1.8 ²⁺ Al_0.8)[Si_6.2Al_1.8O₂₂](OH)₂ (–12316 ± 10 kJ/mol) and Na_0.8K_0.2Ca_2.0(Mg_2.8Fe _1.3 ³⁺ Al_0.9) [Si_6.1Al_1.9O₂₂](OH)₂ (–12 223 ± 9 kJ/mol); and for hastingsite Na_0.3K_0.2Ca_2.0(Mg_0.4Fe _1.3 ²⁺ Fe _0.9 ³⁺ Al_0.2) [Si_6.4Al_1.6O₂₂](OH)₂ (?10909 ± 11 kJ/mol). The standard entropy, enthalpy, and Gibbs free energy of formation are estimated for amphiboles of theoretical composition: end members and intermediate members of the isomorphic series tremolite–ferroactinolite, edenite–ferroedenite, pargasite–ferropargasite, and hastingsite.     

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.     

The crystal chemistry of mordenites

Mordenite is a zeolite whose approximate composition is (Na₂, K₂,Ca)₄[Al₈Si₄₀O₉₆] 28 H₂O. Unit cell dimensions, determined by X-ray powder diffractometry for 35 natural samples, fell within the following ranges: a=18.052–18.168, b=20.404–20.527, c=7.501–7.537 Å. The indexed powder pattern of a typical sample is reported. Complete wet chemical analyses of 12 samples, partial analyses of three others, and 6 analyses from the literature reveal that mordenites vary only slightly in chemical composition. Si occupies 80 to 85% of the tetrahedra, and the exchangeable cations are mainly Na and Ca, with minor K. The lattice constant b is negatively correlated to the ratio Si/(Si+Al+Fe?).     

The crystal structure of sarcolite

Summary The crystal structure of sarcolite from Monte Somma (Vesuvius), Na(Na, K, Fe, Mg)<1 Ca₆[Al₄Si₆O₂₃](OH, H₂O)<2 [(Si,P)O₄]_0.5[(CO₃, Cl)]_0.5, space groupI4/m witha=12,343(5)Å,c=15,463(5)Å andZ=4, has been determined from X-ray data collected on an automatic diffractometer. The 1637 independent reflections withI>2 (I) converged to a conventionalR value of 0.054 with partially anisotropic factors.The tetrahedral framework in sarcolite has a sharing coefficient of 1.85. Mean Si–O and Al–O distances are 1.616 and 1.763 Å, respectively. Isolated (Si, P)O₄, CO₃, OH, H₂O and Cl species occupy cavities in the tetrahedral framework in a partially disordered way. The two crystallographically different Ca atoms coordinate respectively with 5 and 6 framework oxygens; further contacts occur with available anions. Ca–O distances range from 2.34 to 2.69 Å. Na atoms coordinate with 4 oxygens of the tetrahedral frame and one from the CO₃ groups.A structure analysis of a sarcolite crystal baked out at 1100°C confirmed some structural details involving atoms occupying cavities in the tetrahedral framework.

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Die Kristallstruktur des Sarkoliths

Zusammenfassung Die Kristallstruktur des Sarkoliths vom Monte Somma (Vesuv), Na(Na, K, Fe, Mg)<1 Ca₆[Al₄Si₆O₂₃](OH, H₂O)<2[(Si, P)O₄]_0,5[(CO₃, Cl)]_0,5, RaumgruppeI4/m,a ₀=12,343(5)Å,c ₀=15,463(5)Å,Z=4, wurde aus Röntgendaten, die auf einem automatischen Diffraktometer gesammelt worden waren, bestimmt. Der konventionelleR-Wert für 1637 kristallographisch unabhängige Reflexe mitI>2 (I) konvergierte mit partiell anisotropen Temperaturfaktoren auf 0.054.Der Verknüpfungskoeffizient des Tetraedergerüstes in Sarkolith ist 1,85. Die mittleren Si–O-bzw. Al–O-Abstände sind 1,616Å und 1,763 Å. Isolierte Strukturbestandteile (Si, P)O₄, CO₃, OH, H₂O und Cl besetzen zum Teil ungeordnet die Hohlräume des Tetraedergerüstes. Die beiden kristallographisch verschiedenen Ca-Atome werden von funf bzw. sechs Sauerstoffen des Gerüstes koordiniert, weitere Kontakte bestehen zu verfügbaren Anionen. Die Ca–O-Abstände variieren von 2,34 bis 2,69 Å. Die Na–Atome sind von vier Sauerstoffen des Tetraedergerüstes und von einem weiteren der CO₃-Gruppen koordiniert. Die Strukturanalyse eines bei 1100°C getemperten Sarkolithkristalls bestätigte einige Details über die Atome, welche die Hohlräume des Tetraedergerüstes besetzen.

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With 4 Figures     

Fluid inclusions in diamonds from the Diavik mine, Canada and the evolution of diamond-forming fluids

The analysis of micro-inclusions in fibrous diamonds from the Diavik mine, Canada revealed the presence of high density fluids (HDFs) that span a continuous compositional range between carbonatitic and saline end-members. The carbonatitic end-member is rich in Na, Ca, Mg, Fe, Ba and carbonate; the saline one is rich in K, Cl and water. In molar proportions, the composition of the saline end-member is: K₃₈Na_7.7Ca_1.8Mg_1.6Fe_1.5Ba_1.9SiO_3.1Cl₄₆(CO₃)_5.5(H₂O)₅₆ and that of the carbonatitic end member is: K₁₅Na₂₁Ca_6.7Mg_8.1Fe_6.2Ba_5.7Si_4.8Ti_1.4Al_1.9O₁₇Cl₂₉(CO₃)₂₉(H₂O)₂₉. The micro-inclusions in one diamond span a narrow range between a silicic end-member (rich in Si, K and water) and a carbonatitic one (rich in Mg, Ca, Fe and carbonate). Its average composition is: K₂₆Na_5.5Ca_13.8Mg_8.3Fe_9.6Ba_0.9P_2.5Si₂₅Ti_1.6Al_3.8Cl_2.5O₈₁(CO₃)₂₉(H₂O)₇₈. Thus, the Diavik diamonds span most of the known compositional range for fluids trapped in diamonds. Based on these data and previous analyses of fluids trapped in diamonds, we discuss possible models for the evolution of diamond-forming fluids. The most plausible model is where carbonatitic-HDFs are parental to all the other compositions. They evolve by fractionation of divalentions- and alkali-carbonates and by immiscible separation into saline- and silicic-HDFs. Each phase continues to evolve separately, crystallizing carbonates, diamond, and accessory silicates, phosphates, halides and more of the immiscible phase. Other processes, like the mixing of evolved fluids with fresh parental carbonatitic fluids, or metasomatic interactions with the wallrock also play a role in the evolution of the HDFs. We also propose that the parental carbonatitic-HDF evolves through fractional crystallization of an alkali-rich, low degree melt that is similar to the high pressure parental melts of kimberlites or lamproites.     

The Kaersutites and Oxykaersutites from Alkalic Rocks of Japan and Surrounding Areas

Seven new analyses of kaersutites and.two of oxykaersutitesfrom Japan and surrounding areas are given, together with theiroptical properties. The type formula of kaersutite can be writtenas (Na,K)Ca₂Mg₃Fe²⁺(Ti,Fe³⁺)Al^iv₂Si₆O₂₂(OH)₂ and that of oxykaersutiteas (Na,K) Ca₂Mg₃(Ti,Fe³⁺)₂Al^iv₂Si₆O₂₄. Transformation from kaersutiteto oxykaersutite must have taken place when the ratio of Fe³⁺/Fe²⁺was about 2.     

Laser-induced time-resolved luminescence of tugtupite,sodalite and hackmanite

We have interpreted a number of luminescence centers in natural tugtupite Na₈Al₂Be₂Si₈O₂₄Cl₂, sodalite Na₈Al₆Si₆O₂₄C₂ and hackmanite Na₈Al₆Si₆O₂₄(Cl₂,S) by use of laser-induced time-resolved luminescence spectroscopy. The main new results are the following: Fe³⁺, Mn²⁺, Eu²⁺, Ce³⁺, mercury type (potentially Pb²⁺, Tl⁺, Sn²⁺ and/or Sb³⁺), radiation induced luminescence centers; several types of S₂ ⁻ centers. Spectral shift connected with the presence of luminescence centers, which are detected together with S₂ ⁻ centers and impossible to resolve with continuous wave luminescence spectroscopy, is the possible reason for spectral diversity of S₂ ⁻ luminescence centers presented in different publications.     

Comparative compressibilities of majorite-type garnets

Relative compressibilities of five silicate garnets were determined by single-crystal x-ray diffraction on crystals grouped in the same high-pressure mount. The specimens include a natural pyrope [(Mg_2.84Fe_0.10Ca_0,06) Al₂Si₃O₁₂], and four synthetic specimens with octahedrally-coordinated silicon: majorite [Mg₃(MgSi)Si₃O₁₂], calcium-bearing majorite [(Ca_0.49Mg_2.51)(MgSi)Si₃0₁₂], sodium majorite [(Na_1.88Mgp_0.12)(Mg_0.06Si_1.94)Si₃O₁₂], and an intermediate composition [(Na_0.37Mg_2.48)(Mg_0.13Al_1.07 Si₀₈₀) Si₃O₁₂]. Small differences in the compressibilities of these crystals are revealed because they are subjected simultaneously to the same pressure. Bulk-moduli of the garnets range from 164.8 ± 2.3 GPa for calcium majorite to 191.5 ± 2.5 GPa for sodium majorite, assuming K′=4. Two factors, molar volume and octahedral cation valence, appear to control garnet compression.     

Compositional limits and analogs of monoclinic triple-chain silicates

Growing recognition of triple-chain silicates in nature has prompted experimental research into the conditions under which they can form and the extent of solid solution that is feasible for some key chemical substitutions. Experiments were done primarily in the range of 0.1–0.5 GPa and 200–850 °C for durations of 18–1,034 h. A wide range of bulk compositions were explored in this study that can be classified broadly into two groups: those that are Na free and involve various possible chemical substitutions into jimthompsonite (Mg₁₀Si₁₂O₃₂(OH)₄), and those that are Na bearing and involve chemical substitutions into the ideal end-member Na₄Mg₈Si₁₂O₃₂(OH)₄. Numerous attempts to synthesize jimthompsonite or clinojimthompsonite were unsuccessful despite the type of starting material used (reagent oxides, magnesite + SiO₂, talc + enstatite, or anthophyllite). Similarly, the chemical substitutions of F⁻ for OH⁻, Mn²⁺, Ca²⁺, or Fe²⁺ for Mg²⁺, and 2Li⁺ for Mg²⁺ and a vacancy were unsuccessful at nucleating triple-chain silicates. Conversely, nearly pure yields of monoclinic triple-chain silicate could be made at temperatures of 440–630 °C and 0.2 GPa from the composition Na₄Mg₈Si₁₂O₃₂(OH)₄, as found in previous studies, though its composition is most likely depleted in Na as evidenced by electron microprobe and FTIR analysis. Pure yields of triple-chain silicate were also obtained for the F-analog composition Na₄Mg₈Si₁₂O₃₂F₄ at 550–750 °C and 0.2–0.5 GPa if a flux consisting of Na-halide salt and water in a 2:1 ratio by weight was used. In addition, limited chemical substitution could be documented for the substitutions of 2 Na⁺ for Na⁺ + H⁺ and of Mg²⁺ + vacancy for 2Na⁺. For the former, the Na content appears to be limited to 2.5 cations giving the ideal composition of Na_2.5Mg₈Si₁₂O_30.5(OH)_5.5, while for the latter substitution the Na content may go as low as 1.1 cations giving the composition Na_1.1Mg_9.4Si₁₂O_31.9(OH)_4.1 based on a fixed number of Si cations. Further investigation involving Mg for Na cation exchange may provide a pathway for the synthesis of Na-free clinojimthompsonite. Fairly extensive solid solution was also observed for triple-chain silicates made along the compositional join Na₄Mg₈Si₁₂O₃₂(OH)₄–Ca₂Mg₈Si₁₂O₃₂(OH)₄ where the limit of Ca substitution at 450 °C and 0.2 GPa corresponds to Na_0.7Ca_1.8Mg_7.8Si₁₂O_31.9(OH)_4.1 (with the OH content adjusted to achieve charge balance). Aside from the Na content, this composition is similar to that observed as wide-chain lamellae in host actinolite. The relative ease with which Na-rich triple chains can be made experimentally suggests that these phases might exist in nature; this study provides additional insights into the range of compositions and formation conditions at which they might occur.