Synthesis,lattice constants and OH-valence vibrations of an orthorhombic amphibole with excess OH in the system Li2O-MgO-SiO2-H2O

Orthorhombic amphiboles with excess OH, which can be schematically deduced from anthophyllite by the combined substitutions Mg²⁺ + O^2–Li⁺+OH^– and Mg²⁺2 Li⁺, were synthesized at 750–875° C/1 kbar in the system Li₂O-MgO-SiO₂-H₂O. Their phase relations are presented for 800° C/1 kbar . An amphibole with the analytical composition 2.70 wt% Li₂O, 31.1 wt% MgO, 63.0 wt% SiO₂, and 3.29 wt% H₂O has lattice constants a ₀ 18.588 (11), b ₀ 17.966 (10), c ₀ 5.262 (3) Å, V ₀ 1,757.2 (1.5) ų (referred to Space Group Pnma). The OH-valence vibrational spectrum of this amphibole showed v _OH bands at 3,667, 3,708, and 3,725 (shoulder) cm^–1, which are ascribed to OH in the configurations (MgMgMg)-OH, (MgMgMg)-OH-Li (Li in the A-site) of the pseudotrigonal (M1M1M3)-OH arrangement in the amphibole structure, and to Si-OH, respectively. No explanation can at present be offered for an additional shoulder at 3,695 cm^–1. The proposed structural formula is (Li_{0.27 0.73})(Li_1.11 Mg_0.89)· (Mg₅)(Si_8.01O_21.20(OH)_0.80)(OH)_2.00.     

The occurrence of OH absorptions in phenakite—an IR spectroscopic study

Summary IR spectra of phenakite single crystals from different localities show a distinct variability in the region of the OH stretching fundamental. Minute hydrous mineral phases (tourmaline, bertrandite) are included in Piracicaba phenakite. Structural OH, ranging up to 0.005 equivalent wt.% H₂O, is characterized by two extremely pleochroic bands centered at 3380 and 3120 cm^–1. On the basis of their pleochroic scheme it is proposed that (O₂(OH)₂) and (O₃(OH)) tetrahedra occur as structural elements, assuming that the vacancies are on Be sites.

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Das Auftreten von OH Absorptionen in Phenakit—eine IR spektroskopische Untersuchung

Zusammenfassung Die IR Spektren von Phenakit-Einkristallen verschiedener Vorkommen zeigen im Bereich der OH-Streckschwingungen eine deutliche Variabilität. Piracicaba Phenakit enthält feinste Einschlüsse von OH-hältigen Mineralphasen (Turmalin, Bertrandit). Strukturell gebundene OH-Gruppen (bis 0,005 äquivalente Gew.% H₂O) sind durch zwei extrem pleochroitische Banden bei 3380 und 3120 cm^–1 charakterisiert. Unter der Annahme von Be-Leerstellen werden aufgrund des Pleochroismus dieser Banden (O₂(OH)₂) und (O₃(OH)) Tetraeder als strukturelle Baueinheiten vorgeschlagen.

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With 3 Figures     

A Mössbauer and FTIR study of synthetic amphiboles along the magnesioriebeckite – ferri-clinoholmquistite join

A series of amphiboles along the magnesioriebeckite—Na₂Mg₃Fe³⁺ ₂Si₈O₂₂(OH)₂– ferri-clinoholmquistite—Li₂Mg₃Fe³⁺ ₂Si₈O₂₂(OH)2 - join, defined by the ^BLi^B Na_–1 exchange vector, were hydrothermally synthesized at 700°C, 0.4 GPa, NNO + 1 redox conditions. Powder XRD and SEM-EDAX showed a very high (> 90%) amphibole yield for all samples. X-ray patterns were indexed in the C2/m space group; refined cell-parameters show a linear decrease of a and as a function of chemistry. IR spectra in the OH-stretching region show four main and rather sharp bands; these are assigned to Mg and Fe²⁺ at M(1,3), and indicate that the obtained amphiboles depart from the nominal octahedral composition (^M1,3Mg₃). The IR spectra also show that there is an increasing filling-up of the A-site for increasing Na in the system (increasing solid-solution toward, arfvedsonite). Mössbauer spectra show four well-defined quadrupole doublets which are assigned to Fe³⁺ at M2 and to Fe²⁺ at M1, M3 and M4, respectively. The Fe³⁺/Fe²⁺ content derived from fitted peak areas show variable Fe³⁺ concentration along the series. Mössbauer spectra also show a distinct alteration of ⁵⁷Fe hyperfine parameters with changing Na–Li at M4. The most evident variation is observed for the quadrupole splitting of Fe³⁺ at M2, which increases by 50% from ferri-clinoholmquistite to magnesio-riebeckite; this suggest that the M2 octahedron in ferri-clinoholmquistite is much closer to the ideal geometry than the M2 octahedron in magnesio-riebeckite. Mössbauer spectra show also a well-defined increase in the Fe²⁺ quadrupole splitting of the M1 and M3 octahedra, which is attributed to the Na–Li distribution at the B-sites.     

Coupled substitutions in the tourmaline group

Statistical analysis of 136 natural tourmaline compositions from the literature reveals the presence and extent of coupled substitutions involving several cations and structural sites. In schorls and dravites these are a dehydroxylation type substitution (1) (OH)^–+R²⁺ = R³⁺+O^2– and an alkali-defect type substitution (2) R⁺+R²⁺ = R³⁺+, Al³⁺ being the predominant R³⁺ action. Substitution (1) which represents solid solution towards a proton-deficient end-member, R⁺ R ₃ ³⁺ R ₆ ³⁺ (BO₃)₃ Si₆O₁₈O₃(OH), accounts for three times as much of the observed compositional variability as does (2) which represents substitution toward a hypothetical alkali-free end-member, (R ₂ ²⁺ R³⁺) R ₆ ³⁺ (BO₃)₃Si₆O₁₈(OH)₄. The occurrence of both of these substituions produces intermediates between end-member schorl/ dravite, R⁺ R ₃ ²⁺ R ₆ ³⁺ (BO₃)₃Si₆O₁₈(OH)₄, and a new series within the tourmaline group, R _1–x ⁺ R ₃ ³⁺ R ₆ ³⁺ (BO₃)₃Si₆O₁₈O_3–x (OH)_1+x.In addition to dehydroxylation type, 2(OH)^–+Li⁺ = R³⁺+20^2–, and possibly alkali-defect type, 2R⁺+Li⁺ = R³⁺+2, substitutions, a third type Li⁺+O^2– = (OH)^–+, occurs in the elbaites giving rise to Li-poor, proton-rich species. All three substitutions serve to reduce the Li-content of natural elbaite which, as a result, does not attain the composition of the ideal end-member, Na(Li_1.5Al_1.5)Al₆(BO₃)₃Si₆O₁₈(OH)₄. Substitution from elbaite and schorl/dravite toward R _1–x ⁺ R ₃ ³⁺ R ₆ ³⁺ (BO₃)₃Si₆O₁₈O_3–x(OH)_1+x is very extensive and may be complete.Substitution toward R _1–x ⁺ R ₃ ³⁺ R ₆ ³⁺ (BO₃)₃Si₆O₁₈O_3–x(OH)_1+x results in improved local charge balance. The mean deviation from oxygen charge saturation is at a maximum in end-member schorl, dravite and elbaite. Substitutions (1) and (2) progressively decrease but substitution (1) does so more effectively, which may explain its predominance in nature. However, alkali-defective end-members appear to be unstable regardless of . Substitution (3) in the elbaites cannot be discussed on the basis of charge balance considerations at present due to the lack of structural information on proton-rich species.     

Mineral chemistry and geochemistry of vanadian silicates in the Hemlo gold deposit,Ontario, Canada

Some of the most vanadium-rich silicate minerals known are present in green mica schist from the Hemlo gold deposit, Ontario, Canada. Vanadium-rich silicate minerals include green mica (up to 17.6 wt. % V₂O₃), phlogopite (10.1 wt. % V₂O₃), pumpellyite (25.7 wt. % V₂O₃), garnet (18.5 wt. % V₂O₃), epidote-group minerals (9.1 wt. % V₂O₃), antimonian vesuvianite (4.3 wt. % V₂O₃), and titanite (18.5 wt. % V₂O₅). In addition, minor amounts of V (<2 wt. % V₂O₃) are present in tourmaline, chlorite, talc and tremolite in other lithologies of the Hemlo deposit. The principal substitution that incorporates V into most of these silicate minerals is Al³⁺=V³⁺ in octahedral positions. Vanadium is incorporated into phlogopite mainly by the two substitutions: 3Mg²⁺ =2V³⁺+ and ^VIMg²⁺+^IVSi⁴⁺=^VIV³⁺ +^IVAl³⁺, and all of the three substitutions Ti⁴⁺+O^2- =V³⁺+(OH,F)^-, Ti⁴⁺=V⁴⁺, and 5Ti⁴⁺=4V⁵⁺ + may have operated in titanite.Vanadium-enriched green mica schist from the Hemlo gold deposit is characterized by uniform Ti/Zr ratios, systematically low Ti, Ni, Co and Sc abundances, and low levels of incompatible elements Th, U, Hf and Zr and is distinct in these respects from its Cr-enriched counterpart. These geochemical features, along with textural evidence (relict quartz and oligoclase phenocrysts), indicate that the V-enriched green mica schist from Hemlo was most likely derived mainly from quartz-oligoclase porphyry. However, its anomalously high V and Cr contents were probably introduced metasomatically from local maficultramafic sources and were fixed in green mica and oxides during the waning of a second regional metamorphism. Vanadium was further remobilized, and its concentration probably enhanced, during the late hydrothermal alteration, which resulted in the formation of the characteristic V-rich calc-silicate minerals.     

Natural occurrence of a (Fe,Mn, Mg) tetrasilicic potassium mica

A mica whose structural formula: (K_1.76Na_0.31)(Fe_2.22Mn_1.29Mg_0.99Ti_0.28Al_0.240.98) ·(Si_7.33Al_0.67)O_20.26(F_2.16OH_1.58) closely approximates that of tetrasilicic potassium mica K₂(M ₅ ²⁺ )Si₈O₂₀(OH,F)₄ where M²⁺ represents Mg²⁺, Fe²⁺, Mn²⁺, ..., has been discovered in the matrix of a peralkaline rhyolite (comendite) of the Mont-Dore massif (France). These micas had been obtained previously by synthesis only. In the groundmass of the rock, the micaceous phase is accompanied by a manganoan arfvedsonite, pyrophanite, magnetite, apatite, sphene, zircon and fluorite. The crystallographic properties of the mica are typically that of a tetrasilicic mica, with d ₀₆₀ = 1.533Å and space group C2/m. There is a regular decrease of d ₀₆₀ (parameter b) with the ionic radius of the octahedral cation in synthetic micas containing Fe²⁺, Co²⁺, Mg²⁺, Ni²⁺. The purely Mn²⁺ end-member could not be synthesised; its instability is discussed on the basis of structural considerations. The conditions of crystallization of the micaceous phase are estimated to be 760 ° C, 800 bars with a f _{o 2}=10^–14.7 bar. This mica has crystallized from a residual liquid, with high activity of silica and low activity of alumina, whose origin is discussed. The name MONT-DORITE is proposed for this natural tetrasilicic mica having Fe/Fe+Mg >1/2 and Fe/Fe+Mn >1/2. This name is from the stratovolcano Mont-Dore.     

Phase relations to 3 kbar in the systems edenite + H2O and edenite + excess quartz + H2O

Amphiboles approached edenite (NaCa₂Mg₅Si₇AlO₂₂(OH)₂), richterite (Na₂CaMg₅Si₈O₂₂(OH)₂), tremolite (□Ca₂Mg₅Si₈O₂₂(OH)₂) solid solutions were studied by conventional hydrothermal techniques employing the bulk compositions edenite, and edenite + additional quartz, all with excess H₂O. For the stoichiometric edenite bulk composition + excess H₂O, the equilibrium phase assemblage is diopside + Na-phlogopite + forsterite + fluid at, and just above the amphibole high-temperature limit at 850 ± 5°C, 500 bar, and 880 ± 5°C, 1000 bar. The breakdown temperature of sodic phlogopite is 855 ± 3°C at 500 bar, and 890 ± 5°C at 700 bar, producing nepheline + plagioclase (or melt), additional forsterite and fluid. Diopside and Na-phlogopite solid solution coexist over a broad P_fluid-T region, even within the amphibole field, where they are associated with an edenite-richterite (-tremolite) solid solution of approximate composition Ed₃₅Rc₅₀Tr₁₅.In the system edenite + 4 quartz + excess H₂O, nearly pure tremolite and albite coexist stably between 670° and 830°C at 1000 bar and give way to the possibly metastable assemblage diopside + talc + albite below 670°C. In the presence of albite, tremolite reacts to produce diopside + quartz + enstatite + fluid above 830°C at 1000 bar. For the investigated silica-rich bulk composition, amphibole P_fluid-T stability is divided by the albite melting curve into a tremolite + albite field, and a tremolite + aqueous melt field. Substantial equilibrium solid solution of tremolite towards edenite or richterite was not observed for silica-excess bulk compositions. Metastable edenite-rich amphiboles initially synthesized change to tremolite with increasing run length in the presence of free SiO₂.Edenitic amphibole is stable only over a very limited temperature range in silica-undersaturated environments, thus accounting for its rarity in nature. Na-phlogopite solid solutions are also disfavored by high a_SiO2; even for nepheline-normative lithologies, a hypothesized rapid low-temperature conversion to vermiculite or smectite could partly explain the scarcity of sodic phlogopite in rocks.     

Chemical composition of rock-forming minerals in granitoids associated with Au–Bi–Cu,Cu–Mo,and Au–Ag mineralization at the Freegold Mountain,Yukon, Canada: magmatic and hydrothermal fluid chemistry and petrogenetic implications

The chemical compositions of rock-forming minerals have been determined for both altered and least-altered igneous rocks spatially associated with numerous mineralized zones (Nucleus Au–Bi–Cu–As deposit, Revenue Au ± Cu and Stoddart Cu–Mo ± W mineral occurrences, and Laforma Au–Ag deposit) across the Freegold Mountain area, Yukon, Canada. Within the study area, K-feldspar has a narrow compositional range (89.4–91% Or), whereas plagioclase spans a wide range (4.4–70.07% An). In all of the investigated samples, T _Ab = T _An = T _Or, suggesting that magmatic equilibrium between the coexisting plagioclase and K-feldspar was maintained. Igneous amphibole phenocrysts from hypabyssal dikes are typically calcic, whereas the Stoddart Cu–Mo ± W, Laforma Au–Ag, and Goldy Au mineralization are associated with Mg-enriched primary amphibole of edenite composition, and Au–Bi–Cu–As mineralization from Nucleus is related to Al-enriched primary amphibole of ferropargasite composition. Primary biotite phenocrysts across the Freegold Mountain area re-equilibrated with oxidized magma (f(O₂) values between 10–13 and 10–11.5 bars, lying between the Ni/NiO and the magnetite/haematite buffers). However, biotite and amphibole phenocrysts from Stoddart, Goldy, Laforma, and the Highway zones crystallized from a more oxidized magma, as indicated by their elevated X _Mg up to 0.65, relative to biotite and hornblende from Nucleus and Revenue characterized by a lower X _Mg (typically < 0.50). This suggests that various sources and (or) rapid emplacement were involved in magma genesis, as further supported by the considerable variation of pressure (1.8–7.3 kb) of amphibole crystallization and of the total Al content in least-altered biotite (2.6–2.9 afu) within the Freegold Mountain area. Biotite and apatite equilibrated within the T range of 520–780°C, consistent with temperatures of equilibration between ilmenite and magnetite, and their compositions indicate that they formed from an oxidized I-type magma. Magma differentiated by fractional crystallization (indicated by the presence of normally zoned plagioclase with Ca-rich cores and Na-enriched outer rims) and multiple magma mixing (supported by the presence of reversed zoned plagioclase and coexistence of normally and reversely zoned plagioclase). Lower X _Mg biotite associated with the mineralized (Cu–Mo ± W) potassic alteration incorporated more F and Cl relative to least-altered biotite with higher X _Mg. In both Nucleus and Revenue Au–Cu mineralizations, secondary biotite composition varies with respect to the associated alteration mineral assemblages. Although secondary biotite in the skarn re-equilibrated with F-poor fluids, secondary biotite from the pervasive biotitization is related to F- and Cl-enriched fluids, and secondary biotite from the phyllitic zone is related to F-, Cl-, and Mg-depleted fluids, thus consistent with a change in mineralizing fluid composition during mineralization.     

NaSi⇌CaAl exchange equilibrium between plagioclase and amphibole

The exchange equilibrium between plagioclase and amphibole, 2 albite+tschermakite=2 anorthite+glaucophane, has been calibrated empirically using data from natural amphibolites. The partition coefficient, K _D, for the exchange reaction is (X _an/X _ab)_plag ·(Na, M4/Ca, M4)_amph.. Partitioning is systematic between plagioclase and amphibole in suites collected from single exposures, but the solid solutions are highly non-ideal: values of In K _D range from –3.0 at X _an=0.30 to –1.0 at X _an=0.90 in samples from a single roadcut. Changes in both K _D and the topology of the ternary reciprocal exchange diagram occur with increasing metamorphic grade. Temperature dependence of In K _D is moderate with ¯H35 to 47 kcal at X _an=0.25; pressure dependence is small with ¯V –0.24 cal/bar. Usefulness of this exchange equilibrium as a geothermometer is restricted by uncertainties in the calculation of the amphibole formula from a microprobe analysis, especially with regard to Na, M4 in amphibole, to approximately ±50 ° C.     

Synthesis, crystal structure and crystal chemistry of ferri-clinoholmquistite, ?Li 2Mg 3Fe 3+ 2Si 8O 22(OH) 2

This work reports the synthesis of ferri-clinoholmquistite, nominally _Li2(Mg₃Fe³⁺₂)Si₈O₂₂(OH)₂, at varying f_O2 conditions. Amphibole compositions were characterized by X-ray (powder and single-crystal) diffraction, microchemical (EMPA) and spectroscopic (FTIR, Mössbauer and Raman) techniques. Under reducing conditions ( NNO+1, where NNO = Nickel–Nickel oxide buffer), the amphibole yield is very high (>90%), but its composition, and in particular the FeO/Fe₂O₃ ratio, departs significantly from the nominal one. Under oxidizing conditions ( NNO+1.5), the amphibole yield is much lower (<60%, with Li-pyroxene abundant), but its composition is close to the ideal stoichiometry. The exchange vector of relevance for the studied system is ^M2(Mg,Fe²⁺) ^M4(Mg,Fe²⁺) ^M2Fe³⁺_–1 ^M4Li_–1, which is still rather unexplored in natural systems. Amphibole crystals of suitable size for structure refinement were obtained only at 800 °C, 0.4 GPa and NNO conditions (sample 152), and have C2/m symmetry. The X-ray powder patterns for all other samples were indexed in the same symmetry; the amphibole closest to ideal composition has a = 9.428(1) Å, b = 17.878(3) Å, c = 5.282(1) Å, = 102.06(2)°, V = 870.8(3) ų. Mössbauer spectra show that Fe³⁺ is strongly ordered at M2 in all samples, whereas Fe²⁺ is disordered over the B and C sites. FTIR analysis shows that the amount of ^CFe²⁺ increases for increasingly reducing conditions. FTIR data also provide strong evidence for slight but significant amounts of Li at the A sites.     

Experimental studies to 10 kb of the bulk composition tremolite50-tschermakite50+excess H2O

Phase relations for the magnesio-hornblende bulk composition, 2 CaO·4 MgO·Al₂O₃·7 SiO₂+ excess H₂O, have been investigated to 10 kb employing hydrothermal and piston-cylinder techniques. The low-temperature limit of amphibole in this system lies at 519° C, 1,000 bars, 541° C, 2,000 bars, and 718° C, 10 kb. The low-T assemblage consists of an+chl+di+tc(+f), and is related to the adjacent high-T equilibrium assemblage, amph+an+chl+f, by the solid-solid reaction (A): 2 di+tc=tr. Small amounts of aluminum, hypothesized to be preferentially dissolved in the cpx (and in the tc) relative to amph, may account for the broad P-T stability range of the di+tc assemblage in the synthetic work relative to systems involving stoichiometric tr, Ca₂Mg₅Si₈O₂₂(OH)₂, such as are common in natural, Al-poor calc-silicate parageneses. Alternatively, the low-temperature assemblage produced in the experiments may be metastable. For the investigated bulk composition, synthetic tremolitic-cummingtonitic amphibole contains relatively modest amounts of ts, Ca₂Mg₃Al₂ ^IVSi₆-Al₂ ^IVO₂₂(OH)₂; at pressures of 1,000–3,000 bars, solid solution extends from near tremolite only to about cu₁₁tr₆₉ts₂₀, analogous to most analyzed natural magnesio-hornblendic specimens. At 10 kb fluid pressure, the solid solution reaches approximately cu₀₆tr₅₃ts₄₁ for the investigated bulk composition, and appears to be virtually independent of temperature. Amphibole and 14 Å chl react within the amphibole stability field, along curve (B), at about 704° C and 2,000 bars, to produce an, en, fo and f (H=40.9 kcal/ mole); at pressures greater than approximately 7kb, due to the incompatibility of an and fo, the higher temperature assemblage consists of amph, an, en, sp and f. Above P _fluid– T curve (B), the amphibole coexists with an+en+fo+f at low pressures; at higher pressures, the amphibole, which is in equilibrium with an+en+sp+f, is relatively more aluminous. The high-T stability limit of aluminous tr+fo lies approximately 20–25° C below the dehydration curve for stoichiometric tremolite on its own bulk composition. Reaction (C), tr+fo=2 di+5 en+f (H = 39.4 kcal/mole), produces an+di+en+f, the highest temperature subsolidus assemblage investigated for the tr₅₀ts₅₀ bulk composition. Hydrous melt is encountered at temperatures at least as low as 900° C at 10 kb, and at that fluid pressure coexists with amphibole over an interval of more than 60° C. Limited solid solution observed between tr and ts in nature (tr_100-70) is accounted for by the restricted range of amphibole compositions produced in the present study. Such amphiboles, moreover, appear to have both high- and low-temperature stability limits, as demonstrated by the experimental results.Institute of Geophysics and Planetary Physics Publication No. 2811     

Thermal expansion of plagioclase feldspars

The volume thermal expansion coefficient and the anisotropy of thermal expansion were determined for nine natural feldspars with compositions, in terms of albite (NaAlSi₃O₈, Ab) and anorthite (CaAl₂Si₂O₈, An), of Ab₁₀₀, An₂₇Ab₇₃, An₃₅Ab₆₅, An₄₆Ab₅₄, An₆₀Ab₄₀, An₇₈Ab₂₂, An₈₉Ab₁₁, An₉₆Ab₄ and An₁₀₀ by high resolution powder diffraction with a synchrotron radiation source. Unit-cell parameters were determined from 124 powder patterns of each sample, collected over the temperature range 298–935 K. The volume thermal expansion coefficient of the samples determined by a linear fit of V/V ₀ = α(T − T ₀) varies with composition (X _An in mol %) as:

Experimental calibration of the partitioning of Fe and Mg between biotite and garnet

The cation exchange reaction Fe₃Al₂Si₃O₁₂ +KMg₃AlSi₃O₁₀(OH)₂ = Mg₃Al₂Si₃O₁₂+KFe₃-AlSi₃ O₁₀(OH)₂ has been investigated by determining the partitioning of Fe and Mg between synthetic garnet, (Fe, Mg)₃Al₂Si₃O₁₂, and synthetic biotite, K(Fe, Mg)₃AlSi₃O₁₀(OH)₂. Experimental results at 2.07 kbar and 550 °–800 ° C are consistent with In [(Mg/Fe) garnet/(Mg/Fe) biotite] = -2109/T(°K) +0.782. The preferred estimates for ¯H and ¯S of the exchange reaction are 12,454 cal and 4.662 e.u., respectively. Mixtures of garnet and biotite in which the ratio garnet/biotite=49/1 were used in the cation exchange experiments. Consequently the composition of garnet-biotite pairs could approach equilibrium values in the experiments with minimal change in garnet composition (few tenths of a mole percent). Equilibrium was demonstrated at each temperature by reversal of the exchange reaction. Numerical analysis of the experimental data yields a geothermometer for rocks containing biotite and garnet that are close to binary Fe-Mg compounds.     

Compositions and phase relations of calcic amphiboles in epidote- and clinopyroxene-bearing rocks of the amphibolite and lower granulite facies,central Massachusetts,USA

Calcic amphiboles coexisting with epidotegroup minerals (zoisite, clinozoisite, epidote) and/or clinopyroxene±plagioclase±quartz±garnet occur in amphibolites and calc-silicate rocks that underwent amphibolite to lower granulite-facies metamorphism in the Acadian metamorphic high of central Massachusetts, USA. Across the region, peak metamorphic conditions range from about 580° C and 6.2 kbar to 730° C and 6.3 kbar. The coexistence of most Ca-amphiboles with Fe³⁺-rich epidote-group minerals suggests the presence of Fe³⁺ in most of these amphiboles. An empirical Fe³⁺ estimation for the microprobe analyses is based on two constraints: the Na?Ca content of the M4 sites of Ca-saturated, gravimetrically analyzed hornblendes gives the relation: Ca(M4) ^c =-1.479 Na(M4) ^c +2 (c=corrected). The second constraint is the stoichiometric equation Ca(M4)+Na(M4)+FM=15, where FM is the sum of all cations exclusive of Ca, Na, and K. Solving the two equations simultaneously gives: 20.185=0.479 Ca(M4)+1.479 ΣFM. Starting with the uncorrected values of Ca(M4) ^u and ΣFM(M4) ^u (u = uncorrected) of the all ferrous formula, the normalization factor NF for calculating the corrected cations of the ferric formulas is: 20.185/(0.478 Ca(M4) ^u +1.479 ΣFM ^u ). From the deficient oxygen the Fe³⁺ content which is equal to 2(23-ΣOX) can be calculated. Determinations of Fe³⁺ contents of four hornblende separates by Mössbauer spectroscopy are in agreement with the calculated values. The Ca-amphiboles show systematic changes in composition with increasing grade of metamorphism within the amphibolite and lower granulite-facies zones: increasing edenite and tschermakite substitution, increasing Ti content, and increasing Fe²⁺/(Fe²⁺+Mg) ratio. In addition, the coexisting clinopyroxenes are also characterized by an increase in Fe²⁺/(Fe²⁺+Mg) ratio. In quartz-free rocks with coexisting Ca-amphibole and plagioclase there is an increase in the ratio X _Ab/X _Ed, where X _Ab=Na/(Na+Ca) in plagioclase and X _Ed=Na in the amphibole A-site. These chemical changes in mineral composition together with the disappearance of epidote at the transition to granulite-facies metamorphic conditions are attributed to the continuous reaction: albite+epidote+Fe-Mg hornblende→Fe?Mg clinopyroxene+anorthite+(NaAlSi_-1)^Hbl+H₂O.     

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.     

Experimentally determined partitioning of Rb between richterites and aqueous (Na, K)-chloride solutions

The distribution of Rb-Na and Rb-K between richterite and a 2-molal aqueous (Na, K, Rb)-chloride solution has been investigated with hydrothermal experiments at 800^∘C and 200 MPa. Experiments were performed as syntheses in which amphiboles grew in the presence of an excess fluid containing the exchangeable cations Na⁺-Rb⁺ or Na⁺-K⁺-Rb⁺. The obtained amphiboles were large enough (up to 20 m in width) for reliable EMP analysis. They were chemically homogeneous and HRTEM investigations showed that they were structurally well ordered. The Rb, Na, K, Ca and Mg concentrations in coexisting fluids were measured by ICP-AES. According to the possible incorporation of Na, K and Rb on the A-site, solid solutions in the ternary Na(NaCa) Mg₅[Si₈O₂₂/(OH)₂] (richterite)-K(NaCa)Mg₅[Si₈O₂₂/(OH)₂] (K-richterite)-Rb(NaCa)Mg₅[Si₈O₂₂/(OH)₂] (Rb-richterite) were expected. However, Rb-rich richterites always had significant amounts of A-site vacancy concentrations (X _□ ^amph=□ ^A /(Rb^A+K^A +Na^A+□^A) of up to 0.42 in the K-free (Na,Rb)-richterites and of up to 0.67 in the (Na, K, Rb)-richterites which corresponds to the same content of tremolite+cummingtonite-component. Amphiboles containing practically only Rb besides vacancies and no Na and/or K on the A-site were also synthesized, however. The Rb-Na and Rb-K exchange coefficients between fluid and richterites are similar. Rubidium always fractionated strongly into the fluid phase. For low Rb-concentrations in richterite (X _Rb ^amph<0.1) a linear correlation between X _Rb ^fluid and X _Rb ^amph exists. In this concentration range, the derived exchange coefficients K _D(Rb−K) ^amph−fluid and K _D(Rb−Na) ^amph−fluid were 0.08 ± 0.04 and 0.04 ± 0.02, respectively. These low exchange coefficients show that significant amounts of Rb in amphiboles require a Rb-rich fluid phase. The results indicate that K-Rb fractionation between alkali amphiboles and fluids is significantly different from K-Rb fractionation between alkali feldspar/ phlogopite and fluid, with K_Ds of about 0.5 and 1.2, respectively. Formation of richterites will drastically alter the K/Rb-ratios of fluids or melts. These results may have important implications for the genetical interpretation of various geological settings, e.g., MARID-type rocks. Received: 6 October 1997 / Accepted: 7 July 1998     

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.     

Sigioite : The oxidation mechanism in [M 2 3 + (PO4)2(OH)2(H2O)2]2 - structures

Summary The crystal structure of sigloite, Fe³ [(H₂O)₃OH] [Al₂(PO₄)₂(OH)₂(H₂O)₂]- 2 H₂O, triclinic, a 5.190 (2), b 10.419 (4), c 7.033 (3) Å, 105.00 (3), 111.31(3), 70.87 (3)°, V 330.5 (2) Å3, Z = 1, space group P , has been refined to anR index of 5.3% using 1713 observed (I > 2.5 1) reflections collected with graphite-monochromated MoK X-rays. Sigloite is isostructural with the laueite-group minerals. Corner-linked [A1₅] chains (: unspecified ligand) are cross-linked by (PO₄) tetrahedra to form a mixed corner-linked tetrahedral-octahedral sheet of composition [A1₂(PO₄)₂(OH)₂(H₂O)₂]²-. These sheets are linked by (Fe³⁺O₂(OH, H₂O)₄) octahedra and two (H₂O) groups that participate in a hydrogen-bonding network. Sigloite is the oxidized equivalent of paravauxite, Fe²⁺(H₂O)4[Al₂(PO₄)₂(OH)₂(H₂O)₂]-² H₂O, and detailed comparison of the two structures shows that the oxidation mechanism involves loss of hydrogen from one of the (H₂O) groups coordinating the Fe³⁺, and positional disorder of both the Fe³⁺ and (OH) and (H₂O) ligands.

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Siggloit: Der Oxidationsmechanismus in (M ₂ ³ ₊ (PO₄)₂(OH)₂(H2O)₂]²- Strukturen

Zusammenfassung Die Kristallstruktur von Sigloit, Fe³⁺ [(H₂O)₃OH] [Al₂(PO₄)₂(OH)₂(H₂O)₂].2 H₂O, triklin, a 5,190 (2), b 10,419 (4), c 7,033 (3) Å, 105,00 (3), 111,31 (3), 70,87 (3)°, V 330,5 (2) ų,Z = 1, Raumgruppe P , wurdefür 1713 beobachtete Reflexe (I > 2,5 I), die mit MoKa-Röntgenstrahlung (Graphit-Monochromator) gesammelt wurden, auf einen R-Wert von 5,3% verfeinert. Sigloit ist isotyp mit den Mineralen deer Laueit-Gruppe. Über Ecken verknüpfte [A1₅]-Ketten (: nicht spezifizierter Ligand) werden über (P0₄)-Tetraeder zu ebenfalls über Ecken verknüpfte Tetraeder-OktaederSchichten der Zusammensetzung [A1₂(PO₄)₂(OH)₂(H₂O)₂]²- verbunden. Diese Schichten werden über (Fe³⁺O₂(OH, H2O)₄)-Oktaeder und zwei (H₂O)-Gruppen, die amWasserstoffbrücken-Netzwerk beteiligt sind, verbunden. Sigloit ist das oxidierte Analogon zu Paravauxit, Fe²⁺(H₂O)₄[A1₂(PO₄)₂(OH)₂(H₂O)₂] - 2 H₂O; ein detaillierter Vergleich dieser beiden Strukturen zeigt, daß der Oxidationsmechanismus sowohl den Verlust eines Wasserstoffatoms (H₂O)-Gruppe, welche ein Fe³⁺-Atom koordiniert, als auch eine Fehlordnung der Punktlagen von Fe³⁺ und von den (OH) und (H₂O) Liganden bedingt.

     

Characterization of NH4-phlogopite (NH4) (Mg3) [AlSi3O10] (OH)2 and ND4-phlogopite (ND4) (Mg3) [AlSi3O10] (OD)2 using IR spectroscopy and Rietveld refinement of XRD spectra

 A synthesis technique is described which results in >99% pure NH₄-phlogopite (NH₄) (Mg₃) [AlSi₃O₁₀] (OH)₂ and its deuterium analogue ND₄-phlogopite (ND₄) (Mg₃) [AlSi₃O₁₀] (OD)₂. Both phases are characterised using both IR spectroscopy at 298 and 77 K as well as Rietveld refinement of their X-ray powder diffraction pattern. Both NH₄ ⁺ and ND₄ ⁺ are found to occupy the interlayer site in the phlogopite structure. Absorption bands in the IR caused by either NH₄ ⁺ or ND₄ ⁺ can be explained to a good approximation using T_d symmetry as a basis. Rietveld refinement indicates that either phlogopite synthesis contains several mica polytypes. The principle polytype is the one-layer monoclinic polytype (1M), which possesses the space group symmetry C2/m. The next most common polytype is the two-layer polytype (2M ₁ ) with space group symmetry C2/c. Minor amounts of the trigonal polytype 3T with the space group symmetry P3₁12 were found only in the synthesis run for the ND₄-phlogopite. Electron microprobe analyses indicate that NH₄-phlogopite deviates from the ideal phlogopite composition with respect to variable Si/Al and Mg/Al on both the tetrahedral and octahedral sites, respectively, due to the Tschermaks substitution ^VIMg²⁺+^IVSi⁴⁺↔^VIAl³⁺+^IVAl³⁺ and with respect to vacancies on the interlayer site due to the exchange vector ^XII(NH₄)⁺+^IVAl³⁺↔^XII□+^IVSi⁴⁺. Received: 30 August 1999 / Accepted: 2 October 2000     

Dissolution and precipitation processes in deformed amphibolites: an example from the ductile shear zone of the Ryoke metamorphic belt, SW Japan

The granitic mylonite zone in the Cretaceous Ryoke metamorphic belt contains deformed amphibolites as thin layers. The amphibolite layers do not exhibit pinch‐and‐swell or boudinage structures, even when contained in a high‐strain granitic mylonite. This mode of occurrence suggests that they were deformed as much as the surrounding granite mylonite. In the highly deformed zone, strongly foliated amphibolites contain Ti‐rich brown amphibole porphyroclasts rimmed by Ti‐poor green amphibole, titanite and chlorite. These porphyroclasts are elongated, forming shear surfaces defined by preferential distribution of the chlorite and titanite. Porphyroclastic plagioclase in the strongly foliated amphibolites consists of two components: an anorthite‐rich core and an anorthite‐poor rim. Based on these observations, the mass‐balanced reaction occurring during deformation is defined as As the reaction products form a weak interconnected matrix, the strain rate of the amphibolites may be controlled by the rate of dissolution–precipitation through fluids. Weakly foliated amphibolites in the low‐strain zone exhibit cataclastic microstructures, whereas the strongly foliated amphibolites do not exhibit such features. These microstructural and chemical changes suggest that high‐strain amphibolites were initially deformed by cataclasis, followed by deformation through metamorphic reactions. During the metamorphism/deformation, old plagioclase grains with high X_an were not stable and dissolved, and new plagioclase grains with low X_an crystallized at the old plagioclase rim. Dissolution of old plagioclase and precipitation of new plagioclase occurred normal to and parallel to the foliation, respectively, reflecting incongruent pressure solution due to differential stress and changes in P–T–H₂O conditions. The development of incongruent pressure solution is attributed to increased fluid flux in the strongly foliated amphibolites, as evidenced by the greater abundance of hydration‐reaction products in the strongly foliated amphibolites than in the weakly foliated ones.