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1.
Summary Tourmaline is an ubiquitous constituent in the Pinilla de Fermoselle rare-element pegmatite (Zamora, Spain), as well as in barren pegmatitic and quartz–tourmaline veins inside the associated leucogranite. The rare-element pegmatite shows internal zoning, evolving from a barren facies, in the lower border zone, in contact with the leucogranite, to a Li-rich facies in the upper border zone, close to the host-rocks.Tourmalines from the veins within the leucogranite have highest Mg contents, and belong to the schorl–dravite series. The tourmalines from the rare-element pegmatite mostly belong to the schorl–elbaite series, with chemical compositions within the range of the end-members, whereas the tourmalines associated with the most evolved zone in the pegmatite belong to the elbaite–rossmanite series. The broad compositional range shown by the tourmalines correlates quite well with the pegmatite zoning. The most plausible substitution mechanism for the chemical evolution of tourmalines during crystallization seems to be Mg–1Fe2+1, [X]–1YAl–1XNa–1YFe2+1, for the foitite–schorl series; YFe2+–3YAl1.5YLi1.5, for the schorl–elbaite vector; XNa–1YLi–0.5[X]1YAl0.5, for the elbaite–rossmanite series; and, (OH)1F1 for all the tourmalines except the pink elbaites. This chemical variation in tourmaline is consistent with a crystal fractionation model for the evolution of the Pinilla pegmatite.  相似文献   

2.
Six tourmaline samples were investigated as potential reference materials (RMs) for boron isotope measurement by secondary ion mass spectrometry (SIMS). The tourmaline samples are chemically homogeneous and cover a compositional range of tourmaline supergroup minerals (primarily Fe, Mg and Li end‐members). Additionally, they have homogeneous boron delta values with intermediate precision values during SIMS analyses of less than 0.6‰ (2s). These samples were compared with four established tourmaline RMs, that is, schorl IAEA‐B‐4 and three Harvard tourmalines (schorl HS#112566, dravite HS#108796 and elbaite HS#98144). They were re‐evaluated for their major element and boron delta values using the same measurement procedure as the new tourmaline samples investigated. A discrepancy of about 1.5‰ in δ11B was found between the previously published reference values for established RMs and the values determined in this study. Significant instrumental mass fractionation (IMF) of up to 8‰ in δ11B was observed for schorl–dravite–elbaite solid solutions during SIMS analysis. Using the new reference values determined in this study, the IMF of the ten tourmaline samples can be modelled by a linear combination of the chemical parameters FeO + MnO, SiO2 and F. The new tourmaline RMs, together with the four established RMs, extend the boron isotope analysis of tourmaline towards the Mg‐ and Al‐rich compositional range. Consequently, the in situ boron isotope ratio of many natural tourmalines can now be determined with an uncertainty of less than 0.8‰ (2s).  相似文献   

3.
The fractionation of boron isotopes between synthetic dravitic tourmaline and fluid was determined by hydrothermal experiments between 400 and 700°C at 200 MPa and at 500°C, 500 MPa. Tourmaline was crystallized from an oxide mix in presence of water that contained boron in excess. In one series of experiments, [B]fluid/[B]tour was 9 after the run; in another series it was 0.1. All experiments produced tourmaline as the sole boron-bearing solid, along with traces of quartz and talc. Powder XRD and Rietveld refinements revealed no significant amounts of tetrahedrally coordinated boron in tourmaline. 11B always preferentially fractionated into the fluid. For experiments where [B]fluid/[B]tour was 9, a consistent temperature-dependent boron isotope fractionation curve resulted, approximated by Δ11B(tour–fluid) = −4.20 · [1,000/T (K)] + 3.52; R 2 = 0.77, and valid from 400 to 700°C. No pressure dependence was observed. The fractionation (−2.7 ± 0.5‰ at 400°C; and −0.8 ± 0.5‰ at 700°C) is much lower than that previously presented by Palmer et al. (1992). Experiments where [B]fluid/[B]tour was 0.1 showed a significant larger apparent fractionation of up to −4.7‰. In one of these runs, the isotopic composition of handpicked tourmaline crystals of different size varied by 1.3‰. This is interpreted as resulting from fractional crystallization of boron isotopes during tourmaline growth due to the small boron reservoir of the fluid relative to tourmaline, thus indicating larger fractionation than observed at equilibrium. The effect is eliminated or minimized in experiments with very high boron excess in the fluid. We therefore suggest that values given by the above relation represent the true equilibrium fractionations.  相似文献   

4.
A detailed study of the chemical composition and substitutions in calcium tourmalines from a scapolite-bearing rare-metal pegmatite vein from the Sol’bel’der River basin has shown that their species attribution is determined by occupancy of octahedral site Y. The composition of the yellow tourmaline most abundant in the central part of the pegmatite bodyis rather constant and characterized by the ideal formula Ca(Mg2Li)Al6(Si6O18)(BO3)3(OH)3F. Variations in the chemical composition of zonal tourmaline crystals from the contact part of the pegmatite are controlled by abrupt change in the chemical medium during their formation. The yellow cores of these crystals are close in composition to tourmaline from the central part of the pegmatite vein. The Mg content abruptly decreases toward the crystal margin: Mg2+ → Fe2+, 2Mg2+ → Li+ + Al3+, and Mg2+ + OH → Al3+ + O2−. The composition of dark green marginal zones in tourmaline is characterized by the ideal formula Ca(Al1.5Li1.5)Al6(Si6O18)(BO3)3 (OH2O)(F). The results indicate specific formation conditions of pegmatite. The crystallochemical formulas of the studied tourmalines allow us to regard them as new mineral species in the tourmaline group.  相似文献   

5.
Pale-blue to pale-green tourmalines from the contact zone of Permian pegmatites to mica schists and marbles from different localities of the Austroalpine basement units (Rappold Complex) in Styria, Austria, are characterized. All these Mg-rich tourmalines have small but significant Li contents, up to 0.29 wt% Li2O, and can be characterized as dravite, with FeO contents of ?~?0.9–2.7 wt%. Their chemical composition varies from X (Na0.67Ca0.19?K0.02?0.12) Y (Mg1.26Al0.97Fe2+ 0.36Li0.19Ti4+ 0.06Zn0.01?0.15) Z (Al5.31?Mg0.69) (BO3)3 Si6O18 V (OH)3? W [F0.66(OH)0.34], with a?=?15.9220(3), c?=?7.1732(2) Å to X (Na0.67Ca0.24?K0.02?0.07) Y (Mg1.83Al0.88Fe2+ 0.20Li0.08Zn0.01Ti4+ 0.01?0.09) Z (Al5.25?Mg0.75) (BO3)3 Si6O18 V (OH)3? W [F0.87(OH)0.13], with a?=?15.9354(4), c?=?7.1934(4) Å, and they show a significant Al-Mg disorder between the Y and the Z sites (R1?=?0.013–0.015). There is a positive correlation between the Ca content and?<?Y-O?>?distance for all investigated tourmalines (r?≈?1.00), which may reflect short-range order configurations including Ca and Fe2+, Mg, and Li. The tourmalines have XMg (XMg?=?Mg/Mg?+?Fetotal) values in the range 0.84–0.95. The REE patterns show more or less pronounced negative Eu and positive Yb anomalies. In comparison to tourmalines from highly-evolved pegmatites, the tourmaline samples from the border zone of the pegmatites of the Rappold Complex contain relatively low amounts of total REE (~8–36 ppm) and Th (0.1–1.8 ppm) and have low LaN/YbN ratios. There is a positive correlation (r?≈?0.91) between MgO of the tourmalines and the MgO contents of the surrounding mica schists. We conclude that the pegmatites formed by anatectic melting of mica schists and paragneisses in Permian time. The tourmalines crystallized from the pegmatitic melt, influenced by the metacarbonate and metapelitic host rocks.  相似文献   

6.
Heat treatment was performed on selected Fe-dominant tourmalines to establish the nature of any change in optical properties. Two tourmaline samples from Dolní Bory, Czech Republic (TDB) and Vlachovo, Slovakia (TVL) were heated at 450, 700 and 900°C at 0.1 mPa and ambient oxidation conditions for 8 h. EMPA study shows that tourmaline from Vlachovo has schorlitic composition and tourmaline from Dolní Bory is alkali-depleted schorl to foitite. Although the black colour remained unchanged after heating at 450°C, it changed to brown at 700°C and reddish brown at 900°C. No significant changes of chemical composition were observed during heating. X-ray diffraction, infrared and Mössbauer study showed negligible oxidation of tourmaline heated at 450°C, but a significant change in iron valency state and deprotonization at 700°C. The oxidation of Fe is the main cause of tourmaline colour change, and the substitution vector for oxidation of Fe is Fe3+OFe ?1 2+ (OH)?1. The predicted deprotonization of OH was confirmed by infrared spectroscopy, which documented a decrease in OH groups in both samples, mainly at the V site. The oxidation of Fe is mostly significant in the Y site as documented on the compression of the Y-site octahedra and subsequent decrease in the a lattice parameter. This feature is consistent with lattice dimensions in the transition from schorl and foitite dimensions to those consistent with fluor-buergerite. The Z-site octahedra did not compressed and were not affected by heating-induced Fe oxidation, which indicates only negligible content of Z Fe2+ in original samples. After heating at 900°C, the tourmaline structure collapsed likely due to the thermally induced weakening of bonds in Y and Z octahedra, which results in amorphization of tourmaline. Subsequently, breakdown products including Fe-oxides and mullite replaced alkali-depleted amorphized tourmaline.  相似文献   

7.
Summary ?The Yunlong tin deposit is located in the northern part of the Lancangjiang metamorphic zone of the Sanjiang Tethys orogen series in western Yunan province of China. It consists of vein-type cassiterite ores, which are mainly hosted in migmatites of Caledonian age. Abundant tourmaline is associated with the ores, quartz–tourmaline veins and barren migmatized gneiss and migmatites. A detailed electron microprobe study has been carried out to document the chemical compositions of tourmaline from this deposit. The results exhibit a systematic compositional change that might be used as tracer for ore genesis and in prospecting for tin mineralization. Tourmalines from the ore bodies are dravite with Fe/(Fe + Mg) ratios of 0.09 ∼ 0.31 and Ca/(Ca + Na) ratios of 0.03 ∼ 0.40. These tourmalines are also rich in chromium (up to 0.74 wt% Cr2O3) and tin (up to 0.42 wt% Sn). In contrast, tourmalines from the barren migmatites are mostly schorl with Fe/(Fe + Mg) ratios of 0.38 ∼ 0.94 and Ca/(Ca + Na) ratios of 0.00 ∼ 0.14. Tourmalines from quartz–tourmaline veins that occur between ore bodies and the migmatites show intermediate compositions, i.e., Fe/(Fe + Mg) = 0.09 ∼ 0.59, Ca/(Ca + Na) = 0.01 ∼ 0.22. It is suggested that the Mg-rich nature of the tourmaline can be used as an exploration tool in this region to target tin mineralization, because the tourmalines show increasing Mg contents and are more dravitic when approaching the ore bodies. It is likely that the formation of the Yunlong tin deposit was related to migmatitic-hydrothermal processes. The high Mg and Cr contents in tourmalines from the ore bodies were probably derived from the local meta-sedimentary and meta-volcanic rocks of the Precambian Chongshan Group rather than from the granites in the region. Received December 28, 2000; revised version accepted January 25, 2002  相似文献   

8.
Quartz-tourmaline lenses, around which host granite is impregnated by uraninite, have been found among porphyritic granite with large phenocrysts of the Urtui pluton in the Ttansbaikal krai framing the Strel’tsovka volcano-tectonic structure. Two generations of tourmaline are distinguished. Most individual crystals belong to the first generation attributed to “fluor-schorl”; tourmaline-II attributed to schorl occurs as thin rims overgrowing tourmaline-I. The major type of cation isomorphic substitution in both tourmalines is Fe2+ → Mg. The Fe3+/Fetot value and Li content in the average sample are 2% and 80 ppm, respectively. The high F content, comparatively high Li, low Fe3+/Fetot value, and character of cation isomorphic substitution indicate that the tourmaline relates to greisens. The combination of these features allows one to distinguish greisen-type tourmaline-bearing rocks. The impregnated uranium mineralization in granite of the Urtui pluton, one of the probable sources of uranium in economic U ore of the Strel’tsovka deposit, is suggested to be caused by greisenization and the formation of quartz-tourmaline lenses.  相似文献   

9.
Cu- and Mn-bearing tourmalines from Brazil and Mozambique were characterised chemically (EMPA and LA-ICP-MS) and by X-ray single-crystal structure refinement. All these samples are rich in Al, Li and F (fluor-elbaite) and contain significant amounts of CuO (up to ~1.8 wt%) and MnO (up to ~3.5 wt%). Structurally investigated samples show a pronounced positive correlation between the <Y-O> distances and the (Li + Mn2+ + Cu + Fe2+) content (apfu) at this site with R 2 = 0.90. An excellent negative correlation exists between the <Y-O> distances and the Al2O3 content (R 2 = 0.94). The samples at each locality generally show a strong negative correlation between the X-site vacancies and the (MnO + FeO) content. The Mn content in these tourmalines depends on the availability of Mn, on the formation temperature, as well as on stereochemical constraints. Because of a very weak correlation between MnO and CuO we believe that the Cu content in tourmaline is essentially dependent on the availability of Cu and on stereochemical constraints.  相似文献   

10.
Tourmaline is widespread in metapelites and pegmatites from the Neoproterozoic Damara Belt, which form the basement and potential source rocks of the Cretaceous Erongo granite. This study traces the B-isotope variations in tourmalines from the basement, from the Erongo granite and from its hydrothermal stage. Tourmalines from the basement are alkali-deficient schorl-dravites, with B-isotope ratios typical for continental crust (δ11B average −8.4‰ ± 1.4, n = 11; one sample at −13‰, n = 2). Virtually all tourmaline in the Erongo granite occurs in distinctive tourmaline-quartz orbicules. This “main-stage” tourmaline is alkali-deficient schorl (20–30% X-site vacancy, Fe/(Fe + Mg) 0.8–1), with uniform B-isotope compositions (δ11B −8.7‰ ± 1.5, n = 49) that are indistinguishable from the basement average, suggesting that boron was derived from anatexis of the local basement rocks with no significant shift in isotopic composition. Secondary, hydrothermal tourmaline in the granite has a bimodal B-isotope distribution with one peak at about −9‰, like the main-stage tourmaline, and a second at −2‰. We propose that the tourmaline-rich orbicules formed late in the crystallization history from an immiscible Na–B–Fe-rich hydrous melt. The massive precipitation of orbicular tourmaline nearly exhausted the melt in boron and the shift of δ11B to −2‰ in secondary tourmaline can be explained by Rayleigh fractionation after about 90% B-depletion in the residual fluid. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

11.
Tourmalines from the Kalinovka porphyry copper deposit with epithermal bismuth-gold-basemetal mineralization and the Michurino gold-silver-base-metal prospect have been studied in the South Urals. Tourmaline from the Kalinovka deposit occurs as pockets and veinlets in quartz-sericite metasomatic rock and propylite. The early schorl-“oxy-schorl” [Fetot/(Fetot + Mg) = 0.66?0.81] enriched in Fe3+ is characterized by the homovalent isomorphic substitution of Fe3+ for Al typical of propylites at porphyry copper deposits. The overgrowing tourmalines of the second and third generations from propylite and quartz-sericite metasomatic rock are intermediate members of the dravite-magnesio-foitite solid solution series [Fetot/(Fetot + Mg) = 0.05?0.46] with homovalent substitution of Mg for Fe2+ and coupled substitution of X ? + YAl for XNa + YMg. These substitutions differ from the coupled substitution of YAl + WO2? for YFe2+ + WOH? in tourmaline from quartz-sericite rocks at porphyry copper deposits. At the Michurino prospect, the tourmaline hosted in the chlorite-pyrite-quartz veins and veinlets with Ag-Au-Cu-Pb-Zn mineralization is an intermediate member of the dravite-magnesio-foitite solid solution series [Fetot/(Fetot + Mg) = 0.20?0.31] with homovalent substitution of Mg for Fe2+ and coupled substitutions of X ? + YAl for XNa + YMg identical to that of late tourmaline at the Kalinovka deposit. Thus, tourmalines of the porphyry and epithermal stages are different in isomorphic substitutions, which allow us to consider tourmaline as an indicator of super- or juxtaposed mineralization.  相似文献   

12.
Summary. ?Ca-tourmaline has been synthesized hydrothermally in the presence of Ca(OH)2 and CaCl2-bearing solutions of different concentration at T = 300–700 °C at a constant fluid pressure of 200 MPa in the system CaO-MgO-Al2O3-SiO2-B2O3-H2O-HCl. Synthesis of tourmaline was possible at 400 °C, but only above 500 °C considerable amounts of tourmaline formed. Electron microprobe analysis and X-ray powder data indicate that the synthetic tourmalines are essentially solid solutions between oxy-uvite, CaMg3- Al6(Si6O18)(BO3)3(OH)3O, and oxy-Mg-foitite, □(MgAl2)Al6(Si6O18)(BO3)3(OH)3O. The amount of Ca ranges from 0.36 to 0.88 Ca pfu and increases with synthesis temperature as well as with bulk Ca-concentration in the starting mixture. No hydroxy-uvite, CaMg3(MgAl5)(Si6O18)(BO3)3(OH)3(OH), could be synthesized. All tourmalines have < 3 Mg and > 6 Al pfu. The Al/(Al + Mg)-ratio decreases from 0.80 to 0.70 with increasing Ca content. Al is coupled with Mg and Ca via the substitutions Al2□Mg−2Ca−1 and AlMg−1H−1. No single phase tourmaline could be synthesized. Anorthite ( + quartz in most runs) has been found coexisting with tourmaline. Other phases are chlorite, tremolite, enstatite or cordierite. Between solid and fluid, Ca is strongly fractionated into tourmaline ( + anorthite). The concentration ratio D = Ca(fluid)/Ca(tur) increases from 0.20 at 500 °C up to 0.31 at 700 °C. For the assemblage turmaline + anorthite + quartz + chlorite or tremolite or cordierite, the relationship between Ca content in tourmaline and in fluid with temperature can be described by the equation (whereby T = temperature in °C, Ca(tur) = amount of Ca on the X-site in tourmaline, Ca( fluid) = concentration of Ca2+ in the fluid in mol/l). The investigations may serve as a first guideline to evaluate the possibility to use tourmaline as an indicator for the fluid composition.
Zusammenfassung. ?Synthese von Ca-Turmelin im System CaO-MgO-Al 2 O 3 -SiO 2 -B 2 O 3 -H 2 O-HCl Im System CaO-MgO-Al2O3-SiO2-B2O3-H2O-HCl wurde Ca-Turmalin hydrothermal aus Ca(OH)2 and CaCl2-haltigen L?sungen bei T = 300–700 °C und einem konstanten Fluiddruck von 200 MPa synthetisiert. Die Synthese von Turmalin war m?glich ab 400 °C, aber nur oberhalb von 500 °C bildeten sich deutliche Mengen an Turmalin. Elektronenstrahl-Mikrosondenanalysen und R?ntgenpulveraufnahmen zeigen, da? Mischkristalle der Reihe Oxy-Uvit, CaMg3Al6(Si6O18)(BO3)3(OH)3O, und Oxy-Mg-Foitit, □(MgAl2)Al6(Si6O18)(BO3)3(OH)3O gebildet wurden. Der Anteil an Ca variiert zwischen 0.36 und 0.88 Ca pfu und nimmt mit zunehmender Synthesetemperatur und zunehmender Ca-Konzentration im System zu. Hydroxy-Uvit, CaMg3(MgAl5) (Si6O18)(BO3)3(OH)3(OH), konnte nicht synthetisiert werden. Alle Turmaline haben < 3 Mg und > 6 Al pfu. Dabei nimmt das Al/(Al + Mg)- Verh?ltnis mit zunehmendem Ca-Gehalt von 0.80 auf 0.70 ab. Al ist gekoppelt mit Mg und Ca über die Substitutionen Al2□Mg−2Ca−1 und AlMg−1H−1. Einphasiger Turmalin konnte nicht synthetisiert werden. Anorthit (+ Quarz in den meisten F?llen) koexistiert mit Turmalin. Andere Phasen sind Chlorit, Tremolit, Enstatit oder Cordierit. Ca zeigt eine deutliche Fraktionierung in den Festk?rpern Turmalin (+ Anorthit). Das Konzentrationsverh?ltnis D = Ca(fluid)/Ca(tur) nimmt von 0.20 bei 500 °C auf 0.31 bei 700 °C zu. Für die Paragenese Turmalin + Anorthit + Quarz mit Chlorit oder Tremolit oder Cordierit gilt folgende Beziehung zwischen Ca-Gehalt in Turmalin und Fluid und der Temperatur: (wobei T = Temperatur in °C, Ca(tur) = Anteil an Ca auf der X-Position in Turmalin, Ca(fluid) = Konzentration von Ca2+ im Fluid in mol/l). Die Untersuchungen dienen zur ersten Absch?tzung, ob Turmalin als Fluidindikator petrologisch nutzbar ist.

Received July 24, 1998;/revised version accepted October 21, 1999  相似文献   

13.
Two pumpellyites with the general formula W 8 X 4 Y 8 Z 12O56-n (OH) n were studied using 57Fe Mössbauer spectroscopic and X-ray Rietveld methods to investigate the relationship between the crystal chemical behavior of iron and structural change. The samples are ferrian pumpellyite-(Al) collected from Mitsu and Kouragahana, Shimane Peninsula, Japan. Rietveld refinements gave Fe(X):Fe(Y) ratios (%) of 41.5(4):58.5(4) for the Mitsu pumpellyite and 46(1):54(1) for the Kouragahana pumpellyite, where Fe(X) and Fe(Y) represent Fe content at the X and Y sites, respectively. The Mössbauer spectra consisted of two Fe2+ and two Fe3+ doublets for the Mitsu pumpellyite, and one Fe2+ and two Fe3+ doublets for the Kouragahana pumpellyite. In terms of the area ratios of the Mössbauer doublets and the Fe(X):Fe(Y) ratios determined by the Rietveld refinements, Fe2+(X):Fe3+(X):Fe3+(Y) ratios are determined to be 22:14:64 for the Mitsu pumpellyite and 27:8:65 for the Kouragahana pumpellyite. By applying the Fe2+:Fe3+-ratio determined by the Mössbauer analysis and the site occupancies of Fe at the X and Y sites given by the Rietveld method together with chemical analysis, the resulting formula of the Mitsu and Kouragahana pumpellyites are established as Ca8(Fe 0.88 2+ Mg0.68Fe 0.77 3+ Al1.66)Σ3.99(Al5.67Fe 2.34 3+ )Σ8.01Si12O42.41(OH)13.59 and Ca8(Mg1.24Fe 0.65 2+ Fe 0.46 3+ Al1.66)Σ4.01(Al6.71Fe 1.29 3+ )Σ8.00Si12O42.14(OH)13.86, respectively. Mean Y–O distances and volumes of the YO6 octahedra increase with increasing mean ionic radii, i.e., the Fe3+→Al substitution at the Y site. However, change of the sizes of XO6 octahedra against the mean ionic radii at the X site is not distinct, and tends to depend on the volume change of the YO6 octahedra. Thus, the geometrical change of the YO6 octahedra with Fe3+→Al substitution at the Y site is essential for the structural changes of pumpellyite. The expansion of the YO6 octahedra by the ionic substitution of Fe3+ for Al causes gradual change of the octahedra to more symmetrical and regular forms.  相似文献   

14.
 Amphiboles were synthesized from bulk compositions prepared along the join Ca1.8Mg5.2Si8O22(OH)2–Ca1.8Mg3Ga4Si6O22(OH)2 hydrothermally at 750–850 °C and 1.0–1.8 GPa, and along the join Ca2Mg5Si8O22F2–Ca2Mg3Ga4Si6O22F2, anhydrously at 1000 °C and 0.7 GPa to document how closely the tschermak-type substitution is obeyed in these analogues of aluminous amphiboles. Electron-microprobe analyses and Rietveld X-ray diffraction structure refinements were performed to determine cation site occupancies. The extent of Ga substitution was found to be limited in both joins, but with the fluorine series having about twice the Ga content (0.6 atoms per formula unit, apfu) of the hydroxyl-series amphiboles (0.3 apfu). The tschermak-type substitution was followed very closely in the hydroxyl series with essentially equal partitioning of Ga between tetrahedral and octahedral sites. The fluorine-series amphiboles deviated significantly from the tschermak-type substitution and, instead, appeared to follow a substitution that is close to a Ca-pargasite substitution of the type: [6]Ga3++2[4]Ga3++1/2[A] Ca2+ = [6]Mg2++2[4]Si4++1/2[A]□. Infrared spectroscopy revealed an inverse correlation between the intensity of the OH-stretching bands and the Ga content for the hydroxyl- and fluorine-series amphiboles. The direct correlation between the Ga and F content and inverse relationship between the Ga and OH content may be a general phenomenon present in other minerals and suggests, for example, that high F contents in titanite are controlled by the Al content of the host rock and that there may be similar direct Al–F correlations in tschermakitic amphiboles. Evidence for the possibility that Al (Ga) might substitute onto only a subset of the tetrahedral sites in tschermakitic amphiboles was sought but not observed in this study. Received: 5 March 2001 / Accepted: 31 July 2001  相似文献   

15.
Synchrotron radiation boron K-edge XANES spectra collected in fluorescence yield mode are reported for monoclinic metaboric acid [HBO2(II)], sinhalite (MgAlBO4), and a selection of boron oxides in which B is exclusively in trigonal coordination ([3]B). The anomalously high divergence of tetrahedral ([4]B–O) bond lengths in HBO2(II) and sinhalite is used to resolve fine structure at the [4]B K edge due to splitting of σ*(t2) antibonding orbitals. For HBO2(II), XANES peaks at 196.9 and 199.3?eV are assigned to [4]B–O distances of 1.564 and ～1.440 (×3) Å, respectively, and, for sinhalite, peaks at 196.8, 197.9, and 199.6?eV are assigned to distances of 1.586, 1.483 (×2), and 1.442?Å, respectively. A correlation between peak splitting at the [4]B K edge and divergence of tetrahedral bond length is established for borates and borosilicates using data for sinhalite, HBO2(II), ferroaxinite, danburite, datolite, and BPO4. B K-edge XANES spectra collected in total electron yield mode, which probes to <60?Å, show that almost all [4]B in HBO2(II) and about one-third of the [4]B in sinhalite are converted to [3]B in the near-surface structure. Moreover, HBO2(II), HBO2(III), sassolite (boric acid; H3BO3), and v-B2O3, which have markedly different bulk structures, have a similar near-surface layer composed of a relaxed anhydrous network of BO3 groups.  相似文献   

16.
《Chemical Geology》1992,94(3):215-227
Tourmaline is a ubiquitous mineral in the Mid-Proterozoic, peraluminous, syn- to post-tectonic granites and aplites and the related hydrothermal rocks of the Karagwe-Ankolean belt in northwest Tanzania. Electron microprobe analysis indicates that tourmalines from all of the intrusive and hydrothermal lithologies: (1) belong to the schorl-dravite solid-solution series; and (2) plot within the field occupied by tourmaline from Li-poor granitoids on the Fe-Al-Mg classification diagram. Oxygen isotope compositions range from +12.2 to +11.6‰ (SMOW) for magmatic tourmalines and from +10.8 to +9.8‰ for those of hydrothermal origin. Hydrogen isotope compositions vary from −79 to − 65‰ (SMOW) for magmatic tourmalines and from −99 to −84‰ for hydrothermal tourmalines. Water contents measured by manometry are constant at 3.0–3.2 wt.%. Within the broad grouping there arc systematic variations in both chemical [particularly Fetot/(Fetot + Mg ratio)] and isotopic composition that relate to evolving magmatic and hydrothermal conditions. Igneous differentiation [increasing Fetot/(Fetot + Mg) in magmatic tourmaline] has produced trends with higher δ18O in quartz, lower δ18O in tourmaline, and larger ΔQTZ.−TOUR.-values, that reflect a combination of a reduction of crystallization temperature and an increase of Fetot/ (Fetot + Mg) in the residual melt. Subsequent cooling and interaction of an exsolved, B-rich magmatic fluid with the pelitic country rocks, resulted in the deposition of hydrothermal tourmaline with increasing Fetot/(Fetot + Mg) ratios, and progressively lower δ18O and δD -values.  相似文献   

17.
Tourmaline-out isograd formed by the breakdown of tourmaline is defined in the upper amphibolite-facies metapelites in the Yanai area, Ryoke metamorphic belt, SW Japan. The rim composition of tourmaline progressively becomes aluminous with ascending metamorphic grade, and the chemical zoning of tourmaline is controlled by X□AlNa–1Mg–1 and MgTiYAl–2 vectors in low- to medium-grade zones where muscovite is stable, whereas it is controlled by Mg(OH)YAl–1O–1, CaMgOX□–1 YAl–1(OH)–1 and MgTiYAl–2 vectors in further higher–grade, muscovite-unstable zones. The size of tourmaline increases drastically where breakdown of muscovite+quartz takes place, probably due to the growth of tourmaline during breakdown of muscovite. On the high-temperature side of the tourmaline-out isograd, depletion of whole-rock boron is observed. Escape of boron-bearing melt or the fluid evolved from the melt during its crystallization probably caused this depletion, although locally trapped, boron-bearing melt or fluid formed irregularly shaped tourmaline and dumortierite during retrograde metamorphism.  相似文献   

18.
The natural norbergite, Mg2.98Fe0.01Ti0.02Si0.99O4(OH0.31F1.69) is examined by synchrotron X-ray diffraction analysis at pressures up to 8.2 GPa. The measured linear compressibilities of the crystallographic axes are β a  = 2.18(4) × 10−3, β b  = 2.93(7) × 10−3, and β c  = 2.77(7) × 10−3 (GPa−1), respectively and the calculated isothermal bulk modulus of the norbergite is K T = 113(2) GPa based on the Birch–Murnaghan equation of state assuming a pressure derivative of K′ = 4. The crystal structures of norbergite are refined at room temperature and pressures of 4.7, 6.3, and 8.2 GPa, yielding R values for the structure refinements of 4.6, 5.3, and 5.3%, respectively. The bulk moduli of the polyhedral sites are 293(15) GPa for the tetrahedron, 106(5) GPa for the M2 octahedron, 113(2) GPa for the M3 octahedron, and 113(3) GPa for the total void space. The bulk modulus exhibits a good linear correlation with the filling factor for polyhedral sites in structures of the humite minerals and forsterite, reflecting the Si4+ + 4O2− ⇔ □ + 4(OH, F)− substitution in the humite minerals. Moreover, two simply linear trends were observed in the relationship between bulk modulus and packing index for natural minerals and dense hydrous magnesium silicate minerals. This relationship would reflect that the differences in compression mechanism were involved with hydrogen bonding in these minerals. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

19.
Complex oxides of the pyrochlore (space groups Fd3m, [8]A2 [6]B2O7) and garnet (Ia3d, [8]A3 [6]B2 [4]T3O12) structures (“A” = Ca2+, Ln3+/4+, An3+/4+; “B” = (Ti, Sn, Hf, and Zr)4+ in pyrochlore, and Al3+, Ga3+, and Fe3+ in garnet alone; “T” = (Al3+, Ga3+, and Fe3+) are promising matrices for actinide-bearing wastes. In order to identify optimal compositions of these phases, their isomorphic capacity with respect to REE, actinides, and other components of wastes was examined. The long-term behavior of the matrix at a repository was predicted based on data obtained on the behavior of pyrochlores and garnets under ion irradiation and 244Cm decay and on the determined leaching rates of REE from the matrices because of their interaction with aqueous solutions, including that after amorphization. In order to propose efficient synthesis techniques, samples prepared with the use of various methods were studied. The possibility of incorporating long-lived decay products of 99Tc into the crystalline matrices was analyzed.  相似文献   

20.
A dravite from Yemen of near end-member composition was treated in air and hydrogen atmospheres at 600–900 °C to reveal changes in Mg and Al order over the octahedrally coordinated Y and Z sites, and to explore related changes in the characteristic vibrational bands in the principal (OH)-stretching frequency. Relevant information was obtained using electron microprobe analysis (EMPA), structural refinement (SREF) and polarized infrared (IR) single-crystal spectroscopy. Overall, the EMPA, SREF and IR data show that only minor changes occur during thermal treatment up to at least 800 °C, including variations in structural parameters, Mg–Al order–disorder and (OH)-stretching bands, indicating limited hydrogen loss. Untreated and treated dravite samples have very similar long-range and short-range atomic structures, which may be related to the occurrence of stable Al–Mg extended clusters around the O1 (=W) and O3 (=V) sites: W(F)–Y(MgMgMg)–V(OH)3–Z[AlAlAlAlAl(Al,Mg)]; W(OH)–Y(MgMgAl)–V(OH)3–Z[AlAlAlAlAl(Al,Mg)]; W(O2–)–Y(AlAlAl)–V(OH)3–Z[AlAlAlAlAl(Al,Mg)]. These extended clusters remain stable to temperatures close to the observed start of decomposition (~900 °C).  相似文献   

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