Crystal chemistry of Fe-Mg-carpholites

A chemical and X-ray investigation of the Fe-Mg-carpholites of Crete/Greece reveals a large variation in their Fe²⁺/(Fe²⁺+Mg) ratios (0.68 to 0.05). The lattice constants a and b depend linearly on this parameter, and the magnitude of the effect is comparable to that encountered in pyroxenes. The similar behaviour of the lattice dimensions of both these minerals is explained by comparing their structures and pointing out the salient crystal chemical similarities.     

Crystal chemistry of Fe-containing sphalerites

 Cell dimensions and solvus properties of Fe-containing sphalerites, depending on temperature and sulfur fugacity, were investigated using equilibrated powdered materials synthesized from elements and binary sulfides under vacuum. The Fe solvus in sphalerite, determined by optical microscopy and microprobe analysis, are directly correlated with increasing temperature and decreasing sulfur fugacity controlled by solid-state buffers. The increase of lattice parameters with Fe correlates with an increase of FeS independent of sulfur fugacity up to 10 mol% FeS within ZnS. Above about 10 mol% the lattice parameters are strongly depending on the sulfur fugacity controlled Fe³⁺/Fe²⁺ ratios. The Fe³⁺/Fe²⁺ ratios determined by Moessbauer spectroscopy and involving metal vacancies depend on the sulfur fugacity. The critical Fe²⁺ content determined by experimental simulations as well as the minimal Fe³⁺/ Fe²⁺ ratios agree with the required minimal Fe content for CuFeS₂-DIS in sphalerite. The critical Fe²⁺ content also agrees with the change of Moessbauer signal from a singlet to a doublet for Fe²⁺ containing sphalerite. Pyrrhotite exsolutions in sphalerite caused by higher sulfur fugacity show orientationally intergrown with the sphalerite matrix. Density data calculated from lattice parameters and composition are compared with experimental density measurements. Received: 25 April 2001 / Accepted: 14 February 2003     

Crystal chemistry of Sc-bearing synthetic diopsides

Scandium substitution in the diopside structure was studied by single-crystal X-ray diffraction on a series of synthetic diopside samples. These diopsides were doped with increasing amounts of Sc³⁺ through a coupled substitution involving ^M1(Sc³⁺)₁ ^M2[] ₁ ^T (B)₁ ^M1(Mg²⁺)_?1 ^M2(Ca²⁺)_?1 ^T(Si⁴⁺)_?1 exchange, whereby charge compensation is achieved by vacancies at the M2 sites and B at the tetrahedral sites. The substitution of scandium for magnesium at the M1 site results in an increase in volume and distortion of the M1O₆ polyhedron. The accompanying creation of vacancies at the M2 sites causes an increase in the M2 polyhedral volume. The modifications of the M1 and M2 polyhedra result in an increase of the polyhedral strip along the b lattice direction and a straightening of the tetrahedral chain. The geometrical modification of the M1 polyhedron due to scandium incorporation is comparable to those observed when similar amounts of Ti³⁺/Ti⁴⁺ substitute for Mg in the diopside structure, suggesting a structural control on the solubility of Sc and Ti in diopside that may influence the extent of the solid solutions between the Sc and Ti end-members.     

Crystal chemistry and stability of petalite

Mineralogy and Petrology - New data confirm that most petalites are slightly Li-deficient, Al-excessive and (OH)-bearing with respect to the idealized formula LiAlSi4O10. Primary substitution or...     

Crystal chemistry of igneous rock biotites

Summary A study of 304 selected biotite analyses, with 17 chemical variables (Al ^IV , Fe ^IV , Al ^VI Fe ^VI , Mg, Mn, Ti, Li, Na, K, Rb, Ca, Ba, OH, F, Cl,), was carried out using variation diagrams and statistical methods. It was our aim to verify the existence of characteristic variation patterns in the crystal chemistry of igneous biotites related to the geological setting and chemistry of the parent rocks. In the absence of a range of analyses covering the whole spectrum of igneous rocks, the biotites were grouped a priori either as volcanic (rhyolites, rhyodacites and trachyrhyolites, dacites and trachytes, andesites, trachybasalts and nephelinites) or as plutonic (granites, granodiorites, tonalites, diorites, gabbros). Variation diagrams failed to distinguish clearly between the different groups of biotites; the data overlapped considerably and were accordingly difficult to interpret. Statistical analysis, on the other hand, revealed clear chemical differences; moreover, simple statistical equations and careful coefficients were established which make it possible to evaluate the degree of discrimination between the different groups and to classify unknown biotites. The most important petrological factors affecting biotite chemistry are temperature of crystallization, rock acidity and, probably, rock alkalinity and the presence of other Fe-Mg minerals. Factors, such as/tf and , can cause more limited variations.

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Kristallchemie von Biotiten -aus magmatischen Gesteinen

Zusammenfassung Unter Berücksichtigung von 17 chemischen Variabeln wurde eine statistische und geochemische Auswertung von 304 ausgewählten chemischen Analysen von Biotiten ausgeführt, um die Existenz von charakteristischen Variationsschemata der Kristallchemie der magmatischen Biotite, im Bezug auf geologische Lage und Zusammensetzung des Gastgesteines, zu verifizieren. Da kein vollständiger Analysensatz für die gesamte magmatische Abfolge zur Verfügung war, wurden die Biotite a priori entweder als vulkanisch (Rhyolite, Rhyodacite und Trachyrhyolite, Dacite und Trachyte, Andesite, Trachybasalte und Nephelinite) oder als plutonisch (Granite, Granodiorite, Tonalite, Diorite, Gabbros) gruppiert. Variationsdiagramme allein reichen für eine scharfe Unterscheidung der verschiedenen Biotitgruppen nicht aus. Die Daten überlagerten sich teilweise, so daß jede Interpretation zweifelhaft war. Auf der anderen Seite ergaben sich scharfe chemische Unterschiede aus der statistischen Analyse, außerdem wurden einfache statistische Gleichungen und Koeffizienten, die die Ermittlung des Diskriminationsgrades zwischen verschiedenen Gruppen und die Klassifizierung der Biotite unbekannter Herkunft ermöglichten, festgesetzt. Die wichtigsten petrologischen Faktoren, die den Biotitchemismus beeinflussen, sind die Kristallisationstemperatur, die Azidität der Gesteine, und wahrscheinlich auch deren Alkalinität, und die Anwesenheit von anderen Mg-Fe-Mineralien. Faktoren wie und haben nur einen beschränkten Einfluß.

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With 8 Figures     

Crystal chemistry of a highly disordered Mg-Al natural spinel

Summary A Mg-Al spinel from a xenolith found in the Sacrofano volcanic area (Latium, Italy) was investigated by X-ray single crystal diffraction and electron microprobe. Its main structural parameters were: a₀ = 8.0922(3) Å and the oxygen coordinate u = 0.26213(4), which gave to tetrahedral and octahedral bond distances of 1.9220(6) Å and 1.9299(3) Å respectively. Cation distribution, obtained from structural and chemical data, showed a very high Mg-Al disorder, with an Al(T) content of 0.205 and an inversion parameter, i, of about 0.23. Comparison with the cation distribution of a spinel with similar chemical composition but occurring in chlorite schists (Shishimsk Mountains, Urals, Russia) with a₀ = 8.1003(3) Å and u=0.26330(3), and with data from the literature concerning spinels from metamorphosed limestones (Kalkbro, Sweden) and websteritic dikes (Balmuccia, Italy), all characterized by much lower Mg-Al disorder (i about 0.13–0.12), suggests a completely different thermal history, with rapid cooling rates and consequent high closure temperature of intracrystalline exchange, consistent with the Sacrofano geological environment.

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Kristallchemie eines stark ungeordneten, natürlichen Mg-Al-Spinells

Zusammenfassung Ein Mg-Al-Spinell aus einem Xenolith des Vulkangebiets von Sacrifano (Latium, Italien) wurde mit Röngten-Einkristallmethoden und der Elektronenmikrosonde untersucht. Die wichtigsten Strukturparameter sind a_o = 8,0922(3) Å und die Sauerstoffkoordinate u = 0,26213(4), was zu den tetraedrischen und oktaedrischen Bindungsabständen von 1,9220(6) Å bzw. 1,9299(3) Å führt. Die aus den strukturellen und chemischen Daten erhaltene Kationenverteilung zeigt eine sehr starke Unordnung Mg-Al mit einem Al (T)-Gehalt von 0,205 und einem Inversionsparameteri von ca. 0,23. Der Vergleich mit der Kationenverteilung eines Spinells ähnlicher chemischer Zusammensetzung, aber aus Chloritschiefern (Schischimsk-Berge, Ural, Rußland) mit a₀ = 8,1003(3) Å und u=0,26330(3), sowie mit Literaturdaten über Spinelle aus metamorphen Kalken (Kalkbro, Schweden) und websteritischen Gängen (Balmuccia, Italien), die alle durch eine viel geringere Mg-Al-Unordnung charakterisiert sind (i etwa 0,13–0,12), weist auf eine völlig andere thermische Geschichte hin, und zwar mit rascher Abkühlungsgeschwindigkeit und hoher Schließungstemperatur des intrakristallinen Austausches, was mit den geologischen Verhältnissen von Sacrofino in Übereinstimmung steht.

     

Crystal chemistry of diagenetic zeolites in volcanoclastic deposits of Italy

Zeolites from the most important volcanoclastic deposits of Italy include: (1) phillipsite and heulandite from the cinerite of the central northern Apennines; (2) chabazite and phillipsite from the phonolitic tephritic ignimbrite with black pumices; (3) phillipsite from the “tufo lionato” of Vulcano Laziale; (4) chabazite and phillipsite from the Campanian ignimbrite; (5) phillipsite from the Neapolitan yellow tuff; and (6) chabazite and phillipsite from the pyroclastics of Monte Vulture. Compared with sedimentary phillipsites and chabazites described in the literature, the chabazites and phillipsites studied here have lower Si/Al ratios and higher K contents. These chemical peculiarities are correlated with both the K-rich vesuvitic-leucititic, latitic-phonolitic, and potassic alkali-trachytic chemistry of the ash from which they were derived and, very likely, with the character of the hydrologically open system environment in which they formed. The zeolite of the heulandite-clinoptilolite group from the cinerite of the central northern Apennines is classified as a true heulandite on the basis of its chemical composition and thermal behavior.     

Crystal chemistry of volcanic allanites indicative of naturally induced oxidation-dehydrogenation

The crystal chemistry of volcanic allanites from both the Youngest Toba Tuff (YTT), Sumatra, Indonesia and SK100 volcanic ash beds (SK100-VAB), Niigata, Japan has been examined by electron microprobe analysis (EMPA), Fourier-transform infrared spectroscopic analysis (FTIR), and single-crystal structure analysis. In the FTIR study, based on the Diamond ATR accessory, YTT and SK100- VAB allanites were observed to have different OH contents, respectively: the former has 0.64 wt% H₂O (OH: 0.40 apfu.), while the latter has 1.65 wt% H₂O (OH: 1.00 apfu.). The crystal structures of these two allanites have been refined to individual R indices (3.64 and 4.25) based on 1350 observed reflections (|Fo| > 4sig|Fo|) measured using a single-crystal diffractometer with MoKα X-radiation. The OH-poor YTT allanite has a shorter b axis, a longer c axis, and larger β value than the relatively OH-rich SK100-VAB one. The bond valence sums of O4 (accepter oxygen for H atom) and O10 (donor oxygen for H atom) are 1.962 and 1.709 v.u. for YTT allanite (valence sum: 3.671 v.u.) and 1.754 and 1.271 v.u. for SK100-VAB one (valence sum: 3.025 v.u.). The difference from the ideal total bond valence value (4.00 v.u.) of O4 and O10 in YTT allanite (0.33 v.u.) is smaller than that in SK100-VAB (0.98 v.u.). These difference values are also broadly consistent with the corresponding differences in OH content between the YTT (OH: 0.40 apfu.) and SK100-VAB allanites (OH: 1.00 apfu.) determined by FTIR- ATR. Chemical analyses, FTIR-ATR and crystal structure refinement of YTT and SK100-VAB allanites yielded the following crystal chemical formula: YTT: (Ca_0.83Mn²⁺ _0.06Fe²⁺ _0.11)(La_0.24Ce_0.32Pr_0.04Nd_0.11Sm_0.02Th_0.04Ca_0.21)(Al_0.73Fe³⁺ _0.19Ti_0.08)(Al_0.89Fe³⁺ _0.11)(Fe²⁺ _0.22Fe³⁺ _0.62Mg_0.16)(SiO₄)Si₂O₇O_1.6(OH)_0.4, SK100-VAB: (Ca_0.81Fe²⁺ _0.13Mn²⁺ _0.06)(La_0.22Ce_0.34Pr_0.05Nd_0.13Sm_0.02Th_0.02Ca_0.22)(Al_0.76Fe³⁺ _0.19Ti_0.05)Al_1.00(Fe²⁺ _0.73Fe³⁺ _0.17Mg_0.10)(Si_0.96Al_0.04O₄)Si₂O₇O(OH). Therefore, it is concluded that welding of the Youngest Toba Tuff caused the following post-crystallization changes to occur in YTT allanite: oxidation of Fe²⁺ to Fe³⁺, release of H₂, and the concomitant replacement of OH^? by O^2?. These oxidation and dehydrogenation processes advanced during the welding to thereby produce oxyallanite. Oxyallanite had been reported only in laboratory studies where it was produced by heating natural allanite. Our report on natural oxyallanite suggests that it may be present in other welded silicic volcanic rocks as well.     

地球深部金属碳化物的晶体化学

金属碳化物的矿物十分稀少,但人工合成物则在化学成分及晶体结构两方面分布均较为丰富,可分成两种结构类型,即填隙结构型及复杂化合物型,其形成机理与碳原子与金属原子的半径比(Rc/Rm)有关。金属碳化物是西藏罗布莎铬铁矿床地幔矿物群的重要组成部分。列举了在该地区已发现的若干金属碳化物种属。探讨了该类矿物的形成机理以及该类矿物中的某些种属表征其形成的温度、压力状态的可能性。     

Crystal chemistry and optics of bazzite from Furkabasistunnel (Switzerland)

Summary The crystal structure of blue bazzite (space group P6/mcc, Z = 2, = 9.501(1),c = 9.178(1) Å) with the composition Be₃(Sc_1.25Fe³⁺ _0.43Mg_0.32Mn_0.03Al_0.02)_=2.05 Si₆O₁₈[Na_0.32(n H₂O)] was refined from X-ray single-crystal data with 422 unique reflections to R = 2.2%. The structure is of the beryl type with octahedra strongly compressed parallel to the c-axis. The octahedral Me-O distance in bazzite is 2.080 A compared to 1.904 Å in beryl. The flattening of octahedra leads to a larger a cell dimension in bazzite compared to beryl (9.209 A). Two-valent cations (mainly Mg) in octahedral coordination are charge balanced by Na at (0, 0, 0) in the structural channels. Polarized single-crystal IR-spectra recorded between 400 and 8000 cm^–1 indicate that H₂O in the structural channels is oriented with the H-H vector perpendicular to thec-axis. The IR-spectra show more absorption bands than known for type II H₂O in beryl thus the existence of more than one H₂O species or even OH-groups is very likely.Refractive indices of the same bazzite were measured using a spindle-stage and employing the wavelength-temperature variation method yielding n_o = 1.6279(3), n_e = 1.6066(5) for 589 nm at 25°C. The birefringence = 0.0213 is significantly larger than the one of near end-member beryl ( = 0.0047). This high birefringence of bazzite is related to the electronic polarizability of octahedral Sc and Fe which increase n_o at a stronger rate than n_e. Transition metals in bazzite are also responsible for a higher refractive index dispersion than found for beryl.

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Kristallchemie und optische eigenschaften des bazzits aus dem Furkabasistunnel

Zusammenfassung Die Kristallstruktur eines blauen Bazzits (Raumgruppe P6/mcc, Z = 2,a = 9.501(1),c = 9.178(1) Å) mit der Zusammensetzung Be₃(Sc_1.25Fe³⁺ _0.43Mg_0.32Mn_0.03Al_0.02)_2=2.05 Si₆)O₁₈[Na_0.32(n H₂O)] wurde von Röntgeneinkristalldaten mit 422 Reflexen zu R = 2.2% verfeinert. Die Struktur ist die des Berylltyps mit der Besonderheit, daß die Oktaeder entlang der c-Achse stark zusammengedrückt sind. Die oktaedrischen Me-O Abstände im Bazzit betragen 2.080 Å, im Gegensatz zu 1.904Å im Beryll. Die Stauchung der Oktaeder im Bazzit führt zu einer längeren a-Achse als im Beryll (9.209 Å). Zweiwertige Kationen (vor allem Mg) in oktaedrischer Koordination werden durch Na auf (0, 0, 0), in den strukturellen Kanalen, neutralisiert. Polarisierte Einkristall-IR-Spektren zwischen 400 and 8000 cm^–1 zeigen, daß H₂O Moleküle in den strukturellen Kanalen mit dem H-H Vektor senkrecht zur c-Achse orientiert sind. Die IR-Spektren weisen außerdem mehr Absorptionsbanden auf, als für den H₂O Typ II bekannt sind, sodaß entweder mehr als eine H₂O Spezies oder sogar OH-Gruppen sehr wahrscheinlich sind.Brechungsindizes am gleichen Bazzit wurden auf einem Spindeltisch mit der Wellenlängen-Temperatur Variationsmethode gemessen und ergaben n_o = 1.6279(3), n_e = 1.6066(5) bei 589 nm und 25 °C. Die Doppelbrechung A = 0.0210 ist deutlich höher als für einen nahezu Endgliedberyll (A = 0.0047). Diese hohe Doppelbrechung des Bazzits wird durch die elektronische Polarisierbarkeit von oktaedrischem Sc und Fe verursacht, die n_o starker ansteigen läßt als n_e. Übergangselemente im Bazzit sind auch für die höhere Dispersion der Brechungsindizes als im Beryll verantwortlich.

     

Crystal chemistry of a clinopyroxene series in ultrafemic xenoliths from North-Eastern Brazil

A series of clinopyroxenes (Cpx) in peridotitic spinel nodules from Rio Grande do Norte, North-Eastern Brazil, was investigated by X-ray diffraction and electron microprobe analyses and compared with an analogous series from spinel peridotite nodules from Mt. Leura, Victoria, Australia. The examined Cpx series is mainly characterized by increasing Mg/(Mg+Fe²⁺) ratio (i.e. increase of refractory character of the host nodules), by the substitutions of Al^vi vs Mg in the M1 site and Na vs (Ca+Mg) in the M2 site, whereas Al^iv in the T site remains substantially constant. The strong Na depletion in the Brazilian Cpx causes a different charge balance from that in the Australian Cpx, in which Na remains quite constant. This feature, associated with the differences in polyhedral and cell volumes which are significantly higher in the Brazilian Cpx than in those of the Australian Cpx, suggests that the Brazilian Cpx crystal chemistry may be related to a lower pressure regime, compared with that of the Australian Cpx series.     

Crystal chemistry and OH defect concentrations in spodumene from different granitic pegmatites

Thirty spodumene samples of distinct paragenetic types (primary magmatic, secondary after petalite and hydrothermal) from variety of granitic pegmatites were characterized by electron microprobe, polarized FTIR spectroscopy and Mössbauer spectroscopy. The FTIR spectra of OH (weak sharp pleochroic bands at 3,425, 3,410, 3,395 cm⁻¹ and in the 3,500–3,470 spectral region) are strongly polarized with maximum absorption parallel to n_γ. The majority of OH dipoles are presumably generated by a partial replacement of O2 oxygen atoms with an orientation pointing above the Li vacancy site. The separation of the bands probably resulted from a replacement of the coordinating Al by Fe and Si by Al. Homogeneous spodumene mostly close to its ideal formula LiAlSi₂O₆ shows Fe (0.00–0.10 apfu as Fe³⁺; Fe³⁺ >> Fe²⁺) and Na (0.00–0.04 apfu) as the only minor cations and Fe³⁺Al₋₁ substitution up to 10 mol% of the LiFe³⁺Si₂O₆ component. Hydrogen concentrations (from 0.1 up to <5 ppm H₂O by weight) vary as a function of genetic type with the highest amounts in high-temperature magmatic spodumene. Differences among particular genetic types of spodumene are related to maximum solubility of OH in spodumene structure at given P–T conditions and at actual chemical composition of spodumene. OH defect concentrations in spodumene follow a trend, LT/LP pyroxenes containing lower hydrogen contents compared to HT/HP ones. The hydrogen contents in particular genetic types of spodumene and their decrease with decreasing T and P are consistent with petrologic models of the pegmatite (sub)types formations.     

Crystal chemistry and oxidation state of Fe-rich prehnite from a hydrothermally altered dolerite

Mineralogy and Petrology - Fe-rich prehnite, Ca2(Al,Fe)(AlSi3)O10(OH)2, in a hydrothermally altered dolerite sill from Mitsu, Shimane Peninsula, Japan, was studied using 57Fe Mössbauer...     

Crystal chemistry of a natural schorlomite and Ti-andradites synthesized at different oxygen fugacities

Ti-andradites were synthesized at a pressure of P(H₂O)=3 kbar and temperatures of 700–800° C. Oxygen fugacities were controlled by solid state buffers (Ni/NiO; SiO₂ + Fe/Fe₂SiO₄). The Fe²⁺-and Fe³⁺-distribution was determined by low temperature Mössbauer spectroscopy. The water content was measured by a solid's moisture analyzer. The chemical composition of the synthetic and the natural sample has been determined by electron microprobe. Ti-andradites from runs at high oxygen fugacities have Fe³⁺ on octahedral and tetrahedral sites; Ti-andradites from runs at low oxygen fugacities have tetrahedrally and octahedrally coordinated Fe²⁺ as well. These “reduced” garnets must also contain Ti³⁺ on octahedral sites. Charge balance is maintained due to substitution of O^2? by (OH)^? by two mechanisms: (SiO₄)^4? ? (O₄H₄)^4? and (Fe³⁺O₆)^9? ? (Fe²⁺O₅OH)^9?. FTIR spectra of the synthetic samples do show the presence of structurally bound (OH)^?. In a natural sample tetrahedrally and octahedrally coordinated Fe³⁺ are observed together with Fe²⁺ on all three cation sites of the garnet structure.     

Crystal chemistry of cobalt and nickel in lithiophorite and asbolane from New Caledonia

The crystal chemistry of Ni- and Co-bearing manganese oxides (lithiophorite and asbolane) has been investigated by X-ray Absorption Spectroscopy (XAS). The Mn oxides come from the lateritic weathering profiles of the ultrabasites of New Caledonia. The distinct behaviours of Ni and Co concern both oxidation states and local structures.The electronic structure and short range order around Co atoms do not depend on the nature of the Cocontaining phase. Co atoms are trivalent and 6-fold coordinated. Co-(O, OH) and Co-(Co, Mn) interatomic distances derived from EXAFS are equal to those found around Mn atoms which rules out the possibility of an adsorption of Co atoms directly above and below vacancies of MnO₂ layers. The high structural order around Co contrasts with the structural disorder observed around Mn. Cobalt atoms do not occupy specific Mn sites and are not randomly distributed within the octahedral Mn layers.Unlike Co, Ni exhibits distinct surroundings in both phases. In asbolane, Ni atoms build partial Ni(OH)₂ layers. Ni-OH distances are lower as compared with the free Ni hydroxide because of the formation of hydrogen bonds between Ni(OH)₂ and MnO₂ layers. In lithiophorite Ni atoms are located in the hydrargillite layer (Al(OH)₃). Both chemical composition and structural considerations militate for a Ni for Li substitution in lithiophorite. Finally, evidence is given for the existence of a mixed-layering between lithiophorite and asbolane and the chemical variations generally observed in these Mn oxides are interpreted as a variable proportion of (Mn, Co)(O, OH₂, Ni(OH)₂ and (Al, Li, Ni)(OH)₃ layers.     

Crystal chemistry of clinopyroxenes from Oligo-Miocene volcanics of Montresta (Sardinia, Italy)

Summary Augite and diopside crystals from the Oligo-Miocene high-Mg and high-Al basalts, basaltic andesites and andesites of Montresta (Sardinia, Italy) have been analysed by means of X-ray single crystal diffraction and electron microprobe. It has been found that crystallization or equilibration processes took place within the crust at pressures below 5 kbar. In particular, samples from high-Al basalts, basaltic andesites and andesites crystallised at pressures below one kbar while those from high-Mg basalts crystallised in a range from about 1.5 to 4.5 kbar. The intracrystalline temperatures range between about 550 °C for high-Mg basalts and 750 °C for andesites. The M2′ site is occupied in each of the studied crystals, which implies slow cooling rates.     

Crystal chemistry and thin film epitaxy of sulfides and Bi-Sb-sulfosalts and their geological application

Summary Metal substitution studies of the stability, structure and chemical bonding of sulfides and sulfosalts lead to significant results, which can be applied to natural parageneses and crystal chemical systematics. Comparison of experiments on stable and metastable phases with thin films provides data, which exceed known geometrical criteria of the sulfosalt systematics. Synthetic and natural phases have been studied with respect to their substitution, bonding chemistry and temperature dependent metal distribution as well as to the structure and orientation of thin films.

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Zusammenfassung Die Untersuchung der Stabilität, Struktur und chemischen Bindung von Sulfosalzen führt zu aussagekräftigen auf natürliche Paragenesen sowie auf die Systematik dieser Verbindungen anwendbaren Resultaten, wenn systematische Substitutionsexperimente angesetzt werden. Diese liefern im Vergleich von stabilen und metastabilen Phasen sowie durch Vergleich mit dünnen Schichten Ergebnisse, die wesentlich über bekannte strukturgeometrische Ansätze zur Sulfosalzsystematik hinausgehen. Es werden synthetische und natürliche Verbindungen bezüglich ihrer Substitution, Bindungschemie und temperaturabhängigen Metallordnung sowie die Orientierung und Struktur von dünnen Schichten diskutiert.

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With 13 Figures

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In memoriam Prof. Dr. V. Kupcik ( 1990)     

Crystal chemistry of iron in natural grandidierites: an X-ray absorption fine-structure spectroscopy study

 Fe–K edge XAFS spectra (pre-edge, XANES and EXAFS) were collected for eight grandidierites from Madagascar and Zimbabwe, as well as for Fe(II) and Fe(III) model compounds (staurolite, siderite, enstatite, berlinite, yoderite, acmite, and andradite). The pre-edge spectra for these samples are consistent with dominantly 5-coordinated ferrous iron. The analysis of the XANES and EXAFS spectra confirms that Fe(II) substitutes for Mg(II) in grandidierite, with a slight expansion of the local structure around Mg by ∼2%. In addition, ferric iron was also detected in some samples [5–10 mol% of the total Fe or 500–1100 ppm Fe(III)]. Based on theoretical calculations of the EXAFS region, Fe(III) appears to be located in the 5-coordinated sites of Mg(II) or in the most distorted 6-coordinated sites of Al (depending on the sample studied). Special attention is therefore required when using grandidierite as a model for ferrous iron in C_3v geometry, because of the possible presence of an extra contribution related to Fe(III). This additional contribution enhances significantly the Fe–K pre-edge integrated area [+40% for 1000 ppm Fe(III)]. Therefore, only a few grandidierite samples can be used as a robust structural model for the study of the Fe(II) coordination in glasses and melts. Received: 26 June 2000 / Accepted: 19 February 2001