Coordination of water molecules with Na+ cations in a beryl channel as determined by polarized IR spectroscopy

Subtle variations of frequencies in the infrared (IR) absorption spectra of beryl have been predicted based on the coordination between extra-framework cations and water molecules in two orientations (referred to as type I and type II) trapped within the channel. In this study, the polarized IR spectra of hydrated synthetic beryl and natural beryl were measured to clarify the relationships between the frequencies of the absorption bands and the coordination states of type II water. Na⁺ was assumed to be the predominant cation coordinated to type II water in our samples, as determined by chemical analyses. These measurements revealed a clear quantitative linear relationship in absorbance between bands at 3,602 and 1,619 and at 3,589 and 1,631 cm⁻¹. On the basis of experimental and theoretical studies, we assigned these pairs of bands to the ν₁ and ν₂ modes of doubly coordinated type II H₂O and to singly coordinated type II H₂O, respectively. These assignments were supported by IR measurements of annealed natural beryl. We also conducted dehydration studies of natural beryl, in which two observed dehydration peaks, at 600 and 750°C, suggested the dehydration of type I and type II water, respectively.     

Infrared investigation of CO2-bearing cordierites

CO₂ molecules were introduced experimentally into the structural channels of synthetic well ordered Mgcordierite (Mg₂ ^[VI][(Al₄Si₅)^[IV]O₁₈]) at temperatures of 600 and 800° C, and pressures of 7, 8, 10, 12, and 25 kbar. Powder infrared spectra of the run products show five absorption bands in the region of the asymmetric stretching mode of CO₂. Two of them, strong and sharp, occurring at 2353 cm^–1 {2} and 2348 cm^–1 {3}, are related to two different types of CO₂ molecules. The relative intensity of the band {2} (type I) increases with the cell parameter c_o whereas the relative intensity of the band {3} (type II) increases with the parameter a₀ of the crystal. It is concluded that CO₂ molecules of type I may be oriented with their elongation parallel to the c-axis of the crystal, while CO₂ molecules of type II lie with their O-C-O vector parallel to the a-axis. Analytical data indicate that the intensity ratio Z of these two bands ({2}/{3}) is a linear function of the CO₂ content of cordierite. This ratio depends also on the temperature and, to a less extent, on the pressure under which cordierite entrapped CO₂ molecules. It is proposed to combine this infrared parameter Z together with an estimate of the P-T conditions of the incorporation of CO₂ into the channels, in order to determine the CO₂ content of natural cordierites. The samples do not need to be of high purity and only small amounts (<5 mg) are necessary. This semi-empirical analytical method, which does not require complicated data treatments, is suitable for CO₂-rich cordierites of granulite facies rocks.     

Spectroscopic and bond-topological investigation of interstitial volatiles in beryl from Slovakia

Nine beryl samples from Western Carpathians, Slovakia, were investigated by infrared and Raman spectroscopy and differential thermal analysis. Two types of water H₂O I and H₂O II were detected. Infrared spectroscopy proved the presence of water type I and II in the presence of alkali cations with several bands: (1) symmetric stretching vibration—ν₁; (2) antisymmetric stretching mode—ν₃; (3) bending vibration—ν₂. The presence of singly and doubly coordinated type II water (IIs and IId) was confirmed by single-crystal IR spectroscopy. From Raman spectra a band at 3606 cm^?1 was assigned to ν₁ of water type I and the range of 3597–3600 cm^?1 to water type II. The presence of doubly coordinating water indicates a relatively highly hydrated environment with the presence of alkali ions including Na as the dominant cation coordinated by H₂O II. CO₂ bands were detected only by single-crystal IR spectroscopy. Thermal analysis proved total water loss in the range of 1.4–2.0 wt% and three main dehydration events. Based on the study of bond-topological arrangements two molecules of H₂O IId are each bound with two H···O1 bonds and one Na–O_W bond with an angular distortion, and by releasing one H₂O molecule more stable H₂O IIs is produced. The H₂O I molecule is bound only by two equivalent hydrogen bonds. The H₂O IIs molecule with a Na–O_W bond strength of 0.28 vu and two H···O1 bonds of 0.14 vu without any forced angular distortion is the most stable of all.     

Cordierite breakdown under high-pressure,hydrous conditions

Clear evidence exists for a cordierite breakdown reaction to amphibole-kyanite-quartz in high-grade metamorphic rocks of the Arunta Complex, Australia. Using the natural minerals this reaction has been duplicated experimentally. It proceeds over a divariant band with a slope of 12±4 bars/°C, occurring between 8 and 10.4 kb at 750° C and between 9.5 and 11.3 kb at 850°C. The reaction is cut off at low temperature by the appearance of talc and at high temperature by the appearance of orthopyroxene. The maximum pressure stability of the amphibole-kyanite-quartz assemblage is about 20 kb. These data suggest that the natural rock was subjected to pressures of at least 8 kb at 750–850° C for high water fugacities. Other experimental data on the hydration of hypersthene and cordierite-hypersthene stability, point to a temperature below 820° C and an upper pressure limit of 9.5 kb at 750–820°C. Experiments at \(P_{{\text{H}}_{\text{2}} {\text{O}}}\) total indicate that the breakdown of cordierite to amphibole-kyanite-quartz is a hydration reaction, and occurred in the natural rock as a result of an increase of water fugacity at constant total pressure (8–9.5 kb) and temperature (750–820°C).     

Dynamic analysis and two types of kink bands in quartz veins deformed under subgreenschist conditions

In order to clarify deformation mechanisms and behaviours of quartz in a low-temperature regime in the earth's crust, microstructural analyses, particularly on kink bands have been carried out for quartz veins moderately deformed under subgreenschist conditions. Both the dominance of subbasal deformation lamellae and geometry of kink bands suggest that basal (0001) slip was the sole active slip system in the deformed quartz. On a morphological basis, kink bands in the quartz were classified into two types: type I is characterized by conjugate and narrow bands with angular hinge zones, and type II by a wide monoclinal band. Dynamic analyses using deformation lamellae and kink bands have revealed that type I kink bands were formed in grains with basal plane (sub-)parallel to the compression axis, whereas type II kink bands were formed in grains with basal planes inclined to it. Using a numerical model of kinking of elastic multilayers modified after Honea and Johnson (Tectonophysics 30, 197–239, 1976), changes of the level of yielding stress for kinking and the width of kink bands as a function of the angle θ between the slip plane and the compression axis have been examined. The theory predicts that type I kink bands were formed at a higher stress level than type II kink bands, and hence occurrence of type I kink bands suggests that a significant strain hardening occurred in the deformed quartz veins. The theory also well explains the fact that the width of type I kink bands (θ=0 to 10°) is narrower by an order of magnitude than type II kink bands (θ=10 to 80°).     

Polarized Raman spectra of beryl and bazzite

The polarized Raman spectra of four different beryl crystals were studied at room temperature in the range from 30 to 4000 cm^-1. The spectra show significant differences between the samples studied, and corrections are proposed for the reference Raman spectra of beryl previously reported by Adams and Gardner (1974). Type II water is observed in two crystals; the corresponding symmetric Raman stretching band at 3595 cm^-1 is extremely strong for an impurity (about 20% of the strongest beryl lattice mode). Another, sharper, band of similar intensity at 3605 cm^-1 could possibly originate from a hydroxyl stretching mode. Additional weaker bands are observed around 1600 cm^-1 and 3600–3750 cm^-1. The first polarized Raman spectra of bazzite are presented and discussed.     

Characterization of beryl (aquamarine variety) from pegmatites of Minas Gerais,Brazil

Eight samples of the beryl variety aquamarine were selected from four pegmatites in the Governador Valadares and Araçuaí regions in northeastern Minas Gerais State, Brazil. These samples were fully characterized by chemical analysis, infrared and UV-visible spectroscopy, thermal analyses, and high-temperature X-ray diffraction (from room temperature up to 800 °C). Several physical and chemical properties of beryl were found to depend on the amount of water and ions residing in the structural channels. The thermal expansion coefficients from room temperature to about 800 °C are temperature-independent, with αa ? ?3.2 × 10^?6 ° C^?1 and αc ? ?8.7 × 10^?6 ° C^?1. The contraction of both a and c unit-cell parameters with increasing temperature and the shift of the infrared band centered at about 1200 cm^?1 were tentatively ascribed to interactions between channel water and the silicate rings.The color of beryl seems to be dictated by the relative proportions of Fe³⁺ in the octahedralsites and of fe²⁺ in the channels. Thus, deep-blue samples have little Fe³⁺, whereas greener samples have more Fe³⁺ or less channel Fe²⁺.     

Experimental partitioning of Be,Cs, and other trace elements between cordierite and felsic melt,and the chemical signature of S-type granite

The trace-element signature that cordierite (Crd) imparts to silicic magmas was evaluated by experiment using metapelite mineral mixtures to produce cordierite-bearing peraluminous granitic melts at 200 MPa (P_H2O), from 700 to 850 °C. Most elemental partition coefficients vary with T. Beryllium is strongly compatible, with D_Be^Crd/melt values decreasing linearly from 202.0 to 6.7 as T rises from 700 to 850 °C. Manganese is compatible (D_Mn^Crd/melt=7.67 to 1.92 over the same range of T), and shows similar values to those reported for biotite in silicic melts. Incompatible components include Li, Rb, B, F and P, although Cs is nearly compatible in cordierite, especially at higher T (D_Cs^Crd/melt=~0.19 to 0.60) where the large alkalis are better accommodated structurally. Cordierite appears to be the most effective crystalline reservoir of Be and Cs in metapelites and their anatectic melts. Natural data support the hypothesis that Crd, when present in granitic melts, sequesters Be, Cs and, in the absence of garnet, Mn. S-type granitic rocks containing Crd show consistently low Be contents (mean=0.8 ppm Be with an average range of <1 to 1.20) whereas Crd-free granites (e.g., containing accessory garnet) exhibit distinctly higher Be contents (mean=6 ppm Be with an average range of 3 to 12). These values increase further in evolved facies (mean=69 ppm Be with a an average range of 11 to 145) which commonly give rise to beryl-bearing pegmatites. Whole-rock signatures of Be discriminate source environments of silicic magmas at a resolution equal to the boundaries of the cordierite stability field - e.g., at the P-T-X conditions where cordierite gives rise to garnet+aluminum silicate. Cordierite-bearing granitic rocks contain low Cs contents (mean=1.8 ppm Cs) compared to the Crd-free equivalents (mean=18 ppm Cs). Mn contents also correlate with the presence (mean=0.01 wt% MnO) or absence of Crd (mean=0.09 wt% MnO). Depending on its contribution to anatexis, cordierite may either give or take S-type chemical character from granitic liquids, resulting in a distinctive Crd-associated group of S-type elements. This signature is different from that of micas (high Li, F and, to a lesser degree, Be and Mn). Whole-rock compositions of granites, coupled with notable absences of beryl in their associated pegmatites, indicate that a sizable population of S-type granites originated from Crd-bearing sources. The normative Crd component of silicic peraluminous melts is Д wt% to 850 °C. Higher modal contents of cordierite reflect either restite entrainment or peritectic reactions which produce Crd after magma ascent to shallow depths. The distinctive trace-element signature of cordierite now provides improved resolution of the source mineralogy for S-type magmas.     

Optical absorption and electron spin resonance in blue and green natural beryl

A comparative study of blue and green beryl crystals (from the region of Governador Valadares, Minas Gerais, Brazil) using electron paramagnetic resonance (EPR) and optical absorption (OA) spectroscopy is reported. The EPR spectra show that Fe³⁺ in blue beryl occupies a substitutional Al³⁺ site and in green beryl is localized in the structural channels between two O₆ planes. On the other hand the infrared spectra show that the alkali content in the blue beryl is mostly at substitutional and/or interstitial sites and in green beryl is mostly in the structural channels. The OA spectra show two types of Fe²⁺. Thermal treatments above 200° C in green beryl cause the reduction of Fe³⁺ into Fe²⁺ accompanied by a change of color to blue. The blue beryl color does not change on heating. The kinetics of the thermal conversion of Fe³⁺ into Fe²⁺ is composed of two first order processes; the first one has an activation energy ΔE ₁=0.30 eV and the second one has an activation energy ΔE ₂=0.46 eV.     

The single-crystal,polarized-light,FTIR spectrum of stoppaniite,the Fe analogue of beryl

We report here a single-crystal polarized-light study of stoppaniite, ideally (Fe,Al,Mg)₄(Be₆Si₁₂O₃₆)(H₂O)₂(Na,□), from Capranica (Viterbo). Polarized-light FTIR spectra were collected on an oriented (hk0) section, doubly polished to 15 μm. The spectrum shows two main bands at 3,660 and 3,595 cm⁻¹; the former is strongly polarized for E ⊥c, while the latter is polarized for E //c. A sharp and very intense band at 1,620 cm⁻¹, plus minor features at 4,000 and 3,228 cm⁻¹ are also polarized for E //c. On the basis of literature data and considering the pleochroic behavior of the absorptions, the 3,660 cm⁻¹ band is assigned to the ν₃ stretching mode and the 1,620 cm⁻¹ (associated with an overtone 2*ν₂ at 3,230 cm⁻¹) band to the ν₂ bending mode of “type II” water molecules within the structural channels of the studied beryl. The sharp band at 3,595 cm⁻¹ is not associated with a corresponding ν₂ bending mode; thus it is assigned to the stretching vibration of O–H groups in the sample. The minor 4,000 cm⁻¹ feature can be assigned to the combination of the O–H bond parallel to c with a low-frequency metal-oxygen mode such as the Na–O stretching mode. The present results suggest that the interpretation of the FTIR spectrum of Na-rich beryl needs to be carefully reconsidered.     

Characteristics of Corona Textures in the Huangtuling Granulite in the Dabie Comples,China and Their Implications for Tectonic Settings

Widely developed in the Dabie complex are various disequilibrium textures which provide direct evidence for the evolution of metamorphism and late-stage uplifting history.The typical mineral assemblasge in the Opx-Gt-Pl-Bi gneiss in Huangtuling,Luotian County,Hubei Province,Is Opx(I) Gt Pl(I) Bi(I) Q.The corona composed of cordierite and orthopyroxene(Ⅱ）growing around garnets in the granulite makes it clear that there occurres the following metamorphic reaction:Gt Q→Cd Opx(Ⅱ）.It is estimated that the gran ulite-forming temperature(T)and pressure(P)are 857-998℃ and 1.18-1.23Gpa,respectively,and the corona was formed under the following conditions:T=829-911℃ and P=0.52-0.59GPa.The above results indicate that There occurred a rapid and nearly adiabatic uplifting event and a decompressional metamorphism in the Dabie complex after the formation of granulite.As compared with the granulites worldwidely distributed in 90 locations(Harley 1989),the Huangtuling granulite should belong to the high-pressure type,which represents the composition of the crust at a depth of more than 40 kilometers.     

Correlation of Fe4+ optical anisotropy,Brazil twinning and channels in the basal plane of amethyst quartz

The biaxial absorption bands in amethyst quartz, with peaks at 2.28 eV and 3.54 eV related to Fe⁴⁺ and a peak at 3.02 eV—which is the A₃ band related to the [AlO₄]° trapped hole center, have orientations of maximum light absorption in the basal plane of Brazil-twinnedr-growth sectors paralleling the planes of Brazil optical twinning. Absorption minima are at 90° to the maxima in all cases. The Brazil twinning planes always parallel thea-axes(1210,etc) of quartz and in many cases also parallel planes perpendicular to ther-faces(1011,etc.). These are directions of channels in the quartz structure. The anisotropy ratio,σ_max/σ_min, of the Fe⁴⁺ band is that of the A₂ absorption band in smoky quartz as would be expected if Fe³⁺ furnishes electrons to quench the trapped holes causing this absorption band. In the absence of the A₁ and A₂ absorption bands, the A₃ absorption band width at half-maximum decreases from 1.43 to 0.36 eV indicating decreased charge-transfer character of the [AlO₄]° center in the absence of the other types of Al trapped-hole centers in quartz. The key to the Brazil twinning in α-quartz are the channels which fill with large Fe³⁺ ions that force twinning to relieve strain in the structure. Amethyst color results only if aluminum is present substitutionally in the quartz as well as the interstitial iron plus ionizing radiation.     

Blue, complexly zoned, (Na,Mg,Fe,Li)-rich beryl from quartz-calcite veins in low-grade metamorphosed Fe-deposit Sk��ly near Ryma?ov, Czech Republic

Syn-tectonic quartz-calcite veins containing blue beryl are enclosed in hematite > magnetite-rich portions of the low-grade metamorphosed Fe-deposit Skály near Ryma?ov, Czech Republic. Aggregates of pale to deep blue beryl, up to 2?cm in diameter, are associated with euclase, clinochlore, hematite, albite and dravite. Complexly zoned beryl crystals consist of skeletal aggregates of beryl I randomly distributed within volumetrically dominant beryl II with narrow rims of beryl III. All types of beryl have similar contents of Na (0.32?C0.49 apfu) and Mg (0.31?C0.41 apfu) but variable contents of Fe_tot (0.05?C0.34 apfu) and Al (1.20?C1.62 apfu). The LA-ICP-MS study yielded elevated contents of Li, up 1,314?ppm (0.28?wt.% Li₂O) in beryl I. The quartz-calcite veins represent an unusual type of low-T metamorphic-hydrothermal vein related to Fe-ore deposit characterized by single-stage fracturing and mobilization in a closed system at T~200?C300°C and CO ₃ ^2- as a major complexing agent for the mobility of Be.     

Disequilibrium in the Ross of Mull Contact Metamorphic Aureole, Scotland: a Consequence of Polymetamorphism

The Ross of Mull pluton consists of granites and granodioritesand intrudes sediments previously metamorphosed at amphibolitefacies. The high grade and coarse grain size of the protolithis responsible for a high degree of disequilibrium in many partsof the aureole and for some unusual textures. A band of metapelitecontained coarse garnet, biotite and kyanite prior to intrusion,and developed a sequence of textures towards the pluton. InZone I, garnet is rimmed by cordierite and new biotite. In ZoneII, coarse kyanite grains are partly replaced by andalusite,indicating incomplete reaction. Coronas of cordierite + muscovitearound kyanite are due to reaction with biotite. In the higher-gradeparts of this zone there is complete replacement of kyaniteand/or andalusite by muscovite and cordierite. Cordierite chemistryindicates that in Zone II the stable AFM assemblage (not attained)would have been cordierite + biotite + muscovite, without andalusite.The observed andalusite is therefore metastable. Garnet is unstablein Zone II, with regional garnets breaking down to cordierite,new biotite and plagioclase. In Zone III this breakdown is welladvanced, and this zone marks the appearance of fibrolite andK-feldspar in the groundmass as a result of muscovite breakdown.Zone IV shows garnet with cordierite, biotite, sillimanite,K-feldspar and quartz. Some garnets are armoured by cordieriteand are inferred to be relics. Others are euhedral with Mn-richcores. For these, the reaction biotite + sillimanite + quartz garnet + cordierite + K-feldspar + melt is inferred. Usinga petrogenetic grid based on the work of Pattison and Harte,pressure is estimated at 3·2 kbar, and temperature atthe Zone II–III boundary at 650°C and in Zone IV asat least 750°C. KEY WORDS: contact metamorphism; disequilibrium     

Positron annihilation lifetime spectral changes on dehydration of natural beryls and cordierites

The effect on positron annihilation lifetime spectra, measured at room temperature, of the dehydration of single crystals of beryl and cordierite was studied. In each case, the spectra were satisfactorily fitted to three lifetime components. For the beryls, the dehydration considerably enhanced the intensity of the intermediate-lifetime component (I ₂) and reduced the intensity of the longest-lived component (I ₃). I ₂ is attributed to positron annihilation in the empty cages in the channels of the beryl structure and I ₃ to annihilation by a pick-off process via unknown foreign molecules. However, for the cordierites, the main effect of the dehydration was a slight (～10%) increase in the lifetime of the intermediate component, τ₂. Here I ₂ was relatively high both before and after dehydration and the increase in τ₂ is attributed to Si-Al ordering. No changes in the lifetime spectra were produced by γ irradiation.     

四川平武雪宝顶绿柱石的振动光谱

自然界中绿柱石晶体多为柱状,具板状晶形的绿柱石非常少见。对产 于四川雪宝顶 云英岩晶洞中的无色透明板状绿柱石及产于雪宝顶蒲口坡石英脉中的绿柱石进行了红外和拉 曼光谱分析,并与产于阿尔泰三号伟晶岩脉中的柱状绿柱石进行了比较。雪宝顶两个绿柱 石的结构通道中的水以II型水为主,而阿尔泰绿柱石结构通道中的水以I型水为主。雪宝顶 绿柱石中Li对Be的替换也对它的红外及拉曼光谱造成了影响。     

Mineralogical and Geochemical Characteristics of the Utanobori Gold Deposit in Northern Hokkaido,Japan

The Utanobori gold deposit is a low‐sulfidation, epithermal vein‐type deposit located in northern Hokkaido, Japan. The deposit is hosted by conglomerate, sandstone, and tuff of the Middle to Late Miocene Esashi Formation. These rocks were hydrothermally altered. Silica sinters and quartz‐adularia veins are common in the deposit. The quartz‐adularia veins either contain a ginguro band, which corresponds to the main gold‐bearing vein (Type 1 Veins), or do not contain a ginguro band but contain minor adularia (Type 2 Veins). Type 1 Veins are divided into three stages with 12–14 substages. Ore minerals identified include electrum, naumannite, chlorargyrite, bromargyrite, an unidentified Fe‐Sb mineral, and an Fe‐(Sb)‐As mineral. These ore minerals formed in the main mineralization stages I (bands I‐b and I‐d) and II (band II‐a). Scanning electron microscopy with cathodoluminescence images show that cathodoluminescence‐dark microcrystalline quartz exhibiting colloform (ghost‐sphere) texture is closely associated with ore minerals in the Type 1 Vein and Type 2 Vein, and the Al and K contents of such quartz are commonly >1000 ppm. This indicates that the ore minerals were crystallized from alkaline, silica‐saturated fluids at temperatures <200°C, which initially deposited amorphous silica that was recrystallized to microcrystalline quartz. The average Au content of electrum is 52.5 at% Au (n = 10), 65.7 at% Au (n = 20), and 55.5 at% Au (n = 5) in bands I‐b, I‐d, and II‐a, respectively, of Type 1 Veins. The δ³⁴S_CDT values of two fine‐grained disseminated pyrites in the altered conglomerate and bedded tuff in the argillic altered zone are ?4.3 and ?4.2‰. Ar‐Ar dating on adularia yielded 13.6 ± 0.06 Ma, 13.6 ± 0.07 Ma, and 13.6 ± 0.06 Ma for the stages I, II, and III of the Type 1 Vein, respectively. K‐Ar ages determined on adularia in the silica sinter and on whole‐rock of glassy rhyolite of the Esashi Formation are 15.0 ± 0.4 Ma and 14.6 ± 0.4 Ma, respectively. These radiometric ages indicate that silica sinter associated with the rhyolitic volcanic rocks formed prior to the main gold mineralization.     

Dehydration process and structural development of cordierite ceramic precursors derived from FTIR spectroscopic investigations

 Cordierite precursors were prepared by a sol-gel process using tetraethoxysilane, aluminum sec.-butoxide, and Mg metal flakes as starting materials. The precursors were treated by 15-h heating steps in intervals of 100 °C from 200 to 900 °C; they show a continuous decrease in the analytical water content with increasing preheating temperatures. The presence of H₂O and (Si,Al)–OH combination modes in the FTIR powder spectra prove the presence of both H₂O molecules and OH groups as structural components, with invariable OH concentrations up to preheating temperatures of 500 °C. The deconvolution of the absorptions in the (H₂O,OH)-stretching vibrational region into four bands centred at 3584, 3415, 3216 and 3047 cm⁻¹ reveals non-bridging and bridging H₂O molecules and OH groups. The precursor powders remain X-ray amorphous up to preheating temperatures of 800 °C. Above this temperature the precursors crystallize to μ-cordierite; at 1000 °C the structure transforms to α-cordierite. Close similarities exist in the pattern of the 1400–400 cm⁻¹ lattice vibrational region for precursors preheated up to 600 °C. Striking differences are evident at preheating temperatures of 800 °C, where the spectrum of the precursor powder corresponds to that of conventional cordierite glass. Bands centred in the “as-prepared” precursor at 1137 and 1020 cm⁻¹ are assigned to Si–O-stretching vibrations. A weak absorption at 872 cm⁻¹ is assigned to stretching modes of AlO₄ tetrahedral units and the same assignment holds for a band at 783 cm⁻¹ which appears in precursors preheated at 600 °C. With increasing temperatures, these bands show a significant shift to higher wavenumbers and the Al–O stretching modes display a strong increase in their intensities. (Si,Al)–O–(Si,Al)-bending modes occur at 710 cm⁻¹ and the band at 572 cm⁻¹ is assigned to stretching vibrations of AlO₆ octahedral units. A strong band around 440 cm⁻¹ is essentially attributed to Mg–O-stretching vibrations. The strongly increasing intensity of the 872 and 783 cm⁻¹ bands demonstrates a clear preference of Al for a fourfold-coordinated structural position in the precursors preheated at high temperatures. The observed band shift is a strong indication for increasing tetrahedral network condensation along with changes in the Si–O and Al–O distances to tetrahedra dimensions similar to those occurring in crystalline cordierite. These structural changes are correlated to the dehydration process starting essentially above 500 °C, clearly demonstrating the inhibiting role of H₂O molecules and especially of OH groups. Received: 1 March 2002 / Accepted: 26 June 2002     

Quantitative analysis of H2O and CO2 in cordierite using polarized FTIR spectroscopy

We report a FTIR (Fourier transform infrared) study of a set of cordierite samples from different occurrence and with different H₂O/CO₂ content. The specimens were fully characterized by a combination of techniques including optical microscopy, single-crystal X-ray diffraction, EMPA (electron microprobe analysis), SIMS (secondary ion mass spectrometry), and FTIR spectroscopy. All cordierites are orthorhombic Ccmm. According to the EMPA data, the Si/Al ratio is always close to 5:4; X _Mg ranges from 76.31 to 96.63, and additional octahedral constituents occur in very small amounts. Extraframework K and Ca are negligible, while Na reaches the values up to 0.84 apfu. SIMS shows H₂O up to 1.52 and CO₂ up to 1.11 wt%. Optically transparent single crystals were oriented using the spindle stage and examined by FTIR micro-spectroscopy under polarized light. On the basis of the polarizing behaviour, the observed bands were assigned to water molecules in two different orientations and to CO₂ molecules in the structural channels. The IR spectra also show the presence of small amounts of CO in the samples. Refined integrated molar absorption coefficients were calibrated for the quantitative microanalysis of both H₂O and CO₂ in cordierite based on single-crystal polarized-light FTIR spectroscopy. For H₂O the integrated molar coefficients for type I and type II water molecules (ν₃ modes) were calculated separately and are ^[I]ε?=?5,200?±?700?l?mol^?1?cm^?2 and ^[II]ε?=?13,000?±?3,000?l?mol^?1?cm^?2, respectively. For CO₂ the integrated coefficient is $ \varepsilon_{{{\text{CO}}_{ 2} }} $ ?=?19,000?±?2,000?l?mol^?1?cm^?2.