The crystal structure of disordered (Zr,Ti)O2 solid solution including srilankite: evolution towards tetragonal ZrO2 with increasing Zr

Crystal structure data are presented for seven synthetic samples of disordered zirconium-titanate solid solution (Zr,Ti)O₂, ranging in composition from x _Ti=0.43 to 0.67, thus covering compounds such as ZrTiO₄, Zr₅Ti₇O₂₄, and ZrTi₂O₆ (srilankite). The compounds, synthesized at high temperatures and various pressures in their respective stability fields, are well crystallized and of homogeneous composition. The resulting structure data are less scattered compared to previous studies that were based on compounds synthesized metastably at low temperatures and room pressure. The compounds have the structure of scrutinyite (α-PbO₂) with space group Pbcn, Z=4, unit cell parameters a=4.8495(3) Å, b=5.4635(3) Å, c=5.0462(3) Å at x _Ti=0.425 to a=4.7112(2) Å, b=5.4944(1) Å, c=4.9962(1) Å at x _Ti=0.666. The first structure refinement of pure, synthetic srilankite is presented, which is in good agreement with that of the natural counterpart. Structural trends observed in disordered zirconium-titanate solid solution along the binary join ZrO₂–TiO₂ are relatively smooth and continuous, except for rapid lengthening of an unshared octahedral edge which is anomalously short in scrutinyite-structure TiO₂. The shortness of this edge may explain the observed instability of this structure with the relatively small Ti as the dominant cation. With increasing Zr content, the average cation position moves off-centre inside the octahedron, away from two shared edges, which permits the 12 closest cation–cation distances in the structure to become more equal. The shortening of the b dimension with increasing amount of the larger cation Zr decreases the distance between octahedral Zr and two additional oxygens in an adjacent chain of edge-sharing octahedra, implying that the Zr environment is evolving towards eightfold coordination. If the two additional oxygens are considered as part of the Zr coordination polyhedron, the bonding topology of tetragonal zirconia is obtained. The compositional evolution of the cell parameters, Zr atomic coordinates and Zr coordination environment is consistent with the idea that the structure is evolving towards that of tetragonal ZrO₂. Group-theoretical relationships between scrutinyite, tetragonal zirconia, baddeleyite and fluorite structures show that the sequence of structures fluorite > tetragonal zirconia > scrutinyite > baddeleyite are all related by potentially diffusionless phase transitions driven by wavelike displacements of the oxygen substructure. The scrutinyite and tetragonal structures can act outside their stability fields as “transition states” between the structures on either side.     

Yellow fluorescence from baghdadite and synthetic Ca3(Zr,Ti)Si2O9

Baghdadite from Fuka, Okayama Prefecture, Japan shows a bright yellow fluorescence under UV (Hg 253.7 nm) excitation. The photoluminescence (PL) spectrum at 300 K consists of one large band near 580 nm and two small UV bands at 318 and 397 nm. The optical excitation spectrum of the bright yellow fluorescence consists of two bands near 220 and 250 nm. The temperature dependence of the PL intensity exhibits linear thermal quenching. To reveal the origin of the bright yellow fluorescence from baghdadite, powder Ca₃(Zr,Ti)Si₂O₉ crystals are synthesized. Synthetic Ca₃(Zr,Ti)Si₂O₉ shows luminescence spectra similar to those of baghdadite, and the intensity of the yellow fluorescence is markedly increased by titanium addition. The origin of the bright yellow fluorescence from baghdadite is ascribed to the existence of titanium.     

Voltammetric Determination of High Field‐Strength Elements (Ti,Zr, Hf,Nb, Ta) in Geological Matrices

A voltammetric method for the determination of the high field‐strength elements Ti, Zr, Hf, Nb and Ta by adsorptive stripping of their tartrate complexes is presented. The applicability of the method to geological and metallurgical samples is illustrated by the analysis of certified reference materials (USGS BCR‐2 basalt, BCS‐CRM 388 zircon and Euronorm CRM 579‐1 ferroniobium). Suitable sample preparation techniques, involving fusion with LiBO₂ and acidic and basic fluxes, followed by preliminary separation by anion chromatography are described. The method is rapid, affordable and environmentally friendly as it does not require problematic compounds such as hydrofluoric acid or toxic solvents and represents an alternative to more commonly used methods (AAS, ICP‐OES, ICP‐MS).     

Geochronology of high-pressure rocks on Sifnos (Cyclades,Greece)

Polymetamorphic rocks of Sifnos (Greece) have been investigated by Rb-Sr, K-Ar, and fission track methods. Critical mineral assemblages from the northern and southernmost parts of Sifnos include jadeite+quartz+3T phengite, and omphacite+garnet +3T phengite, whereas the central part is characterized by the assemblage albite+chlorite+epidote+2M ₁ phengite.K-Ar and Rb-Sr dates on phengites (predominantly 3T) of the best preserved high P/itTmetamorphic rocks from northern Sifnos gave concordant ages around 42 m.y., indicating a Late Lutetian age for the high P/T metamorphism. Phengites (2M ₁+3T) of less preserved high P/T assemblages yielded K-Ar dates between 48 and 41 m.y. but generally lower Rb-Sr dates. The higher K-Ar dates are interpreted as being elevated by excess argon.K-Ar and Rb-Sr ages on 2M ₁ phengites from central Sifnos vary between 24 and 21 m.y. These ages date a second, greenschist-facies metamorphism which overprinted the earlier high-pressure metamorphic rocks.     

Hydrothermal mobility of Ti, Zr and REE: examples from the Bergell and Adamello contact aureoles (Italy)

Contact metamorphic marbles, affected by metasomatic fluids at the contact to the Bergell and Adamello Intrusives, contain various accessory minerals (zirconolite, allanite, titanite, rutile, geikielite, hoegbomite), which provide new evidence for the hydrothermal mobility of Ti and Zr. In both examples, Ti and Zr migrated along with U, Th, Y and REE in a metasomatic fluid rich in potassium. The composition of the main minerals (fluorine-rich phlogopite, pargasite and titanian clinohumite) and the abundance of fluor-apatite demonstrate that fluorine and phosphorus were important components of the fluid. The textural relationships indicate that the formation of the accessory phases is linked to the crystallization of the hydrous minerals.     

Difference of Ti,Zr, Y and P content in calc-alkaline andesites from island arcs and continental margin (Central Andes)

Ti, Zr, Y and P, known to be chemically immobile elements during alteration and metamorphism, have been ploted in a set of diagrams in order to discriminative between calc-alkaline andesites from island arcs and continental margin. This method may be an appropiate procedure to help in the discrimination between ancient volcanics of both groups.     

表面活性剂存在下姜黄素与铍铁钛锆的显色反应研究

本文研究了姜黄素与一些金属离子的显色反应,探讨了反应机理。结果表明,分别在CPB、TX-100、CPB-TX-100、SDBS存在下,姜黄素可与Be、Fe、Ti、Zr发生灵敏的显色反应。其表观摩尔吸光系数分别为1.25 ×10~5、3.03 ×10~4、6.24×10~4和4.93 ×10~4L·mol~(-1)·cm~(-1)。利用负峰效应提高了Be、Fe两显色体系的灵敏度并测定了络合比。     

Sodium trisilicate: A new high-pressure silicate structure (Na2Si[Si2O7])

Crystals of sodium trisilicate (Na₂Si₃O₇) have been grown in the presence of melt at 9 GPa, 1200 °C using the MA6/8 superpress at Edmonton, and the X-ray structure determined at room pressure (R=2.0%). Na₂Si₃O₇ is monoclinic with a=8.922(2) Å, b= 4.8490(5) Å, c=11.567(1) Å, β=102.64(1)° (C2/c), D _x = 3.295 g·cm^-3. Silicon occurs in both tetrahedral and octahedral coordination (^[6]Si∶^[4]Si = l∶2). The SiO₄ tetrahedra form a diorthosilicate [Si₂O₇] group and are linked by the isolated SiO₆ octahedra via shared corners into a framework of 6-membered (^[4]Si-^[4]Si-^[6]Si^[4]Si-^[4] Si-^[6]Si) and 4-membered (^[4]Si-^[6]Si-^[4]Sr-^[6]Si) rings: 〈^[6]Si-O〉=1.789 Å, 〈^[4]Si-O〉= 1.625 Å, ^[4]Si-O-^[4]Si=132.9° and the bridging oxygen is overbonded (s = 2.22). Channels parallel to b-axis and [110] accommodate Na in irregular 6-fold coordination: 〈Na-O〉 = 2.511 Å.     

Distribution of As,Cr, Ni,Rb, Ti and Zr between peat and its humic fraction along an undisturbed ombrotrophic bog profile (NW Switzerland)

Ombrotrophic bogs are useful records of the impact of historical human activity on heavy metal contamination. Several studies concerning the trace element record (mainly Pb and Hg) in these particular environments have been carried out in recent years, although the role of humic substances has often not been considered. In particular, of the components of peat organic matter, fulvic acids and low molecular weight compounds are generally responsible for the mobility of trace elements through the profile, while humic acids (HAs) are involved in the formation of more stable organo-mineral complexes. In order to study the parallel distribution of As, Cr, Ni, Rb, Ti and Zr in bulk peat and the corresponding HAs, a peat core (10 × 10 × 81 cm) was collected from Etang de la Gruère (Switzerland) and cut into 27 slices of 3 cm. The samples were freeze-dried and milled very finely, and HAs extracted from each sample. Both peat and HAs were analyzed using an energy-dispersive miniprobe X-ray fluorescence multielement analyser (EMMA-XRF). Of the considered elements, Ni showed a great affinity for the humic acid component, while Cr was concentrated mainly into humic material from the deeper layers. On the other hand, Ti, Zr and Rb seemed to reflect the variation in mineral material both in peat and HA samples, while the As content of both materials reflected the environmental conditions characterizing the bog.     

Crystal-chemical and energetic systematics of wadeite-type phases A2BSi3O9 (A = K, Cs; B = Si, Ti, Zr)

Wadeite K₂ZrSi₃O₉ and its analogues K₂TiSi₃O₉ and Cs₂ZrSi₃O₉, synthesized by high-temperature solid-state sintering, have been investigated using powder X-ray diffraction coupled with Rietveld analysis and high-temperature oxide melt solution calorimetry. The crystal chemistry and energetics of these phases, together with K₂Si^VISi₃ ^IVO₉, a high-pressure wadeite analogue containing both tetrahedral and octahedral Si, are discussed in term of ionic substitutions. As the size of the octahedral framework cation increases, Si⁴⁺ → Ti⁴⁺ → Zr⁴⁺, the cell parameter c increases at a much higher rate than a. In contrast, increasing the interstitial alkali cation size (K⁺ → Cs⁺) results in a higher rate of increase in a compared with c. This behavior can be attributed to framework distortion around the interstitial cation. The enthalpies of formation from the constituent oxides (ΔH_f,ox⁰) and from the elements (ΔH_f,el⁰) have been determined from drop-solution calorimetry into 2PbO·B₂O₃ solvent at 975 K. The obtained values (in kJ/mol) are as follows: ΔH_f,ox⁰ (K₂TiSi₃O₉) = −355.8 ± 3.0, ΔH_f,el⁰ (K₂TiSi₃O₉) = −4395.1 ± 4.8, ΔH_f,ox⁰ (K₂ZrSi₃O₉) = −374.3 ± 3.3, ΔH_f,el⁰ (K₂ZrSi₃O₉) = −4569.9 ± 5.0, ΔH_f,ox⁰ (Cs₂ZrSi₃O₉) = −396.6 ± 4.4, and ΔH_f,el⁰ (Cs₂ZrSi₃O₉) = −4575.0 ± 5.5. The enthalpies of formation for K₂Si^VISi₃ ^IVO₉ were calculated from its drop-solution enthalpy of an earlier study (Akaogi et al. 2004), and the obtained ΔH_f,ox⁰ (K₂SiSi₃O₉) = −319.7 ± 3.4 and ΔH_f,el⁰ (K₂SiSi₃O₉) = −4288.7 ± 5.1 kJ/mol. With increasing the size of the octahedral framework cation or of the interstitial alkali cation, the formation enthalpies become more exothermic. This trend is consistent with the general behavior of increasing energetic stability with decreasing ionic potential (z/r) seen in many oxide and silicate systems. Further, increasing the size of the octahedral framework cation appears to induce more rapid increase in stability than increasing the interstitial alkali cation size, suggesting that framework cations play a more dominant role in wadeite stability.     

Magnesioneptunite, KNa2Li(Mg,Fe)2Ti2Si8O24, a new mineral species of the neptunite group

A new mineral of the neptunite group, magnesioneptunite KNa₂Li(Mg,Fe)₂Ti2Si₈O₂₄, a Mg-dominant analogue of neptunite and manganoneptunite, has been found in the Upper Chegem caldera near Mount Lakargi, Kabardino-Balkaria, the North Caucasus, Russia in a xenolith of altered sandstone located between skarnified carbonate xenoliths and ignimbrite. Magnesioneptunite occurs as nearly isometric grains and aggregates up to 0.1 mm in size in the cores of some grains of a Mg-rich variety of neptunite with Mg/(Fe + Mn) = 0.7?1.0. The chemical composition of magnesioneptunite with a maximum Mg content is as follows, wt %: 3.63 K₂O, 8.21 Na₂O, 1.73 Li₂O, 6.47 MgO, 0.04 MnO, 5.87 FeO, 0.07 Al₂O₃, 18.73 TiO₂, 56.88 SiO₂, 99.62 in total. The empirical formula is (K_0.67Na_0.32Ca_0.01)_Σ1.00Na_2.06Li_1.00 · (Mg_1.39Fe _0.71 ²⁺ )_Σ2.10(Si_7.90Al_0.01)_Σ7.91O₂₄. Grains of magnesioneptunite are dark brown to red-brown, translucent, with vitreous luster. D _calc = 3.15 g/cm³, and the Mohs hardness is 5–6. Cleavage parallel to the (110) is perfect. The new mineral is optically biaxial, positive, α = 1.697(2), β = 1.708 (3), γ = 1.725(3), 2V _meas = 45(15)°. The mineral is associated with quartz, alkali feldspar, rutile, aegirine, and neptunite. Magnesioneptunite and the Mg-rich variety of neptunite were formed as products of ilmenite alteration. Magnesioneptunite is monoclinic, C2/c; unit-cell parameters: a = 16.327(7), b = 12.4788(4), c = 9.9666(4) Å, β = 115.6519(5)°, V = 1830.5(1) ų, Z = 4. The type specimen is deposited at the Fersman Mineralogical Museum of the Russian Academy of Sciences, Moscow.     

Coprecipitation of Ti,Mo, Sn and Sb with fluorides and application to determination of B,Ti, Zr,Nb, Mo,Sn, Sb,Hf and Ta by ICP-MS

We examined the coprecipitation behavior of Ti, Mo, Sn and Sb in Ca–Al–Mg fluorides under two different fluoride forming conditions: at < 70 °C in an ultrasonic bath (denoted as the ultrasonic method) and at 245 °C using a Teflon bomb (denoted as the bomb method). In the ultrasonic method, small amounts of Ti, Mo and Sn coprecipitation were observed with 100% Ca and 100% Mg fluorides. No coprecipitation of Ti, Mo, Sn and Sb in Ca–Al–Mg fluorides occurred when the sample was decomposed by the bomb method except for 100% Ca fluoride. Based on our coprecipitation observations, we have developed a simultaneous determination method for B, Ti, Zr, Nb, Mo, Sn, Sb, Hf and Ta by Q-pole type ICP-MS (ICP-QMS) and sector field type ICP-MS (ICP-SFMS). 9–50 mg of samples with Zr–Mo–Sn–Sb–Hf spikes were decomposed by HF using the bomb method and the ultrasonic method with B spike. The sample was then evaporated and re-dissolved into 0.5 mol l^− 1 HF, followed by the removal of fluorides by centrifuging. B, Zr, Mo, Sn, Sb and Hf were measured by ID method. Nb and Ta were measured by the ID-internal standardization method, based on Nb/Mo and Ta/Mo ratios using ICP-QMS, for which pseudo-FI was developed and applied. When 100% recovery yields of Zr and Hf are expected, Nb/Zr and Ta/Hf ratios may also be used. Ti was determined by the ID-internal standardization method, based on the Ti/Nb ratio from ICP-SFMS. Only 0.053 ml sample solution was required for measurement of all 9 elements. Dilution factors of ≤ 340 were aspirated without matrix effects. To demonstrate the applicability of our method, 4 carbonaceous chondrites (Ivuna, Orgueil, Cold Bokkeveld and Allende) as well as GSJ and USGS silicate reference materials of basalts, andesites and peridotites were analyzed. Our analytical results are consistent with previous studies, and the mean reproducibility of each element is 1.0–4.6% for basalts and andesites, and 6.7–11% for peridotites except for TiO₂.     

Local structure of (Ca, Sr)2 (Mg, Co, Zn) Si2O7 melilite solid-solution with modulated structure

The local structure around Co, Zn and Sr atoms in incommensurately modulated, melilite-type X₂T¹ T ₂ ² O₇ (X=Ca and Sr, T¹=Mg, Co and Zn, T²=Si) solid-solutions has been investigated by EXAFS analyses. The modulated structure was confirmed in Ca_2-xSr_xCoSi₂O₇ solid-solutions with X=0.0 to 0.6 and for both Ca₂Mg_1-YCo_YSi₂O₇ and Ca₂Mg_1-YZn_YSi₂O₇ solid-solutions over the whole compositional range at room temperature. The actual bond-distances determined by the EXAFS method for the T¹ site (Co-, Zn-O) in the modulated structure are longer than the mean bond-distances obtained from the X-ray diffraction method. This is attributable to the libration of the T¹ tetrahedra. In the Ca_1-XSr_XCoSi₂O₇ solid-solution both the Sr-O and Co-O distances by the EXAFS method for the X-site increase from Ca end-member to Sr end-member. These increases are respectively 0.8% and 0.6%. This means the local expansions of the tetrahedral sheets and of the XO polyhedra are well matched. In the modulated Ca₂Co_1-YMg_YSi₂O₇ and Ca₂Zn_1-YMg_YSi₂O₇ solid-solutions, the actual Co-O and Zn-O distances for the T¹-sites are nearly constant in the whole compositional range. The compositional variations of the local structure around the cations in the solid-solution are different for the X and T¹ sites. It is concluded that the local geometric restriction for the size of substituted cation in X site is larger than that in T¹ site. The dimension of the tetrahedral sheet puts restriction on the size of the cations situated at the interlayer X sites. In other words, the different behavior of the local geometric restriction between the X and T¹ sites is an important feature of the melilite structure and is also related to the modulated structure.     

Perrierite-(La), (La,Ce,Ca)4(Fe2+,Mn)(Ti,Fe3+,Al)4(Si2O7)2O8, a new mineral species from the Eifel volcanic district, Germany

Non-metamict perrierite-(La) discovered in the Dellen pumice quarry, near Mendig, in the Eifel volcanic district, Rheinland-Pfalz, Germany has been approved as a new mineral species (IMA no. 2010-089). The mineral was found in the late assemblage of sanidine, phlogopite, pyrophanite, zirconolite, members of the jacobsite-magnetite series, fluorcalciopyrochlore, and zircon. Perrierite-(La) occurs as isolated prismatic crystals up to 0.5 × 1 mm in size within cavities in sanidinite. The new mineral is black with brown streak; it is brittle, with the Mohs hardness of 6 and distinct cleavage parallel to (001). The calculated density is 4.791 g/cm³. The IR spectrum does not contain absorption bands that correspond to H₂O and OH groups. Perrierite-(La) is biaxial (-), α = 1.94(1), β = 2.020(15), γ = 2.040(15), 2V _meas = 50(10)°, 2V _calc = 51°. The chemical composition (electron microprobe, average of seven point analyses, the Fe²⁺/Fe³⁺ ratio determined from the X-ray structural data, wt %) is as follows: 3.26 CaO, 22.92 La₂O₃, 19.64 Ce₂O₃, 0.83 Pr₂O₂, 2.09 Nd₂O₃, 0.25 MgO, 2.25 MnO, 3.16 FeO, 5.28 Fe₂O₃, 2.59 Al₂O₃, 16.13 TiO₂, 0.75 Nb₂O₅, and 20.06 SiO₂, total is 99.21. The empirical formula is (La_1.70Ce_1.45Nd_0.15Pr_0.06Ca_0.70)_Σ4.06(Fe _0.53 ²⁺ Mn_0.38Mg_0.08)_Σ0.99(Ti_2.44Fe _0.80 ³⁺ Al_0.62Nb_0.07)_Σ3.93Si_4.04O₂₂. The simplified formula is (La,Ce,Ca)₄(Fe²⁺,Mn)(Ti,Fe³⁺,Al)₄(Si₂O₇)₂O₈. The crystal structure was determined by a single crystal. Perrierite-(La) is monoclinic, space group P2₁/a, and the unit-cell dimensions are as follows: a =13.668(1), b = 5.6601(6), c = 11.743(1) Å, β = 113.64(1)°; V = 832.2(2) ų, Z = 2. The strong reflections in the X-ray powder diffraction pattern are [d, Å (I, %) (hkl)]: 5.19 (40) (110), 3.53 (40) ( $\overline 3 $ 11), 2.96 (100) ( $\overline 3 $ 13, 311), 2.80 (50) (020), 2.14 (50) ( $\overline 4 $ 22, $\overline 3 $ 15, 313), 1.947 (50) (024, 223), 1.657 (40) ( $\overline 4 $ 07, $\overline 4 $ 33, 331). The holotype specimen of perrierite-(La) is deposited at the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow, Russia, with the registration number 4059/1.     

Origin of minerals with intermediate chlorite-vermiculite structure (Szklary, Poland)

The vermiculite-like minerals show varied relative intensities of basal reflections and do not collapse fully when saturated with K and heated up to 700°C.

Transmission oblique texture X-ray diffraction patterns were used to determine a continuous series of the vermiculite-chlorite intermediate structures. Relative diffraction intensities in the region (060) were correlated with the amount of water released at 500–700°C to show that the investigated samples belong to two structurally distinctive series: vermiculitic and chloritic types. The structural premises indicate that the parent mineral for the chloritic intergrades should be chlorite and that for the vermiculitic series phlogopite.     

Fluid-controlled crustal metasomatism within a high-pressure subducted mélange (Mt. Hochwart, Eastern Italian Alps)

The Nonsberg–Ultental Region of northern Italy contains a Palaeozoic mélange that was partially subducted during the Variscan orogeny. This mélange is constituted mainly by metapelites characterized by shale-type REE-patterns, displaying partial melting which began under high-pressure conditions. The resulting migmatites enclose minor slivers of mantle-wedge peridotites that have been incorporated into the mélange during subduction. Peridotites display important large ion lithophile elements (LILE) enrichment consequent to amphibole recrystallization contemporaneously with metapelite migmatization at P ≈ 2.7 GPa and T ≈ 850 °C in the garnet–peridotite field. Crustal and mantle (ultramafic) rocks of the mélange display the same Sm–Nd ages of about 330 ± 6 Ma, which dates both the metamorphic peak and the migmatization event. The zircon U–Pb age of the metasomatic amphibolitic contact between garnet peridotite and migmatite is identical (333.3 ± 2.4 Ma) within analytical errors. Therefore, metasomatism, migmatization and peak metamorphism are constrained to the same event. The presence of Cl-rich apatite and ferrokinoshitalite in the contact amphibolite, together with the trace-element patterns of peridotites, suggest that metasomatism was driven by Cl- and LILE-rich fluids derived from ocean water transported into the subduction zone by sediments and crustal rocks. These fluids interacted with the crust, prompting partial melting under water oversaturated conditions and partitioning LILE from the crust itself. Peridotites, which were well below their wet solidus temperature, could not melt but they recrystallized in the crustal mélange under garnet-facies conditions. Crustal fluids caused extensive hydration and LILE-enrichment in peridotites and severe Sm–Nd isotope disequilibrium between minerals, especially in the recrystallized peridotites. The proposed scenario suggests massive entrapment of crustal aqueous fluids at high-pressure conditions within subduction zones.     

水镁石——寿山石的一种新型仿制品

在大批量流通的寿山石收藏品中混有异常样品,本文在对其进行详细常规宝石学参数测验的基础上,进行了红外光谱与X射线能量色散荧光光谱仪分析,确定了矿物成分为水镁石。并在红外光谱测试手段的帮助下,确定了水镁石中常见碳酸盐次要矿物的种类。