Mendigite,Mn2Mn2MnCa(Si3O9)2, a new mineral species of the bustamite group from the Eifel volcanic region,Germany

A new mineral, mendigite (IMA no. 2014-007), isostructural with bustamite, has been found in the In den Dellen pumice quarry near Mendig, Laacher Lake area, Eifel Mountains, Rhineland-Palatinate (Rheinland-Pfalz), Germany. Associated minerals are sanidine, nosean, rhodonite, tephroite, magnetite, and a pyrochlore-group mineral. Mendigite occurs as clusters of long-prismatic crystals (up to 0.1 × 0.2 × 2.5 mm in size) in cavities within sanidinite. The color is dark brown with a brown streak. Perfect cleavage is parallel to (001). D _calc = 3.56 g/cm³. The IR spectrum shows the absence of H₂O and OH groups. Mendigite is biaxial (–), α = 1.722 (calc), β = 1.782(5), γ = 1.796(5), 2V _meas = 50(10)°. The chemical composition (electron microprobe, mean of 4 point analyses, the Mn²⁺/Mn³⁺ ratio determined from structural data and charge-balance constraints) is as follows (wt %): 0.36 MgO, 10.78 CaO, 37.47 MnO, 2.91 Mn₂O₃, 4.42 Fe₂O₃, 1.08 Al₂O₃, 43.80 SiO₂, total 100.82. The empirical formula is Mn_2.00(Mn_1.33Ca_0.67) (Mn_0.50 ²⁺ Mn_0.28 ³⁺ Fe_0.15 ³⁺ Mg_0.07)(Ca_0.80 (Mn_0.20 ²⁺)(Si_5.57 Fe_0.27 ³⁺ Al_0.16O₁₈). The idealized formula is Mn₂Mn₂MnCa(Si₃O₉)₂. The crystal structure has been refined for a single crystal. Mendigite is triclinic, space group \(P\bar 1\); the unit-cell parameters are a = 7.0993(4), b = 7.6370(5), c = 7.7037(4) Å, α = 79.58(1)°, β = 62.62(1)°, γ = 76.47(1)°; V = 359.29(4) ų, Z = 1. The strongest reflections on the X-ray powder diffraction pattern [d, Å (I, %) (hkl)] are: 3.72 (32) (020), 3.40 (20) (002, 021), 3.199 (25) (012), 3.000 (26), (\(01\bar 2\), \(1\bar 20\)), 2.885 (100) (221, \(2\bar 11\), \(1\bar 21\)), 2.691 (21) (222, \(2\bar 10\)), 2.397 (21) (\(02\bar 2\), \(21\bar 1\), 203, 031), 1.774 (37) (412, \(3\bar 21\)). The type specimen is deposited in the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow, registration number 4420/1.     

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.     

Batiferrite, Ba[Ti2Fe10]O19, a new ferrimagnetic magnetoplumbite-type mineral from the Quaternary volcanic rocks of the western Eifel area, Germany

Summary Batiferrite, ideally Ba[Ti₂Fe₁₀]O₁₉, was found in the Quaternary volcanic rocks near üdersdorf, Graulai, and Altburg, western Eifel area, Germany. The new mineral typically occurs as euhedral platy grains in cavities of melilite- and leucite-nephelinite basalts. Associated minerals are hematite, magnetite, titanite, g?tzenite, clinopyroxene, nepheline, and biotite. It exhibits a hexagonal tabular habit flattened on {0001}, diameter 0.5–1 mm, thickness 20–125 μm, and {10&1macr;3}, {10&1macr;0} as observable forms. The mineral is opaque, of black color with submetallic lustre, and shows a ferrimagnetic behavior. VHN₅₀ is 793 with a range of 710–841 from ten indentations. The quantitative reflectance measurements of R_o/R_e on oriented grains in air and oil immersion, respectively, are [%]: for 470 nm 22.1/20.1 and 8.4/7.1, for 546 nm 21.0/19.4 and 7.8/6.6, for 589 nm 20.2/18.8 and 7.4/6.3, and for 650 nm 19.3/18.3 and 6.8/5.9. The bireflectance is distinct (air) to weak (oil), and parallel (0001) a moderate anisotropy with straight extinction can be observed. Typical microprobe analyses give [wt%] K₂O 0.28–0.33, Na₂O 0.17–0.20, SrO 0.46–0.55, BaO 11.80–12.17, MgO 1.27–1.47, Al₂O₃ 0.31–0.33, TiO₂ 13.11–13.63, MnO 2.38–2.57, Fe₂O₃ 61.36–63.12, FeO 5.49–5.86 (Fe³⁺/Fe²⁺ calculated for charge compensation), which is equivalent to (Ba_0.84Na_0.06K_0.06Sr_0.05)_1.01(Fe_8.48 ³⁺Fe_0.86 ²⁺Ti_1.82Mg_0.37Mn_0.37Al_0.06)_11.96O₁₉ as the average composition based on 19 oxygen atoms. Batiferrite is a magnetoplumbite-type mineral with hexagonal symmetry, space group P6 ₃ /mmc (no. 194), a = 5.909(1) ?, c = 23.369(4) ?, V = 706.6(2) ?³, Z = 2, and a calculated density of 5.016 gcm⁻³. The structure was refined to R1 = 0.031 for 278 unique reflections with F_o ² > 4σ (F_o ²) and R1 = 0.079 for all 452 unique observations using single crystal X-ray data. The strongest reflections of the X-ray powder diffraction pattern are [d _obs, I/I_o, (hkl)]: 2.631, 100, (114); 2.799, 80, (107); 1.478, 70, (220); 2.429, 60, (203); 1.672, 50, (217). The new mineral is comparable to the other Ba containing magnetoplumbite-type minerals haggertyite and hawthorneite, the iron content, however, is much higher and in the range of magnetoplumbite. The large cation site (A) is dominated by Ba, and four of the five remaining crystallographic cation sites in the structure are dominated by Fe (M1, 2, 3, 5), the octahedrally coordinated M4-site is dominated by Ti. No oxygen vacancy on the O3-site like in plumboferrite can be observed. Batiferrite is named for its main chemical composition and the relationship to the M-type hexaferrites (polytype 5H).

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Zusammenfassung Batiferrit, ein neues ferrimagnetisches Mineral des Magnetoplumbit-Typs aus den quart?ren Vulkaniten der West-Eifel, Deutschland Das neue Mineral Batiferrite, mit der Idealformel Ba[Ti₂Fe₁₀]O₁₉, wurde an drei Fundpunkten in den Quart?ren Vulkangesteinen der westlichen Eifel, Deutschland, in der N?he von üdersdorf, Graulai und Altburg gefunden. Das neue Mineral tritt typischerweise bl?ttchenf?rmig in kleinen Hohlr?umen von Melilith- und Leucit-Nephelininit Basalten auf. Vergesellschaftete Minerale sind H?matit, Magnetit, Titanit, G?tzenit, Klinopyroxen, Nephelin und Biotit. Der Habitus ist hexagonal tafelig nach {0001}, mit einem Durchmesser von 0.5–1 mm und einer Dicke von 20–125 μm, zus?tzlich k?nnen die Formen {10&1macr;3} und {10&1macr;0} beobachtet werden. Das Mineral ist opak, hat eine schwarze Farbe mit einem leicht metallischen Glanz, und ist ferromagnetisch. Die H?rte VHN₅₀ ist 793 mit einem Bereich von 710–841 aus 10 Eindruckbestimmungen. Die quantitativen Reflexionsmessungen von R_o/R_e an orientierten K?rnern in Luft beziehungsweise ?limmersion, ergaben [%]: für 470 nm 22.1/20.1 und 8.4/7.1, für 546 nm 21.0/19.4 und 7.8/6.6, für 589 nm 20.2/18.8 und 7.4/6.3, und für 650 nm 19.3/18.3 und 6.8/5.9. Die Bireflexion ist deutlich (Luft) bis schwach (?l) und parallel (0001) kann eine mittlere Anisotropie mit gerader Ausl?schung beobachtet werden. Eine typische Mikrosondenanalyse ergibt [wt%] K₂O 0.28–0.33, Na₂O 0.17–0.20, SrO 0.46–0.55, BaO 11.80–12.17, MgO 1.27–1.47, Al₂O₃ 0.31–0.33, TiO₂ 13.11–13.63, MnO 2.38–2.57, Fe₂O₃ 61.36–63.12, FeO 5.49–5.86 (Fe³⁺/Fe²⁺ berechnet zum Ladungsausgleich), die mittlere chemische Formel auf der Basis von 19 Sauerstoffatomen lautet (Ba_0.84Na_0.06K_0.06Sr_0.05)_1.01 (Fe_8.48 ³⁺Fe_0.86 ²⁺Ti_1.82Mg_0.37Mn_0.37Al_0.06)_11.96O ₁₉. Batiferrit ist ein Mineral der Magnetoplumbitgruppe, hat hexagonale Symmetrie mit der Raumgruppe P6₃/mmc (Nr. 194), a = 5.909(1) ?, c = 23.369(4) ?, V = 706.6(2) ?³, Z = 2, und einer berechneten Dichte von 5.016 gcm⁻³. Die Struktur wurde aus Einkristall-R?ntgendaten bis zu einem R1-Wert von 0.031 für 278 F_o ² > 4σ(F_o ²), und einem R1-Wert von 0.079 für alle 452 F_o ² verfeinert. Die st?rksten Beugungsreflexe der Pulver-R?ntgendaten sind [d_obs, I/I_o, (hkl)]: 2.631, 100, (114); 2.799, 80, (107); 1.478, 70, (220); 2.429, 60, (203); 1.672, 50, (217). Das neue Mineral weist deutliche ?hnlichkeiten zu den anderen beiden Ba-reichen Mineralen Haggertyit und Hawthorneit der Magnetoplumbit-Gruppe auf, jedoch ist der Eisengehalt wesentlich h?her und im Bereich des Minerals Magnetoplumbit. Der gro?e Kationenplatz (A) ist von Barium dominiert, vier (M1, 2, 3, 5) der restlichen fünf kristallographischen Kationenpl?tze in der Struktur sind fast ausschlie?lich mit Fe, die oktaedrisch koordinierte M4-Position ist überwiegend mit Ti besetzt. An der O3-Position konnte kein Sauerstoffdefizit wie in Plumboferrit festgestellt werden. Batiferrit ist nach seiner chemischen Beschaffenheit und nach seiner Zugeh?hrigkeit zu den M-Typ Hexaferriten (Polytyp 5H) benannt.

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Received December 14, 1999; accepted March 2, 2000     

Ternesite, Ca5(SiO4)2SO4, a new mineral from the Ettringer Bellerberg/Eifel, Germany

Summary The new mineral ternesite, Ca₅(SiO₄)₂SO₄, has been found at the Ettringer Bellerberg near Mayen, Eifel, Germany. The crystal structure, already known from the synthetic analogue, was refined from single crystal X-ray data: orthorhombic, space group Puma with a= 6.863(1)Å, b=15.387(2) Å, c=10.181(1) Å Z=4, R=0.058, R_w=0.046 for 820 unique reflections with F₀> 3(F₀) and 96 variable parameters. The strongest peaks in the powder pattern are (d-value (Å),I, hkl): 2.830, 100, (033)/2.853, 63, (230)/2.565, 55, (060)/3.198, 42, (132)/1.892, 39, (035) + (125). The mineral is optically biaxial negative with refractive indices n_x = 1.630(1) (parallel [100]), ny = 1.637(2) (parallel [001]), and n_z = 1.640(1) (parallel [010]). The optical angle 2V_x was measured as 63.5(5)°.

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Ternesit, Ca₅(SiO₄)₂SO₄, ein neues Mineral vom Ettringer Bellerberg, Eifel, Deutschland

Zusammenfassung Das neue Mineral Ternesit, Ca₅(SiO₄)₂SO₄, wurde am Ettringer Bellerberg bei Mayen, Eifel, Deutschland gefunden. Die schon vom synthetischen Analogen her bekannte Kristallstruktur wurde aus Einkristalldaten von natürlichem Material verfeinert: Das Mineral ist orthorhombisch, Raumgruppe Pnma mit a= 6.863(1)Å, b=15.387(2) Å, c=10.181(1) Å, Z=4, R=0.058, R_w=0.046 für 820 unabhängige Reflexe mit F₀> 3(F₀) und 96 variablen Parametern. Die stärksten Maxima im Pulverbeugungsdiagramm sind (d-Wert (Å),I, hkl): 2.830, 100, (033)/2.853, 63, (230)/2.565, 55, (060)/ 3.198, 42, (132)/1.892, 39, (035) + (125). Das Mineral ist optisch zweiachsig negativ mit Brechungsindizes n_x = 1.630(1) (parallel [100]), n_y = 1.637 (2) (parallel [001]), und n_z = 1.640(1) (parallel [010]). Der optische Achsenwinkel 2V_x wurde zu 63.5(5)° gemessen.

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With 1 figure     

Experimental and theoretical study of (Fe2+, Mg)(Al,Fe3+)2O4 spinels: Activity-composition relationships,miscibility gaps,vacancy contents

The compositions of (Fe²⁺, Mg)(Al, Fe³⁺)₂O₄ spinels equilibrated with a l M (Fe²⁺, Mg)Cl₂ aqueous solution at 800°C, 4 kbars were determined. General considerations of reciprocal systems allow derivation of the exchange isotherm between a chloride aqueous solution and (Mg, Fe²⁺)Al₂O₄ spinels. They enable calculation of ΔG of the reaction: FeCl₂ + MgAl₂O₄ = MgCl₂ + FeAl₂O₄ΔG = 2.9 kcal at 800°C, 4 kbars and provide the activity-composition relationships for the binary join FeAl₂O₄-MgAl₂O₄, which shows a substantial positive deviation from ideality. Some tie-lines between coexisting aluminous and ferric spinels were also obtained in the (Fe²⁺, Mg)(Al, Fe³⁺)₂O₄ system.These experimental data are modeled by a Gibbs free energy formulation of the spinel solid solution (Lehmann and Roux, 1984), where the corrective function g₂, necessary to reproduce the deviations from ideality, is artificially split into two parts:

• 1.(1) A homogeneous second degree polynomial in the composition variables, containing only the terms specific to the reciprocal nature of the system, whose coefficients are deduced from ΔG of the exchange reaction: MgAl₂O₄ + FeFe₂O₄ = MgFe₂O₄ + FeAl₂O₄ΔG = 4.5 kcal at 800°C, 4 kbars
• 2.(2) A homogeneous second degree polynomial in the site occupancy fractions, to model the non-ideal behavior of the (Fe²⁺, Mg)Al₂O₄ and (Fe₂₊, Mg)Fe₂O₄ spinels and the miscibility gap along the Fe(Al, Fe³⁺)₂O₄ join.

A model of reciprocal spinel solution involving defect end-members is used to estimate the vacancy contents of the spinels in equilibrium with sesquioxides. In this case, the corrective function necessary to take into account the reciprocal nature of the system is no longer a second degree polynomial, but a rational fraction.     

(Na,Ca)(Ti3+,Mg)Si2O6-clinopyroxenes at high pressure: influence of cation substitution on elastic behavior and phase transition

A compressional study of (Na,Ca)(Ti³⁺,Mg)Si₂O₆-clinopyroxenes was carried out at high pressures between 10⁻⁴ and 10.2 GPa using in situ single-crystal X-ray diffraction, Raman spectroscopy and optical absorption spectroscopy. Compressional discontinuities accompanied by structural changes, in particular, the appearance of two distinct Ti³⁺–Ti³⁺ distances within the octahedral chains at 4.37 GPa, provide evidence for the occurrence of a phase transition in NaTi³⁺Si₂O₆. Equation-of-state parameters are K ₀ = 115.9(7) GPa with K′ = −0.9(3) and K ₀ = 102.7(8) GPa with K′ = 4.08(5) for the low- and high-pressure range, respectively. The transition involves a C2/c–P [`1] \overline{1} symmetry change, which can be confirmed by the occurrence of new modes in Raman spectra. Since no significant discontinuity in the evolution of the unit-cell volume with pressure has been observed, the transition appears to be second-order in character. The influence of the coupled substitution Na⁺Ti³⁺↔Ca²⁺Mg²⁺ on the static compression behavior and the structural stability has been investigated using a sample of the intermediate composition (Na_0.54Ca_0.46)(Mg_0.46Ti_0.54)Si₂O₆. No evidence for a deviation from continuous compression behavior has been found, neither in lattice parameter nor in structural data and the fit of a third-order Birch–Murnaghan equation-of-state to the pressure–volume data yields a bulk modulus of K ₀ = 109.1(5) GPa and K′ = 5.02(13). Raman and polarized absorption spectra have been compared to NaTiSi₂O₆ and reveal major similarities. The main driving force for the phase transition in NaTi³⁺Si₂O₆ is the localization of the Ti³⁺ d-electron and the accompanying distortion, which is suppressed in the (Na,Ca)(Ti³⁺,Mg)Si₂O₆-clinopyroxene.     

The distribution of Fe3+ and Ga3+ between two tetrahedral sites in melilites,Ca2(Mg,Fe3+, Ga,Si)3O7

The distribution of Fe³⁺ and Ga³⁺ between the two tetrahedral sites in three synthetic melilites has been studied by using ⁵⁷Fe Mössbauer spectroscopy. In the melilite, (Ca₂Ga₂SiO₇)₅₀ (Ca₂Fe³⁺GaSiO₇)₅₀ (mol %), the distribution of Fe³⁺ and Ga³⁺ in T1 and T2 sites is apparently random, which can be explained in terms of the electrostatic valence rule. However in the melilites, (Ca₂MgSi₂O₇)₅₂ (Ca₂Fe³⁺GaSiO₇)₄₂ (Ca₂Ga₂SiO₇)₆ and (Ca₂MgSi₂O₇)₆₂ (Ca₂Fe³⁺GaSiO₇)₃₆ (Ca₂Ga₂SiO₇)₂ (mol %), Fe³⁺ shows preference for the more ionic T1 site and Ga³⁺ for the more covalent T2 site. If the electronegativity of Ga³⁺ is assumed to be larger than that of Fe³⁺, the mode of distribution of Fe³⁺ and Ga³⁺ can be explained in terms of our previous hypothesis that a large electronegativity induces a stronger preference for the more covalent T2 site.     

等离子体发射光谱法同时测定大洋富钴结壳中硅锰铁钙镁铝钛

大洋富钴结壳试样经ＨＣｌ＋ＨＮＯ３＋ＨＦ溶解,在０．２ｍｏｌ／ＬＨＦ和０．１３ｍｏｌ／ＬＨ３ＢＯ３介质中,用感耦等离子发射光谱法同时测定Ｓｉ、Ｍｎ、Ｆｅ、Ｃａ、Ｍｇ、Ａｌ、Ｔｉ元素的含量。方法经国家标准物质ＧＢＷ０７２４９大洋多金属结核验证,其结果与标准值相符,精密度ＲＳＤ〈３．２％（ｎ＝６）;已应用于太平洋富钴结壳中多元素分析。     

Determination of structures of Ca2CoSi2O7, Ca2MgSi2O7, and Ca2(Mg0.55Fe0.45)Si2O7 in incommensurate and normal phases and observation of diffuse streaks at high temperature

 The structures of Ca₂CoSi₂O₇, Ca₂MgSi₂O₇, and Ca₂(Mg_0.55Fe_0.45)Si₂O₇ have been determined in the temperature range between 297 and 773 K with arbitrary intervals. The structures of the incommensurate phase of the three compounds are characterized by the presence of the six-, seven-, and eight-coordinated Ca–O polyhedra and of the bundles along the c-axes consisting of four arrays of the six-coordinated Ca–O polyhedra and an array of T¹O₄ (T¹: Co, Mg, or Mg–Fe) tetrahedra in the structures. The number of bundles in each material decreases at elevated temperatures. The incommensurate phase undergoes a phase transition into the normal phase at 493 K in Ca₂CoSi₂O₇, at 360 K in Ca₂MgSi₂O₇, and at 510 K in Ca₂(Mg_0.55Fe_0.45)Si₂O₇. The features of the structures of the normal phase are almost the same as those found in the basic structures (the averaged structures of the incommensurate structures), and this fact implies that the characteristics of the structures, such as the six-coordinated Ca–O polyhedra or fragments of the bundles, should be partially preserved at higher temperatures both in the incommensurate structures and also in the structures of the normal phase. Analyses of anisotropic displacement parameters clarified that disorder of the modulation waves is developed in the structures at higher temperatures. The evolution of a disorder in the structures was ascertained by observation of the circular diffuse streaks in the vicinity of the transition temperature between the incommensurate and normal phases. Received: 3 July 2000 / Accepted: 26 October 2000     

Synthesis and physical properties of piemontite Ca2Al3-pMn p 3+ (Si2O7/SiO4/O/OH)

Mn³⁺-bearing piemontites and orthozoisites, Ca₂(Al_3-pMn³⁺ _p)-(Si₂O₇/SiO₄/O/OH), have been synthesized on the join Cz (p = 0.0)-Pm (p = 3.0) of the system CaO-Al₂O₃-(MnO·MnO₂)-SiO₂-H₂O atP = 15 kb,T= 800 °C, and \(f_{O_2 } \) of the Mn₂O₃/MnO₂ buffer. Pure Al-Mn³⁺-piemontites were obtained with 0.5≦p≦1.75, whereas atp=0.25 Mn³⁺-bearing orthozoisite (thulite) formed as single phase product. The limit of piemontite solid solubility is found near p=1.9 at the above conditions. Withp>1.9, the maximum piemontite coexisted with a new high pressure phase CMS-X1, a Ca-bearing braunite (Mn _0.2 ²⁺ Ca_0.8)Mn ₆ ³⁺ O₈(SiO₄), and quartz. Al-Mn³⁺-piemontite lattice constants (LC),b ₀,c ₀,V ₀, increase with increasingp:

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.