Marble in the supracrustal rocks of the Lewisian Complex, Tiree, includes chlorine-bearing amphiboles, chlorine-rich apatite, sulphur-rich scapolite, albite and phlogopite, all of which are regarded as evidence for evaporites in other metamorphosed sequences. Titanite yields U–Pb ages of ∼1.6 Ga, i.e. late Laxfordian, which excludes a younger imprint of sodium metasomatism. Traces of anhydrite, and isotopically heavy pyrite, also indicate deposition from seawater. Elsewhere in the Hebrides, tourmaline in Lewisian Complex marbles may represent seafloor exhalative deposits. Combined, the evidence suggests Lewisian Complex supracrustal marbles formed in an evaporative environment, like other Palaeoproterozoic successions across the North Atlantic region.

A synthetic analogue, Ca(Ti0.6Al0.2Ta0.16Nb0.04)OSiO4, of an aluminoan tantalian titanite previously described from Craveggia pegmatite (Piemonte, Italy) has been prepared by a ceramic synthesis technique and its crystal structure determined by Rietveld analysis of the powder X-ray diffraction pattern. The synthetic Al-Ta-Nb-rich titanite adopts space group A2/a implying that substitutions at the single octahedral site destroy the coherence of the off-centering of octahedral chains in the titanite structure resulting in a P 21/a → A2/a phase transition. Unit-cell dimensions obtained for the Al-Ta-Nb-rich titanite are: a = 7.0649(1) Å; b = 8.7187(1) Å; c = 6.5701(1) Å; β = 113.755(1)°, V = 370.41(1) Å3. The extensive replacement of Ti by Al, Ta and Nb results in a considerable decrease in the distortion of all coordination polyhedra in the structure of this titanite. These structural data suggest that a solid solution CaTi1-x(Alx /2 [Ta,Nb]x /2)OSiO4 (0 ≤ x ≤ 0.4) adopting the titanite structure might exist.

Recent studies on albitite rocks located in the granodiorite complex of Central Sardinia have revealed that epidote has a widespread occurrence as a light rare-earth element (LREE)-bearing accessory common phase. Titanite has been recorded as a heavy rare earth element (HREE)-bearing mineral. The Hercynian granodiorite complex of Central Sardinia is composed chiefly of quartz, Ca-plagioclase, K-feldspar and biotite and of a wide variety of secondary assemblages, mainly allanite, titanite and zircon. Albitic plagioclase and quartz are the main mineral components of the albitites. Additional minerals include, besides allanite and epidote, a more calcic-plagioclase (oligoclase), K-feldspar, chlorite, titanite and more rarely muscovite. The mineral assemblages and REE-bearing minerals of albitites were analysed by wavelength dispersive spectrometry (WDS). Chemical data suggest that there is a near complete solid-solution between epidote and allanite whereas little variations in HREE of titanites were detected. In epidote-group minerals a pronounced zoning in REE was observed while titanite was recorded unzoned. Textural relations were studied by SEM to distinguish primary from secondary epidotes. Chemical criteria to recognize magmatic from alteration epidotes were also applied. The alteration epidotes mainly occur and generally originate from plagioclase alteration and from leaching of magmatic allanite. Comparison of textures using both the SEM technique and EPMA data showed that the characteristic ‘patchy zoning’, observed in epidotes, corresponds with different amounts of REE in these minerals.

The schematic model proposed for the epidote-forming reactions during the metasomatic processes that affected the granodiorites involves: (i) the instability of the anorthitic component of plagioclase; (ii) the simultaneous formation of albite; (iii) the leaching of the magmatic allanite with a redistribution of REE in the epidotes of the albitites.

The petrographical, crystal-chemical and petrogenetical aspects of rutile rich in antimony (up to 33.75 wt.% Sb2O5; equal to 0.2 Sb5+ per O = 2) from St. Marcel-Praborna in the Aosta Valley, Italy, were re-examined. These compositions occur in two different petrographical environments (within the rock matrix or as microinclusions within Sb-rich titanite) in the manganese concentrations at this locality. The new data confirm our earlier hypothesis that two distinct petrogenetical/crystal-chemical processes both occurred: 1. Sb-metasomatism of pre-existing Sb-free rutile inclusions; and 2. creation of neoblastic Sb-rich rutile by the expulsion of Ti from pre-existing Sb-free titanite being metasomatized by Sb to form Sb-rich titanite. In the literature, Sb in minerals is variably considered as being trivalent and/or pentavalent. This work demonstrates that within rutile it is entirely Sb5+, substituting for Ti4+ by the following heterovalent cation exchange mechanism which is also the dominant one in the host Sb-rich titanite: 2 viR4+ = viR3+ + viR5+, where viR3+ = (Al,Cr,Mn,Fe)3+. A near-perfect correlation of ΣR5+vs. ΣR3+ (r > 0.98) is perturbed only by the presence of trace amounts of Ca2+, Sr2+ and Ba2+. Traces of Mn4+, Si4+ and/or (OH)− might also be present. These alkaline earth cations are the largest cations ever recorded in the rutile structure and are seemingly too large to occupy normal octahedral sites. The cation exchange mechanism involved might be that found in the ‘trirutile’ mineral group: 3 viR4+ = viR2+ + 2 viR5+. Alternatively these large divalent cations may be situated in the lozenge-shaped tunnels of the rutile structure, by analogy with other large cations occupying the wider subrectangular tunnels in the analogous cryptomelane/hollandite/priderite, romanéchite and todorokite mineral groups. This leads to a possible new cation exchange mechanism for the rutile structure: 2 viR4+ + tunelvacant = 2 viR3+ + tunnelR2+.

SHRIMP U-Pb zircon and titanite dating have been used to constrain the timing of mid- to lower- crustal metamorphism (∼650—700°C and 8—11 kbar) and syn-kinematic melting in the granitoid gneiss- dominated terrane south of the Barberton greenstone belt, South Africa. This study is concentrated on a clastic metasedimentary unit exposed in one of several greenstone remnants and a late-kinematic trondhjemite intrusive into spatially associated mixed gneisses. Locally, the clastic metasediments show extensive replacement of garnet and plagioclase by epidote and titanite. The titanites yield an upper intercept date of 3229±9 Ma, and provide a minimum age for the peak of metamorphism. Zircons separated from the same unit record a range of concordant and near-concordant 207Pb/206Pb dates between ∼3560 and 3230 Ma, the youngest group yielding a weighted mean date of 3227±7 Ma. This range of dates is interpreted to be due to a combination of metamorphic recrystallization and high- temperature Pb-loss in originally detrital zircons during regional metamorphism. A minimum age for the timing of deformation is given by the emplacement age of 3229±5 Ma for the late-kinematic trondhjemite. Thus, geochronological data support the notion of a major metamorphic episode that coincided with the proposed short-lived terrane accretion event in the centre of the Barberton greenstone belt.

Natrotitanite, ideally (Na0.5Y0.5)Ti(SiO4)O, is a new mineral from the Verkhnee Espe rare-element deposit at the northern exo-contact of the Akjailyautas granite massif in the northern part of the Tarbagatai mountain range, Eastern Kazakhstan. Both the mineral and the name have been approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association (IMA 2010-033). Star-shaped aggregates of small short prisms of yellow or yellowish white (Na,Y,REE)-bearing titanite rimmed by thin (∼2 μm) rims of natrotitanite are embedded in yttrium-bearing fluorite and replace narsarsukite. Associated minerals are microcline, albite, quartz, riebeckite, aegirine, biotite, astrophyllite, rutile, zircon and elpidite. Natrotitanite is milky white to yellowish grey, transparent to translucent, and has a white streak and a vitreous lustre. It shows pale orange cathodoluminescence but does not fluoresce under ultraviolet light. It shows no cleavage or parting, and is brittle; the calculated density is 3.833 g cm–3. The indices of refraction, measured with the Bloss spindle stage for the wavelength 590 nm using a gel filter, are α = 1.904, γ = 2.030, and these values are in accord with the mean refractive index, 1.988, calculated from the Gladstone-Dale relation. Natrotitanite is monoclinic, C2/c, a = 6.5691(2), b = 8.6869(3), c = 7.0924(2) Å, β = 114.1269(4)°, V = 369.4(2) Å3, Z = 4, a:b:c = 0.7562:1: 0.8164. The seven strongest lines in the X-ray powder diffraction pattern [in the order d (Å), I, (hkl)] are as follows: 2.597, 10, (130); 3.248, 8, (11); 2.994, 6, (200); 1.641, 4, (330); 4.941, 3, (110); 1.498, 3, (400); 2.273, 3, (11). Chemical analysis by electron microprobe gave Nb2O5 1.28, SiO2 27.83, TiO2 35.00, SnO2 0.57, V2O3 0.36, Fe2O3 0.23, Y2O3 7.87, Ce2O3 0.83, Sm2O3 0.26, Gd2O3 0.46, Tb2O3 0.17, Dy2O3 2.45, Ho2O3 0.16, Er2O3 2.24, Tm2O3 0.50, Yb2O3 2.53, Nd2O3 0.35, Lu2O3 0.28, MnO 0.33, CaO 8.16, Na2O 5.55, F 1.52 O ≡ F –0.64, sum 98.71 wt.%. The resulting empirical formula is (Na0.39Ca0.32Y0.15Dy0.03Yb0.03Er0.03Ce0.01Ho0.01Tm0.01Gd0.01Nd0.01)Σ1.00(Ti0.95Nb0.02Sn0.01Fe3+0.01Mn0.01V0.01)Σ1.01Si1.01O4.00(O0.83F0.17), calculated on the basis of 3 cations per formula unit. The general formula is written as (Na,Ca,Y,REE)TiSiO4(O,F), and the endmember formula is (Na0.5Y0.5)Ti(SiO4)O.

The crystal structure of a composite optically continuous crystal of natrotitanite and (Na, Y)-bearing titanite was mounted on a Bruker D8 three-circle diffractometer equipped with a rotating anode generator (MoKα radiation), a multi-layer optics incident-beam path and an APEX-II CCD detector. The crystal structure was refined in space group C2/c to a final R1 index of 1.8%. Natrotitanite is isostructural with titanite, (Na + Y + REE) replacing Ca at the Ca site in the titanite structure.

Lattice parameters of synthetic titanite powder, CaTiOSiO4, have been determined between room temperature and 1023 K. Only the e11 and e13 components contribute significantly to the strain tensor associated with the antiferroelectric-paraelectric phase transition at Tc = 487 K. A finite strain component e13 is observed in the paraelectric phase for 487 K < T < 825 K. The disappearance of this shear strain marks the isosymmetric transition near 825 K. The temperature evolution of the volume strain and of e11 is proportional to the squared order parameter observed in single-crystal diffraction experiments. The magnitude of the volume strain is sufficiently large to relate the observed near tricritical behaviour of the antiferroelectric-paraelectric phase transition to strain coupling.

Euhedral crystals of complexly zoned niobian titanite (up to 0.3 mm) are enclosed in hedenbergite (Hd53—81Di15—43Jh3-5) and quartz from a hedenbergite vein skarn at Kamenne doly near Pisek, Czech Republic. They are associated with minor clinozoisite-epidote (Ps3—22), calcite, plagioclase (An95). scapolite (Me80—82), scheelite, pyrrhotite, fluorapatite, arsenopyrite, native bismuth and Bi,Te-minerals. The following textural and compositional subtypes were recognized: (I) Nb-rich titanite, (II) Nb-moderate titanite in the central zone, (III) Nb-poor, Sn-enriched titanite and (IV) Nb-poor, Al,F-rich titanite in the outer zone. The substitution Al(Nb,Ta)Ti—2 is dominant in subtypes I and II, the titanite subtype I being characterized by elevated contents of Al ≤ 0.257 atoms per formula unit (a.p.f.u.), Nb (≤ 0.161 a.p.f.u.) and Ta (≤ 0.037 a.p.f.u.). Amounts of Al, Nb and Ta in subtype II are smaller and more variable. The minor substitution SnTi—1 occurs chiefly in titanite subtype III with a content of Sn ≤ 0.039 a.p.f.u.. The substitution Al(F,OH)(TiO)_i is typical for titanite subtype IV exhibiting elevated contents of Al (s£ 0.221 a.p.f.u.), F (≤ 0.196 a.p.f.u.) and Fe (≤ 0.039 a.p.f.u.).

The negative relationship of substitutions Al(F,OH)(TiO)_i vs. SnTi—1 and Al(Nb,Ta)Ti—1 is constrained chiefly by crystal structure rather than by the composition of parent medium alone. Textural relations suggest that the Nb-moderate titanite in the core zone and entire outer zone are products of fluids-induced dissolution-reprecipitation processes. The studied niobian titanite represents a new F-enriched type from a medium-grade, calc-silicate rock.

Titanites rich in antimony (up to 12.59 wt.% Sb2O5; equal to 0.165 Sb5+ per Si4+ = 1.000) arc described for the first time. They coexist with various greenschist-facies minerals in three different petrographical environments in the manganese concentrations at St. Marcel-Praborna in the Aosta Valley, Italy. These titanites are chemically zoned, the Sb-richest parts generally occurring alongside grain boundaries, microfractures, pores or inclusions. Moderately-good positive correlations exist between the Sb, Al and Fe contents, with negative correlations of each of these elements with Ti. Cr has perturbed the Al and Fe contents since a better negative correlation with Ti is obtained with [Al + Cr + Mn + Fe]. The Sr, Ba, Mn and F contents are rather small and vary irregularly. Several crystal-chemical hypotheses are presented concerning the method of structural formula calculation and the valencies and site distributions of Sb and the companion additional minor elements. The favoured interpretation is to place: Sr2+, Ba2+, Mn2+, Fe2+ and possibly also Sb3+ in the viiCa2+ site; Sb5+, Cr3+, Al3+, Sb3+, Fe3+ and possibly also Mn3+ in the viTi4+ site; and Al3+ in the ivSi4+ site; this indicates the existence of a natural silicate containing not only both trivalent and pentavalent Sb, but also both valencies in the same site. The principal ionic substitution is believed to be: 2 viTi4+ = vi[Al3+ + Cr3+ + Mn3+ + Fe3+] + viSb5+ accompanied by a substantial minor proportion of: 2 viTi4+ = viSb3+ + viSb5, or possibly = 2 viSb4+ The data indicate a very late stage penetration of pre-existing titanites by mobilized Sb, Al, Cr, Mn, Fe, F and presumably also (OH) at this locality, whereas Sr and Ba were mobile at an earlier stage. Manganese, which existed in the sedimentary protoliths, did not enter the titanite structure in very significant quantities.

Titanite occurs in the groundmass of a holocrystalline volcanic ejectum collected in the pyroclastic rocks of the Vico Volcanic complex at Tre Croci, near Viterbo, Italy. The host rock is composed of abundant K-feldspar and minor plagioclase, biotite, clinopyroxene and a feldspathoid (sodalite). Titanite is typically associated with zirconolite, biotite and Fe-oxides. It has a medium Al content (Al2O3 + Fe2O3 = 4–6 wt.%) and contains significant amounts of Zr and LREE, with a chondrite- normalised REE pattern similar to those of titanites from other alkaline rocks. Titanite has been corroded by fluids probably rich in dissolved F and P during a late alteration stage, with evidence for some remobilization and redistribution of the REE and actinide elements.

The rocks of the Jasra intrusive complex (Shillong Plateau, northeastern India) include phlogopite clinopyroxenites (with olivine or perovskite relics), alkali gabbros/monzodiorites, syenites and nepheline syenites. They have a potassic affinity (Na2O/K2O ∼1), and their mineralogy is dominated by clinopyroxene with which phlogopite, olivine, amphibole, feldspars, feldspathoids, oxides, orthopyroxenes, perovskite, titanite and other accessory phases are variably associated. The Jasra intrusive rocks are cumulates derived from at least two distinct magmatic liquids. The potassic affinity of the Jasra rocks differs from the nearby Sung Valley ijolitic-carbonatitic complex and from the ultrapotassic lamproitic rocks of the Damodar Valley, which are of approximately the same age. This suggests major variability in the mantle sources of small-volume alkaline volcanism in the Early Cretaceous of northeastern India.

Allanite-(La) (containing up to 7.80 wt.% V2O3 and with La/ΣREE and La/Ce atomic ratios up to 0.54 and 1.45, respectively) and allanite-(Ce) (up to 8.46 wt.% V2O3) occur in close association with vanadian muscovite, barian tomichite and vanadian titanite in the main ore zone of the Hemlo gold deposit, Ontario, Canada. Allanite-(Ce) generally occurs as a minor constituent in cross-cutting veins or along foliation planes, whereas allanite-(La) invariably occurs in direct contact with titanite. The high V concentrations in the allanites from Hemlo are readily attributable to an adequate local source of this element, and are most likely controlled mainly by a simple substitution of V for Al in octahedral coordination. Vanadian allanite-(La) and vanadian allanite-(Ce), without any systematic differences in other constituents, are clearly distinct in REE composition, in respect to both the relative concentrations of La and Ce and abundances of other REE. The formation of both allanites (Ce- and La-rich) indicates very localised remobilisation and concentration of REE during a late hydrothermal alteration. The unusual REE composition of vanadian allanite-(La) directly reflects partitioning of REE with coexisting titanite, and the formation of this unusual phase may be attributable to replacement of earlier titanite with redistribution of REE in the solid state.