Liguowuite, WO3, a new member of the A-site vacant perovskite type minerals from the Panzhihua–Xichang region, China

A new member of the non-stoichiometric perovskite group mineral species, liguowuite, ideally WO3, has been found in the Neoproterozoic Sinian biotite-quartz monzonite in the southern part of the Panzhihua– Xichang region (Nanyang village: 26468.21 N, 1012713.86 E), China. It is associated with hornblende, pargasite, ferro-hornblende, annite, hydrobiotite, phlogopite, orthoclase, microcline, albite, quartz, kaolinite, ilmenite, goethite, hematite, magnetite, pyrite, zircon, zoisite, titanite, epidote, diopside, tourmaline, almandine, fluorapatite, monazite-(Ce), allanite-(Ce), bastnäsite-(Ce), xenotime-(Y), scheelite, moissanite, tellurite, wumuite, and tewite. Liguowuite occurs as greenish yellow prisms, ranging from 0.05 to 0.1 mm in diameter, and it is transparent with a greasy luster and a white streak. Liguowuite exhibits a triclinic pseudomorphism composed of nanoparticles with many cracks and nanovoids. This mineral is brittle and has a Mohs hardness value of approximately 3–4. The calculated density is 7.22 g cm−3. Electron microprobe analyses gave (average weight percent, wt %, of 15 spot analyses of 4 samples) K2O= 0.01, WO3= 99.23, TeO2= 0.03, CaO= 0.06, Na2O= 0.04, and total 99.37, yielding the empirical formula W1.00O3, based on Oapfu = 3 and ideally WO3. The strongest five diffraction lines (d Å (I )(hkl)) are 3.8552 (88)(002), 3.7685 (88)(020), 3.6590 (100)(– 200), 2.6928 (43)(022), and 2.6258 (60)(202). Liguowuite is monoclinic and is in space group P 21/n, with a = 7.32582(18) Å, b = 7.54767(18) Å, c = 7.71128(18) Å, β = 90.678(3), V = 426.348(19) Å3, and Z = 8. The crystal structure data were refined using the Rietveld refinement method and X-ray powder diffraction data. The reliability factors (R factors) were Rwp = 0.0604 and Rp = 0.0454, with χ2= 1.707. Liguowuite consists of corner-sharing distorted and tilted [WO6] octahedra, in which the W atoms are off-center and form six W–O bonds ranging from 1.7 to 2.2 Å with the surrounding oxygen atoms. According to the hierarchical scheme for perovskite supergroup minerals, liguowuite is the first reported example of A-site vacant single oxide, i.e., a new perovskite subgroup. Published by Copernicus Publications on behalf of the European mineralogical societies DMG, SEM, SIMP & SFMC. 96 Y. Xue et al.: Liguowuite, WO3, a new member of the A-site vacant perovskite type minerals

The perovskite supergroup minerals defined by Mitchell et al. (2017) refer to minerals of ABX 3 compounds with A = A site; B = B site; and X = O, F, and Cl but also OH and As. Their structures are composed of three-dimensional networks of tilted and/or distorted corner-sharing octahedra, and they have an aristotypic ABX 3 perovskite structure or its derivatives. The B-site cations can be randomly distributed and defined as single perovskite (ABX 3 ) or ordered and defined as double perovskite (A 2 BB X 6 ). The A and B sites can be partially or entirely vacant. The perovskite supergroup is divided into stoichiometric and non-stoichiometric perovskite groups, which can both be further classified into single or double perovskite. Subgroups and potential subgroups of non-stoichiometric perovskites involve (1) A-site vacant hydroxide or double hydroxide perovskites, (2) A-site vacant quadruple perovskites, (3) B-site vacant single perovskites, (4) B-site vacant inverse single perovskites, (5) B-site vacant double perovskites, (6) anion-deficient partly inverse B-site quadruple perovskites, and (7) anion-deficient perovskites.
The application of the hierarchical scheme for perovskite supergroup minerals proposed by Mitchell et al. (2017) results in the identification of a perovskite supergroup including about 17 subgroups and 47 mineral species. According to this hierarchical scheme, liguowuite belongs to the nonstoichiometric perovskite group and is the first reported example of A-site vacant single perovskite as an oxide mineral for this group, i.e., a new subgroup. Chesnokov et al. (1998) used to report "krasnogorite" (formula: WO 3 ; space group: Pmnb) occurring as pseudomorphs after hard alloy VK8 (a type of artificial alloy) on the plates of the cutting element of a drilling machine found in burned rocks. But it is invalid because current International Mineralogical Association (IMA) regulations do not allow such substances associated with human factors to be approved as valid mineral species. The liguowuite found in this study is naturally formed nano-monoclinic WO 3 .
The mineral was named liguowuite after Li Guowu (1964-) in recognition of his great contributions to new mineral research, including tewite and wumuite in this area. The new mineral and the mineral name have been approved by the International Mineralogical Association Commission on New Minerals, Nomenclature, and Classification (IMA-CNMNC) (IMA2020-097). Type material has been deposited at the China University of Geosciences (Beijing) Museum, Beijing, PR China, under registration number 21K005, and at the Ge-  (Fig. 1). The mineral occurs in Neoproterozoic Sinian semi-weathered biotite adamellite, and the rock mass's edge is near the contact zone with Permian basites. An independent sulfide-type tellurium deposit related to hydrothermal activity has been discovered in the Dashuigou sulfide ore in Shimian County, northern Pan-Xi region (Chen et al., 1994;Li et al., 2019). A quartz vein gold deposit 300 m south of the location for the liguowuite was found within a fault zone in Permian mafic rocks (gabbro). Although the liguowuite was found in the Proterozoic monzonitic rocks, the mineral formation process may be related to this nearby pyrite quartz vein-type gold mineralization in the younger basic rocks. The hightemperature fluids of the gold mineralization are rich in W, Te, and Au. The minerals crystallized and filled the fissures in the monzonitic rocks.

Occurrence and physical and optical properties
Liguowuite occurs as greenish yellow prismatic grains, and it is translucent with a greasy luster and a white streak (Fig. 2). As is shown in back-scattered electron (BSE) images (Fig. 2), liguowuite exhibits a triclinic appearance and pseudomorphism (0.05 to 0.1 mm in diameter). It is composed of nanoparticles with many cracks and nanovoids. The nanoparticle size varies from 100 to 200 nm. It is brittle with uneven fractures. No cleavage or parting was observed. This mineral has a Mohs hardness of about 3-4 and a calculated density of 7.22 g cm −3 based on the empirical formula and unit cell volume refined from the X-ray powder diffraction data. An average refraction index of 2.24 was calculated based on the Gladstone-Dale relationship and its composition (Mandarino, 1981). The sample is non-fluorescent.

Electron microprobe analysis (EMPA)
The composition of the liguowuite was determined via wavelength-dispersive spectroscopy at the Beijing Research Institute of Uranium Geology (BRIUG) using a JEOL JXA-8100 electron microprobe, with an accelerating voltage of 20 kV, a beam current of 10 nA, and a 2 µm beam diameter. The standards analyzed included albite for Na, Ca, and Al; scheelite for W; microcline for K; and Sb 2 Te 3 for Te.

Infrared spectra
The infrared (IR) spectrum of liguowuite ( Fig. 3) was acquired with the polished face of an aggregate grain using a Bruker HYPERION 1000 FTIR microscope operated in reflection mode. The spectrum data were processed using the OPUS software (Bruker Optics, 2019) during a 32-cycle scan at a resolution of 4 cm −1 . The samples were kept at 110 • C for 2 h in a drying oven before the test to avoid the effect of adsorbed water on the test results.

Raman spectra
The Raman spectrum (Fig. 4) of the liguowuite was obtained using a RENISHAW in a Via-Reflex spectrometer, with a laser excitation wavelength of 532 nm. The spectrum in the 100-3200 cm −1 region was obtained using a collection time of 10.00 s with the polished grain described above.

Powder X-ray diffraction
As is shown in Fig. 2c, the liguowuite crystal is composed of nanoparticles less than 200 nm in diameter, so it is difficult to obtain single-crystal X-ray diffraction data (Fig. 5). The crystal structure was refined using the Rietveld refinement method and X-ray powder diffraction data.
Owing to the lack of samples, the X-ray powder diffraction data were collected twice using single-crystal diffrac-  tometers. The first study involved the use of a Rigaku Oxford diffraction XtaLAB PRO-007HF rotating anode microfocus X-ray source (50 kV, 24 mA, 1.2 kW, Mo Kα, and exposure time of 500 s) with a hybrid pixel array detector and a singlecrystal diffractometer. The second study adopted a singlecrystal diffractometer with a 2D detector system (PHOTON III CPAD detector, Bruker D8 VENTURE) equipped with a kappa geometry-based goniometer 2D detector and the XRD 2D scan software APEX3 (Francart et al., 2008), with a 0.1 × 0.1 × 0.1 mm grain. A Cu Incoatec Microfocus Source Iµs generated the X-ray beam (Cu Kα, λ = 1.5418 Å). Two 2D diffraction patterns were collected using the detector at positions 2θ = −15 and −30 • , with an exposure time of 120 s (Phi 360 • ).

Transmission electron microscope (TEM)
The transmission electron microscopy (TEM) observations were performed using an FEI Talos F200S scanning and transmission electron microscope at a 200 kV accelerating voltage, equipped with an X-ray energy-dispersive detector at the Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, China. The specimen was prepared by adding crushed powder to ethanol and ultrasonically dispersing the powder for 10 min. A droplet of the resultant dispersion was deposited on a carbon-coated copper microgrid and was naturally dried at room temperature. Highresolution transmission electron microscope (HRTEM) images and selected area electron diffraction (SAED) patterns were obtained via TEM. Compositional mapping scanning of nanocrystallites of liguowuite was conducted using energydispersive spectroscopy (EDS) under the following conditions: a 200 kV accelerating voltage, a 1 nA beam current, and a beam size of ∼ 5 nm in STEM mode.

Chemical composition
The results of electron microprobe analyses of 15 spots on 4 grains are summarized in Table 1. The total amount of the electron microprobe analysis varies within a certain range (

Raman spectra
The Raman spectrum of liguowuite is shown in Fig. 4, and it is quite consistent with the spectrum of synthetic WO 3 in the KnowItAll database. The band at 134 cm −1 represents the lattice mode. The 272 and 327 cm −1 bands could be assigned to δ(O-W-O). The bands at 716 and 806 cm −1 could be assigned to ν(O-W-O) (Daniel et al., 1987).
The phase identification was performed using the Searchmatch software (Oxford Cryosystems Ltd., 1999), and the X-ray diffraction pattern of liguowuite corresponds to that of synthetic monoclinic WO 3 (ICSD 16080, P 2 1 /n (no. 14)) ( Fig. 6). Based on the XRD pattern, 44 diffraction peaks were assigned to liguowuite. The index process was conducted using the CheckCell software (Laugier and Bochu, 2000), and all 44 of the diffraction peaks matched were successfully indexed. The unit cell parameters refined using the powder data are as follows: a = 7.32582 (18)    Rietveld powder structure refinement was conducted using the GSAS (General Structure Analysis System) software (Larson and Von Dreele, 1994) and crystal structure model data from ICSD 16080. The reliability factors (R factors) were R wp = 0.0604 and R p = 0.0454, with χ 2 = 1.707. The fitting results of the Rietveld refinement in space group P 2 1 /n are shown in Fig. 7. The atom coordinates and selected geometric parameters are listed in Tables 3 and 4. The bond-valence sums (BVSs) were calculated using the interatomic distances following the procedure of Brown (1977) and using the parameters of Hong et al. (2004). The BVSs for the W1 and W2 positions are 6. 033 and 6.195 valence units (v.u.), and those for the O1, O2, O3, O4, O5,  (Table 5), and the results meet the charge balance requirement.

Transmission electron microscope (TEM)
The nanocrystallites of the liguowuite were analyzed using transmission electron microscopy combined with energydispersive spectroscopy (EDS) to confirm their compositions (Fig. 8). The EDS element maps reveal that the W, O, Te, Na, and Ca are evenly distributed throughout the particle (Fig. 8). These nanocrystallites were further characterized using TEM and selected area electron diffraction (SAED) (Fig. 9). Figure 10 shows electron diffraction patterns of the [010] and [10-1] zone axes of liguowuite. Using space group P 2 1 /n (no. 14) and the monoclinic cell parameters, all of the intense reflections in the directions of the [010] and [10-1] zone axes were successfully indexed and are consistent with the electron diffraction simulation. Most of the reflections accord with the systematic absence condition of glide plane n (h + l = 2n (k = 0)). The presence of several weak reflections with h + l = 2n in the SAED pattern and the absence of these types of reflections in the PXRD pattern (Fig. 6) indicate short-range ordering in the liguowuite structure, but generally the structure is in agreement with the P 2 1 /n model. Based on the indexed data, d(200) = 0.37126 nm, d(020) = 0.37586 nm, and d(002) = 0.38682 nm were obtained, so the calculated axis lengths based on the electron diffraction data are a = 0.74252 nm, b = 0.75174 nm, and c = 0.77365 nm, which are close to those obtained from the powder crystal refinement. The lattice fringes of the liguowuite with spacings of 0.3773 and 0.4375 nm, which correspond to the {020} and {111} planes, respectively, were observed using high-resolution TEM (Fig. 9b).

Crystal structure characteristics
A schematic projection view of the liguowuite crystal structure is shown in Fig. 11. The structure is composed of cornersharing distorted and tilted [WO 6 ] octahedra to form a threedimensional network containing large l2-fold coordinated cavities. The W atoms in [WO 6 ] octahedra are off-center and form six W-O bonds ranging from 1.7 to 2.2 Å with the surrounding oxygen atoms. The structure is derived from the perovskite-or ReO 3 -type structures (Hyde and Andersson, 1989). Based on the model reported in the ICSD 16080, our study confirmed that liguowuite is characterized by (1) tilting and distortion of the corner-sharing BX 6 octahedra, (2) disordering of the B-site cations, and (3) the formation of A-site vacancies. According to the hierarchical scheme, liguowuite is a member of the perovskite supergroup minerals, in the form of the first example of an A-cation-free single perovskite as an oxide mineral, i.e., a new subgroup of the nonstoichiometric perovskite group. A revised version of the hierarchical categories of the non-stoichiometric perovskite subgroup minerals is provided in Fig. 12 based on the original version of Mitchell et al. (2017).

[WO 6 ] octahedra framework of WO 3
Although liguowuite was discovered as a rare new mineral, artificial WO 3 is a common material with a variety of structural symmetries. For comparison, comparable synthetic phases are listed in Table 6. WO 3 can be regarded as a [WO 6 ] octahedra framework joined by corners and the ba-   Fig. 10a and b, respectively. (b) The HRTEM image of the right particle in Fig. 9a, with lattice fringe spacings of 0.3773 and 0.4375 nm corresponding to the {020} and {111} planes, respectively. sic structure of tungsten bronze compounds. By comparing the crystal structure characteristics of synthetic WO 3 materials, the [WO 6 ] framework commonly forms trigonal, square, rhombic, irregular pentagon, or hexagonal tunnels. The structures are mainly pyrochlore-type, perovskite-type, and typical tungsten-bronze-type, and all can be viewed as being made up of a slab structure.
From the projection onto (001) of the hexagonal tungsten bronze (HTB) (Fig. 13a), tetragonal tungsten bronze (TTB) (Fig. 13b), and orthorhombic tungsten bronze (OTB) (Fig. 13c), 1D tunnels including trigonal + hexagonal tunnels, trigonal + square + irregular pentagon tunnels, and trigonal + hexagonal tunnels can be observed running along the c axis, respectively. The tungsten bronze slab structure consists of [WO 6 ] octahedra layers with a hexagonal, tetragonal, or orthorhombic tungsten bronze topology and a thickness of 3.7-3.9 Å. These structural slabs connect to each other directly as they do in the perovskite structure, whereas only square or rhombic tunnels can be observed on (100), (010), and (001) in the perovskite structure (Fig. 13d).
The cubic WO 3 phase has a pyrochlore-type structure with empty 3D tunnels. The structure can be described as distorted (001) layers of hexagonal WO 3 linked along the [111] direction, and 3D interconnected tunnels are formed (Fig. 13e). The pyrochlore slab is composed of two types of trigonal layers, with a thickness of about 6 Å.
If the 6 Å wide pyrochlore slabs are indicated by Py and the 3.7-3.9 Å wide tungsten bronze/perovskite slabs by TB/Per, then the translational repeat of the pyrochlore structure is < Py >, tungsten bronze is < TB >, and perovskite is < Per >. In these three cases, the slab framework is composed of corner-sharing [WO 6 ] octahedra, so the WO 3 stoichiometry of the framework is consistent.
Tungsten bronze specifically refers to a non-stoichiometric compound with a general formula of A x WO 3 (0<x<1). However, as more and more minerals with such a chemical formula are found, the tungsten bronze structure is not an accurate concept from a mineralogical point of view. Minerals with a [WO 6 ] octahedra corner-sharing framework should be divided into perovskite-type structure, such as liguowuite;  pyrochlore-type structure, such as hydrokenoelsmoreite; or tungsten bronze structure, such as wumuite.
The liguowuite found in this study is naturally formed nano-monoclinic WO 3 . From a mineralogical viewpoint, liguowuite was found in the same sample as scheelite, tellurite, tewite ((K 1.5 0.5 ) 2 (Te 4+ 1.25 W 0.25 0.5 ) 2 W 5 O 19 ), and wumuite (KAl 0.33 W 2.67 O 9 ), which also contain K, Ca, W, and Te, indicating that the formation of these three new minerals may have been related to the same geological event. The trace amounts of K, Na, Ca, and Te in the liguowuite also convincingly indicate its natural origin. Considering the presence of scheelite, it can be reasonably speculated that in the natural metallogenic environment, the WO 2− 4 groups reacted with an acidic hydrothermal solution to generate tungstic acid and the excess WO 2− 4 groups reacting with Ca 2+ ions to generate scheelite. Then, the tungstate acid was thermally decomposed into liguowuite and water.
As is shown in the BSE images (Fig. 2), the liguowuite exhibits triclinic pseudomorphism composed of nanoparticles. This is very similar to the process in which stokesite (CaSnSi 3 O 9 q 2H 2 O) crystals are heated to dehydrate and decompose into nano-sized mineral particles of cassiterite, malayaite, and cristobalite, but the original crystal morphologies of stokesite are preserved (Xue et al., 2016). Li (2013) studied the phase changes in the tungsten oxide and its hy- Figure 13. [WO 6 ] octahedra framework for tungsten-bronze-type, perovskite-type, and pyrochlore-type structures. (a) Hexagonal tungsten bronze (HTB), (b) tetragonal tungsten bronze (TTB), (c) orthorhombic tungsten bronze (OTB), (d) perovskite-type structure (Per), (e) pyrochlore-type structure (Py). Pyrochlore slab is denoted by Py, while TB and perovskite slabs are indicated by TB and Per, respectively. A and Y sites are omitted for clarity. drate products prepared through hydrothermal reactions under heated conditions (>140 • C) and found that the structure of the tungsten oxide hydrate has a tendency to gradually lose H 2 O molecules, and the mode of the water loss varies at different reaction temperatures. At low temperatures, the products tend to lose part of the H 2 O molecules and undergo a phase transformation (i.e., WO 3 q H 2 O → WO 3 q 0.33H 2 O). When the temperature increases, the H 2 O molecules in the crystal structure totally escape, leaving a new WO 3 structure (i.e., m-WO 3 ).
During the mineralogical evolution, minerals can transform into another mineral and inherit its crystal structure (Krivovichev et al., 2013), such as the transformational series observed for the "zirsinalite Na 6 CaZrSi 6 O 18 -lovozerite Na 3 CaZrSi 6 O 15 (OH) 3 " (Gerasimovskii, 1939;Khomyakov, 1977;Yamnova, et al., 2001) and "parakeldyshite Na 2 ZrSi 2 O 7 -keldyshite Na 2 ZrSi 2 O 7 " (Khomyakov, 1977;Kabanova et al., 2020). It seems that liguowuite forms a similar series with H 2 O-bearing WO 3 phases. Three hydrous tungsten oxide minerals have been described (Table 7) and may be related to the genesis of liguowuite. Therefore, it is speculated that the dehydration of a mineral containing W and volatiles leads to structural contraction and phase transformation, resulting in the preservation of WO 3 nanoparticles and changes in the crystal structure. In conclusion, the liguowuite found in this study may have a natural thermal transformation origin, indicating that this W-containing mineral may be transformed via thermal activity after crystallization.
To explore the formation mechanism of the W-bearing minerals in this area, we also conducted a series of synthetic experiments. Wumuite was obtained from pure m-WO 3 and natural potassium feldspar (orthoclase) at 700 • C (Xue et al., 2020), and tewite was successfully synthesized by mixing synthetic wumuite with m-WO 3 and TeO 2 , followed by heating at 650 • C for 10 h (Li et al., 2019). These two reactions revealed that the wumuite and tewite probably crystallized from ore fluids at relatively high temperatures.
In addition, tellurite (TeO 2 ) crystals were also found among the associated minerals. The experimental results demonstrate that both TeO 2 and H 2 WO 4 are volatile components at high temperatures. The experiments indicate that W can be transported in the form of K 2 WO 2 F 4 in acidic hydrothermal solutions and in the form of H 2 WO 4 at high temperatures regardless of the pH of the solution (Zhao et al., 1977).
The hydrothermal-activity stage related to volcanism or magmatism is the most important enrichment and mineralization stage of tellurium. This series of new Te-and W-bearing minerals may have been formed by a hightemperature hydrothermal fluids rich in Te and W interspersed in the quartz monzonite in the early stage of the gold mineralization. The liguowuite, wumuite, and tewite may have been formed in different stages of the hydrothermal fluid, were controlled by factors such as temperature and pH, and widely underwent metasomatic reactions.
Data availability. Crystallographic data for liguowuite (CIF) are available in the Supplement.
Author contributions. YX found the mineral. YX and NS made XRD analyses, determined physical and optical properties, and obtained spectroscopic data. HH and YY made TEM analyses. AC made Rietveld refinements. YX and NS prepared the manuscript with contributions from all co-authors.
Competing interests. The contact author has declared that neither they nor their co-authors have any competing interests.
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