Oral cancer survival rates have seen little improvement over the past few decades. This is mainly due to late detection and a lack of reliable markers to predict disease progression in oral potentially malignant disorders (OPMDs). There is a need for highly specific and sensitive screening tools to enable early detection of malignant transformation. Biochemical alterations to tissues occur as an early response to pathological processes; manifesting as modifications to molecular structure, concentration or conformation. Raman spectroscopy is a powerful analytical technique that can probe these biochemical changes and can be exploited for the generation of novel disease-specific biomarkers. Therefore, Raman spectroscopy has the potential as an adjunct tool that can assist in the early diagnosis of oral cancer and the detection of disease progression in OPMDs. This review describes the use of Raman spectroscopy for the diagnosis of oral cancer and OPMDs based on ex vivo and liquid biopsies as well as in vivo applications that show the potential of this powerful tool to progress from benchtop to chairside.

Fluor-rossmanite, ideally □(Al2Li)Al6(Si6O18)(BO3)3(OH)3F, is a new mineral of the tourmaline supergroup, found at the Krutaya pegmatite, Malkhan pegmatite field, Zabaykalskiy Krai, Western Siberia, Russia. It forms an intermediate zone up to 3 mm thick in a chemically heterogeneous, concentrically zoned, polychrome tourmaline crystal 3 × 2 cm in size. The new mineral is light pink, transparent with a white streak and a vitreous lustre. It is brittle, with conchoidal fracture. The Mohs hardness is 7. The Dmeas = 3.07(2) g cm–3 and Dcalc = 3.071 g cm–3. Optically, fluor-rossmanite is non-pleochroic, uniaxial (–), ω = 1.647(2) and ɛ = 1.628(2) (589 nm). The empirical formula calculated on the basis of 31 anions (O+OH+F) is: X(□0.46Na0.32Ca0.20Pb0.02)Σ1.00 Y(Al1.84Li1.05Mn0.05Fe2+0.02Ti0.02Cr0.01)Σ2.99 ZAl6.00 T(Si5.79Al0.21)Σ6.00B2.99O27 V(OH)3 W[F0.44(OH)0.20O0.36]Σ1.00. Fluor-rossmanite is trigonal, R3m; the unit-cell parameters are: a = 15.7951(3), c = 7.08646(17) Å, V = 1531.11(7) Å3 and Z = 3. The crystal structure is refined from single-crystal X-ray diffraction data [R = 0.0211 for 1178 unique reflections with I > 2σ(I)]. The new mineral is a ‘fluor-’ species belonging to the X-vacant group of the tourmaline supergroup. The closest end-member compositions of valid tourmaline species are those of rossmanite and fluor-elbaite, to which fluor-rossmanite is related by the substitutions WF– ↔ WOH– and X2□ + YAl3+ ↔ X2Na+ + YLi+, respectively.

Ermeloite is a new aluminium phosphate mineral from Galicia, Spain, in the northwest of the Iberian Peninsula. It is the third formally recognised mineral discovered in Galicia since morenosite and cervantite in the 19th Century. The name and symbol (Erm) were approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association (IMA2021–017a) in recognition of the geographical location where it was found. The mineral occurs as a light blue to white fine aggregate over quartz and microcline associated with wardite. Crystals of ~0.04 mm are transparent and have a waxy lustre. The simplified empirical formula determined using electron microprobe analysis is Al1.02P0.95F0.06O3.88⋅1.06 H2O, which is near to the ideal formula Al(PO4)⋅H2O. The mineral is an alteration product within a phosphate pegmatite. Ermeloite is the second phosphate isostructural with the sulfates of the kieserite group. Single-crystal X-ray diffraction showed that ermeloite crystallises in the monoclinic C2/c space group with cell parameters a = 6.5371(4) Å, b = 7.5670(5) Å, c = 7.1146(5) Å, β = 115.335(2)°, V = 318.08(4) Å3 and Z = 4 at room temperature. Comparative analysis of the crystallographic data, with isostructural phosphates, revealed an interesting behaviour for these compounds.

The new eudialyte-group mineral amableite-(Ce), ideally Na15[(Ce1.5Na1.5)Mn3]Mn2Zr3□Si[Si24O69(OH)3](OH)2⋅H2O, was discovered in a peralkaline pegmatite at Saint-Amable Sill, Montérégie, Québec, Canada. The associated minerals are albite, microcline, aegirine, serandite, natrolite, yofortierite, and an unidentified titanosilicate forming minute grains. Amableite-(Ce) occurs as yellow equant or thick tabular crystals up to 2 mm across. The observed crystal forms are {0001}; the subordinate forms are {11$\bar{2}$0}, {10$\bar{1}$1}, and {10$\bar{1}$0}. Amableite-(Ce) is brittle, with a Mohs hardness of 5. D(meas) = 2.89(1), D(calc) = 2.899 g⋅cm–3. Amableite-(Ce) is optically anomalously biaxial (+) with α ≈ β = 1.603(2) and γ = 1.608(2). The chemical composition is (wt.%, electron microprobe, H2O measured by means of a modified Penfield method): Na2O 14.20, K2O 0.41, CaO 1.89, MnO 8.25, Fe2O3 2.40, La2O3 3.10, Ce2O3 4.19, Pr2O3 0.16, Nd2O3 0.59, SiO2 49.41, ZrO2 11.17, HfO2 0.24, TiO2 0.68, Nb2О5 1.54, Cl 0.26, H2O 1.70, –O≡Cl –0.06, total 100.13. The crystal structure was determined using single-crystal X-ray diffraction data and refined to R1 = 0.0423. Amableite-(Ce) is trigonal, space group R3, with a = 14.1340(3) Å, c = 30.3780(11) Å and V = 5255.6(3) Å3. The crystal-chemical formula is (Na12.93K0.27Ce0.06)Σ13.26[(Mn2.49Ce0.30Ca0.21)Σ3.00(Ce1.14Na1.04Ca0.82)Σ3.00](Mn1.05Fe0.90□1.05)Σ3.00(Zr2.85Ti0.12Hf0.03)Σ3.00(□0.40Nb0.36Si0.24)Σ1.00(Si0.88□0.12)Σ1.00[Si24(O70.44(OH)1.56)Σ72.00][(OH)2.20(H2O)1.27]Σ3.47Cl0.22 (Z = 3). Infrared and Raman spectra are given. The strongest lines of the powder X-ray diffraction pattern [d, Å (I, %)(hkl)] are: 11.34 (51)(101), 7.06 (76)(110), 4.312 (63)(205), 3.783 (38)(033), 3.538 (43)(027, 220), 2.963 (84)($\bar{3}$45), 2.837 (100)(404). The mineral is named after the discovery locality.

The vibrational modes of clay minerals in aqueous suspension are uniquely accessible to Raman spectroscopy, but this potentially powerful approach has not been applied heretofore to study clays in aqueous samples. In this paper, Raman spectra in the 100- to 4000-cm−1 region were obtained for kaolinite in aqueous suspension and in air-dry samples. Contact with water perturbed the low-wavenumber Raman spectrum (100 to 1000 cm−1) significantly with respect to relative band intensities and resulted in a pH dependence of the integrated intensity in the OH-stretching region. Comparison of the Raman and infrared (IR) spectra of air-dry kaolinite samples confirmed five Raman-active OH-stretching modes at 3621, 3652, 3668, 3688, and 3696 cm−1, in contrast to four IR-active modes at 3621, 3652, 3668, and 3695 cm−1. The Raman spectra of two kaolinites of different origin showed differences in band positions and intensities. These results suggest that Raman spectroscopy may provide a useful method to study clay mineral-water interactions, colloidal behavior in clay suspensions, and variations in clay mineral structure.

The adsorption and reaction of thiophene and methylthiophenes in the interlayer of Cu2+- and Fe3+-montmorillonites were investigated by resonance Raman spectroscopy. Thiophene and 3-methylthiophene polymerized to form cations of polythiophene and polymethylthiophene respectively, which were characterized by absorption bands in the near-infrared region. These polymer cations formed in the interlayer were reduced to their neutral polymers if the clay-polymer complexes were in contact with water, and the formation of their neutral polymers was clearly demonstrated by their resonance Raman spectra. 2,5-Dimethylthiophene in which polymerization was hindered by methyl substitution at the 2 and 5 positions, was oxidized to 2,5-dimethylthiophene cation in the interlayer.

Raman and Fourier-transformed infrared spectra of natural trioctahedral chlorites of polytype IIb were obtained for a series of samples characterized by distinct Fe/(Fe + Mg) and Si/Al ratios ranging, respectively, from 0.04 to 0.94 and from 5.18 to 1.86. All samples were characterized by X-ray powder diffraction, and quantitative electron microprobe analysis. In the 3683-3610-cm−1 spectral range, the wave number of the OH-stretching band from the 2:1 layer (band I) decreased with an increase of iron content at constant Al(IV) content. The more intense bands II and III at about 3600 cm−1 and 3500 cm−1, were assigned to hydroxyl groups involved in hydrogen bonds: (SiSi)O... HO, with the hydrogen bonds being roughly perpendicular to the basal plane, and (SiAl)O... HO, respectively. At higher tetrahedral Al and octahedral Fe contents, spectra exhibited OH-bands II and III, respectively, at a lower frequency. Band III intensity increased and band II was enlarged for chlorites displaying higher Al(IV) contents.

In the 1300–1350-cm−1 spectral range, most infrared spectra displayed intense bands at 1090, 1050, 990, and 960 cm−1, which were assigned to T-O stretching of symmetry species Al and E1. The second type of bands observed both in Raman and infrared spectra were at about 650–800 cm−1; they were assigned to OH vibrations and were strongly dependent on the composition of the interlayer octahedral sheet, especially on the Fe content.

Raman and Fourier-transform-infrared (FTIR) spectroscopic methods and X-ray powder diffraction (XRD) techniques have been used to study the influence of hydrazine on the vibrational modes of kaolinite. Strong vibrational perturbations of the OH-stretching and -deformation bands were observed in the Raman and FTIR spectra on intercalation. The intensities of the Raman- and IR-active OH-stretching bands decreased significantly upon intercalation; the intensities of the Raman bands were reduced to a greater extent than the IR bands. The deformation bands were also strongly perturbed by the presence of hydrazine in the interlamellar region. Upon evacuation of the intercalate, two new bands at 3628 and 912 cm−1 were noted, indicating the presence of a different structural conformation of the complex under vacuum. Similar results were obtained using XRD, on evacuation of the kaolinite-hy-drazine (KH) complex the d(001) value decreased from 10.4 to 9.6 Å. Partial collapse of the intercalate from 10.4 to 9.6 Å was probably due to keying of the -NH2 moiety of hydrazine into the siloxane ditrigonal cavity, as indicated by a blue-shift of the inner-OH band from 3620 to 3628 cm-1. Structural OH vibrational modes may therefore be useful probes of amine interactions with clay mineral surfaces.

The Raman spectra of a tubular halloysite originating from Matauri Bay, New Zealand, have been obtained using a Renishaw 1000 Raman microscope system. The Raman microprobe enables the Raman spectra of crystals as small as 0.8 μm diameter to be obtained over the complete wavelength range and allows spectral variations along the different crystal axes to be studied. Three bands in the hydroxyl stretching region were observed at 3616.5, 3623.4 and 3629.7 cm-1 and are attributed to the inner hydroxyls of the shared lower plane of the octahedral sheet of the halloysite. Two bands at 3698.2 and 3705 cm−1 were obtained for the outer hydroxyls of the unshared outer octahedral plane. The relative intensity of the 3629.7 cm−1 band varied according to the tube orientation. Lattice vibrations of the halloysite were also found to be orientation-dependent.

The high-temperature behaviour of a feldspar-group mineral, filatovite (with the simplified formula: K(Al,Zn)2(As,Si)2O8), in which the Al:As:Si ratio is close to 2:1:1), was studied by in situ high-temperature single-crystal X-ray diffraction and in situ high-temperature (hot stage) Raman spectroscopy up to 600°C. In the temperature range studied (25–600°С) filatovite does not undergo any phase transition, whereas at 800°C it decomposes to X-ray amorphous phase(s). The evolution of 12 main Raman bands was traced during heating, which indicates a gradual change in the crystal structure. The thermal expansion coefficients of filatovite demonstrate a sharply anisotropic character of thermal expansion: the maximal expansion is close to the a axis (α11 = 17.7(1) × 10–6 °C–1), whereas along the b and c axes the thermal expansion coefficients are close to zero. Such behaviour is typical for minerals with a similar crystal structure topology; it indicates the dominant role of structure geometry in the thermal behaviour of the mineral.

The new columbite-supergroup mineral dmitryvarlamovite, ideally Ti2(Fe3+Nb)O8, was discovered in weathered alkaline metasomatic assemblages formed after late Riphaean sedimentary carbonate rocks of the Verkhne-Shchugorskoe deposit, Middle Timan Mts., Russia. The associated minerals are columbite-(Fe), pyrochlore-group minerals, monazite-(Ce), xenotime-(Y), baryte, pyrite, drugmanite and plumbogummite. Dmitryvarlamovite occurs as isolated anhedral equant grains up to 0.5 mm across. The colour of dmitryvarlamovite is black, the streak is black and the lustre is submetallic. The new mineral is brittle, with the mean VHN hardness of 753 kg mm–2 corresponding to the Mohs’ hardness of 6. No cleavage is observed. The fracture is conchoidal. The calculated density is 4.891 g⋅cm–3. In reflected light, dmitryvarlamovite is light grey; no pleochroism is observed. The reflectance values (Rmin, % / Rmax, % / λ, nm) are: 19.8/20.3/470, 18.3/18.9/546, 17.8/18.5/589 and 17.3/17.8/650. The chemical composition is (electron microprobe data, with iron divided into Fe2O3 and FeO based on the charge balance, wt.%): MnO 0.11, FeO 1.51, V2O3 0.89, Cr2O3 0.28, Fe2O3 19.26, TiO2 37.72, Nb2O5 40.08, total 99.85. The IR and Raman spectra indicate the absence of H-, C- and N-bearing groups. The empirical formula is (Fe2+0.08V3+0.05Cr3+0.01Fe3+0.92Ti1.79Nb1.15)Σ4.00O8. The crystal structure was determined using single-crystal X-ray diffraction data and refined to R = 0.048. Dmitryvarlamovite is orthorhombic, space group P21212, a = 4.9825(6), b = 4.6268(4), c = 5.5952(6) Å and V = 5.5952(6) Å3 (Z = 1). The structure is related to those of wolframite-group minerals but differs in the scheme of cation ordering. The crystal-chemical formula derived based on the structural data is (Ti0.57Nb0.21Fe3+0.15Fe2+0.04V0.02Cr0.01)2(Nb0.36Ti0.33Fe3+0.31)2O8. The strongest lines of the powder X-ray diffraction pattern [d, Å (I, %) (hkl)] are: 3.58 (40) (011), 2.911 (100) (111), 2.809 (40) (002), 2.497 (38) (020), 2.447 (29) (103), 1.7363 (32) (103) and 1.7047 (29) (220). Dmitryvarlamovite is named after Dmitry Anatol'evich Varlamov (b. 1965).

The new mineral naalasite (IMA2023–027), NaAl(AsO3OH)2⋅H2O, was found at the Torrecillas mine, Iquique Province, Chile, where it is a secondary alteration phase associated with anhydrite, juansilvaite, magnesiokoritnigite and a lavendulan-like phase. Naalasite occurs in tightly intergrown aggregates and druses of equant crystals. Crystals are light to medium pink and transparent, with vitreous lustre and white streak. The Mohs hardness is ~3½. The density is 3.19(2) g⋅cm–3. Optically, naalasite is uniaxial (+), with ω = 1.630(3) and ɛ = 1.660(3) (white light). The empirical formula (based on 9 O apfu) is Na0.92Al0.61Fe3+0.39As2O9H4.07. Naalasite is trigonal, space group R32, with cell parameters: a = 8.494(4), c = 26.430(13) Å, V = 1651.5(4) Å3 and Z = 9. The structure, refined to R1 = 3.78% for 641 I > 2σI reflections, is based on a loose 3D framework of alternating AsO3OH tetrahedra and AlO6 octahedra. The structure is topologically equivalent to that of nafeasite and can be regarded as its Al analogue, even though nafeasite is monoclinic with space group C2.

The interaction of the water-soluble 5,10,15,20-tetrakis(l -methyl-4-pyridyl)-21H,23H-porphine (TMPyP) with different 2:1 phyllosilicates was examined by Raman and UV-visible spectroscopies. The clay samples were saturated with the tetracationic porphyrin and isolated from the aqueous suspension. A red shift of the Soret band was observed for all the clay-TMPyP systems in the order vermiculite < Laponite < mica-smectite (Syn-1) < montmorillonite (SWy-2). Furthermore, three components were observed for the Soret band (at ~425, 455 and 488 nm). Raman spectra of the isolated solids excited at 457.9 nm, 488.0 nm and 514.5 nm suggest the occurrence of porphyrin protonation, nonplanar distortion and rotation of the meso substituent. Based on the vibrational data, an acidity scale was proposed for the clays: vermiculite < Laponite < SWy-2 < Syn-1. The relative contribution of the protonated spectra is larger at 457.9 nm than at 488.0 nm, suggesting that the peak at 455 nm corresponds to the protonated species. In Laponite, the relative intensity of the meso substituent band at ~1635 cm-1 indicates that the dihedral angle formed between the porphyrin and the methyl-pyridyl rings decreased in the non-protonated porphyrin as a consequence of intercalation. Raman data are thus consistent with the presence of at least two porphyrin species in resonance at 457.9 nm: the protonated and a more planar non-protonated porphyrin. At 488.0 nm the number of enhanced modes increases suggesting a decrease in the porphyrin symmetry. This allows assignment of the absorption band centered at 488 nm to a non-planar porphyrin conformation.

The Raman spectra of many kaolins are dominated by bands from ancillary anatase. Fired samples of a commercial anatase-bearing kaolin from the Jari River deposit in Brazil showed significant variations of Raman spectra as a function of the firing temperature. The spectra showed the full range of anatase bands up to a firing temperature of 900°C. From 950°C the background increased significantly, leading to an unfavorable signal/noise ratio that allowed observation of only the most intense (Eg) band at ~144 cm−1. X-ray diffraction (XRD), however, confirmed that this band, which persists up to 1200°C, results from anatase. Two factors may be responsible for the high thermal stability of anatase in this sample: its relatively large particle size of ~120 nm and possible reactions with Si and Al that become liberated during kaolinite breakdown. When evaluated with circumspection, Raman and XRD data on anatase can serve as ‘thermometers’ to elucidate the thermal history of fired anatase-bearing kaolins and other anatase-bearing clays.

Oxy-dravite, ideally Na(Al2Mg)(Al5Mg)(Si6O18)(BO3)3(OH)3(O), was found in a composition near its ideal end-member at the Beluga occurrence, Nunavut territory, Canada. It occurs in retrograde albite–muscovite–corundum–calcite domains in a calc-silicate rock. This uncommon oxy-dravite occurs as dark brown, equant to short-prismatic, idiomorphic crystals with vitreous lustre and up to ca. 4 × 3 cm in size. The oxy-dravite is optically uniaxial (–), with ω = 1.6453(5) and ɛ = 1.6074(18); its calculated density is 3.069 g.cm–3 with a compatibility index of 0.016. The Beluga oxy-dravite has trigonal symmetry, space group R3m with a = 15.9121(2) Å, c = 7.1788(10) Å, V = 1574.12(5) Å3 and Z = 3. The crystal structure was refined to R1 = 1.45 using 1613 unique reflections. The empirical crystal-chemical formula is X(Na0.88Ca0.08□0.03K0.01)Y(Al1.49Mg1.31Fe0.15Ti0.04Zn0.01)Z(Al5.42Mg0.58)T(Si5.84Al0.16O18)B(BO3)3V(OH2.95O0.05)W(O0.84OH0.01F0.15).

Oxy-dravite in nature commonly occurs in a solid solution with foitite, schorl and oxy-schorl. At the Beluga occurrence, its minor contents of Al, vacancy [□], and Ca are most likely compensated by (□Al)(NaR2+)–1 and (CaMg)(NaAl)–1 exchanges of the oxy-magnesio-foitite and magnesio-lucchesiite components. The Beluga occurrence of oxy-dravite is characterised by an Mg-rich environment related to a metamorphic overprint of the original sedimentary sequence. This sequence of marine dolomitic argillaceous marl was influenced by (B,Cl)-rich fluids, probably proximally-derived from mineral breakdown reactions in the calc-silicate during the retrograde stage of metamorphism. The locality is a rare example of a tourmaline + corundum assemblage.

The new mineral mazorite, ideally Ba3(PO4)2, a P-analogue of gurimite Ba3(VO4)2, was discovered in rankinite paralava hosted by the massive gehlenite-bearing pyrometamorphic rocks of the Hatrurim Complex in Israel. It has also recently been discovered in xenolith samples from the Bellerberg volcano in Germany. Holotype mazorite usually forms colourless plate-like crystals up to 70–100 μm in length but also occurs in small aggregates in association with other rare Ba-bearing minerals such as zadovite, celsian, hexacelsian, bennesherite, sanbornite, walstromite, fresnoite, gurimite, alforsite and barioferrite. The mineral is transparent, exhibits vitreous lustre and has a good cleavage on (001). Optically, mazorite is uniaxial (+), with ω = 1.760(3) and ɛ = 1.766(3) (λ = 589 nm). The empirical formula of the holotype mazorite calculated on 8O is (Ba2.69K0.22Na0.04Ca0.02Sr0.01)Σ2.98(P1.16V0.57S0.24Al0.04Si0.03)Σ2.04O8. Mazorite crystallises in space group R$\bar{3}$m, with unit-cell parameters a = 5.6617(5) Å, c = 21.1696(17) Å, V = 587.68(9) Å3 and Z = 3. Its crystal structure consists of BaO12, BaO10, and PO4 polyhedra, ordered along the c-axis in PO4–BaO10–BaO12–BaO10–PO4 columnar arrangement characteristic for palmierite-supergroup minerals. A tetrahedrally coordinated site is generally occupied by P5+ but can be partially substituted by V5+ and S6+. This substitution is shown in the Raman spectrum of mazorite, which reveals bands that can be assigned to the stretching and bending vibrations of (PO4)3–, (VO4)3– and (SO4)2– groups. The Raman spectra of mazorite from two localities (Hatrurim and Bellerberg) and spectra of minerals belonging to the mazorite Ba3(PO4)2 to gurimite Ba3(VO4)2 solid-solution series are presented. The gradual shift of the Raman bands, caused by cation substitutions, is well observed. The high V5+ → P5+ substitution is also observed for gurimite, for which the first X-ray structural data are also presented. Mazorite and other Ba-bearing minerals crystallised from a small portion of residual melt enriched in incompatible elements, such as Ba, V, P, U, S, Ti and Nb, at a temperature of ~1000°C.

Rewitzerite, K(H2O)Mn2(Al2Ti)(PO4)4[O(OH)](H2O)10⋅4H2O, is a new monoclinic member of the paulkerrite group, from the Hagendorf-Süd pegmatite, Oberpfalz, Bavaria, Germany. It was found in specimens of altered zwieselite, in association with rockbridgeite. Rewitzerite forms clusters of colourless elongated hexagonal-shaped prisms, up to 0.1 mm long. The crystals are flattened on {010} and elongated along [100], with forms {010}, {001}, {111} and {$\bar{1}$11}. The calculated density is 2.33 g⋅cm–3. Optically, rewitzerite crystals are biaxial (+), with α = 1.585(2), β = 1.586(2), γ = 1.615(2) (measured in white light) and 2V(meas) = 25(2)°. The empirical formula from electron microprobe analyses and structure refinement is A1[K0.77(H2O)0.23]A2[H2O] M1(Mn2+0.82Mg0.64Fe3+0.43□0.11)Σ2.00 M2+M3(Al1.51Ti4+1.06Fe3+0.43)Σ3.00(PO4)4 X[(OH)0.54F0.42O1.04]Σ2.00(H2O)10⋅4H2O, where □ = vacancy.

Rewitzerite has monoclinic symmetry with space group P21/c and unit-cell parameters a = 10.444(2) Å, b = 20.445(2) Å, c = 12.2690(10)Å, β = 90.17(3)°, V = 2619.8(6) Å3 and Z = 4. The crystal structure was refined using synchrotron single-crystal data to wRobs = 0.068 for 5894 reflections with I > 3σ(I). The crystal structure has the same topology as that for orthorhombic paulkerrite-group minerals but differs primarily in having an ordering of K+ and H2O molecules in different A sites, whereas they are disordered at a single A site in the orthorhombic members of the group.

A new occurrence of austinite, CaZnAsO4(OH), conichalcite, CaCuAsO4(OH), and zincolivenite, CuZnAsO4(OH), is described from the Tripi mine, Peloritani Mountains, Sicily, Italy. These species have been observed in euhedral crystals in vugs of a calcite vein and were characterised using single-crystal X-ray diffraction, electron microprobe analysis and micro-Raman spectroscopy. Austinite and conichalcite have isotypic relations, both crystallising in space group P212121. Unit-cell parameters of austinite are a = 7.4931(5), b = 9.0256(6), c = 5.9155(4) Å, V = 400.06(5) Å3; its crystal structure was refined on the basis of 1210 unique reflections with Fo > 4σ(Fo) and 77 least-square parameters to R1 = 0.0236. Conichalcite has unit-cell parameters a = 7.419(10), b = 9.111(11), c = 5.867(7) Å and V = 396.6(1.4) Å3; the diffraction quality of its available grains was not good enough to allow a high-quality structural refinement. Chemical formulae of austinite and conichalcite are Ca1.04(1)Zn0.86(4)Cu0.09(4)As0.98(2)P0.02(1)O4(OH)0.98 and Ca0.98(1)Fe2+0.02(4)Cu0.69(10)Zn0.30(6)As0.97(2)P0.03(1)O4(OH)0.98, respectively. The new chemical data on the austinite–conichalcite isotypic pair, coupled with previous analyses, supports a possible miscibility gap between the compositions (Zn0.25Cu0.75) and (Zn0.50Cu0.50). Zincolivenite has unit-cell parameters a = 8.4594(9), b = 8.5324(8), c = 5.9893(6) Å, V = 432.30(12) Å3 and space group Pnnm; its crystal structure was refined to R1 = 0.0230 for 523 unique reflections with Fo > 4σ(Fo) and 47 least-square parameters. Its chemical composition is Cu0.73(5)Zn1.25(5)As1.01(1)O4(OH)1.01. The refinement of the crystal structure supports the ordering of Cu and Zn in two different crystallographic sites. Micro-Raman spectra of austinite, conichalcite and zincolivenite are discussed, with a focus on the O–H stretching region where local Zn and Cu arrangements affect the position of Raman bands in zincolivenite. These arsenates probably play an environmental role in the Peloritani area, where the occurrence of high contents of some potentially toxic elements in soils and stream sediments has been reported.

Gismondine-Sr, recently discovered in the Hatrurim Complex in Israel, has been recognised in a xenolith sample from the Bellerberg volcano in Germany. The empirical crystal-chemical formula indicates elevated K content: (Sr1.74Ca1.05Ba0.09K1.56Na0.49)Σ4.93[Al7.98Si8.06O32]⋅9.62H2O. Additionally, Ba-rich gismondine and amicite have been found in the low-temperature mineral association of the pyrometamorphic rock from the Hatrurim Complex. The Raman spectra of the studied zeolites and the crystal structure of gismondine-Sr from the second occurrence are presented. A review of zeolites with GIS framework-type structure leads to the following conclusions: (1) garronite-Na and gobbinsite are equivalent and constitute a solid solution with garronite-Ca; (2) gismondine-Ca, -Sr, and amicite belong to one mineral series; (3) two zeolites series with different R-factors (defined as Si/(Si+Al+Fe)) can be distinguished within GIS topology: the garronite series (R > 0.6) including garronite-Ca and gobbinsite, with general formula (MyD0.5(x–y))[AlxSi(16–x)O32]⋅nH2O, where M and D refer to monovalent and divalent cations, respectively; and the gismondine series, including amicite, gismondine-Sr and gismondine-Ca, with R ≈ 0.5, and the general formula (MyD0.5(8–y))[Al8Si8O32]⋅nH2O. The Raman band between 475 cm–1 and 485 cm–1 is distinctive for the garronite series, whereas the band around 460 cm–1 is characteristic of the gismondine series. On the basis of these findings, a revision of GIS zeolites nomenclature is suggested.

The new mineral libbyite (IMA2022-091), (NH4)2(Na2□)[(UO2)2(SO4)3(H2O)]2⋅7H2O, was found in the Blue Lizard mine, San Juan County, Utah, USA, where it occurs as tightly intergrown aggregates of light green–yellow equant crystals in a secondary assemblage with bobcookite, coquimbite, halotrichite, metavoltine, rhomboclase, römerite, tamarugite, voltaite and zincorietveldite. The streak is very pale green yellow and the fluorescence is strong green under 405 nm ultraviolet light. Crystals are transparent with vitreous lustre. The tenacity is brittle, the Mohs hardness is ~2½, the fracture is curved. The mineral is soluble in H2O and has a calculated density of 3.465 g⋅cm–3. The mineral is optically uniaxial (–) with ω = 1.581(2) and ɛ = 1.540(2). Electron microprobe analyses provided (NH4)1.92K0.08Na2.00U4.00S6.00O41H18.00. Libbyite is tetragonal, P41212, a = 10.7037(11), c = 31.824(2) Å, V = 3646.0(8) Å3 and Z = 4. The structural unit is a uranyl–sulfate sheet that has the same topology as the sheets in several synthetic uranyl selenates.