The distribution and crystal-chemical characteristics of chlorite, corrensite, and mica in samples from a stratigraphic profile in the Cameros basin are controlled by changes in the sedimentary facies. The lacustrine marls and limestones from the base and the top of the profile contain quartz + calcite + illite ± dolomite ± chlorite ± albite ± paragonite ± Na, K-rich mica. Chlorite is rich in Mg, with Fe/(Fe + Mg) ratios ranging between 0.18–0.37. A formation mechanism involving reaction between Mg-rich carbonate and dioctahedral phyllosilicates is proposed for these Mg-rich chlorites, on the basis of the mutually exclusive relationship found between Mg-rich chlorite and dolomite, together with the relative increase in the proportion of calcite in samples containing chlorite.

The mudrocks from the middle part of the profile are composed of quartz + albite + illite + corrensite (with a mean coefficient of variability of 0.60%) ± chlorite. Corrensite and chlorite are richer in Fe2+ than those from the base or top of the profile, with mean Fe/(Fe + Mg) ratios of 0.51 and 0.56, respectively. Textural and compositional features suggest a formation mechanism for the corrensite, chlorite, and chlorite-mica crystals through replacement of detrital igneous biotite. Whether or not corrensite occurs with chlorite appears to be related to redox conditions. The presence of corrensite alone is apparently favored by oxidizing conditions, whereas the occurrence of corrensite + chlorite is related to more reducing conditions. Corrensite shows higher Si and Na + K + Ca contents, and slightly lower Fe/(Fe + Mg) ratios than chlorite. The presence of corrensite and the lack of random chlorite-smectite interlayering is discussed in terms of the fluid/rock ratio; the occurrence is related to the hydrothermal character of metamorphism in the Cameros basin.

Submicroscopic intergrowths of K biotite, Na biotite and intermediate Na-K biotite from a schist near Málaga (Betic Cordilleras, Spain) were discovered using high-resolution transmission electron microscopy and analytical electron microscopy. The sample was also studied with X-ray diffraction, electron microprobe analysis, and scanning electron microscopy. Scanning electron microscopy revealed that the Na-enriched biotite is concentrated in albite-rich microdomains, albite being partially replaced by biotite. These images also revealed that both K and Na-K biotite grains appear locally retrograded to kaolinite. Transmission electron microscopic data indicated that K biotite, Na biotite and Na-K biotite form parallel or subparallel packets with interfaces parallel to the basal planes of biotite. Potassium biotite forms thick packets, chemically homogeneous, with a basal spacing of 10.1 Å. Sodium biotite also occurs as chemically homogeneous stacks of layers with a 9.78 Å periodicity. Sodium-K biotite shows, on the contrary, variable composition and basal spacings intermediate between K and Na biotites. Analytical electron microscopic data revealed important chemical differences between Na and K biotites, which affect both the tetrahedral and the octahedral sheets. Both electron microprobe analysis and analytical electron microscopy indicated that the trioctahedral micas show relatively low interlayer occupancy, suggesting the presence of H3O+ replacing the interlayer cations. Partial hydration of biotite explains the presence of a weak 14 Å reflection in the X-ray patterns. Both chemical and textural data suggested that these trioctahedral micas grew during a common prograde metamorphic episode, the phases with intermediate composition probably being metastable.

Altered basaltic tephra from Haleakala, Maui, are characterized using multiple techniques in order to identify the minerals formed under a variety of conditions and to understand the soil formation processes here. We collected samples that are representative of typical bulk weathered material in the crater, as well as solfataric alteration in a hydrothermal environment. For this study X-ray diffraction, electron probe microanalysis, scanning electron microscopy and transmission electron microscopy are coupled with spectroscopic techniques including Mössbauer, visible-infrared reflectance, transmission infrared, and thermal infrared emission spectroscopies to analyze these samples. The unaltered tephra are composed of feldspar, glass, pyroxene and olivine. Observed alteration products include Fe oxides, phyllosilicates and sulfates, as well as SAED amorphous Al-Si-bearing material. These samples are potential analogs for altered volcanic material on Mars as the pedogenic influences and contact with plants and animals are minimal. Results from this study may help to determine spectral signatures of these samples that could be used for identification on Mars of the minerals observed here.

Chlorites formed as a replacement of phenocrysts in metabasites from the pumpellyite-actinolite to lower-greenschist facies Mikabu and North Chichibu belts in southwest Japan were studied by X-ray powder diffraction, electron microprobe analysis (EMPA) and high-resolution transmission electron microscopy (HRTEM). The metabasites contain a small quantity of fine-grained smectite and corrensite in the <1 μm size fraction. The chlorite also contains trace amounts of Ca, Na and K, which generally appear to be associated with smectite stacked in chlorite packets. The smectite layers comprise up to 13% of the chlorite domains. Theoretical estimates of the smectite ratio by the Wise method using EMPA data coincide well with the ratio determined based on HRTEM observations in most chlorites. However, in some chlorites with high proportions of Ca, Na and K, the cations cannot be reasonably attributed to smectite alone. Based on the present analyses, Ca, Na and K cations are also hosted in discrete interstitial phases of fine-grained smectite and corrensite as possible retrograde metamorphic products. These findings suggest that care should be taken in application of the Wise method to estimate the smectite ratio, and that the whole-rock chlorite composition may not be suitable as a geothermometer.

Myrmekites occurring in monzodiorite from the Meichuan pluton in the Dabie ultrahigh-pressure metamorphic belt were investigated. The petrographic evidence demonstrates a metasomatic origin for myrmekite formation at the scale of individual alkali feldspar grains, and that the myrmekitic quartz and plagioclase matrix are generated simultaneously replacing precursor feldspar. Energy-dispersive X-ray spectroscopy and electron microprobe analysis indicate a low anorthite content in the narrow rim of host plagioclase near the myrmekite–alkali-feldspar interface. The Ca2+, Na+ proportion of hydrothermal fluids replacing precursor alkali feldspar is 1:5.4, calculated from the anorthite content of the inner part of the host plagioclase and the neighbouring alkali feldspar. Electron back-scattered diffraction was used to identify the crystallographic orientation of the myrmekitic quartz, plagioclase matrix and the precursor alkali feldspar. The crystallographic orientation relationships (110)Kfs//(11$\bar{2}\bar{1}$)Qtz, (20$\bar{1}$)Kfs//(11$\bar{2}$1)Qtz and [11$\bar{2}3]$Qtz//[001]Kfs between myrmekitic quartz and adjacent alkali feldspar were obtained from statistical analysis. No clear crystallographic orientation relationship between quartz and plagioclase was found. The growth of myrmekitic quartz is constrained by the precursor alkali feldspar rather than the simultaneously crystallised plagioclase. This research is helpful for understanding the intergrowth mechanism during metasomatism.

Molybdenite from two porphyry copper mineralisation sites within the South Urals was studied by electron microprobe (EMPA), micro x-ray diffraction (μXRD) and electron backscattered diffraction (EBSD) methods. Elevated contents of rhenium (0.2 to 0.4, sometimes up to 1.1 wt.%) form linear zones from several to tens of micrometres wide and up to hundreds of micrometres long parallel to the elongation of molybdenite flakes. In most cases Re-rich zones are composed of the rhombohedral (3R) polytype of molybdenite, while the rest of the molybdenite flakes with ca. 0.1 wt.% of Re consist of hexagonal (2H) molybdenite. In rare cases Re-rich zones are confined to grain boundaries of molybdenite-2H. It is shown that both μXRD and EBSD are the most appropriate tools to distinguish different polytypes within a single grain of molybdenite.

Early Copper Age pottery sherds discovered in a cave within the crystalline dolomites of the Southern Carpathians (Romania) were investigated by polarized light optical microscopy (OM), X-ray powder diffraction (XRPD) and electron microprobe analysis (EMPA) to obtain information on the pottery production in the Copper Age in the territory of present-day Romania. Microscopically, the clayey matrix of the ceramic body is highly birefringent or consists of low-birefringent and isotropic parts mixed together, containing fragments of quartz, muscovite, alkali feldspar, plagioclase, biotite, chlorite, heavy minerals and metamorphic and magmatic rocks, as well as an opaque material. The EMPA data revealed an Fe-rich illite-like matrix and helped to identify the mineral nature of the inclusions. Local pottery production in bonfires or surface clamps is envisaged. Miocene illitic clays may have been used as raw materials, mixed with a small amount of sandy temper. The thermal changes revealed by OM, the modification of the XRPD peaks and the EMPA data suggest firing temperatures of between 800 and 850°C.

This study addresses the crystal chemistry of a set of five samples of F-rich amphiboles from the Franklin marble (USA), using a combination of microchemical (Electron microprobe analysis (EMPA)), single-crystal refinement (SREF) and Fourier transform infrared (FTIR) spectroscopy methods. The EMPA data show that three samples fall into the compositional field of fluoro-edenite (Hawthorne et al., 2012), whereas two samples are enriched in high-charged C cations and – although very close to the CR3+ boundary – must be classified as fluoro-pargasite. Magnesium is by far the dominant C cation, Ca is the dominant B cation (with BNa in the range 0.00−0.05 a.p.f.u., atoms per formula unit) and Na is the dominant A cation, with A☐ (vacancy) in the range 0.07−0.21 a.p.f.u.; WF is in the range 1.18−1.46 a.p.f.u. SREF data show that: TAl is completely ordered at the T(1) site; the M(1) site is occupied only by divalent cations (Mg and Fe2+); CAl is disordered between the M(2) and M(3) sites; ANa is ordered at the A(m) site, as expected in F-rich compositions. The FTIR spectra show a triplet of intense and sharp components at ~3690, 3675 and 3660 cm−1, which are assigned to the amphibole and the systematic presence of two very broad absorptions at 3560 and 3430 cm−1. These latter are assigned, on the basis of polarized measurements and FPA (focal plane array) imaging, to chlorite-type inclusions within the amphibole matrix. Up to eight components can be fitted to the spectra; band assignment based on previous literature on similar compositions shows that CAl is disordered over the M(2) and M(3) sites, thus supporting the SREF conclusions based on the <M−O> bond distance analysis. The measured frequencies of all components are typical of O−H groups pointing towards Si−O(7)−Al tetrahedral linkages, thus allowing characterization of the SRO (shortrange- order) of TAl in the double chain. Accordingly, the spectra show that in the fluoro-edenite/ pargasite structure, the T cations, Si and Al, are ordered in such a way that Si−O(7)−Si linkages regularly alternate with Si−O(7)−Al linkages along the double chain.

Sazhinite-(La) is a new mineral from the Aris phonolite, Windhoek, Namibia. It occurs in vesicles within the phonolite, together with other species crystallized from late-stage hydrothermal fluids: natrolite, aegirine, microcline, apophyllite, sphalerite, analcime, fluorite, villiaumite, hydroxylapatite, galena, makatite, quartz, eudialyte, kanemite, tuperssuatsiaite and korobitsynite. Sazhinite-(La) forms small euhedral crystals up to 1 mm long and 0.4 mm wide, elongated along [001] and flattened on (010), exhibiting the forms {h0l}, {100} and {001}. It has good cleavage parallel to {010} and {001}. Twinning was not observed. Crystals are brittle with a Mohs hardness of 3, creamy white with a white streak, vitreous to pearly lustre, and translucent to transparent. In plane-polarized light, crystals are colourless with a = Z, b = Y, c = X. It is biaxial positive with α = 1.524, β = 1.528, γ = 1.544, all ±0.002, 2Vz(obs) = 46(1)°, and 2Vz(calc.) = 53.6°.

Sazhmite-(La) is orthorhombic Pmm2, a = 7.415(2), b = 15.515(3), c = 7.164(1) Å, and V = 824.2 Å3. One crystal was studied by X-ray diffraction, electron microprobe and secondary ion mass spectrometry (SIMS) microanalysis, leading to the average composition (Na2.87K0.02Sr0.01)Σ2.90 [La0.41Ce0.35Pr0.02Nd0.04(Sm,Gd,Dy,Er,Yb)Σ0.01Th0.09U0.01Y0.01Zr0.01Ca0.08Li0.01]Σ1.04 (S15.87S0.06B0.01) (O14.86F0.14).(H2O)2.

Weighted full-matrix least-squares refinement on 3369 reflections yielded Rall = 3.8%. The structure is built of corrugated [Si6O15]6- layers linked by [7]-coordinated REE and R4+ cations. This framework leaves channels that contain three [5]- and [6]-coordinated Na cations per formula unit that compensate for the residual charge on the silicate layers. The SIMS analyses confirm a Na content of 3 atoms per formula unit, leading to an ideal formula of Na3LaSi6O15(H2O)2. The third Na atom is bonded to H2O groups and therefore the total content of both Na and H2O may be reduced to 2 and 1 per formula, respectively. The depletion in Na allows for the entrance of high-charge cations such as Th4+.

The crystal structure of allanite from granitic pegmatite, the Daibosatsu Pass, Yamanashi, Japan, has been refined under the constraint of chemical composition determined by electron microprobe analysis of rare earth elements. Back-scattered-electron images and X-ray element maps of the allanites show that each of their crystal grains has chemically homogeneous distribution of major elements. A typical formula for the chemistry is: (Ca0.920☐0.080)Σ1.000(La0.238Ce0.443Pr0.048Nd0.100Sm0.019Th0.042Mn0.008☐0.102)Σ1.000(Al0.607Fe0.3173+Ti0.076)Σ1.000(Al1.000)(Fe0.5432+Fe0.3653+Mn0.055Mg0.037)Σ1.000(SiO4)(Si2O7)O(OH).

The crystal structure of allanite, monoclinic, a 8.905 (1), b 5.7606 (5), c 10.123 (1) Å, β 114.78°(1), space group P21/m, Z = 2, has been refined to an unweighted R factor of 3.46% for 1459 observed reflections. Although the H atom position was not determined on the Difference-Fourier map, inspection of the bond valence sums demonstrates that the H atom is uniquely located at the O10 atom and involved in a hydrogen bond to O4. A systematic examination as to crystal chemistry of allanites suggests that the isolated SiO4 tetrahedron has the largest distortion of three kinds of the tetrahedron containing Si2O7 groups in the allanite structure. This observation is common to the epidote group minerals, while the larger distortion of A2 sites caused by occupancy by REE in allanites contrasts with the smaller one of A sites in other epidote group minerals. In the allanite groups the bond angles between the O10–H bond and hydrogen bond H···O4 are found to range from 170 to 180°.

Compilation of the chemical compositions of the title allanite and the others from granitic rocks, Japan, which reveals Th-incorporation as the coupled substitution of 3Th4+ + ☐ (vacancy) ⇌ 4REE3+, provides an explanation for the observation that higher Th concentrations characterize allanites from the island arcs. The ternary Al2O3-Fe2O3-ΣREE diagram illustrates that allanites are grouped, according to their origins, into three classes suggestive of tectonic backgrounds for the crystallization localities; (1) intracontinental, (2) island arc and (3) continental margin.

Bavenite is an orthorhombic calcium beryllium aluminosilicate, a ≈ 23.2, b ≈ 5.0, c ≈ 19.4 Å, V ≈ 2250 Å3, Z = 4, that crystallizes in the space group Cmcm. The crystal structures of 24 bavenite samples from various localities worldwide were refined to R1 values from 2.4 to 7.5% based on ∼1330 unique reflections collected with Mo-Kα X-radiation on a Bruker P4 CCD single-crystal diffractometer. The composition of each crystal was determined by electron microprobe analysis. There is extensive solid-solution in bavenite according to O(2)OH– + T(4)Si4+ + T(3)Be2+ ⇌ O(2)O2– + T(4)Al3+ + T(3)Si4+, such that the general formula may be written Ca4BexSi9Al4–xO28–x(OH)x, where x ranges from 2.00 to ∼3.00 a.p.f.u. Small amounts of additional Be may be incorporated into bavenite via the substitution T(3)Be + O(2)OH– + Na + T(4)Si2 ⇌ T(3)Si + O(2)O2– + Ca + T(4)Al2. Local (short-range) bond-valence considerations indicate that Short-Range Order (SRO) should be extensive in the bavenite structure, and this is confirmed by Fourier Transform Infrared (FTIR) spectroscopy in the principal OH-stretching region and by 27Al Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) spectroscopy. Short-range bond-valence considerations indicate that the T(3)–T(4)–T(3)–T(4) rings of the framework can incorporate any short-range arrangement of cations consonant with their site populations [T(3) = Be,Si; T(4) = Si,Al], and 27Al MAS NMR spectroscopy confirms this, showing the presence of the local clusters T(3)Be–T(4)Al–T(3)Be, T(3)Si–T(4)Al–T(3)Be and T(3)Si–T(4)Al–T(3)Si. Incorporation of Be at the T(3) site is accompanied by local replacement of O2– by (OH)– at the O(2) site and hydrogen bonding to the adjacent O(3) anion; the latter promotes Be → Si substitution at the T(3) tetrahedron adjacent in the b direction. T(3)–T(4)–T(3)–T(4) rings link in the c direction through a T(3)–(1)–(3) linkage [T(1) = Si]. Local bond-valence considerations show that occupancy of both T(3) tetrahedra by Be violates the valence-sum rule, and that the linkage T(3)Be–T(1)Si–T(3)Si provides the constraint whereby Be does not exceed 3 a.p.f.u. in bavenite when incorporated via the substitution O(2)OH– + T(4)Si4+ + T(3)Be2+ ⇌ O(2)O2– + T(4)Al3+ + T(3)Si4+.

The crystal chemistry of wavellite from Zbirov (Czech Republic), ideally Al3(PO4)2(OH,F)3·5H2O, was addressed by means of a multi-methodological approach based on electron microprobe analysis (EMPA) using wave-dispersive spectroscopy, single-crystal X-ray diffraction, powder and singlecrystal infrared spectroscopy and Raman spectroscopy. The EMPA data showed the presence of significant F replacing OH in the sample studied. The structure was solved in the Pcmn orthorhombic space group, with the following unit-cell constants: a = 9.6422(7), b = 17.4146(15), c = 7.0094(2) Å, V = 1176.98(10) Å3. Phosphorus atoms display tetrahedral (PO4) coordination, while Al cations display octahedral coordination. The mineral framework can be viewed as the repetition of cationic arrays made up of AlO6 polyhedra, bridged by PO4 groups and further joined by O–H⋯O hydrogen bonds. The single-crystal unpolarized Fourier transform infrared (FTIR) spectrum shows combination bands indicating the presence of both OH and H2O in the structure. Both FTIR and Raman spectra show a broad absorption extending from 3600 to 2800 cm−1 resulting from the overlapping of several components due to the water molecules and the OH group. The frequencies observed are comparable to those expected on the basis of the Libowitzky relationship for the range of D–H⋯A bond systems in the structure.

The Zarza la Mayor and Zarza de Montánchez tonalites and Arroyo de la Luz granodiorite are part of a tonalitic–granodioritic belt located along the Schistose-Greywacke Domain of the Central Iberian Zone. These intrusions are also part of the Central Extremadura Batholith, a set of plutons ranging from tonalite to leucogranite that have been considered a prime example of Variscan syn-kinematic plutonism. New LA-ICP-MS and CA-ID-TIMS U–Pb dating reveals that the Zarza la Mayor tonalite–granodiorite is an Early Ordovician intrusion. The LA-ICP-MS data show that there is an absence of inherited cores, despite some complex internal zoning with obvious resorption features in some of the zircon crystals. Dating of monazite and zircon by CA-ID-TIMS provides a concordant age of 478.1 ± 0.8 Ma. This age coincides with electron microprobe analysis (EMPA) monazite chemical ages for the Zarza de Montánchez (482 ± 10 Ma) and Arroyo de la Luz (470 ± 15 Ma) intrusions. These new data indicate the presence of an Early Ordovician belt of calc-alkaline tonalite–granodiorite in the Schistose-Greywacke Domain – the Beira Baixa–Central Extremadura tonalite–granodiorite belt – which resembles a continental magmatic arc. This belt is contemporaneous with the Ollo de Sapo magmatic event further north in the Central Iberian Zone.