Sperlingite, (H2O)K(Mn2+Fe3+)(Al2Ti)(PO4)4[O(OH)][(H2O)9(OH)]⋅4H2O, is a new monoclinic member of the paulkerrite group, from the Hagendorf-Süd pegmatite, Oberpfalz, Bavaria, Germany. It was found in corrosion pits of altered zwieselite, in association with columbite, hopeite, leucophosphite, mitridatite, scholzite, orange–brown zincoberaunite sprays and tiny green crystals of zincolibethenite. Sperlingite forms colourless prisms with pyramidal terminations, which are predominantly only 5 to 20 μm in size, rarely to 60 μm and frequently are multiply intergrown and are overgrown with smaller crystals. The crystals are flattened on {010} and slightly elongated along [100] with forms {010}, {001} and {111}. Twinning occurs by rotation about c. The calculated density is 2.40 g⋅cm–3. Optically, sperlingite crystals are biaxial (+), α = 1.600(est), β = 1.615(5), γ = 1.635(5) (white light) and 2V (calc.) = 82.7°. The optical orientation is X = b, Y = c and Z = a. Neither dispersion nor pleochroism were observed. The empirical formula from electron microprobe analyses and structure refinement is A1[(H2O)0.96K0.04]Σ1.00 A2(K0.52□0.48)Σ1.00 M1(Mn2+0.60Mg0.33Zn0.29Fe3+0.77)Σ1.99 M2+M3(Al1.05Ti4+1.33Fe3+0.62)Σ3.00(PO4)4 X[F0.19(OH)0.94O0.87]Σ2.00[(H2O)9.23(OH)0.77]Σ10.00⋅3.96H2O. Sperlingite has monoclinic symmetry with space group P21/c and unit-cell parameters a = 10.428(2) Å, b = 20.281(4) Å, c = 12.223(2) Å, β = 90.10(3)°, V = 2585.0(8) Å3 and Z = 4. The crystal structure was refined using synchrotron single-crystal data to wRobs = 0.058 for 5608 reflections with I > 3σ(I). Sperlingite is the first paulkerrite-group mineral to have co-dominant divalent and trivalent cations at the M1 sites; All other reported members have Mn2+ or Mg dominant at M1. Local charge balance for Fe3+ at M1 is achieved by H2O → OH– at H2O coordinated to M1.

An Al–Cu–Li aerospace alloy has been investigated to determine the order in which corrosion at different types of sites occurs in AA2099-T83. Specifically, the sequence of galvanic attack on intermetallic (IM) particles and other sites of AA2099-T83 was determined as a function of time, in 0.1 M NaCl, through the use of scanning electron microscopy and electron backscatter diffraction characterization techniques. The earliest attack occurred at isolated grains and grain boundaries and on Li-containing dispersoids. Similarly, some constituent IM particles showed evidence of trenching in the surrounding alloy matrix. These IM particles included Al7Cu2Fe and another group of unidentified particles which displayed complete trenching within the first 10 min of exposure. Al13(Fe, Mn)4 were next most active followed by Al37Fe12Cu2 with Al6(Fe,Mn) and large TiB2 particles being the least active.

Samples from the sphalerite-dominated zone of a seafloor massive sulfide chimney, the Satanic Mills Chimney of the PACMANUS hydrothermal field, have been investigated to determine the internal macrostructure and microstructure of this zone, the phases present, and the distribution of metals. A combination of electron probe microanalysis, electron backscattered diffraction, and x-ray diffraction has been used. At the macroscale, this zone of the chimney wall is heavily porous and is comprised primarily of sphalerite, enclosing minor chalcopyrite, pyrite, and wurtzite. A Pb–As sulfosalt layer of possible microbial origins is present at the outer edge of the sphalerite matrix, next to a pore. The sphalerite has grown in globules on the order of 300 μm in diameter. At the microscale, the sphalerite features a colloform texture and a duplex-type grain structure consisting of either fine-grain regions in the center surrounded by coarse-grained regions or radiating coarse grains only. Pb- and As-rich bands have been detected in the colloform sphalerite, and growth twins have been observed in both the sphalerite and chalcopyrite crystals. A qualitative description of the growth of a typical globule is given, including nucleation, crystal growth, and solute redistribution.

Accurate elemental quantification of materials by X-ray detection techniques in electron microscopes or microprobes can only be carried out if the appropriate mass absorption coefficients (MACs) are known. With continuous advancements in experimental techniques, databases of MACs must be expanded in order to account for new detection limits. Soft X-ray emission spectroscopy (SXES) is a characterization technique that can detect emitted X-rays whose energies are in the range of 10 eV to 2 keV by using a varied-line-spaced grating. Transitions producing soft X-rays can be detected and accurate MACs are required for use in quantification. This work uses Monte Carlo modeling coupled with multivoltage SXES measurements in an electron probe micro-analyzer (EPMA) to compute MACs for the L2,3-M and Li Kα transitions in a variety of aluminum alloys. Electron depth distribution curves obtained by the software MC X-ray are used in a parametrized fitting equation. The MACs are calculated using a least-squares regression analysis. It is shown that X-ray distribution cross-sections at such low energies need to take into account additional contributions, such as Coster–Kronig transitions, Auger yields, and wave function effects in order to be accurate.

Alluvial mineral sands rank among the most complex subjects for mineral characterization due to the diverse range of minerals present in the sediments, which may collectively contain a daunting number of elements (>20) in major or minor concentrations (>1 wt%). To comprehensively characterize the phase abundance and chemistry of these complex mineral specimens, a method was developed using hyperspectral x-ray and cathodoluminescence mapping in an electron probe microanalyser (EPMA), coupled with automated cluster analysis and quantitative analysis of clustered x-ray spectra. This method proved successful in identifying and quantifying over 40 phases from mineral sand specimens, including unexpected phases with low modal abundance (<0.1%). The standard-based quantification method measured compositions in agreement with expected stoichiometry, with elemental detection limits in the range of <10–1,000 ppm, depending on phase abundance, and proved reliable even for challenging mineral species, such as the multi-rare earth element (REE) bearing mineral xenotime [(Y,REE)PO4] for which 24 elements were analyzed, including 12 overlapped REEs. The mineral identification procedure was also capable of characterizing mineral groups that exhibit significant compositional variability due to the substitution of multiple elements, such as garnets (Mg, Ca, Fe, Mn, Cr), pyroxenes (Mg, Ca, Fe), and amphiboles (Na, Mg, Ca, Fe, Al).

Hyperspectral soft X-ray emission (SXE) and cathodoluminescence (CL) spectrometry have been used to investigate a carbonaceous-rich geological deposit to understand the crystallinity and morphology of the carbon and the associated quartz. Panchromatic CL maps show both the growth of the quartz and the evidence of recrystallization. A fitted CL map reveals the distribution of Ti4+ within the grains and shows subtle growth zoning, together with radiation halos from 238U decay. The sensitivity of the SXE spectrometer to carbon, together with the anisotropic X-ray emission from highly orientated pyrolytic graphite, has enabled the C Kα peak shape to be used to measure the crystal orientation of individual graphite regions. Mapping has revealed that most grains are predominantly of a single orientation, and a number of graphite grains have been investigated to demonstrate the application of this new SXE technique. A peak fitting approach to analyzing the SXE spectra was developed to project the C Kα 2pz and 2p(x+y) orbital components of the graphite. The shape of these two end-member components is comparable to those produced by electron density of states calculations. The angular sensitivity of the SXE spectrometer has been shown to be comparable to that of electron backscatter diffraction.

The type specimen of liskeardite, (Al, Fe)3AsO4(OH)6·5H2O, from the Marke Valley Mine, Liskeard District, Cornwall, has been reinvestigated. The revised composition from electron microprobe analyses and structure refinement is [Al29.2Fe2.8(AsO4)18(OH)42(H2O)22]·52H2O. The crystal structure was determined using synchrotron data collected on a 2 μm diameter fibre at 100 K. Liskeardite has monoclinic symmetry, space group I2, with the unit-cell parameters a = 24.576(5), b = 7.754(2) Å, c = 24.641(5) Å, and β = 90.19(1)º. The structure was refined to R = 0.059 for 9769 reflections with I > 3σ(I). It is of an open framework type in which intersecting polyhedral slabs parallel to (101) and (10) form 17.4 Å × 17.4 Å channels along [010], with water molecules occupying the channels. Small amounts (<1 wt.%) of Na, K and Cu are probably adsorbed at the channel walls The framework comprises columns of pharmacoalumite-type, intergrown with chiral chains of six cis edge-shared octahedra. It can be described in terms of cubic close packing, with vacancies at both the anion and cation sites. The compositional and structural relationships between liskeardite and pharmacoalumite are discussed and a possible mechanism for liskeardite formation is presented.

Kleberite, ideally Fe3+Ti6O11(OH)5, is a new mineral (IMA 2012-023) from Tertiary sands at Königshain, Saxony, northeast Germany. It is also found in heavy mineral sands from the Murray Basin, southeast Australia and at Kalimantan, Indonesia. It occurs as rounded anhedral to euhedral translucent grains, 0.04 0.3 mm across, which are generally red-brown, but grade to orange with decreasing iron content. Associated minerals include ilmenite, pseudorutile, 'leucoxene', tourmaline and spinel. The density measured by pycnometry is 3.28 g cm-3, which is lower than the calculated density of 3.91 g cm-3, due to intragrain porosity which is not penetrated by the immersion fluid. The intragrain pores, of median diameter 18 nm, are partially filled with impurity phases including kaolinite, diaspore and quartz. Kleberite grains have a uniaxial (–) character, but localized regions are weakly biaxial (–) with 2V close to zero. The mean refractive index, calculated from reflectance measurements, is 2.16(3). The mean empirical formula from electron-microprobe analyses of 15 Königshain kleberite grains is Fe3+1.01Mg0.06Ti6O11.2(OH)4.8[Al0.59Si0.31P0.04O1.60·1.8H2O], where the formula element in square brackets represents impurities in the pores. Kleberite forms over a compositional range with [Ti]/[Fe + Ti] atomic ratios from 0.8–0.9. It has monoclinic symmetry, P21/c, with a = 7.537(1), b = 4.5795(4), c = 9.885(1) Å , β = 131.02(1)°. The six strongest lines in the powder X-ray diffraction (XRD) pattern [listed as d in Å (I)] are as follows: 1.676(100), 2.170(82), 2.466(27), 1.423(22), 3.933(8), 2.764(9). The structure was refined by the Rietveld method on powder XRD data to Rp = 6.3, Rwp = 8.1, RB = 4.0. Kleberite is isostructural with tivanite; their structural formulae are [Ti4+3□][Ti4+3Fe3+]O11 (OH)5 and [Ti4+4][V3+4]O12(OH)4, respectively. Kleberite has dominant Ti4+ in place of V3+ in the M(2) metal-atom site. The related mineral pseudorutile, [Ti4][(Fe3+,Ti)4](O,OH)16, with Fe3+ > Ti4+ has dominant Fe3+ in this site. Kleberite grains from different localities commonly contain residual MgO-rich ferrian ilmenite. The chemical and physical relationships between the ilmenite and coexisting kleberite are used to evaluate different alteration mechanisms involving selective leaching of divalent oxides from ilmenite and pseudomorphic replacement reactions, respectively.

Aluminium-bearing strunzite, [Mn0.65Fe0.26Zn0.08Mg0.01]2+[Fe1.50Al0.50]3+(PO4)2(OH)2·6H2O, occurs as fibrous aggregates in a crystallographically oriented association with jahnsite on altered zwieselite samples from the phosphate pegmatite at Hagendorf Süd, Bavaria, Germany. Synchrotron X-ray data were collected from a 3 μm diameter fibre and refined in space group P to R1 = 0.054 for 1484 observed reflections. The refinement confirmed the results of chemical analyses which showed that one quarter of the trivalent iron in the strunzite crystals is replaced by aluminium. The paragenesis revealed by scanning electron microscopy, in combination with chemical analyses and a crystal-chemical comparison of the strunzite and jahnsite structures, are consistent with strunzite being formed from jahnsite by selective leaching of (100) metal—phosphate layers containing large divalent Ca and Mn atoms.

Bariopharmacoalumite-Q2a2b2c, Ba0.5(Cu,ZnO)0.1H0.6[Al4(OH)4(As0.9Al0.1O4)3]·5.5H2O, from the south mine of the old copper mine at Cap Garonne, France, has a 2 × 2 × 2 I-centred tetragonal superstructure of the basic pharmacosiderite-type structure. Cell parameters are a = 15.405(2) Å and c = 15.553(3) Å. The structure was determined and refined in I 2m to R 1= 0.057 for 2697 reflections with I > 2σ(I), using synchrotron X-ray data on a twinned crystal. The origin of the superlattice cell doubling was determined to be due predominantly to the ordering of Ba atoms in half of the [0 0 1] channels, centred at (0, 0, 0) and (½, ½, 0). The other channels, centred at (½, 0, 0) and (0, ½, 0), were found to be occupied by corner-connected chains of Cu/Zn-centred square planar units.

Lead-bearing phyllotungstite from the Clara mine in the central Black Forest, Germany has a formula (Cs0.41)Na0.14K0.05Pb2+2.01Ca0.26[W6+10.87Fe3+3.13O35.75(OH)6.25](O(H2O)3). X-ray diffraction patterns exhibit pseudohexagonal symmetry, but refinement of single-crystal synchrotron data has shown that the true symmetry is orthorhombic, Cmcm, with a = 7.298(1), b = 12.640(2), c = 19.582(4) Å, and that the pseudohexagonal character is due to submicrometre-scale cyclical twinning by rotation about the pseudohexagonal c axis. The structure can be described in terms of an ordered intergrowth, parallel to (001), of (111)py blocks with pyrochlore-type structures, which are ~6 Å in width, and two-layer wide regions with a hexagonal tungsten bronze (HTB) type structure. Caesium atoms occupy 18-coordinate cavities in the HTB regions, and H2O molecules occupy Φ sites in the A2B2O6Φ pyrochlore blocks. The lowering of symmetry from hexagonal to orthorhombic is due to partial ordering of W and Fe in the octahedral B sites and of Pb and vacancies in the A sites of the pyrochlore blocks. The ideal formula for the intergrowth structure (with no vacancies) is C 2A10[B14(O,OH)42]Φ4, where C is the cavity site in the HTB slabs. The mineral has only 21% occupancy of the C site and 25% occupancy of the A site, but full occupancy of the Φ site. There may be some mixing of Cs and H2O between the C and Φ sites.

Electron and proton microprobes, along with electron backscatter diffraction (EBSD) analysis were used to study the microstructure of the contemporary Al–Cu–Li alloy AA2099-T8. In electron probe microanalysis, wavelength and energy dispersive X-ray spectrometry were used in parallel with soft X-ray emission spectroscopy (SXES) to characterize the microstructure of AA2099-T8. The electron microprobe was able to identify five unique compositions for constituent intermetallic (IM) particles containing combinations of Al, Cu, Fe, Mn, and Zn. A sixth IM type was found to be rich in Ti and B (suggesting TiB2), and a seventh IM type contained Si. EBSD patterns for the five constituent IM particles containing Al, Cu, Fe, Mn, and Zn indicated that they were isomorphous with four phases in the 2xxx series aluminium alloys including Al6(Fe, Mn), Al13(Fe, Mn)4 (two slightly different compositions), Al37Cu2Fe12 and Al7Cu2Fe. SXES revealed that Li was present in some constituent IM particles. Al SXES mapping revealed an Al-enriched (i.e., Cu, Li-depleted) zone in the grain boundary network. From the EBSD analysis, the kernel average misorientation map showed higher levels of localized misorientation in this region, suggesting greater deformation or stored energy. Proton-induced X-ray emission revealed banding of the TiB2 IM particles and Cu inter-band enrichment.

Flurlite, ideally Zn3Mn2+Fe3+(PO4)3(OH)2·9H2O, is a new mineral from the Hagendorf-Süd pegmatite, Hagendorf, Oberpfalz, Bavaria, Germany. Flurlite occurs as ultrathin (<1 μm) translucent platelets that form characteristic twisted accordion-like aggregates. The colour varies from bright orange red to dark maroon red. Cleavage is perfect parallel to (001). The mineral occurs on mitridatite and is closely associated with plimerite. Other associated minerals are beraunite, schoonerite, parascholzite, robertsite and altered phosphophyllite. The calculated density of flurlite is 2.84 g cm–3. It is optically biaxial (–), α = 1.60(1), β= 1.65(1) and γ = 1.68(1), with weak dispersion and parallel extinction, X ≈ c, Y ≈ a, Z ≈ b. Pleochroism is weak, with colours: X = pale yellow, Y = pale orange, Z = orange brown. Electron microprobe analyses (average of seven) with FeO and Fe2O3 apportioned and H2O calculated on structural grounds, gave ZnO 25.4, MnO 5.28, MgO 0.52, FeO 7.40, Fe2O3 10.3, P2O5 27.2, H2O 23.1, total 99.2 wt.%. The empirical formula, based on 3 P a.p.f.u. is Zn2.5Mn2+0.6Fe2+0.8Mg0.1Fe3+(PO4)3(OH)2·9H2O. Flurlite is monoclinic, P21/m, with the unit-cell parameters (at 100 K) of a = 6.3710(13), b = 11.020(2), c = 13.016(3) Å, β = 99.34 (3)°. The strongest lines in the X-ray powder diffraction pattern are [dobs in Å(I) (hkl)] 12.900(100)(001); 8.375(10)(011); 6.072(14)(101); 5.567(8)(012); 4.297(21)(003); 2.763(35)(040). Flurlite (R1 = 0.057 for 995 F > 4σ(F)) has a heteropolyhedral layer structure, with layers parallel to (001) and with water molecules packing between the layers. The slab-like layers contain two types of polyhedral chains running parallel to [100]: (a) chains of edge-sharing octahedra containing predominantly Zn and (b) chains in which Fe3+-centred octahedra share their apices with dimers comprising Zn-centred trigonal bipyramids sharing an edge with PO4 tetrahedra. The two types of chains are interconnected by corner-sharing along [010]. A second type of PO4 tetrahedron connects the chains to MnO2(H2O)4 octahedra along [010] to complete the structure of the (001) slabs. Flurlite has the same stoichiometry as schoonerite, but with dominant Zn rather than Fe2+ in the edge-shared chains. Schoonerite has a similar heteropolyhedral layer structure with the same layer dimensions 6.4 × 11.1 Å. The different symmetry (orthorhombic, Pmab) for schoonerite reflects a different topology of the layers.

Crystals of laueite, Mn2+Fe23+(PO4)2(OH)2·8H2O, from the Cornelia mine open cut, Hagendorf Süd, Bavaria, are zoned due to aluminium incorporation at the iron sites, with analysed Al2O3 contents varying up to 11 wt.%. Synchrotron X-ray data were collected on two crystals with different Al contents and the structures refined. The laueite structure contains two independent Fe3+-containing sites; M2 and M3, which alternate in 7 Å corner-connected octahedral chains. The coordination polyhedra are different for the two sites, M2O4(OH)2 and M3O2(OH)2(H2O)2 respectively. The structure refinements show that Al preferentially orders into site M3. Refined site occupancies for M2 and M3 for the two crystals are: for crystal L-1, M2 = 0.70(1) Fe + 0.30(1) Al, M3 = 0.54(1) Fe + 0.46(1) Al and for crystal L-2, M2 = 0.67(1) Fe + 0.33(1) Al, M3 = 0.48(1) Fe + 0.52(1) Al. For crystal L-2, the octahedral chains have dominant Fe in M2, alternating with dominant Al in M3 along the chain, an ordering phenomenon not previously reported for laueite-related minerals.

A comparative study is presented of the chemistry and crystallography of zinc-bearing strunzites from Hagendorf Süd, Bavaria, Germany and the Sitio do Castelo mine, Folgosinho, Portugal. Electron microprobe analyses of samples from the two localities show quite different cation substitutions. The Hagendorf Süd mineral is a Zn-bearing ferristrunzite, with compositional zoning due to Zn2+ replacing predominantly Fe3+ as well as minor Mn2+, whereas the Portugese mineral is a Zn-bearing strunzite, in which Zn2+ replaces Mn2+, with minor replacement of Fe3+ by Mn3+. Zincostrunzite, with dominant Zn in the interlayer octahedrally coordinated site, is a new strunzite-group mineral that has been characterized at both locations. Analysis of single-crystal synchrotron data for zinc-bearing ferristrunzite and zincostrunzite crystals from Hagendorf Süd show that the structures of both minerals contain zeolitic water in the interlayer region. The formula for strunzite-group minerals containing the zeolitic water is MFe23+(PO4)2(OH)2·6.5H2O, M=Fe, Mn, Zn. This formulation agrees with that found for zincostrunzite from the Sitio do Castelo mine, but differs from that reported previously for strunzite, MFe2+(PO4)2(OH)2·6H2O, which has no interlayer water. Interestingly, the zincostrunzites from the two localities differ in the location of the interlayer water molecule, with a corresponding difference in the H bonding.