Petewilliamsite, ideally (Ni,Co)30(As2O7)15, monoclinic, space group C2, a = 33.256(5), b = 8.482(1), c = 14.191(2) Å, ß = 104.145(3)°, V = 3881.6(11) Å3, a:b:c = 3.9209:1:1.6731, Z = 2, is a new mineral found on a single nickeline-veined quartz specimen from Johanngeorgenstadt, Saxony, Germany. The mineral possesses a pronounced subcell-supercell: a (subcell) = 1/5 a (supercell); b (subcell) = b (supercell); c (subcell) = 1/3 c (supercell), and the strongest six lines of the X-ray powder-diffraction pattern are [d in Å (I) (hkl)]: 4.235(30)(020) ; 3.118(100)(513, 023); 3.005(60); 2.567(50); 1.637(50)(536 ); 1.507(30b)(553, ). It occurs predominantly as scattered patches of mm-sized aggregates which are intimately associated with varicoloured xanthiosite; additional associations include bunsenite, aerugite, rooseveltite, native bismuth, paganoite and two undefined arsenates. Subhedral equant crystals with rounded faces are intimately intergrown in 1 mm-sized aggregates and individual grains do not exceed 0.5 mm in maximum diameter. The average crystal size is variable from 20 μm to 0.3 mm. The colour varies from dark violet-red to dark brownish-red and the streak is pale reddish-brown to pale purplish-brown. Crystals are translucent, brittle, vitreous, and do not fluoresce under ultraviolet light. The mineral shows neither twinning nor cleavage, has an uneven fracture, and the calculated density (for the empirical formula) is 4.904 g/cm3. Electron-microprobe analyses gave NiO 19.45, CoO 18.39, CuO 3.40, CaO 0.17, FeO 0.04, As2O5 60.32, total 101.77 wt.%. The empirical formula, derived from crystal-structure analysis and electron-microprobe analyses, is (Ni14.662+Co13.822+Cu2.412+Ca0.17Fe0.032+)Σ31.09(As1.975+O7)15, based on O = 105 atoms per formula unit (a.p.f.u.). In reflected plane-polarized light in air, petewilliamsite is dark grey with orange to spectral (multicoloured) internal reflections and no obvious bireflectance, anisotropy or pleochroism. Measured reflectance values in air are tabulated; the index of refraction calculated at 589 nm is 1.88. The mineral name honours Professor Peter (‘Pete’) Allan Williams of the University of Western Sydney, New South Wales, Australia, for his contributions to the study of secondary minerals.

The crystal structure of petewilliamsite has been solved by direct methods and refined on the basis of F2 using 9212 unique reflections measured with Mo-Kα X-radiation on a diffractometer equipped with a CCDbased detector. The final R1 was 7.68%, calculated for 1273 observed reflections. The structure contains 15 symmetrically distinct As5+ cations, each of which is tetrahedrally coordinated by four O atoms, and pairs of these AsO4 tetrahedra share a vertex which results in As2O7 pyroarsenate groups that are in layers parallel to (010). The structure also has 16 distinct transition-metal M (M: Ni,Co) sites of which there are one tetrahedral, four square bipyramidal, and 11 octahedral arrangements. Adjacent pyroarsenate groups are linked through bonds to M cations. The structure of petewilliamsite is not closely related to other naturally occurring arsenates and it is the first pyroarsenate mineral.

Aurivilliusite, ideally Hg2+Hg1+OI, is monoclinic, C 2/c, with unit-cell parameters refined from X-ray powder data: a= 17.580(6), b= 6.979(1), c= 6.693(3)Å, β = 101.71(4)°, V = 804.0(5)Å3, a:b:c= 2.5190:1:0.9590,Z = 8. The strongest six lines of the X-ray powder-diffraction pattern [din Å (I )(hkl)] are: 8.547(70)(200), 3.275(100)(002), 2.993(80)(21), 2.873(80)(600), 2.404(50b)(02, 421, 22) and 1.878(50)(23). This extremely rare mineral was collected from a small prospect pit near the longabandoned Clear Creek mercury mine, New Idria district, San Benito County, California, USA. It is intimately intermixed with another new undefined Hg-O-I phase (‘CCUK-15’), and is also closely associated with native mercury, cinnabar and edgarbaileyite in a host rock principally composed of quartz and magnesite. Aurivilliusite occurs in a cm-wide quartz vein predominantly as irregular-shaped thin patches ‘splattered’ on the quartz surface; patches vary in size from 10–20 μm up to 0.5 mm. The only known subhedral platy brightly reflecting crystal fragment, with major ﹛100﹜ form and distinct ﹛100﹜ cleavage, did not exceed 0.2 mm in longest dimension. The mineral is dark grey-black with a dark red-brown streak. Physical properties include: metallic lustre; opaque; non-fluorescent; brittle; uneven fracture; calculated density 8.96 g/cm3 (empirical formula), 8.99 g/cm3 (ideal formula). In polished section in plane-polarized reflected light, aurivilliusite resembles cinnabar, is extremely light sensitive, shows twinning and no internal reflections, and exhibits an unusual ‘red light’ coalescing phenomena. Averaged and corrected results of electron-microprobe analyses yielded HgO 40.10, Hg2O 38.62, I 22.76, Br 0.22, Cl 0.06, sum 101.76, less O = I + Br + Cl –1.46, total 100.30 wt.%, corresponding to Hg1.002+Hg1.001+ O1.01(I0.97Br0.01Cl0.01)Σ0.99, based on O + I + Br + Cl = 2 atoms per formula unit (a.p.f.u.). The original value for Hg, 74.27 wt.%, was partitioned in a HgO:Hg2O ratio of 1:1 after the discovery of the crystal-structure paper dealing with the synthetic equivalent of aurivilliusite. The mineral name is in honour of the late Dr Karin Aurivillius (1920 –1982), chemistcrystallographer at the University of Lund, Sweden, for her significant contributions to the crystal chemistry of Hg-bearing inorganic compounds. Aurivilliusite is related chemically to terlinguaite, Hg2+Hg1+OCl, but has a different structure and X-ray characteristics.

The original structure determination of asisite, nominally Pb7SiO8Cl2, has been re-evaluated in the light of electron-diffraction data (TEM) on the original sample material. Electron diffraction patterns indicate a super-structure based upon a metrically tetragonal 26-cation-site super-sheet motif (14x14x23 Å). Given the strong ordering of elements substituting for Pb in closely-related litharge-based oxychlorides (parkinsonite, symesite, kombatite, schwartzembergite), the asisite superstructure is inferred to be due to strong ordering of Si within the PbO sheet. The original chemical analyses of asisite given by Rouse et al. (1988) are shown to be consistent with such a super-structure, which has a 12Pb:1Si cation ratio. A new formula for asisite is proposed that is based upon this superstructure: Pb12(SiO4)O8Cl4 (Z = 8). The structure of asisite determined by Rouse et al. (1988) is that of the average Pb/Si-disordered tetragonal sub-cell (I4/mmm: 4x4x23 Å) and belies the highly ordered real state. The structure of the tetragonal sub-cell has been re-determined here: R = 5.6% for 178 unique Fo > 4σFo and an anisotropic model. A significantly reduced 72% occupancy of the Pb(2) site was found that implies the nominal formula Pb7SiO8Cl2, thus confirming the findings of Rouse et al. (1988). Comparisons with kombatite and symesite support the assignment of Si to Pb(2) and imply that Si in asisite is also likely to be in tetrahedral coordination, with the apical oxygen cross-linking PbO sheets. However, because most of the key information relating to the location of Si is provided by the super-lattice reflections, the inability of X-ray diffraction to register these reflections introduces a significant ambiguity into the interpretation of Pb/Si ordering behaviour in this mineral.

Mesothermal gold ores in the Archaean Yilgarn Craton of Western Australia are dominated by a pyrite ± arsenopyrite ± pyrrhotite sulphide assemblage. Many of these ores are refractory to varying degrees and require treatment by roasting, bacterial oxidation or finer milling. The most common sulphide ore types can be sub-divided broadly into pyritic (pyrite±pyrrhotite) and arsenical types (pyrite+arsenopyrite± pyrrhotite). Arsenical ores vary from highly refractory to free-milling. Arsenopyrite in highly refractory ores is finer grained, As-deficient (27 –32.5 at.% As), contains high average concentrations of submicroscopic gold (60 –270 ppm), but does not contain inclusions of particulate gold. Arsenopyrite in free-milling ores is coarser grained, less As-deficient to slightly As-rich (30 –35 at.% As), contains low or negligible concentrations of submicroscopic gold, but contains inclusions and fracture fillings of particulate gold. In some refractory arsenical ores, pyrite also contains moderately high levels of submicroscopic gold (20 –40 ppm), the concentration of which is directly related to As content of the pyrite.

Pyritic ores are free-milling to mildly refractory, or rarely moderately refractory. Pyrite in pyritic ores contains negligible to low levels of submicroscopic gold (<5 ppm). Other reasons for refractory behaviour in pyritic ores include very fine-grained native gold inclusions in pyrite, or the presence of gold-bearing tellurides.

It is concluded that submicroscopic gold is incorporated into the crystal lattices of arsenopyite and arsenical pyrite at sub-greenschist to lower greenschist-facies temperatures, and is progressively expelled as inclusions and fracture fillings of native gold in sulphides, and ultimately into the gangue, as recrystallization proceeds through upper greenschist- into amphibolite-facies temperatures, during deformation and burial. Submicroscopic gold is expelled more rapidly from pyrite than arsenopyrite.

Pyrrhotite progressively replaces primary pyrite at higher temperatures, but rarely contains gold. Finally, a metallurgical classification scheme for refractory ores is presented which incorporates the above mineralogical conclusions.

Coherent intergrowths, at the lattice scale, between cuprobismutite (N = 2) and structurally related paděraite along both major axes (15 Å and 17 Å repeats) of the two minerals are reported within skarn from Ocna de Fier, Romania. The structural subunit, DTD, 3 layers of paděraite, is involved at interfaces of the two minerals along the 15 Å repeat, as well as in transposition of 1 paděraite unit to 2 cuprobismutite units along the 17 Å repeat in slip defects. Lattice images obtained by HRTEM across intervals of 200–400 nm show short- to long-range stacking sequences of cuprobismutite and padeÏ raite ribbons. Such nanoscale slabs mimic mm-scale intergrowths observed in back-scattered electron images at three orders of magnitude greater. These slabs are compositionally equivalent to intermediaries in the cuprobismutite-paděraite range encountered during microanalysis. Hodrushite (N = 1.5) is identified in the mm-scale intergrowths, but its absence in the lattice images indicates that, in this case, formation of polysomes between structurally related phases is favoured instead of stacking disorder among cuprobismutite homologues. The tendency for short-range ordering and semi-periodic occurrence of polysomes suggests they are the result of an oscillatory chemical signal with periodicity varying from one to three repeats of 15 Å, rather than simple ‘accidents’ or irregular structural defects. Lead distribution along the polysomes is modelled as an output signal modulated by the periodicity of stacking sequences, with Pb carried within the D units of paděraite. This type of modulator acts as a patterning operator activated by chemical waves with amplitudes that encompass the chemical difference between the minerals. Conversion of the paděraite structural subunit DTD to the C unit of cuprobismutite, conserving interval width, emphasizes that polysomatic modularity also assists interference of chemical signals with opposite amplitudes. Observed coarsening of lattice-scale intergrowths up to the mm-scale implies coupling between diffusion-controlled structural modulation, and rhythmic precipitation at the skarn front during crystallization.

Intermediate levels of the Larga-Fatţa Báii field, Metaliferi Mts., Romania, are host to epithermal vein mineralization, small skarn-like bodies and ‘geode’-like replacement ores, that together form a complex hydrothermal system rooted in the subjacent andesite stock. Silver-Pb-Bi sulphosalts, some with Sb and/or Se, are intimately associated with hessite and a range of Bi-tellurides with Bi/(Te+S+Se) ≤1 (tetradymite, tellurobismuthite, tsumoite, Pb-free rucklidgeite) within all these ore types. Lillianite homologues, both ordered 4L and 7L derivatives (lillianite, gustavite), and disordered varieties are the most abundant sulphosalts, with subordinate bismuthinite derivatives (aikinite, krupkaite, bismuthinite). An exceptionally Ag-rich lillianite homologue, intimately intergrown with tetradymite and hessite, is identified as treasureite on the basis of chemical composition. Porphyry-style mineralization from 600 m beneath the studied level contains rucklidgeite as the single stable Bi-telluride. The trace mineralogy of the system is suggestive of a hydrothermal system strongly zoned with respect to fTe2 and, to a lesser extent, also fS2. Mineralogical and textural evidence suggests that initial crystallization took place at temperatures in excess of 400°C. The association of gold with Bi-minerals is linked to the role of Bimelt as a scavenger for gold, and deposition within ‘droplets’ simultaneous with the formation of arsenopyrite from löllingite + pyrrhotite. Both Bi-tellurosulphides and sulphosalts are commonly non-stoichiometric, a fact that can be correlated with order-disorder in both series. When widely distributed, as in the Larga system, trace amounts of Bi-minerals (sulphosalts, tellurides/tellurosulphides) have considerable, untapped potential as tracers of the physical-chemical character of an evolving hydrothermal system.

Multispectral imaging of ore minerals under the microscope is a logical extension of quantitative colour analysis and microspectrophotometric analysis of minerals. This paper describes, step by step, how the proper calibration of a scientific video camera can be performed in order to obtain precise reflectance measurements at each pixel within the field of view. After having reviewed the different sources of noise and aberration, practical formulae are presented that allow for the acquisition of a set of images at different wavelengths in the visible spectrum.

The advantage of using a multispectral image acquisition system based on narrow bandwidth (10 nm) interference filters is discussed and quantitatively compared to colour imaging using tristimulus (red, green, blue) filters.

Images taken from major sulphide parageneses are shown as examples of well contrasted multispectral images. Finally, the potential for automatic identification of ore minerals is discussed with reference to supervised multivariate image classification algorithms similar to those used in remote sensing. Additional comments on extending the principles for handling optical anisotropy and developing a multiradial imaging system are made.

Four relatively intense and broad absorption bands centred at ∼12500, ∼19500, ∼21500 and ∼23000 cm–1 were recorded in polarized electronic single-crystal spectra of natural, optically uniaxial and pleochroic hydrogarnets with henritermierite contents ranging from 35 to 97 mol.%. These absorption bands arise from spin-allowed electronic d-d transitions in trivalent Mn located at the axially distorted six-coordinated site of the tetragonal hydrogarnet structure.

The crystal field stabilization energy (CFSE) for trivalent Mn at the Mn site, as derived from band energies, is ∼185 kJ/mol. This considerably higher CFSE for Mn3+ in tetragonal hydrogarnets as compared to cubic garnets (130 –145 kJ/mol) explains the natural occurrence of close to end-member tetragonal Mn3+-hydrogarnets while only limited Mn3+-substitution is observed in natural cubic garnets.

The fact that incorporation of Mn3+ at intermediate concentrations stabilizes the tetragonal hydrogarnets indicates the potential natural existence of a number of new, partially Mn3+-substituted, hydrogarnets, e.g. tetragonal Mn3+-bearing ‘hydroandradite’.

The kinetics and mechanisms of dissolution of the major base metal sulphide minerals, pyrite, chalcopyrite, galena and sphalerite in acidic (chloride) media have been investigated. Minerals were ground in air, then dissolved in air-equilibrated solutions at pH 2.5, while monitoring the redox potential. Solution samples were analysed by ICP-AES and HPLC, and surfaces of residual sulphides analysed using XPS. Dissolution of aerial oxidation products on pyrite particles in the first 15 min apparently led to a sulphur-rich surface, and was followed by slower dissolution of pyrite itself, driven by oxygen reduction, and resulting in net production of protons. Chalcopyrite dissolution resulted in a Cu, S-rich (near) surface layer, accompanied by net consumption of protons. Apparently incongruent dissolution of galena and sphalerite may reflect the formation of elemental S at the surface. The rates of dissolution of chalcopyrite, galena and sphalerite in the presence of pyrite were determined, respectively, as 18, 31 and 1.5 times more rapid than in single-mineral experiments. These data were consistent with galvanically-promoted mineral oxidation of the other sulphides in the presence of pyrite. In the case of galena, the experimental data suggested extensive release of Pb ions and development of a sulphur-rich surface during galvanically-promoted dissolution.

We examined grains of the platinum-group mineral, laurite (RuS2), from the type locality, Pontyn River, Tanah Laut, Borneo, and from the Tambanio River, southeast Borneo. The grains show a variety of morphologies, including euhedral grains with conchoidal fractures and pits, and spherical grains with no crystal faces, probably because of abrasion. Inclusions are rare, but one grain contains Ca-Al amphibole inclusions, and another contains an inclusion of chalcopyrite+bornite+pentlandite+heazlewoodite (Ni3S2) that is considered to have formed by a two-stage process of exsolution and crystallization from a once homogeneous Fe-Cu-Ni sulphide melt.

All grains examined are solid solutions of Ru and Os with Ir (2.71 –11.76 wt.%) and Pd (0.31–0.66 wt.%). Their compositions are similar to laurite from ophiolitic rocks. The compositions show broad negative correlations between Os and Ir, between As and Ir, and between As (0.4 –0.74 wt.%) and Se (140 to 240 ppm). Laurite with higher Os contains more Se and less Ir and As. The negative correlations between Se and As may be attributed to their occupancy of the S site, but the compositional variations of Os, Ir and As probably reflect the compositional variation of rocks where the crystals grew.

Ratios of S/Se in laurite show a narrow spread from 1380 to 2300, which are similar to ratios for sulphides from the refractory sub-arc mantle. Sulphur isotopic compositions of laurite are independent of chemical compositions and morphologies and are similar to the chondritic value of 0%. The data suggest that S in laurite has not undergone redox changes and originated from the refractory mantle. The data support the formation of laurite in the residual mantle or in a magma generated from such a refractory mantle, followed by erosion after the obduction of the host ultramafic rocks.

A reappraisal of Hermann's ‘irite’, described in 1836 and 1841, has been attempted by examining and analysing three museum samples, accessioned before 1865. The three samples were determined to be mixtures of chromite, native Os and Ir, rutheniridosmine, platinum, laurite, hongshiite, irarsite, cuprorhodsite, iridsite, prassoite, hollingworthite, erlichmannite, several Ru-Ir-Pt-Ti-Cr-Fe oxide/ hydroxide compounds (sometimes well crystallized), Pt-Ir-K chlorocompounds, and Pt-Ir-Ru-K-Clcontaining opal. The latter two are considered as artifacts generated by the hydrometallurgical processes applied to the crude platinum ores. Individual particles of native iridium and osmium display baroque crystal habits (filaments, leafs, blades, hollow crystals) that could be their natural, although rarely observed, states. There is still doubt about the origin (either natural or artificial) of all Ru-Ir-Pt- Ti-Cr-Fe oxides, but they can be compared with those found in several pristine placer and hard-rock deposits worldwide and in the Urals.

Arsenic-rich magmatic sulphide mineralization is hosted by a diorite intrusion at Talnotry, southwest Scotland. A relatively abundant and diverse platinum-group mineral assemblage is present and is dominated by sperrylite, irarsite and electrum with subordinate merenskyite, michenerite and froodite. Early euhedral gersdorffite is enriched with respect to Rh, Ir and Pt and in some cases contains exsolved blebs of irarsite or euhedral grains of sperrylite. Sperrylite is also enclosed within silicates and sulphides indicating that it crystallized directly from an As-rich sulphide liquid. Pyrrhotite-chalcopyrite mineral assemblages are consistent with the fractional crystallization of monosulphide solid solution and are overlain by PGE-, Ni- and As-rich mineral assemblages indicative of crystallization from a NiAs liquid. Late-stage, cross-cutting, electrum-bearing chalcopyrite veins are consistent with the crystallization of Cu- and Au-rich intermediate solid solution. The chemistry, mineralogy and lithological relationships of the diorite suggest that it may be an appinite and as such is potentially analogous to the Au-rich lamprophyre dykes present within southwest Scotland.