The review focuses on the evolution of five contiguous peralkaline salic complexes in the south-central Kenya Rift Valley, stressing new developments of general significance to peralkaline magmatism. The complexes have evolved dominantly by combinations of fractional crystallization and magma mixing; volatile-melt interactions, remobilization of plutonic rocks and crystal mushes, and carbonate-silicate liquid immiscibility have been additional petrogenetic processes. Geochemical and experimental studies have shown that pantelleritic magmas can be generated by fractional crystallization of trachyte and high-silica rhyolite. Melts of comenditic composition were also formed by fractionation of trachyte but also locally by partial meltingof syenites. Studies of apparent partition coefficients have provided some of the first data on element distribution between phenocrysts and peralkaline silicic melts. Compositional zonation has been ubiquitous in the complexes, probably a result of the very low viscosity of the magmas.

The crystal structure of stephanite fromthe type locality, Freiberg District, Saxony, Germany, was refined in the space group Cmc21, up to a final R index of 0.0427. Unit-cell parameters are: a 7.8329(6) Å, b 12.458(1) Å, c 8.5272(7) Å, V 832.1(1) Å3; Z = 4. The previously reported structural model is confirmed, but a higher-precision refinement was achieved herein by the introduction of thirdorder non-harmonic Gram-Charlier tensors for one Ag atom. In the structure of stephanite, Sb forms isolated SbS3 pyramids, which typically occur in sulphosalts, and Ag occupies sites with coordination ranging fromtriangular to almost tetrahedral. Both the Sb–S and Ag–S bond distances closely match the values commonly observed in the structures of other Ag sulphosalts and sulphides.

The use of non-harmonic parameters for Ag allowed a better description of the electron density related to Ag, which is usually difficult to refine in good ionic conductors. A careful analysis of the energy barriers between the Ag sites defines preferred ion-diffusion pathways within the crystal structure of stephanite. The diffusion of Ag ions occurs preferentially along the sites Ag1 and Ag2, giving rise to two-dimensional nets of Ag atoms in which the ion conduction probably takes place.

Arsenic is a very common by-product of the processing of Cu, Au and polymetallic ores worldwide, where the ore is roasted (calcined) to remove volatile elements. In southwest England, a diverse range of As-mineral species occur as efflorescent secondary mineral growths on historic calciner buildings. Gypsum occurs as abundant dendritic growths comprising either interlocking blades or tabular crystals. Ca-arsenate minerals are locally very abundant as white colloform masses. Positively identified Ca arsenates include pharmacolite, weilite and haidingerite. Other secondary minerals include arsenolite, scorodite, bukovskyite and an As-bearing potassium alum, together with a wide variety of unidentified minerals, including an Al-As-S phase and As-rich F-bearing phases. Gypsum contains As concentrations up to ~7 wt.%. Efflorescent growth at sites exposed to the prevailing weather systems is less abundant than at sheltered sites. This is interpreted as being due to ‘pressure washing’ of exposed sites by driving rain. Successive concentric growths of gypsum and Ca arsenate on masonry are interpreted as being the result of seasonal crystallization.

Understanding both current and historicalmining and mineralprocessing methods is criticalin the evaluation of the potential impact on the modern environment. In particular, due to the abundance of As-bearing minerals in a wide range of ore types, many buildings worldwide are potentially significantly contaminated with As even though few are directly related to As production or handling. Characterizing the secondary As mineralspecies present at mine and mineralprocessing sites is critical in understanding the potentialheal th risk these sites might pose.

Mavlyanovite, ideally Mn5Si3, is a new mineral from a lamproite diatreme close to the upper reaches of the Koshmansay river, Chatkal ridge, Uzbekistan. It occurs together with unnamed manganese siliciphosphide and manganese silicicarbide minerals in round to ovoid segregations, up to 10 cm in diameter, in volcanic glass. Segregations of hexagonal prismatic mavlyanovite up to 1–2 mm occur in interstices in the matrix and tiny inclusions (1–2 μm) of alabandite and khamrabaevite occur within mavlyanovite. It is opaque with a metallic lustre, has a dark-grey streak, is brittle with a conchoidal fracture and a near-perfect basal cleavage. VHN100 is 1029–1098 kg/mm2 (Mohs hardness ~7). In plane-polarized reflected light, mavlyanovite is a pale-brownish-grey against the accompanying unnamed manganese silicicarbide (white). Reflectance values and colour data are tabulated. Average results of 19 electronmicroprobe analyses give Mn70.84, Fe 6.12, Si 22.57, Ti 0.15, P 0.18, total 99.86 wt.% leading to an empirical formula of (Mn4.66Fe0.40)5.06(Si2.91Ti0.01P0.02)2.94 based on8 a.p.f.u. The calculated density is 6.06 g/cm3, (on the basis of the empirical formula and unit-cell parameters from the structure determination). Mavlyanovite is hexagonal (P63/mcm) with a 6.8971(7), c 4.8075(4) Å, V 198.05(3) Å3 and Z = 2. The structure has been determined and refined to R1 = 0.017, wR2 = 0.044, GoF = 1.16. Mavlyanovite is the naturally-occurring analogue of synthetic Mn5Si3 which is the parent aristotype structure of the Nowotny intermetallic phases studied extensively by the material-science community. It is also the Mn-dominant analogue of xifengite Fe5Si3. The mineral name honours Academician Gani Arifkhanovich Mavlyanov (1910–1988), for his contributions to the understanding of the geology of Uzbekistan.

A new mineral, eldfellite, was found among fumarolic encrustations collected in 1990 on the Eldfell volcano, Heimaey Island, Iceland. Associated minerals are ralstonite, anhydrite, gypsum, bassanite, hematite, opal and tamarugite, as well as a presumably new mineral with the composition Na3Fe(SO4)3. Along with opal and tamarugite, eldfellite forms soft and fragile aggregates built of thin, platy crystals of micrometre size. The mineral is yellowish-green to greenish-white, with a white streak. The calculated density is 3.062 g/cm3. Eldfellite is monoclinic, C2/m, a 8.043(4) Å, b 5.139(2) Å, c 7.115(4) Å, β 92.13(2)º, Vuc 293.9(2) Å3, Z = 2 and is isostructural with yavapaiite[KFe (SO4)2]. The strongest lines in the powder diffraction diagram are [d (Å), I (relative to 10)]: 3.72, 8; 3.64, 5; 3.43, 5; 2.77, 10; 2.72, 6; 2.57, 3; 2.370, 6; 1.650, 3. Theche mical analysis and theX-ray diffraction data of eldfellite correspond to those of the synthetic compound NaFe(SO4)2.

The Saghro Cenozoic lavas form a bimodal suite of nephelinites (with carbonatite xenoliths) and phonolites emplaced in the Anti-Atlas belt of Morocco. Despite the paucity of samples with intermediate composition between the two main types of lava (only one phonotephrite flow is reported in this area), whole-rock major element modelling shows that the two main lithologies can be linked by fractional crystallization. The most primitive modelled cumulates are calcite-bearing olivine clinopyroxenites, whereas the final stages of differentiation are characterized by the formation of nepheline-syenite cumulates. This evolution trend is classically observed in plutonic alkaline massifs associated with carbonatites. Late-stage evolution is responsible for the crystallization of hainite- and delhayelite-bearing microdomains, for the transformation of aegirine-augite into aegirine (or augite into aegirine-augite), and for the crystallization of lorenzenite and a eudialyte-group mineral as replacement products of titanite. These phases were probably formed, either by crystallization from late residual peralkaline melts, or by reaction of pre-existing minerals with such melt, or hydrothermal peralkaline fluid.

The first single-crystal structure refinement of aschamalmite (Pb6Bi2S9) from Susa Valley (Piedmont, Italy) is reported. The mineral is monoclinic, C2/m, a = 13.719(1) Å, b = 4.132(1) Å, c = 31.419(3) Å, β = 90.94(1)º, V = 1 780.8(4) A ˚3, Z = 4. The Pb6Bi2S9 compound crystallizes also in an orthorhombic form as heyrovskyite (Cmcm) and our study is focused on understanding the reason leading to a change in symmetry. The aschamalmite structure forms because of ordering between Pb and Bi on the margins of the two octahedral layers that are symmetrically equivalent in heyrovskyite. The two alternate set of octahedral slabs are not related by a crystallographic mirror plane and the symmetry decreases to monoclinic. The cation ordering couples opposite sequences of Pb and Bi octahedra at the margins of slabs. In particular,the succession [Me4A]Bi-[Me5A]Pb-[Me4A]Bi-[Me5A]Pb faced to the series [Me4B]Pb- [Me5B]Bi-[Me4B]Pb-[Me5B]Bi occurs in about 70% of the unit-cells of the crystal,while the contrary sequence ([Me4A]Pb-[Me5A]Bi-[Me4A]Pb-[Me5A]Bi faced to [Me4B]Bi-[Me5B]Pb-[Me4B]Bi-[Me5B]Pb) occurs in the remaining unit-cells. The marginal octahedra have ideal populations (a.p.f.u.): [Me4A]1.40Bi+0.60Pb, [Me4B]1.40Pb+0.60Bi, [Me5A]1.40Pb+0.60Bi, [Me5B]1.40Bi+0.60Pb,in agreement with our structurerefinement results.

The probable site populations for pure heyrovskyite have been proposed,as well as the reasons that prevent the formation of a completely ordered monoclinic phase.

In situ X-raydiffraction measurements on almandine, (Fe0.86Mg0.07Mn0.07)3Al2Si3O12, were performed using a heating diamond-anvil cell instrument with synchrotron radiation at Beijing Synchrotron Radiation Facilityup to 27.7 GPa and 533 K. The pressure-volume-temperature data were fitted to a third-order Birch-Murnaghan equation of state. The isothermal bulk modulus of K0 = 177±2 GPa, a temperature derivative of the bulk modulus of (∂K/∂T)P= –0.032±0.016 GPaK–1 and a thermal expansion coefficient (α0) of (3.1±0.7)×10–5 K–1 were obtained. This is the first time that the temperature derivative of the bulk modulus of almandine has been determined at high pressure and high temperature. Combining these results with previous results, the compositional dependence of the bulk modulus, thermal expansion, and temperature derivative of the bulk modulus are discussed.

The crystal structure of mereheadite (monoclinic, Cm, a = 17.372(1), b = 27.9419(19), c = 10.6661(6) Å, β = 93.152(5)°, V = 5169.6(5) Å3) has been solved by direct methods and refined to R1 = 0.058 for 6279 unique observed reflections. The structure consists of alternating Pb–O/OH blocks and Pb–Cl sheets oriented parallel toth e (201) plane and belongs toth e 1:1 type of lead oxide halides with PbO blocks. It contains 30 symmetrically independent Pb positions, 28 of which belong to the PbO blocks, whilst two positions (Pb12 and Pb16) are located within the tetragonal sheets of the Cl– anions. Mereheadite is thus the first naturally occurring lead oxychloride mineral with inter-layer Pb ions. The coordination configurations of the Pb atoms of the PbO blocks are distorted versions of the square antiprism. In one half of the coordination hemisphere, they are coordinated by hard O2– and OH– anions whose number varies from three to four, whereas the other coordination hemisphere invariably consists of four soft Cl– anions located at the vertices of a distorted square. The Pb12 and Pb16 atoms in between the PbO blocks have an almost planar square coordination of four Cl– anions. These PbCl4 squares are complemented by triangular TO3 groups (T = B, C) so that a sevenfold coordination is achieved. The Pb–O/OH block in mereheadite can be obtained from the ideal PbO block by the following list of procedures: (1) removal of some PbO4 groups that results in the formation of square-shaped vacancies; (2) insertion of TO3 groups into these vacancies; (3) removal of some Pb atoms (that correspond to the Pb1A and Pb2A sites), thus transforming coordination of associated O sites from tetrahedral OPb4 tot riangular OHPb3; and (4) replacement of two O2– anions by one OH– anion with twofold coordination; this results in formation of the 1×2 elongated rectangular vacancy. The structural formula that can be derived on the basis of the results of single-crystal structure determination is Pb47O24(OH)13Cl25(BO3)2(CO3). Welch et al. (1998) proposed the formula Pb2O(OH)Cl for mereheadite, which assumes that neither borate nor carbonate is an essential constituent of mereheadite and their presence in the mineral is due to disordered replacements of Cl– anions. However, our study demonstrates that this is not the case, as BO3 and CO3 groups have well-defined structural positions confined in the vacancies of the Pb–O/OH blocks and are therefore essential constituents. Our results also show that mereheadite is not a polymorph of blixite, but is in fact related to symesite. Symesite thus becomes the baseline member of a group of structurallyrelated minerals.

Two feldspars of composition Ca0.3Sr0.7Al2Si2O8 (An30SrF70) and Ca0.6Sr0.4Al2Si2O8 (An60SrF40) were synthesized from gel and annealed at temperatures between 1150 and 1480ºC for durations between 0.025 (1.5 min) and 1073 h. The An60SrF40 feldspar is triclinic for all annealing temperatures, whereas the An30SrF70 possesses, at room temperature, a monoclinic symmetry, C2/m in the shortest annealing runs and I2/c after slightly longer heating, and becomes triclinic after prolonged annealing. A TTT plot for the triclinic–monclinic transition shows an activation energy of 101±12 kcal, less than, but still close to, that observed for Al-Si order in anorthite. TEM investigation shows antiphase domains and Carlsbad twins the size of which increases with annealing. IR spectroscopy was performed on a series of samples of An30SrF70, annealed at T = 1350ºC. The linewidth in hard mode is related to the spontaneous strain of the monoclinic–triclinic transition via . The evolution of the order parameter with time can be modelled as lnt, as predicted in order-disorder processes at intermediate degrees of order. It is shown that even after the longest annealing runs in An30SrF70, equilibrium was not obtained whereas, under the same conditions, equilibrium Al-Si order can be obtained in anorthite and Sr-feldspar.

Plimerite, ideally Zn (PO4)3(OH)5, is a new mineral from the Block 14 Opencut, Broken Hill, New SouthWales. It occurs as pale-green to dark-olive-green, almost black, acicular to prismatic and bladed crystals up to 0.5 mm long and as hemispherical aggregates of radiating acicular crystals up to 3 mm across. Crystals are elongated along [001] and the principal form observed is {100} with minor {010} and {001}. The mineral is associated with hinsdalite-plumbogummite, pyromorphite, libethenite, brochantite, malachite, tsumebite and strengite. Plimerite is translucent with a pale-greyish-green streak and a vitreous lustre. It shows an excellent cleavage parallel to {100} and {010} and distinct cleavage parallel to {001}. It is brittle, has an uneven fracture, a Mohs’ hardness of 3.5–4, D(meas.) = 3.67(5) g/cm3 and D(calc.) = 3.62 g/cm3 (for the empirical formula). Optically, it is biaxial negative with α = 1.756(5), β = 1.764(4), γ = 1.767(4) and 2V(calc.) of –63º; pleochroism is X pale-greenish-brown, Y pale-brown, Z pale-bluish-green; absorption Z > X > Y; optical orientation XYZ = cab. Plimerite is orthorhombic, space group Bbmm, unit-cell parameters: a = 13.865(3) Å, b = 16.798(3) Å, c = 5.151(10) Å, V = 1187.0(4) Å3 (single-crystal data) and Z = 4. Strongest lines in the X-ray powder diffraction pattern are [d (A˚ ), I, hkl]: 4.638, (50), (111); 3.388, (50), (041); 3.369, (55), (131); 3.168, (100), (132); 2.753, (60), (115); 2.575, (90), (200); 2.414, (75), (220); 2.400, (50), (221); 1.957, (40), (225). Electron microprobe analysis yielded (wt.%): PbO 0.36, CaO 0.17, ZnO 20.17, MnO 0.02, Fe2O3 29.82, FeO 2.98, Al2O3 4.48, P2O5 32.37, As2O5 0.09, H2O (calc) 6.84, total 97.30 (Fe3+/Fe2+ ratio determined by Mössbauer spectroscopy). The empirical formula calculated on the basis of 17 oxygens is Ca0.02Pb0.01Zn1.68Al0.60P3.09As0.01O17.00H5.15. The crystal structure was solved by direct methods and refined to an R1 index of 6.41% for 1332 observed reflections from single-crystal X-ray diffraction data (Mo-Kα radiation, CCD area detector). The structure of plimerite is isotypic with that of rockbridgeite and is based on face-sharing trimers of (Mϕ6) octahedra which link by sharing edges to form chains, that extend in the b-direction. Chains link to clusters comprising pairs of corner-sharing (Mϕ6) octahedra that link to PO4 tetrahedra forming sheets parallel to (001). The sheets link via octahedra and tetrahedra corners into a heteropolyhedral framework structure. The mineral name honours Professor Ian Plimer for his contributions to the study of the geology of ore deposits.

Electron microprobe data are presented for chevkinite-group minerals from granulite-facies rocks and associated pegmatites of the Napier Complex and Mawson Station charnockite in East Antarctica and from the Eastern Ghats, South India. Their compositions conform to the general formula for this group, viz. A4BC2D2Si4O22 where, in the analysed specimens A = (rare-earth elements (REE), Ca, Y, Th), B = Fe2+, Mg, C = (Al, Mg, Ti, Fe2+, Fe3+, Zr) and D = Ti and plot within the perrierite field of the total Fe (as FeO) (wt.%) vs. CaO (wt.%) discriminator diagram of Macdonald and Belkin (2002). In contrast to most chevkinite-group minerals, the A site shows unusual enrichment in the MREE and HREE relative to the LREE and Ca. In one sample from the Napier Complex, Y is the dominant cation among the total REE + Y in the A site, the first reported case of Y-dominance in the chevkinite group. The minerals include the most Al-rich yet reported in the chevkinite group (≤9.15 wt.% Al2O3), sufficient to fill the C site in two samples. Conversely, the amount of Ti in these samples does not fill the D site, and, thus, some of the Al could be making up the deficiency at D, a situation not previously reported in the chevkinite group. Fe abundances are low, requiring Mg to occupy up to 45% of the B site. The chevkinite-group minerals analysed originated from three distinct parageneses: (1) pegmatites containing hornblende and orthopyroxene or garnet; (2) orthopyroxene-bearing gneiss and granulite; (3) highly aluminous paragneisses in which the associated minerals are relatively magnesian or aluminous. Chevkinite-group minerals from the first two parageneses have relatively high FeO content and low MgO and Al2O3 contents; their compositions plot in the field for mafic and intermediate igneous rocks. In contrast, chevkinite-group minerals from the third paragenesis are notably more aluminous and have greater Mg/Fe ratios.