A study of the composition and unit cell data of a suite of lead-rich minerals of the alunite-jarosite group from the oxidized zone of the ore body at Broken Hill, New South Wales, Australia, has revealed almost complete XO4 (X = As, P, S) solid solution in these minerals at this deposit. The species in the group noted are hidalgoite, hinsdalite, beudantite, segnitite and plumbogummite. These minerals at Broken Hill exhibit a number of growth textures, including oscillatory zoning, colloform banding and replacements. Zoning in these minerals is due to the segregation of Al- and Fe-rich members, and compositions indicate a strong coupling of Fe3+ with and Al with

The Afon Goch (Anglesey, UK) is a short (12 km source to estuary) stream highly contaminated by acid mine drainage (AMD) throughout its length, due to past-mining at the head of the stream. Metal distribution is strongly controlled by the pH, which increases downstream particularly at confluences with two unpolluted tributaries. A pH increase causes precipitation of metals, primarily Fe as hydroxide, thus altering the transport of the metal load, potentially allowing storage of metal within the river as deposited material. However, further work suggests that the controls on whether metal can behave non-conservatively, and therefore the controls on metal distribution, are more complicated than being purely pH dependent. This is because much of the Fe load, even at the low pH at the head of the stream, is not soluble Fe3+ but colloidal Fe hydroxide. Consequently, coagulation is a requisite intermediate step between precipitation and potential for settling. It is possible that in reaches of the stream away from tributary confluences, the process of coagulation is the predominant influence on metal distribution. Furthermore, because much of the metal load in the water column is very fine, its deposition results in a sediment in which the metals can be intimately associated with a biofilm at the sediment/water interface. Such associations change both deposition and erosion characteristics of the sediment and have implications for subsequent diagenesis and mineral morphology.

Compositional convection in magma chambers is thought to be an important process in the fractionation of liquid from crystals during the differentiation of magmas. It has been tested for in this study by undertaking isothermal crystal growth experiments in a silicate melt at atmospheric pressure in air. The melt used is a synthetic basalt in which iron is replaced by cobalt to minimise redox problems. Co-Mg olivine rims were overgrown on forsteritic olivine seeds cemented to the floor of a 2.4 cm deep alumina crucible. Following quenching and sectioning, glasses were examined optically for colour variations and by EPMA for compositional variations. It had been expected that the colour intensity of the blue glass would diminish in the Co-depleted zone that develops around crystal overgrowths, whereas in fact little difference is normally found, except for a slight fading of colour in glass above the apex of a seed in a few experiments. By contrast EPMA revealed zones up to 50 μm wide around seeds that are depleted in Co and Mg by up to 25 % at the crystal-glass interface and in patches above some crystals. Contour maps of X-ray count-rate data obtained in grids of analytical points show Co- and Mg-depleted glass around the overgrowths and in patches above the highest point of each seed, demonstrating that convection in the melt does occur during growth of individual crystals. As the experiments were carried out in a stable temperature gradient and the crystal seeds had no contact with the melt meniscus, thermal and surface-tensional convection are both eliminated, and the convection is inferred to be caused by a density difference resulting from compositional variation across the chemical boundary layer around a growing crystal. The density difference between the inside and outside of a boundary layer is calculated to be approximately −1%.

Golden iridescent, <1–100 mm crystals of alternating lamellae of anthophyllite and gedrite constitute the bulk of orthoamphibolite pods within quartz-cordierite gneisses of the Akulleq terrane at Simiuttat, SW Greenland. X-ray powder diffraction powder gave a = 18.526(7),b = 17.979(15), c = 5.285(23) Å; a single crystal has a = 18.546(7), b = 17.950(16), c = 5.280(1) Å, space group Pnma with some reflections being notably broader than others. Spot EMPA yielded composite analyses: AlIV = 0.89–1.3, Mg/(Mg+Fe2+) = 0.57–0.61, Na/AlIV = 0.22–0.26. AFM imaging of {210} cleavage surfaces, showed a uniform corrugated morphology parallel to [001]; wavelength was 190–350 nm, mean 250 nm, amplitude 3 nm. A plan view resembles TEM images of (010)-parallel exsolution textures of orthoamphiboles. A second set of corrugations may crosscut the [001]-parallel ridges at 20–25°, akin to reported lamellar intergrowths developed parallel to both (010) and (120). Unequivocal evidence linking topography with lamellae is absent. In contrast to the conventional multi-layer reflector model, the ridged surface provides an additional origin for iridescence, acting as a diffraction grating. Included zircons, 50–10 μm, have Hf/Zr = 0.008–0.012, Hf+FeIIc. 0.16. 207Pb/206Pb ages are from 2690 to 2770 Ma, averaging 2732±10 Ma. Coexisting, included Th-, La-, Ce-, Pr-, Nd-, Gd-, Y-monazites have 207Pb/206Pb ages from 2680 to 2720 Ma, averaging 2707±12 Ma. The included crystals grew during a late Archaean metamorphism that produced overgrowths on zircons within gneisses to the north, but with Simiuttat grains showing a more complex history. The lamellae may have developed at the same time, or during a reheating c. 2550 Ma, or in a subsequent Proterozoic metamorphism.

Meurigite is a new hydrated potassium iron phosphate related to kidwellite and with structural similarities to other late-stage fibrous ferric phosphate species. It has been found at four localities so far — the Santa Rita mine, New Mexico, U.S.A.; the Hagendorf-Sud pegmatite in Bavaria, Germany; granite pegmatite veins at Wycheproof, Victoria, Australia; and at the Gold Quarry Mine, Nevada, U.S.A. The Santa Rita mine is the designated type locality. Meurigite occurs as tabular, elongated crystals forming spherical and hemispherical clusters and drusy coatings. The colour ranges from creamy white to pale yellow and yellowish brown. At the type locality, the hemispheres may reach 2 mm across, but the maximum diameter reached in the other occurrences is usually less than 0.5 mm. A wide variety of secondary phosphate minerals accompanies meurigite at each locality, with dufrenite, cyrilovite, beraunite, rockbridgeite and leucophosphite amongst the most common. Vanadates and uranates occur with meurigite at the Gold Quarry mine.

Electron microprobe analysis and separate determination of H2O and CO2 on meurigite from the type locality gave a composition for which several empirical formulae could be calculated. The preferred formula, obtained on the basis of 35 oxygen atoms, is which simplies Qualitative analyses only were obtained for meurigite from the other localities, due to the softness and openness of the aggregates. Because of the fibrous nature of meurigite, it was not possible to determine the crystal structure, hence the exact stoichiometry remains uncertain. The lustre of meurigite varies from vitreous to waxy for the Santa Rita mine mineral, to silky for the more open sprays and internal surfaces elsewhere. The streak is very pale yellow to cream and the estimated Mohs hardness is about 3. Cleavage is perfect on {001} and fragments from the type material have a mean specific gravity of 2.96.

The strongest lines in the X-ray powder pattern for the type material are (dobs,Iobs,hkl) 3.216(100)404; 4.84(90)111; 3.116(80)205; 4.32(70)112; 9.41(60)201; 3.470(60)800. The X-ray data were indexed on the basis of a monoclinic unit cell determined from electron diffraction patterns. The cell parameters, refined by least squares methods, are a = 29.52(4), b = 5.249(6), c = 18.26(1) Å, β = 109.27(7)°, V = 2672(3) Å3, and Z = 4. The calculated density is 2.89 gcm−3. The space group is either C2, Cm or C2/m. X-ray powder data for meurigite are closely similar to those for kidwellite and phosphofibrite, but meurigite appears to be characterised by a strong 14 Å reflection. The relationship between these three minerals remains uncertain in the absence of structural data. On the available evidence, meurigite and kidwellite are not the respective K and Na-endmembers of a solid solution series. The meurigite cell parameters suggest it belongs to a structural family of fibrous ferric phosphates, such as rockbridgeite, dufrenite and beraunite, which have a discrete 5 Å fibre axis. Meurigite occurs in widely varying environments, its formation probably favoured by late-stage solutions rich in K rather than Na.

Radial and longitudinal temperature gradients within cold-seal pressure vessels can contribute significantly to the total temperature unccrtainty in any one experiment and it is important to calibrate such gradients before experiments are undertaken. We have measured temperature gradients in vertically mounted large cold-seal vessels at 1 atm and 1 kbar and in the temperature range 500–800°C Radial gradients were measured with the vessel at various positions within the furnace by recording the temperature difference between a thermocouple in the internal bore of the vessel and one in a well in the top of the vessel. We find that when the vessel is at a certain position in the furnace, the temperatures read by these two thermocouples are equivalent to within 1°C. The contribution of radial gradients to temperature uncertainty can be thus be substantially minimized if experiments are undertaken with the vessel in this position. Longitudinal gradients of 2.8°C/cm at 500°C and 3°C/cm at 800°C were recorded at 1 kbar. These profiles are significantly steeper than those recorded at 1 atm. Not to calibrate temperature gradients at the experimental conditions or failure to calibrate vessels at all could lead to large temperature uncertainties.

Ruby-sapphire-sapphirine-spinel forms small, corroded, crystalline aggregates in corundum bearing alluvials shed from the Tertiary Barrington basalt shield volcano. Sapphirine is near a 7:9:3 (MgO-Al2O3-SiO2) composition and, together with the corundum, shows reaction rims of pleonaste spinel. Spinel in the aggregates has a compositional range Sp 68–73 Hc 27–29 Cm 0–3. The aggregates give new insights into the ruby-sapphire source rocks. Potential origins include metamorphic recrystallization of aluminous material (below 1460°C) or high temperature-high pressure crystallization reactions related to lamprophyric or basaltic magmas (up to 1300°C and 20 kbar). Sapphirine-spinel thermometry suggests final crystallization temperatures for the aggregates around 780 to 940°C and reaction with host magmas at over 1000°C.

The Barrington gemfield includes two distinct corundum suites. One, typical in eastern Australia, is dominated by blue-green, well-crystallized, growth-zoned sapphire, commonly containing rutile silk and Ferich spinel inclusions (Hc 51–73, Mt 18–35, Mf 6–8, Usp 2–6). The other, an unusual suite, is dominated by ruby and pastel coloured sapphires, with little crystal shape or growth zonation and restricted mineral inclusions, mostly chromian pleonaste and pleonaste. The ruby-sapphire-sapphirine-spinel aggregates provoke new thoughts on the origin of rubies and sapphires and their indicator minerals in eastern Australian and southeastern Asian volcanic gemfields.

Baotite occurs as an accessory mineral in carbonatites, fenites, and carbothermal veins associated with a lamprophyre dyke swarm in the Haast River area of south Westland, New Zealand. Carbonatites are petrogenetically evolved, with assemblages dominated by ankerite, siderite and Ba-Sr-REE carbonates. Microprobe analysis indicates baotite compositions more Nb-rich than previously recorded, with compositions close to Ba4[Ti3(Nb,Fe)5]Si4O28Cl. Ti must be partially replaced in both crystallographically-independent octahedral sites. Compositional zoning, and stoichiometric considerations suggest that the dominant octahedral substitution is the same as that described in rutile, namely 3Ti4+ ⇌ 2Nb5+ + Fe2+. Contrary to previous suggestions, Fe in the octahedral site should, therefore, be dominated by Fe2+.

The presence of baotite further documents the involvement of halogens in carbonatite magmas. In the New Zealand occurrences it is suggested that the chlorine originates from associated phonolitic magmas and is partitioned into carbonatite during liquid immiscibility.

Kornerupine and prismatine were introduced independently by Lorenzen in 1884 (but published in 1886 and 1893) and by Sauer in 1886, respectively. Ussing (1889) showed that the two minerals were sufficiently close crystallographically and chemically to be regarded as one species. However, recent analyses of boron using the ion microprobe and crystal structure refinement, indicate that the boron content of one tetrahedral site in kornerupine ranges from 0 to 1. Kornerupine and prismatine, from their respective type localities of Fiskenæsset, Greenland and Waldheim, Germany, are distinct minerals, members of an isomorphic series differing in boron content. For this reason, we re-introduce Sauer’s name prismatine for kornerupines with B > 0.5 atoms per formula unit (p.f.u.) of 22(O,OH,F), and restrict the name kornerupine sensu stricto to kornerupines with B < 0.5 p.f.u. Kornerupine sensu lato is an appropriate group name for kornerupine of unknown boron content. Kornerupine sensu stricto and prismatine from the type localities differ also in Fe2+/Mg ratio, Si − (Mg + Fe2+ + Mn) content, Al content, F content, colour, density, cell parameters, and paragenesis. Both minerals formed under granulite-facies conditions with sapphirine and phlogopite, but kornerupine sensu stricto is associated with anorthite and hornblende or gedrite, whereas prismatine is found with oligoclase (An9–13), sillimanite, garnet, and/or tourmaline. Occurrences at other localities suggest that increasing boron content extends the stability range of prismatine relative to that of kornerupine sensu stricto.

The compositions and textural relationships of the oxide minerals zirconolite, pyrochlore and baddeleyite are described. These occur as accessory minerals, often intergrown with each other, from a phoscorite rock associated with the Kovdor carbonatite complex. Both the zirconolite and baddeleyite have relatively high concentrations of Nb and Ta; the pyrochlore is rich in U and Ta. Backscattered electron images, coupled with detailed microprobe analyses, reveal complex compositional zoning in zirconolite and pyrochlore which reflect changes in the fluid composition during growth of these minerals. A comparison is made of incompatible element ratios Zr/Hf, Nb/Ta and Th/U between the three accessory minerals.

A detailed geochemical study is presented of the uppermost Critical Zone, especially of the footwall and hanging wall to the Merensky Reef, at Impala Platinum Mines in the Bushveld Complex. The approximately 100 m-thick sequence below the Merensky Reef consists of 13 distinct layers which have sharp boundaries. They are adcumulates with varying proportions of cumulus plagioclase, orthopyroxene and chromite.

Experimental studies on the composition of coexisting orthopyroxene liquid indicate that the magma which produced this sequence contained between 4 and 6% MgO. The magma from which the Merensky Reef formed was more evolved than the footwall magma.

Significant variations exist for both the En content of orthopyroxene and mg# number of whole-rock analyses in short vertical sections. Pyroxenite and norite always have higher values than anorthosite. Extremely sharp breaks in these values correlate with changes in modal proportions, and argue against both significant fractionation within the studied interval, and infiltration metasomatism. Quantitative modelling shows that the entire footwall section could have contained pyroxene with a uniform primary composition of En82, and that all the variation now observed reflects the effect of reaction with trapped magma.

Two independent methods for determining the proportion of trapped liquid are presented, based on mg# number and incompatible element abundances. Both yield a uniform proportion in all samples of approximately 10%. Immiscible sulphide liquid from the Merensky Reef can be shown to have infiltrated downwards for <5 m, despite its high density contrast with silicate magma, very low viscosity and low crystallization temperature. Residual silicate magma would have had even more restricted mobility. The migration of residual liquid or fluid through pothole structures in the floor of the Merensky Reef is not supported by the present data.

Wesselsite, SrCu[Si4O10], is a new mineral species from the Wessels mine, Kalahari Manganese Field, South Africa, and it belongs to the gillespite group. Wesselsite is tetragonal, space group P4/ncc; the unit cell parameters, refined from Gandolfi film data, are a = 7.366(1), c = 15.574(3) Å V = 845.01 Å3. The strongest lines are (dobs/lobs/hkl) (7.79/35/002), (4.33/20/112), (3.89/20/004), (3.44/40/104), (3.33/100/202), (3.12/55/114), (3.03/50/212), (2.68/25/204), (2.61/30/220) and (2.32/30/116). Wesselsite is associated with hennomartinite, embedded in a matrix of sugilite, xonotlite, quartz and pectolite. Microprobe analyses of 111 samples show that it is the end-member of a solid solution series with effenbergerite, BaCu[Si4O10], with substitutions of Sr by Ba up to 50 mol.%. Wesselsite forms tiny subhedral plates in sizes not exceeding 50 × 50 × 5 µm, arranged in clusters of up to 200 µm. It shows a perfect cleavage parallel to {001}, has blue colour, white to light blue streak, and is uniaxial negative with ω = 1.630(2), ε = 1.590(5), strongly pleochroic from blue (ω) to pale blue (ε). The calculated density is 3.32 g cm−3, the measured density is 3.2(1) g cm−3.

Thermal expansion coefficients were measured for a cancrinite from Bancroft, Ontario, Canada. Measurements of cell parameters and unit-cell volumes were obtained at room temperature and at heating intervals of 50°C over the temperature range from 50 to 1400°C. The unit-cell parameters for cancrinite increase non-linearly with temperature up to 1200°C and shortly thereafter, the mineral melted. The c parameter increases more rapidly than the a parameter, and the c/a ratio increases linearly with temperature. A plausible thermal expansion mechanism for cancrinite, which is based on the framework expansion that occurs as a function of cavity content, is presented. In the thermal expansion of cancrinite, the short Na-H2O in the H2O-Na—H2O chain expands to form equal distances to the two H2O molecules in the chain. This causes the Na atoms to move towards the plane of the six-membered rings and forces the tetrahedra to rotate and the rings become more planar. The Na atoms then form bonds to all six (O1 and O2) oxygen atoms in a ring; the Na-O1 bonds become shorter and the Na-O2 bonds become longer. These effects cause an increase in both a and c, and thus an increase in the c/a ratio. A similar thermal expansion mechanism operates in the sodalite-group minerals where the six-membered rings and Na-Cl bond are involved.

Armalcolite and pseudobrookite have been crystallized from synthetic melts of basaltic composition with variable amounts of added TiO2. It was found that the composition of the armalcolite and pseudobrookite are dependent on the TiO2 content of the melt and the conditions (particularly oxygen fugacity, but also temperature and quenching rate) of formation. The maximum Al2O3 content of pseudobrookite appears to be ∼14–15 wt.% Al2O3, a spinel-like phase being exsolved at higher Al2O3 concentrations. Generally armalcolite is formed at low pO2 and pseudobrookite at higher oxygen fugacities.

Three natural spinels of different places of occurrence and compositions were investigated by means of microprobe chemical analysis, single crystal X-ray diffraction and Mössbauer spectroscopy. All cation distributions between T and M sites were calculated from microprobe and XRD experimental data, by means of a mathematical model with appropriate assumptions. Fe2+ and Fe3+ assignments calculated in this way were compared with those observed in Mössbauer spectra. The satisfactory agreement found proves, at least in the samples studied, the reliability of the model and the assumptions used. In the spinels examined, such results show Fe2+ and Fe3+ virtually ordered in T and M sites respectively. Mössbauer data also revealed Fe2+ in different tetrahedral sites due to the next-nearest neighbour effect, probably as a consequence of spinel genetic conditions.

Selected-area electron diffraction patterns for the [110] zone of MgSiO3 perovskite are consistent with the orthorhombic unit cell obtained by X-ray diffraction (a = 4.775, b = 4.929, c = 6.897 Å). Various areas of a crystal fragment show diffuse streaking along c*, and well-developed satellite reflections that give a 3-fold repeat along [10]*. Another fragment shows doubled cell dimensions when viewed down [30]. The variable occurrence of the satellite reflectioncs and diffuse streaking indicate subtle variations in ordering, chemistry, or both. Images obtained by high-resolution transmission electron microscopy contain perfectly ordered regions, out-of-phase boundaries, and intergrowths of the two orthorhombic forms of perovskite.

Viséite is a poorly crystalline mineral which is difficult to study by X-ray diffraction pattern. NMR is a very useful technique to study such poorly crystalline minerals, and 31P, 27Al, and 29Si MAS NMR in conjunction with powder XRD results show that at least our Viséite sample is not a single phase with a structure analogous to that of analcime as previously reported. Rather, it is very disordered with a structure similar to that of crandallite and includes other phases including an undefined aluminophosphate, opal, and a framework aluminosilicate, probably a zeolite. The previously reported variations in the Si content of Viséite are probably due to variable amounts of opal and the framework aluminosilicate.

High-pressure amorphization of anorthite has been observed by energy-dispersive X-ray diffraction of powdered samples held under static pressure in a diamond anvil cell. The onset of amorphization is accompanied by a significant reduction in the intensity of Bragg reflections at pressures between 10 and 14 GPa, and anorthite becomes completely X-ray amorphous between 14 and 20 GPa. These pressures are significantly lower than those suggested by earlier birefringence studies. The discrepancy can be reconciled in terms of a model of high-pressure amorphization in which partially amorphized anorthite can be regarded as a spatially heterogeneous anti-glass, with long-range order maintained but translational disorder dominating at shorter correlation lengths.

Lacking the pronounced modal layering of the underlying Critical Zone, the Main Zone of the Bushveld Complex nevertheless displays well-developed cryptic layering, expressed in a series of iron-enrichment trends, each defining a unit of the order of 100 to 200 m thick. At the base of one such unit, 1100 m above the Main Zone — Critical Zone contact, a 10 m thick pyroxenitic layer was intersected in an exploration borehole from the southern sector of the western Bushveld.

Within the pyroxenitic layer, mineral chemistry defines a series of five cycles of upward Mg and Cr enrichment in pyroxenes, and Ca enrichment in plagioclase. The mineral chemistry, supported by textural evidence, suggests the influx of successive surges of magma. Sustained streaming of magma gave rise to adcumulate textures in the central portion of each cycle, with orthocumulate textures at bases and tops of cycles representing waxing and waning stages of magma surges.

Ferrous substituted saléeite is a new variety of saléeite from Arcu su Linnarbu, Sardinia. It is tetragonal with a = 6.982(2) c = 19.660(2) Å, Z = 2; the ideal formula is (Mg,Fe2+)(UO2)2(PO4)2·4H2O. The strongest lines in the X-ray powder diffraction pattern are: 3.473(100)(114), 4.95(50)(110), 4.91(40)(004), 4.443(40)(112), 2.200(30)(118), 2.193(30)(303) and 2.178(30)(009). The mineral is light-yellow in colour and is dull fluorescent. The measured density is 3.242 g/cm3 and Z = 2. There is a prominent (001) cleavage. Refractive indices are : α = 1.572(2) β = 1.577(2) γ = 1.581(2) and 2V = 48°(2). The pleochroism is very weak and the elongation is positive parallel to Y. The mineral occurs as subparallel crystal aggregates with a quadratic outline.