The Lovozero alkaline massif is the largest of the world's layered peralkaline intrusions (∼650 km2). We describe the evolution of clinopyroxene from the liquidus to the late residual stage throughout the whole vertical section (2.5 km thick) of the Lovozero Complex. Microprobe data (∼990 analyses) of the clinopyroxenes define a relatively continuous trend from diopside containing 15–20% hedenbergite and 10–12% aegirine components, to pure aegirine. The main substitutions during the evolution of the Lovozero pyroxenes are (Na,Fe3+,Ti) for (Ca,Mg,Fe2+). The composition of the pyroxene changes systematically upwards through the intrusion with an increase in Na, Fe3+ and Ti and decrease in Ca and Mg.

The compositional evolution of the Lovozero pyroxene reflects primary fractionation processes in the alkaline magma that differentiated in situ from the bottom to the top of the magma chamber as a result of magmatic convection, coupled with the sedimentation of minerals with different settling velocities.

The temperature interval of pyroxene crystallization is very wide and probably extends from 970 to 450°C. The redox conditions of pyroxene crystallization in the Lovozero intrusion were relatively low, approximating the QFM buffer.

The uptake of inorganic Hg2+ and organometallic CH3Hg+ from aqueous solutions by 11 different natural zeolites has been investigated using a batch distribution coefficient (Kd) method and supported by a preliminary voltammetric study. The effect of mercury concentration on the Kd response is shown over an environmentally appropriate concentration range of 0.1–5 ppm inorganic and organometallic Hg using a batch factor of 100 ml g-1 and 20 h equilibration. Analcime and a Na-chabazite displayed the greatest methylmercury uptakes (Kd values at 1.5 ppm of 4023 and 3456, respectively), with mordenite as the smallest at 578. All uptake responses were greater for methylmercury than for the inorganic mercuric nitrate solutions, suggesting a distinctive sensitivity of zeolites to reaction with different types of solute species. It is likely that this sensitivity is attributable to the precise nature of the resultant Hg-zeolite bonds. Additionally, both the Si-Al ratio and the Na content of the initial natural zeolite samples are shown to influence the Kd responses, with positive correlations between Kd and Na content for all zeolites excluding mordenite.

The crystallographic orientation of carlsbergite (CrN) in the north Chile meteorite (hexahedrite) was investigated using electron backscatter diffraction and transmission electron microscopy. These studies examined the CrN crystals in the rhabdites (idiomorphic schreibersite) and in kamacite. It was found that the CrN crystals embedded in rhabdite show a number of different orientation relationships with the host crystals. These orientations can be explained based on the lattice dimensions of both coexisting crystalline materials. It was also found that both carlsbergite and kamacite are characterized by a high dislocation density (≥ l09 cm-2) while rhabdite is free of dislocations. It is supposed that in spite of the deformed metallic matrix, a general connection between the orientation relation of all the phases involved exists.

We have investigated the thermal expansion of nepheline-kalsilite crystalline solutions having 12.5% excess silicon relative to the stoichiometric composition. It is proposed that differences in the thermal expansion among various members of the series, and also between this series and a previously studied low-Si series, can be explained by three factors: (1) shrinkage of the tetrahedral rings caused by the substitution of Na for K, especially in the case of kalsilite, allows for greater expansion from the increased vibrational amplitude of Na ions with increasing temperature. (2) The occupancy of alkali sites by ions rather than vacancies draws tetrahedral rings inward via electrical attraction to these ions, providing the potential for greater expansion with ionic vibration as temperature increases. (3) Structural differences between nepheline and kalsilite, in particular the existence of two alkali sites in nepheline, account for the increased thermal expansion of K-enriched nepheline relative to Na-nepheline, as the occupation of the larger alkali position by K+ results in greater thermal expansion than is the case with Na+ occupancy of the same sites.

Kamphaugite-(Y) occurs as white to cream-coloured spherical to semi-spherical aggregates of radial crystals in the La Cabrera granitic pluton (Spanish Central System). It mainly occurs on the free surfaces of alkali feldspar, quartz, calcite, kainosite-(Y) and laumontite, and inside miarolitic cavities. La Cabrera kamphaugite-(Y) has an average composition of Ca0.94Y0.89REE0.21(CO3)2 [F0.05(OH)0.95]·1.19H2O. Negative δ13CV-PDB values (–14 to –15‰) indicate a meteoric carbon source. Textural relations between kamphaugite-(Y) and coexisting minerals, its relatively high δ18OV-SMOW values (+25 to +26‰), and the occurrence of laumontite inclusions in kamphaugite-(Y), point to a genesis at < 50°C during very low-temperature post-magmatic hydrothermal activity.

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+.

Allanite is present in most samples of the tonalitic Bell Island Pluton, with an average mode near 0.05 wt.%. Allanite occurs as cores in igneous epidote-clinozoisite and exhibits characteristic and consistent zoning patterns. REE-rich cores (All40-70) grade out towards epidote-clinozoisite with REE below electron microprobe detection limits. La, Ce and Pr contents are highest in the REE-rich cores of zoned crystals. Nd and Sm contents both initially increase as total REE decreases and are highest in intermediate zones. Y contents are generally low throughout, but tend to be highest in analyses with A115-20. The zoning behaviour exhibited by the allanite, specifically the rimward increases in Nd, Sm, and Y, cannot be accounted for by simple fractionation and are best explained by increases in allanite/ melt partition coefficients (Kd values) for these elements during crystallization. We propose that the variation in Kd values reflects modification of the allanite structure with changing REE content. These modifications are manifested by changes in colour, extinction, and pleochroism within the zoned crystals and include changes in unit-cell volume and dimensions. The changes in Kd values are large enough to result in crossing REE patterns within single allanite crystals. Fractional crystallization of zoned allanite can have noticeable effects on LREE contents and La/Sm (and almost certainly La/Lu) in magmas. In the Bell Island pluton, 80% of La, but <3% of Y is contained in allanite. Although some of the variation in the LREE chemistry of the pluton is attributable to statistical sampling error, much of it appears to reflect petrogenetic processes that controlled LREE abundance and, ultimately, allanite mode. One sample of Bell Island tonalite is depleted in LREE and has low La/Lu and La/Sm. These chemical features can be modelled by fractionation of zoned allanite.

Stalactites formed by the chemical weathering of natrocarbonatite lava decorate the roofs of hollow inactive hornitos at Oldoinyo Lengai, Tanzania. The stalactites are composed principally of trona with lesser and very variable amounts of nahcolite, (NaHCO3), thermonatrite (Na2CO3.H2O), aphthitalite [(K,Na)3Na(SO4)2], kogarkoite [Na3(SO4)F], schairerite [Na21 (SO4)7F6Cl], halite and sylvite. Stalactites are considered to form by the evaporation of Ca-free highly alkaline brines seeping from the altered lavas which form the roofs of the hornitos. The principal subaerial weathering products of natrocarbonatite, i.e. pirsonnite, gaylussite, shortite and calcite are not found in the stalactites and are retained in the altered lavas of the homito roof. Fluorine required for the formation of kogarkoite and schairerite is derived from the decomposition of fluorite at high pH (>10). Sulphur is derived from the decomposition of gregoryite.

Extreme silver enrichment at the surface of the complex sulphide, tennantite (ideal formula: Cu12As4S13), occurs following exposure to alkaline solutions, and involves the development of an Ag-rich sulphide surface species. The tennantite has a low bulk Ag content of 0.3 at.%, and a percentage surface enrichment of Ag is thirty-six times that of the bulk. The techniques of X-ray photoelectron spectroscopy (XPS) and reflection extended X-ray absorption fine structure spectroscopy show the new phase to be a Ag sulphide species compositionally similar to cupriferous proustite ((Cu,Ag)3AsS3). Solution experiments and XPS depth profiling show that the surface is most depleted in Cu and Zn, and enriched in Ag compared to the bulk tennantite. Selective dissolution and reprecipitation at the tennantite surface cannot explain the enrichment of Ag relative to the bulk. Migration must have occurred and could have been driven by the leaching out of Cu which produces a metal-depleted surface, coupled to the relative incompatibility of Ag in the tennantite lattice. To account for the extreme enrichment at the surface, Ag must have diffused from depths of up to 9 nm, probably via structural weaknesses and vacancies in the tennantite lattice.