White mineral coating joint-faces in quarries in the Northampton ironstone (Inferior Oolite) was long ago recorded as allophane. W. D. Herman who determined the mineral from the surface of a sandstone rock in a quarry opened in 1871 also analysed an unnamed white earthy mineral from crevices in the ironstone and obtained a composition close to that of fully hydrated halloysite.

During the six-inch geological survey of that ironstone field in 1939–44 the occurrence of similarly situated white incrustations and joint infillings was found to be widespread especially in the shallow workings where the ferrous minerals chamosite and chalybite have been oxidizedto produce a limonitie ore.

Zoned barian muscovite (2.52-5.66% BaO) and unzoned biotite (0.99-1.77% BaO) occur in two amphibolite grade metacherts of the Alpine schists, Southern Alps, New Zealand. The Ba-micas are associated with quartz-chlorite-Mn-garnet-tourmaline-apatite-sulphide ± oligoclase ± rutile ± magnetite ± ankerite. Increasing Ba (core to rim) in the muscovite is accompanied by a decrease in Si, Ti, Fe + Mg, and K and an increase in [4]Al, [6]Al, and Na. The main substitution that accounts for entry of Ba into both micas is [A]Ba2+ + [4]Al3+ ⇋ [A]K+ + [4]Si4+ and possibly [A]Ba2+ ⇋ [A]K+ + □. Compositional variation of the muscovite is also governed by the substitutions, [6]Al3+ + [4]Al3+ ⇋ [6](Mg,Fe)2+ + [4]si4+, and [A]Na+ ⇋ [A]K+. The presence or absence of oligoclase, rutile, magnetite and Mg/(Mg + Fe) ratio of coexisting biotite control the Na, Ti, Fe and Mg contents of muscovite in the respective metacherts. Important variables controlling the occurrence of Ba-mica is the Ba-rich composition of the metacherts (1387 and 2741 ppm Ba) and metamorphic grade. In metacherts, siliceous and quartzofeldspathic schists with <1000 ppm Ba barium increases with increasing K2O content indicating that in K-feldspar-absent rocks barium is mainly contained in micas (<0.70% BaO). In greenschist facies metacherts and siliceous schists with high Ba (>1000 ppm) and low K2O, barian micas are not present and most of the Ba occurs in baryte ± barian carbonate with implication of a significant original hydrothermal-hydrogenous input. Although low grade illite/sericite/smectites containing Ba are the most likely precursor of the barian micas in the metacherts, strong marginal Ba enrichment in the muscovite indicates a later Ba-metasomatism resulting from the breakdown of baryte under reducing conditions during amphibolite facies metamorphism.

Major, minor, and trace elements were measured with electron and ion microprobes for eighteen anorthoclase megacrysts from five locations. Comparisons with concentration ranges tabulated by Smith (1974) show excellent agreement except for consistently lower values of Mg and B. The discrepancy for Mg probably reflects Mg-rich impurities contaminating samples analysed by bulk methods. The cause of the discrepancy for B is unknown and deserves further study. Samples from Mt. Erebus, Antarctica, contain glass inclusions from which the following crystal/liquid partition coefficients ensue: Mg, 0.008; P, 0.04; Ti, 0.08; Fe, 0.04; Ba, 5.2; Sr, 8; Rb, 0.27.

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.

Chemical compositions, unit-cell contents, and optical properties of six clinopyroxenes from the Upper Layered Series are presented. There is a gradual enrichment in iron upwards in the intrusion although there is no measurable effect on the optical properties, possibly because of Cr variation and exsolution of Fe and Ti as oxides. The chemistry of the clinopyroxenes is consistent with crystallization from a water-rich magma of transitional nature between tholeiite and alkali-olivine basalt. X-ray oscillation photographs of single crystals reveal the presence of sub-microscopic exsolution lamellae of pigeonite, a feature consistent with the transitional nature of the parent magma. Exsolution lamellae of titanomagnetite are ubiquitous and were formed at subsolidus temperatures in response to high buffered oxygen fugacity. Comparisons are made between the properties of clinopyroxenes from the Lower, Middle, and Upper Layered Series, and the conditions of crystallization of each series.

Basalt glass from Kilauea, Hawaii (SBG) starts to crystallize upon heat treatment in air at ∽840°C. In addition, oxidation takes place. The kinetics of both processes may be readily quantified though the mechanism is difficult to access. This work investigates the relationship between these processes, crystallization and oxidation, and the escape of volatiles from the glass/liquid upon reheating. Evolved gas analyses and differential scanning calorimetry are the techniques used. In addition, isothermal heat treatment in argon is carried out in order to eliminate the external reason for oxidation, the oxygen gradient, and to focus on intrinsic oxidation. Products are examined with 57Fe Mössbauer spectroscopy. As expected, degassing temperatures of SBG, and of two MORB samples, considered for comparison, are above the glass transition temperature. We find no convincing evidence of intrinsic oxidation. Degassing is likely to induce interface-controlled crystallization.

The available data on compositional zoning in grossular-andradite (grandite) garnets occurring at different scales, mainly due to the variations of their Fe3+/Al ratios, and the hypotheses on the origin of this zoning are reviewed. Four zoned crystals of grandites showing different optical properties have been studied by means of X-ray diffraction. Optical and structural studies suggest three superimposed scales of Fe3+/Al zonality along [110]. The drastic change of the structural characteristics from sample to sample correlates with the change of their optical patterns. The superfine oscillatory zoning has been described in terms of irregular interstratified structures with a high degree of segregation. The self-affinity of zoning at different scales testify to the possible origin of the zonality due to the non-linear dynamics at the growth front. The wide variation of the layer compositions revealed by the modelling of the X-ray diffraction profiles seems to contradict the hypothesis of unmixing in grandite garnets.

Hydrothermal ruffles from a suite of rocks at Mount Perry, Queensland, have been studied in thin section, by electron microprobe analysis, and by transmission electron microscopy. The iron-bearing rutiles, while originally singte-phase, are found to exsolve a sequence of iron-rich precipitates on experimental annealing, with hematite being formed as the stable equilibrium precipitate. Experiments at different temperatures and annealing times enable a time-temperature-transformation plot to be drawn for the exsolution process. The kinetics of this process are used to conclude that the rutiles formed below about 450 °C.

Preliminary atomic force microscopy investigations of the {104} calcite surface cleaved in ethanol indicate a different surface behaviour than that of the {104} surface cleaved in air. The results are consistent with recent theoretical studies and suggest strong ordering of ethanol over the termination of the bulk calcite structure.

The rare zeolite mineral gobbinsite has been found in vugs of altered basalts at the Magheramorne Quarry, Lane, Northern Ireland, intimately associated with phillipsite. The crystal chemistry of the sample (Na4.3Ca0.6Si10.4Al5.6O32·12H2O) is close to that reported for gobbinsite from the type locality. The crystal structure of the Magheramorne gobbinsite has been refined from X-ray powder diffraction data using the multiphase Rietveld full profile technique. The orthorhombic Pmn21 space group is confirmed. The refined cell parameters (a = 10.1027(5), b = 9.8016(5), and c = 10.1682(6) Å) are slightly different from those reported in the literature for the K-rich gobbinsite from Island Magee (a = 10.108(1), b = 9.766(1), and c = 10.171(1) Å), whose structure was also refined from powder data.

Eight new and fourteen published analyses of astrophyllites are used to examine chemical variation within the group. Al, Ca, Cs, F, Mg, Mn, Nb, Rb, Sn, Zn, and Zr may all substitute in moderate to large amounts in the unit cell, whose basic formula is (K,Na)3Fe7Ti2Si8(O,OH)31; the natural Mn- and Nb- analogues of astrophyllite have been recorded. Ba, Cl, Cu, Li, P, Pb, Sr, and Ta are present, but in smaller amounts. The majority of specimens show appreciable cation deficiencies, up to 5 % of sites remaining vacant. Astrophyllites from undersaturated igneous rocks are characterized by higher Al, Ca, Mg, Mn, (OH+F), (K+Na) and Zr, and lower Li, Pb, and Zn contents than those from oversaturated igneous rocks. A ‘high-alkali’ type of astrophyllite is distinguished. A new occurrence of nigerite is noted.

We report a new type of högbomite in a spinel- and sapphirine-bearing silica-deficient Mg-Al rock from Manavadi at the northern margin of the Madurai Block along the Palghat-Cauvery shear zone system, which defines the Archaean-Proterozoic collisional boundary in southern India. Högbomite occurs here as fine- to medium-grained euhedral to subhedral crystals enclosed within or along grain boundaries of greenish spinel. It is compositionally very unique due to the lack of TiO2 (<0.2 wt.%) and enrichment in Al2O3 (66.4—70.8 wt.%) compared to other occurrences. The variety of högbomite described in this study, confirmed by laser Raman spectroscopy, has not been reported elsewhere previously. Högbomite in this study is subdivided into three groups based on the XMg (=Mg/ (FeTotal+Mg)) ratio; 0.54—0.57, 0.61—0.73 and 0.77—0.79. Compositional data suggest a linear element substitution of 3(Fe+Mg) = 2Al for the Ti-free högbomite, a trend that is distinct from previously reported Ti-bearing högbomites. Textures and mineral chemistry data suggest that the following reaction took place at retrograde stage (T <800°C): spinel + H2O + O2 → högbomite + corundum + magnetite, implying that introduction of hydrous and oxidized fluid as well as low bulk-Ti content played an important role in the formation of Ti-free högbomite.

The high-temperature (HT) behaviour of a sample of natural alunite was investigated by means of in situ HT single-crystal X-ray diffraction from room temperature up to the dehydroxylation temperature and consequent collapse of the crystal structure. In the temperature range 25–500°C, alunite expands anisotropically, with most of the contribution to volume dilatation being produced by expansion in the c direction. The thermal expansion coefficients determined over the temperature range investigated are: αa = 0.61(2) × 10–5 K–1 (R2 = 0.988), αc = 4.20(7) × 10–5 K–1 (R2 = 0.996), αc/αa = 6.89, αV = 5.45(7) × 10–5 K–1 (R2 = 0.998). At ∼275–300°C, a minor discontinuity in the variation of unit-cell parameters with temperature is observed and interpreted on the basis of loss of H3O+ that partially substitutes for K+ at the monovalent A site in the alunite structure. Increasing temperature causes the Al(O,OH)6 sheets, which remain almost unaltered along the basal plane, to move further apart, and this results in an expansion of the coordination polyhedron around the intercalated potassium cation. Sulfate tetrahedra act as nearly rigid units, they contract a little in the lower temperature range to accommodate the elongation of the Al octahedra.

Hydroxynatropyrochlore, (Na,Сa,Ce)2Nb2O6(OH), is a new Na–Nb–OH-dominant member of the pyrochlore supergroup from the Kovdor phoscorite–carbonatite pipe, Kola Peninsula, Russia. It is cubic, Fd$\bar{3}$m, a = 10.3211(3) Å, V = 1099.46(8) Å3 and Z = 8 (from powder diffraction data) or a = 10.3276(5) Å, V = 1101.5(2) Å3 and Z = 8 (from single-crystal diffraction data). Hydroxynatropyrochlore is a characteristic accessory mineral of the low-carbonate phoscorite in the contact zone of the phoscorite–carbonatite pipe with host foidolite as well as in the carbonate-rich phoscorite and carbonatite of the pipe axial zone. It usually forms zonal cubic or cubooctahedral crystals (up to 0.5 mm in diameter) with irregularly shaped relics of amorphous U–Ta-rich hydroxykenopyrochlore inside. Characteristic associated minerals include rock-forming calcite, dolomite, forsterite, hydroxylapatite, magnetite and phlogopite, accessory baddeleyite, baryte, barytocalcite, chalcopyrite, chamosite–clinochlore, galena, gladiusite, juonniite, ilmenite, magnesite, pyrite, pyrrhotite, quintinite, spinel, strontianite, valleriite and zirconolite. Hydroxynatropyrochlore is pale brown, with an adamantine to greasy lustre and a white streak. The cleavage is average on {111} and the fracture is conchoidal. Mohs hardness is ~5. In transmitted light, the mineral is light brown, isotropic and n = 2.10(5) (λ = 589 nm). The calculated and measured densities are 4.77 and 4.60(5) g cm−3, respectively. The mean chemical composition determined by electron microprobe is: F 0.05, Na2O 7.97, CaO 10.38, TiO2 4.71, FeO 0.42, Nb2O5 56.44, Ce2O3 3.56, Ta2O5 4.73, ThO2 5.73, UO2 3.66, total 97.65 wt.%. The empirical formula calculated on the basis of Nb + Ta + Ti = 2 apfu is (Na1.02Ca0.73Ce0.09Th0.09 U0.05${\rm Fe}_{{\rm 0}{\rm. 02}}^{2 +} $)Σ2.00(Nb1.68Ti0.23Ta0.09)Σ2.00O6.03(OH1.04F0.01)Σ1.05. The simplified formula is (Na,Ca,Ce)2Nb2O6(OH). The mineral dissolves slowly in hot HCl. The strongest X-ray powder-diffraction lines [listed as (d in Å)(I)(hkl)] are as follows: 5.96(47)(111), 3.110(30)(311), 2.580(100)(222), 2.368(19)(400), 1.9875(6)(333), 1.8257(25)(440) and 1.5561(14)(622). The crystal structure of hydroxynatropyrochlore was refined to R1 = 0.026 on the basis of 80 unique observed reflections. The mineral belongs to the pyrochlore structure type A2B2O6Y1 with octahedral framework of corner-sharing BO6 octahedra with A cations and OH groups in the interstices. The Raman spectrum of hydroxynatropyrochlore contains characteristic bands of the lattice, BO6, B–O and O–H vibrations and no characteristic bands of the H2O vibrations. Within the Kovdor phoscorite–carbonatite pipe, hydroxynatropyrochlore is the latest hydrothermal mineral of the pyrochlore supergroup, which forms external rims around grains of earlier U-rich hydroxykenopyrochlore and separated crystals in voids of dolomite carbonatite veins. The mineral is named in accordance with the pyrochlore supergroup nomenclature.

Several examples of magma mixing exist within the undersaturated alkaline magma series of the Tertiary/Quaternary volcanics in the French Massif Central. This study describes magma mixing in the Puy Griou/Griounot area of the Cantal volcano (10-3 Ma). Petrographic evidence for injection of blebs of basic magma into phonolitic host magmas is abundant (cauliform inclusions, liquid-liquid contacts, vesiculation and chilling). Compositions of the inclusions are basic tephrite, whereas the hosts are miaskitic phonolites. Petrographic examination reveals the presence of disequilibrium mineralogical features (e.g. Mg-rich olivine in phonolites) and strong zoning in many clinopyroxenes. Transfer of phenocrysts between basic inclusions and phonolite hosts was common, and can be seen clearly in the wide range of compositions of clinopyroxene. Hornblende, magnetite and olivine were also transferred from inclusions to host.

Sr and Nd isotope data indicate that, unlike most other fractionated magmas of the region, phonolites which show evidence for magma mixing are uncontaminated by the continental crust and have isotopic ratios similar to local primitive basic magmas. This leads to the suggestion that the magma mixing event took place at great depth, rather than being a high-level phenomenon. The phonolites were thus generated by high-pressure fractional crystallisation of an earlier basanitic or tephritic parent, perhaps at upper-mantle depths. This conclusion may explain why some phonolites elsewhere in the world have entrained spinel Iherzolite mantle xenoliths.

Due to its favourable properties, in particular, low permeability and swelling capacity, bentonite has been favoured as an engineered-barrier and backfill material for the geological storage of radioactive waste. To ensure its safe long-term performance it is important to understand any changes in these properties when the material is subject to heat-emitting waste. As such, this study investigates the hydraulic response of bentonite under multi-step thermal loading subject to a constant-volume boundary condition, to represent a barrier system used in a crystalline or other hard-rock host rock. The experimental set up allows continuous measurement of the hydraulic and mechanical responses during each phase of the thermal cycle. After the initial hydration of the bentonite, the temperature was raised in 20°C increments from 20 to 80°C followed by a final step to reach 120°C. Each temperature was held constant for at least 7–10 days to allow the hydraulic transients to equilibrate. The data suggest that the permeability of bentonite appears to be sensitive to changes in temperature which may extend beyond those explained by simple changes in water viscosity. However, permeability may be boundary-condition dependent and this should be considered when designing experiments or applying these results to other repository host rocks. Either way, the magnitude of the change in permeability observed in this study is minor and its impact on the hydraulic performance of the barrier is negligible.

The discovery of nigerite, a new tin-bearing mineral, by R. Jacobson and J. S. Webb claims more than the passing interest of an addition to the few known species containing appreciable tin. Nigerite is the first mineral to be discovered in which both tin and aluminium are essential constituents. Its chief interest to mineralogists lies in its close relationship to minerals like spinel and corundum based on a close-packed or nearly close-packed assemblage of oxygen ions.

Samples of nigerite submitted to us for investigation consist of brittle, lustrous, brown, weakly magnetic, hexagonal plates up to 5 x 2 mm. in size but mostly much smaller. These samples also contained grains of cassiterite, columbite, gahnite, sillimanite, quartz, andalusite, and chrysoberyl, which were easily separated by hand-picking.

An X-ray study of a number of rare-earth silicates has been carried out; single-crystal and powder data are presented.

It is found that cerites can contain up to at least 6 % CaO without disruption of the structure, which is trigonal with probable space-group P321 etc. The cell dimensions are a ca. 10·8 Å., c ca. 37–38 Å., although there is a strong pseudo-cell with halved c-axis. An ideal formula (Ca,Ln†)3Si2(O,OH,F)9 is proposed for this series.

Lessingite and beckelite can be regarded chemically as lime-rich members of this cerite series. They do not, however, have the same crystal structure as cerite; their diffraction patterns are very similar to that of britholite, and indicate a structure dimensionally comparable with apatite. For a hexagonal cell, the dimensions are a ca. 9·7 Å., c ca. 7·1 Å., with probable space-group P63, &c. An ideal formula (Ca,Ln)2(Si,Al,P)(O,OH,F)5 is proposed for this series. Marked biaxial optical properties suggest that the structure may be truly orthorhombic, with a very close dimensional approximation to a hexagonal cell.

The new mineral, stillwellite, is unrelated to either of these series. It is trigonal with cell dimensions a ca. 6·9 Å., c ca. 6·7 Å., with probable space-group P3112. An ideal formula (Ca,Ln)(Si,Al,P)B(O,OH,F)5 suggested by previous work is confirmed.