Zirconolite and baddeleyite from polymetamorphosed metacarbonates of the Oetztal-Stubai complex (northern Tyrol, Austria) are described in terms of their paragenetic relationship and chemical compositions. For the first time an analysis of a chemically zoned niobian zirconolite (high Nb and low Ti in core, low Nb and high Ti at rim) is presented. Genetic possibilities for the origin of the metacarbonates are discussed in the light of zirconolite- and baddeleyite-formation.

Radioactive particulate matter (identified as hot particles) is present in the effluent discharged by the British Nuclear Fuels Ltd (BNFL) uranium reprocessing plant at Sellafield, Cumbria, UK. There is very little information on the abundance or chemical and physical forms of solid matter in the effluent; even less is known of the significance of particulate debris in relation to the uptake of radionuclides for non-occupationally exposed people as a result of transfer along marine foodchains. Some observations on the occurrence and abundance of hot particles in the vicinity of Sellafield are reported, with special reference to those that contain transuranic radionuclides (Pu,Am,Cm). Some of the uncertainties are discussed in an evaluation of the significance of hot particles, albeit aggregates of colloids for the smallest particles, and exposure to man from ionizing radiation. There is no evidence that hot particles derived from BNFL and subsequently dispersed into the marine environment represent a hazard to man. However, further studies are required in order to determine whether or not the pathways followed by the particles are significant, or different to those of other radionuclides through which the radiation exposure of man within this region of Cumbria is assessed.

Low-temperature metamorphism of the Franciscan complex at Pacheco Pass occurs at P-T conditions near the so-called jadeite isograd. Along Highway 152 in the Diablo Range, from west to east, four distinct prograde metamorphic zones are defined: (I) albite-quartz zone, (II) albite-rich, albite-quartz-clinopyroxene assemblage, (III) clinopyroxene-rich, albite-quartz-clinopyroxene assemblage, and (IV) clinopyroxene zone. Metamorphic pyroxenes are restricted to zones II, III, and IV in metagreywackes, but metabasites contain augite-rich pyroxenes even in zone I. With increasing grade, the compositions of pyroxene in metagreywackes change in XJd from nearly 100 in zone II to about 60 in zone III. The diopside component has little effect on the XJd of pyroxene. The apparent change of XJd reflects differences in pressure and temperature rather than in bulk rock composition. In metagreywackes, at the onset of zone II, albite breaks down to form Jd100 according to the reaction Ab = Jd+Qz. With increasing grade, this reaction leads to less jadeitic pyroxene. From zones II to III, a continuous reaction is delineated: Qz+2 pyroxenes (Jd80Ac15Aug5)=pyroxene (Jd60Ac30Aug10) + Ab.

The metamorphic temperatures are estimated to be about 170°C in zones I and II, and about 230°C in zones II and III. The temperature variation recorded in a single rock is probably less than 30°C The pressure estimate depends on the choice of experimental data for the jadeite-albite-quartz curve; it ranges from 4.5 to 8 kbar. A gently folded thermal structure of the Cretaceous subduction zone metamorphism is postulated for this area.

Bredigite is a constituent of the very high-temperature, low-pressure, exomorphic suite of Carneal, Co. Antrim. Although this mineral is very rare in nature, it is an important constituent of some slags and cement clinkers but there has been much controversy about its nature, most of the evidence having come from artificial materials. Chemical analysis of the Carneal mineral shows it to be remarkably similar to that from the type locality, Scawt Hill (also analysed here), and that it is an individual mineral species of generalized ionic composition (Ca,Na)14(Mg,Fe2+Fe3+Mn)2(Si,P)8O32. Ba (abundant in the original analysis of the slag mineral) is not a constituent. Accurate X-ray powder data of the natural mineral are given. Bredigite is not Ca2SiO4, nor is it part of a solid solution of variable composition between larnite and merwinite. Analyses are presented for the associated minerals larnite (allowing appraisal of its composition), spurrite, and spinels. The paragenesis is discussed.

The structures of bustamite and the poly-types of wollastonite are shown to be derived from variations in the stacking sequence of a single type of structural unit. This structural unit is a column of unit cells of wollastonite along the b-axis and is bounded by (100) and (001) planes (P1̄ cell); these units may be stacked together along [100] and [001] with either zero displacement between successive units, or a relative displacement of 1/2[010]. Regular stacking sequences give rise to the ordered structures of wollastonite polytypes and of bustamite, while the transformations between these structures proceed by the propagation of line defects with Burgers vectors of 1/2[010] which thus change the stacking sequence of the structural units.

An X-ray diffraction method has been successfully applied to the quantitative determination of mineral mixtures. The absorptive properties of the samples and the number of components determine the analytical procedure to be used. The methods described (external standard plus empirical determination of the mass attenuation coefficient) provides an accurate and rapid alternative to the direct measurement of the mass attenuation, Compton diffusion or internal standard methods. The relative accuracy obtained is of the order of 10% at the 0.1% level, independent of the sample composition.

A borosilicate glass, containing 25 wt. % of simulated high-level radioactive waste has been reacted with water at 350°C and 500 bars for 14 and 48 days using large-volume ‘cold-seal’ high-pressure equipment. Under these conditions the glass crystallizes a suite of mineral phases including: albite, NaAlSi3O8; aegirine, NaFeSi2O6; riebeckite, Na2Fe2(Fe,Mg)3Si8O22(OH)2; zektzerite, LiNaZrSi6O15; barium-strontium molybdate, (Ba,Sr)MoO4; stillwellite, (Nd,Ce,La)BSiO5; willemite, Zn2SiO4; smectite; a lithium-sodium borosilicate hydrate; melilite (åkermanite), Ca2MgSi2O7. A description of the morphology of these phases is given, together with a number of chemical analyses. The implications of the incorporation of waste species in these mineral phases to the disposal of high-level radioactive waste is discussed.

Using previously published data and a few new data the compositions of protopyroxene, orthopyroxene, and pigeonite, coexisting with liquid in the system CaO-MgO-SiO2, are reviewed and shown to depend subtly on the number and nature of the coexisting phases such as forsterite, silica, other pyroxene, and liquid. Broadly, protopyroxene contains 0 to 1.0 wt. % CaO, orthopyroxene 1.4 to 2.2%, and pigeonite 3.0 to 6.5%, but pigeonite coexisting with olivine contains up to 1.5 wt. % more CaO than pigeonite coexisting with SiO2 at the same temperature.

In the system CaO-MgO-Al2O3-SiO2 some new analyses and all previously published microprobe analyses of pyroxenes fall into three compositional groups, which are hereafter used to name the pyroxene irrespective of whatever description the original authors gave to their products. For these groups, the compositional subtleties depend on the number and nature of coexisting phases and these are illustrated using sketches of the solid solution polyhedron for each phase, to illustrate, in particular, the decomposition of pigeonite as temperature drops, at 1276°C when forsterite, diopside and liquid coexist, but at other temperatures when other phases coexist. The assemblage orthopyroxene, anorthite, diopside, forsterite is established as the solidus at 1244°C by X-ray diffraction and by new microprobe analyses, and not protopyroxene with anorthite, diopside, and forsterite as was previously accepted. Liquidus surfaces for forsterite and protopyroxene, forsterite and orthopyroxene, and forsterite and pigeonite, are drawn, with temperature data, and several crystallization paths demonstrate the double resorption boundaries, forsterite-protopyroxene-orthopyroxene-liquid and forsterite-orthopyroxene-pigeonite-liquid, and demonstrate crystallization of four pyroxenes, resorption of three of them, and reprecipitation of a second generation of one of them.

No new data are presented for the solidus of the system CaO-MgO-SiO2, but a reinterpretation of the existing data suggests that the solvi of these alumina-free pyroxenes do not show an increase in CaO as temperature decreases. This is contrary to previous interpretations which have mingled data for alumina-bearing and alumina-free pyroxenes. The reinterpretation also favours the reaction protoenstatite + pigeonite ⇌ orthopyroxene at 1375°C and a revision of the previously accepted P-T (Schreinemaker's) net for the pyroxenes is proposed which does not accept orthopyroxene ⇌ protopyroxene + diopside at 1100°C at one bar, which previously has always been accepted by extrapolation from the experimental data at 1 kbar.

The Tyndrum Pb-Zn mineralization occurs as veins and vein breccias in NE-SW trending fractures associated with the Tyndrum-Glen-Fyne fault. The major minerals are quartz, galena, and sphalerite with minor chalcopyrite and baryte. Tetrahedrite (sometimes silver-and cadmium-rich), pyrargyrite, marcasite, and pyrite occur as small inclusions (< 100 µm) in the galena-rich veins. Sphalerite formed early in the depositional sequence, mainly in breccias, with increasing amounts of galena and chalcopyrite deposited in the later vein stages of mineralization. Uraniferous veins post-date the main Pb-Zn mineralization and contain uraninite, calcite, baryte, galena, sphalerite, chalcopyrite, argentite, chalcocite, tetrahedrite, and safflorite.

Fluid inclusion studies reveal that the mineralizing solutions contained c.20 wt. % equivalent NaCl + KCl, had an Na/K ratio of 3 : 1 and were boiling during mineral precipitation.

The Tyndrum fault controlled the upward flow of the hydrothermal solutions and its intersection with fractures in quartzites favoured the siting of the veins. The depositional sequence is explained by an increase in temperature during the mineralizing episode. The uraniferous veins may be a late oxidized stage of the main Pb-Zn mineralization.

A study of low-grade metamorphism in late Silurian to early Carboniferous rocks in the North Hill End Synclinorium and adjacent anticlinoria has been made by the determination of illite crystallinity and bo values of K-white mica in eighty slates and phyllites. Illite crystallinity values vary from 0.40 Δ°2θ on the Molong Anticlinorium to 0.12 Δ°2θ within the axis of the synclinorium, suggesting anchizonal to epizonal metamorphic conditions. This is in agreement with previous observations on Ca-Al-hydrosilicate assemblages which indicated a change from prehnite-pumpellyite facies in the anticlinoria adjacent to the synclinorium to middle greenschist facies in the axis. Local variations in crystallinity are attributed to variation in ak+ in fluids migrating along cleavage zones.

The mean bo value obtained from the pelites is 9.017 Å (σn = 0.008; n = 80) which is in close agreement with that obtained from part of the adjacent Capertee Anticlinorium ( = 9.019 Å; σn = 0.007; n = 52). However, ‘t’ tests indicate that two bo populations are present in the synclinorium ( = 9.019 and 9.022 Å), with the lower values concentrated in the southern portion of this structure. The two populations are considered to be the result of slightly different metamorphic conditions prevailing during the deformation of the rocks in the synclinorium. A higher geothermal gradient affecting rocks giving the lower bo values is attributed to the presence of granitoids at shallower depths than elsewhere in the synclinorium.

The dissolution rates of spheres of two magnesian olivines, two plagioclases, and quartz in tholeiitic basalt have been determined at three super-liquidus temperatures and one-atmosphere pressure. There are considerable differences in the rates among the minerals, e.g. at 1210°, 12° above the liquidus temperature of the basalt, labradorite dissolves at 86 µm/h. and the magnesian olivines at 9 and 14 µm/h. The rates are not time dependent and this, coupled with the existence of concentration gradients in the composition of quenched melt adjacent to partially dissolved crystals, indicates that the dissolution rates are dictated by a combination of diffusion and convection of components to and from the crystal-liquid interface. Values for the activation enthalpy of dissolution are small for quartz and plagioclase (40–50 kcal mol−1) but large for olivine 73–118 kcal mol−1). Dissolution of plagioclase in rock melts seems to be a much more rapid process than crystal growth, whereas olivines apparently dissolve and grow at similar rates. Crystal dissolution is sufficiently slow that ascending, crystal-bearing magma may become superheated and yet fail to dissolve the crystal fraction before quenching; this may be the reason that olivine phenocrysts are often rounded.

The north coast of Cornwall, from Bude to Newquay, provides a continuous section through a major Variscan fold/thrust complex. Illite crystallinity studies have revealed a transition from diagenesis in the north to greenschist facies metamorphism in the south in the Upper Palaeozoic succession. More detailed studies of mineral assemblages in both metabasites and pelitic rocks support the regional pattern of metamorphism indicated by illite crystallinity, and show that locally in the Tintagel district, the grade of metamorphism may have reached middle to upper greenschist facies. An attempt to correlate the above data with temperatures (108–985°C) derived from O-isotope geothermometers is made. Interpretation of the metamorphic data presented helps to emphasize the tectonic importance of the major structures seen in the fold/thrust complex.

Two samples of garnet-kyanite-staurolite schist from Lukmanier, Switzerland, each contain two chemical varieties of kyanite which occur in texturally distinct areas of the rock. Type 1 form large idiomorphic crystals within an open crenulation cleavage S3. They exhibit a systematic zonation of F2O3, with core values of 0.8% decreasing to 0.3% at the crystal margin. Type 2 form small, much less abundant crystals in areas between S3 cleavage zones, and have a homogeneous distribution of 0.3% Fe2O3 throughout the crystal.

It is suggested that the first-nucleated crystals contain the highest core concentration of Fe2O3 and are the largest. A positive correlation between core Fe2O3 values and crystal size is interpreted as a nucleation and growth sequence. This indicates that the first crystals formed preferentially in S3 (Type 1), with Type 2 crystals growing later outside the S3 zones.

Concentration of kyanite in S3 zones produces a distinct mineral banding in the rock. A mechanism for the development of metamorphic differentiation by preferred nucleation of kyanite in S3 is proposed.

The uptake of 137-Cs and 90-Sr on to synthetic zeolite A has been studied. The use of a combined barium exchange followed by a relatively mild heat treatment has been shown to fix the isotopes within a collapsed zeolite structure. Leaching experiments using deionized and simulated sea and pond waters were carried out on zeolite compacts and zeolite/cement composites. They demonstrated the effectiveness of the calcination and cement containment. Some comments on the interpretation of leach test data are made.

Measurements of fine-grained dolerites by optical automatic image analysis are used to illustrate the effects of magnification and resolution on the values obtained for grain ‘size’, grain boundary length, surface area per unit volume, and other parameters. Within the measured range of optical magnifications (× 26 to × 3571) and resolutions (1.20 × 10−3 cm to 8.50 × 10−6 cm), it is found that the values of all grain parameters estimated by chord size analysis vary with magnification. These results are interpreted in terms of the concepts of ‘fractal dimensions’ introduced by Mandelbrot (1967, 1977). For some comparative purposes the fractal relationships may be of little significance as relative changes of size, surface area, and other parameters can be expressed adequately at given magnification(s). But for many studies, for instance in kinetics of grain growth, the actual diameter or surface area per unit volume is an important dimension. The consequences are disconcerting and suggest that it may be difficult in some instances to specify the ‘true’ measurements of various characteristics of fine-grained aggregates.

A range of authigenic sedimentary chlorites from sandstones has been studied by analytical transmission electron microscopy. Selected area (single crystal) electron diffraction patterns are of the Ib (β = 90°) polytype confirming the earlier observations of Hayes (1970).

TEM analyses show all samples to be relatively rich in both Al and Fe. In the general formula (Mg,Fe,Al)n [Si8−xAlxO20](OH)16, x varies between 1.5 and 2.6; Fe/(Fe + Mg) between 0.47 and 0.83 and n between 10.80 and 11.54. Octahedral Al is close to 3 in this formulation and Fe2+ predominates over Fe3+. Swelling chlorites have significantly different compositions which are consistent with smectite/chlorite interstratifications.

The Ib (β = 90°) polytype appears to be stable under conditions of moderate to deep burial. It replaces berthierine and swelling chlorites formed at lower temperatures. As commonly seen in grain coatings, however, it precipitates from porewater; solutes probably being contributed from several mineral decomposition reactions.

The crystal structure and compositional limits of the ternary compound Pt2FeCu (tulameenite), formed either by quenching from above the critical temperature of 1178°C or by slow cooling, have been investigated using X-ray diffraction, transmission electron microscopy, differential thermal analysis and electron probe microanalysis.

The crystal structure of Pt2FeCu, established using electron density maps constructed from the measured and calculated intensities of X-ray diffraction patterns of powdered specimens, has the (000) and (½½0) lattice sites occupied by Pt atoms and the (½0½) and (0½½) sites occupied by either Cu or Fe atoms in a random manner. The resulting face-centred tetragonal structure undergoes a disordering transformation at the critical temperature to a postulated non-quenchable face-centred cubic structure. Stresses on quenching, arising from the ordering reaction, are relieved by twinning along {101} planes or by recrystallization along with deformation twinning; always involving grain boundary fracturing.

Phase relations in the system Pt-Fe-Cu have been investigated through the construction of isothermal sections at 1000 and 600°C. At 1000°C there is an extensive single phase region of solid solution around Pt2FeCu and extending to the binary composition PtFe. At 600°C the composition Pt2FeCu lies just outside this now reduced area of solid solution in a two-phase field. Comparison of the experimental results with data for tulameenite suggests that some observed compositions may be metastably preserved. The occurrence of fine veinlets of silicate or other gangue minerals in tulameenite is suggested to result from grain boundary fracturing on cooling below the critical temperature of 1178°C and to be evidence of a magmatic origin.

The peraluminous granitoid intrusions of southern Nova Scotia contain several mineralogical expressions of the excess alumina, including variable amounts of cordierite, in different textural types of granitoids, ranging from fine-grained aplites through coarser grained monzogranites and granodiorites, to very coarse-grained pegmatites. A detailed study of the spatial, textural and chemical characteristics of these cordierites suggests that the majority are of relict metamorphic origin, but that primary magmatic cordierites, as well as cordierites which grew in equilibrium with a water-rich fluid phase, also occur.

Schultenite, PbHAsO4, known only from Tsumeb, Namibia, has been identified from a second occurrence: near North Bend, King County, Washington, USA. It occurs as euhedral crystals in a quartz-arsenopyrite-galena vein. It has a measured density of 6.07(3) g/cm3 and a calculated density of 6.079(4) g/cm3. The white to colourless crystals have a white streak, adamantine lustre, and fluoresce dull yellow under long wave ultraviolet light. Schultenite is monoclinic. Pa or P2/a; the unit cell parameters refined from the X-ray powder diffraction data are: a 5.827(3), b 6.743(3), c 4.847(3) Å, β 95.34(5)°; V 189.6(1) Å3; Z = 2; a:b:c = 0.8642:1:0.7188. The forms {010}, {001}, and {3̄22} were observed on the Washington schultenite crystals.

Cementitious matrices are being assessed for immobilization of radioactive wastes. This paper discusses some mineralogical aspects of cement chemistry and the uses of siliceous minerals as selective sorbants to enhance immobilization potential.

Studies of sorption and leaching of caesium from pulverized fuel ash (PFA), blast furnace slag, tobermorite, xonotlite, and clinoptilolite are reported. The role of incorporation of these additives in cement and the effect on the nature of the composite matrix on caesium behaviour has been investigated. Specific mechanisms of the interaction of additives with highly alkaline cement environment are described. While slags, PFA, and clinoptilolite undergo reaction at different rates, tobermorite and xonotlite appear to be stable in cement.