In the past decade, differential thermal analysis has developed into a very useful mineralogical technique. The theoretical background for this method has been treated by Speil, Berkelhamer, Pask, and Da vies (1945) and has been modified by Kerr and Kulp (1948, 1949). The application of the method to the clay minerals has been carried out with considerable success by a number of workers in Europe and America. In particular, Grim and co-workers (1942, 1947, 1948) have produced a number of significant papers dealing with the thermal analysis of clays. The method has been extended to other mineral groups such as the carbonates (Faust, 1949; Beck, 1946; Kerr and Kulp, 1947; Cuthbert and Rowland, 1947; Kulp, Kent, and Kerr, 1950), phosphates (Manly, 1950), sulphates (Kulp and Adler, 1950), quartz (Faust, 1948), and the hydrous iron oxides (Kulp and Trites, 1950).

A new mineral arsenowagnerite, Mg2(AsO4)F, the arsenate analogue of wagnerite, was found in sublimates of the Arsenatnaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. It is associated closely with johillerite, tilasite, anhydrite, hematite, fluorophlogopite, cassiterite, calciojohillerite, aphthitalite and fluoborite. Arsenowagnerite occurs as equant to tabular crystals up to 1 mm across combined in interrupted crusts up to 0.1 cm × 1.5 cm × 3 cm. The mineral is transparent, light yellow, lemon-yellow, greenish-yellow or colourless and has a vitreous lustre. Arsenowagnerite is brittle, with Mohs hardness of ~5. Cleavage is distinct, the fracture is uneven. Dcalc = 3.70 g cm–3. Arsenowagnerite is optically biaxial (+), α = 1.614(2), β = 1.615(2), γ = 1.640(2) and 2Vmeas = 25(5)°. Wavenumbers of the strongest absorption bands in the IR spectrum (cm–1) are: 874, 861, 507, 491 and 470. The chemical composition (average of six electron-microprobe analyses, wt.%) is: MgO 38.72, CaO 0.23, MnO 0.32, CuO 0.60, ZnO 0.05, Fe2O3 0.11, TiO2 0.03, SiO2 0.08, P2O5 0.18, V2O5 0.03, As2O5 54.96, SO3 0.10, F 8.91 and –O=F –3.75, total 100.57. The empirical formula calculated on the basis of 5 (O + F) apfu is: (Mg1.98Cu0.02Mn0.01Ca0.01)Σ2.02(As0.99P0.01)Σ1.00O4.03F0.97. Arsenowagnerite is monoclinic, P21/c, a = 9.8638(3), b = 12.9830(3), c = 12.3284(3) Å, β = 109.291(3)°, V = 1490.15(7) Å3 and Z = 16. The strongest reflections of the powder X-ray diffraction pattern [d,Å(I)(hkl)] are: 5.80(41)(002), 5.31(35)(120), 3.916(37)($\bar 2$21), 3.339(98)(221, 023), 3.155(65)(202), 3.043(100)($\bar 1$41), 2.940(72)($\bar 2$04), 2.879(34)($\bar 3$22) and 2.787(51)(320, $\bar 1$24). The crystal structure was solved from single-crystal X-ray diffraction data, R = 0.0485. Arsenowagnerite is isostructural to wagnerite-Ma2bc. The crystal structure is built by almost regular AsO4 tetrahedra, distorted MgO4F2 octahedra and distorted MgO4F trigonal bipyramids.

The transformation was followed in Amelia albite powders by variation in 2θ131−2θ13̄1 with time under isothermal conditions at various temperatures in the range 920°–1080°C. The activation energy of about 74 kcal mole-1 is rather larger than that obtained for the ordering process in synthetic NaAlSi3O8 under hydrothermal conditions.

Eringaite, Ca3Sc2(SiO4)3, a new mineral of the garnet group, is an accessory mineral in metasomatic rodingite-like rocks from the Wiluy River, Sakha-Yakutia Republic, Russia. Eringaite forms regular growth zones and irregular spots in complex garnet crystals containing a kimzeyite core. An electron back-scatter diffraction pattern with an excellent match to a garnet model with a = 12.19 Å was obtained for a grain with the largest Sc2O3 content having the crystal chemical formula (Ca2.98Y0.01Mg0.01)Σ3(Sc0.82Ti4+0.44Fe3+0.30Zr0.21Mg0.10Al0.09Cr3+0.08Fe2+0.05V3+0.01)Σ2.01(Si2.48Al0.30Fe3+0.22)Σ3O12. Eringaite is light brown to yellow with a creamy white streak. The crystals are transparent with a vitreous lustre. The calculated density of eringaite is 3.654 g cm–3. The following main modes of the Raman spectrum are characteristic of eringaite: 335, 511, 735, 880 and 937 cm–1. The strongest lines of the calculated powder diffraction data are as follows [(hkl) dhkl (I)] (400) 3.064 (69), (420) 2.740 (100), (422) 2.502 (68), (640) 1.670 (30), (642) 1.638 (82), (840) 1.370 (20), (842) 1.137 (19), (10.4.2) 1.119 (29).

Seven samples of pelletat glauconites with varying iron and potassium contents were investigated using the electron microprobe. In-sample variation of pelletal compositions is quite important, even for samples previously separated according to grain-size, density, and magnetic susceptibility. This observation should lead to a reconsideration of previous work based upon multigrain samples.

During the evolution of pelletal material towards micaceous glauconite compositions it is apparent that iron can be added to as wellas subtracted from the bulk pelletal composition. This transfer appears to be effected when the pellet contains a multiphase mineral assemblage as well as during the evolution of a single-phase mixed layered mineral.

A schematic phase diagram is presented which attempts to describe the phase changes as a function of K, Si, and Fe variables.

The thermal stability of the synthetic iodine analogue of vanadinite, Pb5(VO4)3I, in air has been investigated by in situ high temperature X-ray powder diffraction between 300 and 1070 K. Rietveld refinement of phase fractions shows that breakdown to lead orthovanadate, Pb3(VO4)2, begins at temperatures above 540 K, with complete loss of iodine above 680 K. More than 50 K below the onset of breakdown, the unit-cell parameters of Pb5(VO4)3I show anomalous contraction in the crystallographic x–y plane (reduction of a) which we associate with movement of iodine within the [0001] channels of the structure. The implications of these results for immobilization of 129I in potential apatite-related crystalline radioactive waste forms are discussed.

Naturally weathered olivine from metamorphosed, tectonized metadunite is corroded by funnel-shaped etch pits. Large etch pits form by weathering, and are not inherited from pre-weathering alteration of these rocks. Comparison of etch pits on olivine in naturally weathered metadunite with naturally weathered olivine phenocrysts from volcanic rocks suggests that olivine etch pits are similar in all sample suites, despite differences in crystallization and weathering/exposure ages, and regolith history.

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.

Hakite, ideally Cu10Hg2Sb4Se13, is a Se-dominant member of the tetrahedrite group occurring at only a few localities in the World. A new occurrence of this mineral in the Příbram uranium and base-metal ore district, Central Bohemia, Czech Republic, is reported in this paper. Hakite was found to be locally abundant and was identified in several samples with Se mineralization. Three chemically distinct types of hakite were distinguished based on electron microprobe study, Hg-rich hakite (hakite sensu stricto), Zn-rich hakite and Cd-rich hakite. Hg-hakite dominates among the samples studied. Its average empirical formula based on 29 apfu (n = 54) is (Cu5.61Ag0.39)∑6.00Cu4.00(Hg1.61Zn0.20Cu0.19Cd0.15Fe0.04)∑2.19(Sb3.85As0.28)∑4.13(Se11.55S1.14)∑12.69 . Less common is the Zn-hakite, (Cu5.80Ag0.20)∑6.00Cu4.00(Zn1.33Hg0.42Cd0.22Cu0.18Fe0.01)∑2.16(Sb3.85As0.26)∑4.11(Se10.92S1.81)∑12.73 (n = 22), and rare Cd-hakite has an empirical formula (n = 7) of (Cu5.84Ag0.16)∑6.00Cu4.00(Cd1.27Zn0.60Cu0.10Hg0.07Fe0.02)∑2.06(Sb4.00As0.19)∑4.19(Se12.14S0.61)∑12.75. The refined unit cell of Hg-hakite from Příbram, obtained from powder X-ray diffraction data, is a = 10.8783(3) Å with V = 1287.3(1) Å3 (Z = 4, for the cubic space group I4̄3m). Structure refinement from the precession electron diffraction data collected on the transmission electron microscope (R = 24.4% for 424 observed reflections), confirmed that hakite is isostructural with tetrahedrite. The evolution of hydrothermal fluids, from which Se mineralization formed, suggests a distinct enrichment in sulfur and depletion in selenium over the time span of crystallization.

Ion microprobe analysis ofperovskite from kimberlites and alnöites permits the accurate determination of La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er and Yb at the part per million level. Other rare earth elements (REE) are subject to interferences in the mass spectrum caused by matrix-derived molecular ions and cannot easily be determined with comparable precision. Chondrite-normalized plots of the ion probe REE data are smooth curves, confirming the superiority of this technique over electron microprobe methods at the levels of REE abundance found in these perovskites. The perovskites analysed contain between 2.8 and 7.1 wt. % REE oxides and are highly enriched in the light REE, having La/Yb ratios of 577–3229. These La/Yb ratios are not representative of the parental magmas but result from REE fractionation during crystallization of the perovskite. Parental magma La/Yb ratios are estimated to be of the order of 120–650. The lower La/Yb ratios (80–200) found for whole-rock kimberlites are considered to result from contamination by relatively heavy REE-enriched crustal material.

Allanite-(La) (containing up to 7.80 wt.% V2O3 and with La/ΣREE and La/Ce atomic ratios up to 0.54 and 1.45, respectively) and allanite-(Ce) (up to 8.46 wt.% V2O3) occur in close association with vanadian muscovite, barian tomichite and vanadian titanite in the main ore zone of the Hemlo gold deposit, Ontario, Canada. Allanite-(Ce) generally occurs as a minor constituent in cross-cutting veins or along foliation planes, whereas allanite-(La) invariably occurs in direct contact with titanite. The high V concentrations in the allanites from Hemlo are readily attributable to an adequate local source of this element, and are most likely controlled mainly by a simple substitution of V for Al in octahedral coordination. Vanadian allanite-(La) and vanadian allanite-(Ce), without any systematic differences in other constituents, are clearly distinct in REE composition, in respect to both the relative concentrations of La and Ce and abundances of other REE. The formation of both allanites (Ce- and La-rich) indicates very localised remobilisation and concentration of REE during a late hydrothermal alteration. The unusual REE composition of vanadian allanite-(La) directly reflects partitioning of REE with coexisting titanite, and the formation of this unusual phase may be attributable to replacement of earlier titanite with redistribution of REE in the solid state.

Ferrinatrite crystallizes in space group P, with a = 15·566(5), c = 8·69(1) Å, and Z = 6. The crystal structure was solved by three-dimensional Patterson and Fourier syntheses, and refined by least squares employing 2378 independent reflexions to a final R value of 0·068. The iron ions occupy special positions and are surrounded octahedrally by oxygen atoms. Fe3+O6 octahedra and SO4, tetrahedra are linked together to form infinite chains of Fe-O-S linkages in the [0001] direction. These chains are linked to each other by [NaO5(H2O)2] polyhedra and probably by hydrogen bonds. The topology of the arrangement is the same as that of the hypothetical P312 structure proposed by Moore and Araki (1974).

Many layered intrusions are considered to have been repeatedly inflated by magma additions, but rates of magma mixing relative to rates of layer accumulation are difficult to model. The nature of magma recharge through the interval including the Pyroxenite Marker (PM), Main Zone, Bushveld Complex, South Africa, is examined with regard to such processes. The plagioclase compositions (An value) in five previously published and three new profiles (presented here and focusing on the core compositions) that are at least 600 m in vertical extent and spread along a strike length of 110 km are evaluated. The compilation of the eight profiles shows the following trends. Upward reversals in compositions show considerable lateral as well as vertical variations. Lateral variations show a range in: (1) the minimum An value reached in each profile prior to the onset of magma recharge (An51 to An59); (2) the depth below the PM at which the minimum value is observed (50 to 575 m); (3) the An value close to the PM (An54 to An75); (4) the maximum value recorded above the PM (An63 to An76); (5) the height above the PM at which this maximum value is reached (0 to 300 m) – in all cases, the highest values of An occur at the northern end of the studied sections; and (6) the vertical extents over which the reversals occur range from 150 to over 600 m indicating very protracted magma additions and/or slow mixing. The PM terminates toward the south, and close to this termination the immediate footwall rocks to the PM change from north to south from gabbronorite to magnetite gabbronorite. A cross-section through these profiles defines two basins, with an intervening structural upwarp. The magma pulses that were added to produce very gradual and protracted reversals in mineral compositions through the PM interval ponded initially at the base of the northern basin, and did not homogenize the entire magma column. These added magmas did not overflow and have an effect on mineral compositions in the southern basin until after considerable replenishment and crystallization (including the PM) had taken place in the northern basin. We emphasize the prolonged period(s) of magma input and slow rate of vertical homogenization of the magma column during the formation of this sequence of as much as 400 m of the Main Zone.

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 cause of coloration of Blue John fluorite from Castleton, Derbyshire, and blue banded fluorites from Ashover, Derbyshire, and Weardale, Co. Durham, has been investigated by a number of techniques, including mass spectrometry, optical spectroscopy, and paramagnetic resonance measurements on natural and irradiated samples. In all respects Blue John is indistinguishable from the other blue banded fluorites. Although traces of hydrocarbons were found in all the natural fluorites including Blue John, they are shown not to be the cause of the colouration. The optical spectra and bleaching behaviour are consistent with colouration by colloidal calcium rather than F-centres. The causes of colour banding are discussed.

Rhodesite, from Kimberley, S. Africa, has been examined by electron-microscope, X-ray, and other methods. The acicular crystals are orthorhombic, with a 23·8, b 6·54, c 7·05 Å.; elongation c, cleavage (100); unit-cell contents approximately (Ca,Na2,K2)8Si16O40.11H2O; optical properties α 1·502, β 1·505, γ 1·515; α = b, β = α, γ = c. With it occurs a similar but distinct fibrous mineral, which appears to be a new species for which the name mountainite is proposed; it is monoclinic, with a 13·51, b 13·10, c 13·51 Å., β 104° elongation b, cleavage (001); unit-cell contents approximately (Ca,Na2,K2)16Si32O80.24H2O; optical properties α 1·504, β 1·510, γ 1·519; β = b (elongation). Both rhodesite and mountainite show close similarities to the fibrous zeolites, mountainite in particular resembling thomsonite. The possible structural basis of these similarities is discussed.

Available experimental data on chemical composition and crystal structure of K-bearing clinopyroxenes are compiled together with the results of atomistic simulations and thermodynamic calculations of mineral equilibria. It is shown that the limited solubility of K2O in clinopyroxene from crustal rocks cannot be ascribed to the strong non-ideality of mixing between diopside (CaMgSi2O6) and K-jadeite (KAlSi2O6) components. The more likely reason is the instability of the potassic endmember with respect to other K-bearing phases. As the volume effects of typical K-jadeite-forming reactions are negative, the incorporation of K in the clinopyroxene structure becomes less difficult at higher pressure. Atomistic simulations predict that the thermodynamic mixing properties of diopside-K-jadeite solid-solutions at high temperature approach those of a regular mixture with a relatively small positive excess enthalpy. The standard enthalpy of formation (ΔfH° = —2932.7 kJ/mol), the standard volume (V° = 6.479 J mol–1 bar–1) and the isothermal bulk modulus (K0 = 145 GPa) of K-jadeite were calculated from first principles, and the standard entropy (S° = 141.24 J mol–1 K–1) and thermal-expansion coefficient (α = 3.3 x 1CP–5 K–1) of the K-jadeite endmember were estimated using quasi-harmonic lattice-dynamic calculations based on a force-field model. The estimated thermodynamic data are used to compute compositions of K-bearing clinopyroxenes in diverse mineral assemblages within a wide P-T interval. The review substantiates the conclusion that clinopyroxene can serve as an effective container for K at upper-mantle conditions.

Electron-microprobe analyses of Russian and Mongolian chevkinite-group minerals from little-known host lithologies, including various metasomatic rocks, quartzolites and an apatite deposit, are presented. The mineral species analysed include chevkinite-(Ce), perrierite-(Ce), polyakovite-(Ce) and Sr- and Zr-rich perrierite-(Ce). Compositional variation in the Sr-rich members of the group is broadly represented by the exchange vector (Fe + Mn + Al + REE) ↔ (Ca + Sr + Ti + Zr). Despite the varied parageneses, the chevkinite-(Ce) compositions are similar to previously published data. Many crystals have strong internal compositional variations, partly produced during primary crystallization and partly during low-temperature hydrothermal alteration.

The crystal structure of hydrothermally synthesized Rb-feldspar (monoclinic, space group C2/m, a= 8.839(2)Å, b= 13.035(2)Å, c= 7.175(2)Å, β = 116.11(1)8, V= 742.3(3)Å3, Z= 4) has been refined to a final R of 0.0574 for 692 independent X-ray reflections. Microprobe analyses of the Rb-feldspar suggest deviation from stoichiometry, with excess Si and Al, resulting in a unit formula of Rb0.811□0.127Al1.059Si3.003O8. Infrared (IR) spectra indicate the structural occupancy of large H2O content, which implies that the □Si4O8 substitution favours the structural incorporation of the H2O molecule at the M-site. The mean T–O distances are 1.632 Å for T1 and 1.645 Å for T2, revealing highly disordered (Al,Si) distribution with Al/Si = 0.245/0.755 (T1 site) and 0.255/0.745 (T2 site).

There are two geochemical implications from this refinement: (1) identification of both rubicline triclinic with (Al,Si) ordered distribution and synthetic monoclinic RbAlSi3O8 with (Al,Si) disordered distribution implies that Rb cannot be one of factors disrupting the (Al,Si) ordered and disordered distributions in feldspars; and (2) natural and synthetic feldspars capable of accommodating the large cations tend to incorporate □Si4O8, excess Al and H2O components in their crystal structures.