The application of ion microprobe analysis to REE determination is discussed, with special reference to REE-bearing accessory minerals (e.g. allanite, monazite, apatite, xenotime, sphene). The main analytical problems are shown to be (a) interferences in the mass spectrum caused by molecular ions, and (b) matrix effects, i.e. variations in ion yield with sample composition. Interference suppression using either high mass resolution or secondary-ion energy discrimination is fairly effective, but entails a significant sacrifice in peak intensity. In the absence of a viable model for predicting matrix effects, it is proposed that empirical standardization should be used. Often better absolute accuracy can be obtained by combining ion microprobe and electron microprobe data for REE present in sufficiently high concentrations. Detection limits for REE are in the part per million region at present, with spatial resolution typically around 10 μm, but there is considerable scope for improvement. Better standards and improved understanding of matrix effects should also lead to greater accuracy in quantitative analysis.

Veins of tourmalinite were formed by wallrock alteration adjacent to steep fractures in bleached, indurated Skiddaw Group metasedimentary rocks around Crummock Water, north-west Lake District. The vein rock is a fine-grained granoblastic mosaic of tourmaline, quartz, and minor rutile in which bedding is preserved. Brecciation, in which tourmalinite fragments are set in a coarser quartz-tourmaline matrix, is present in some veins. Networks of cross-cutting quartz veinlets with tourmaline, chlorite, and muscovite are very common. The tourmaline is intermediate schorl dravite and mostly brown in plane polarized light, though prisms in breccia matrix and veinlets have blue, low-Ti cores and brown rims. Comparison of tourmalinite and host-rock analyses indicates almost complete loss during tourmalinization of K, Rb, Li, Ba, As, and La, plus depletion in Ce, Y, Na, Sr, P, and Mn. The elements Si, B, Mo, and erratically, minor F, W, and Sn were introduced. Cu, Pb, Zn, and Ca show both gains and losses probably due to initial depletion and subsequent local enrichment. Reduction in Al, Zr, and Ti concentrations relates to dilution by introduced silica. The tourmalinite veins were formed by the action of hydrothermal fluids derived from the concealed late-Caledonian granitic intrusion responsible for the thermal metamorphism of the country rocks.

A picrite dyke with an olivine-bearing chilled margin and an olivine-rich centre has been used to test for the presence of a boundary layer around rapidly grown olivine crystals and for any variations in the olivine/melt partition coefficient for uranium as a result of probably different crystal growth rates. The technique of fission-track mapping is shown to be suitable for this kind of study despite the very low uranium concentrations in the olivines. A boundary layer appears to be present around some olivine crystals but it is not a consistent feature. Uranium partition between olivine and melt was not affected by different crystal growth rates, as revealed by different crystal morphologies.

The free energies of formation of the minerals libethenite, Cu2PO4OH, pseudomalachite, Cu5(PO4)2(OH)4, cornetite, Cu3PO4(OH)3, tarbuttite, Zn2PO4OH, spencerite, Zn2PO4OH · 1.5H2O, and scholzite, CaZn2(PO4)2 · 2H2O, have been determined at 298.2 K using solution techniques. The values of ΔfG° (298.2 K) for the above minerals are, respectively, −1228.8±3.0, −2840.3±4.2, −1600.9±5.9, −1632.1±4.0, −1982.4±3.1, and −3556.7±7.6 kJ mol−1. These results, together with others from the literature concerning hopeite, Zn3(PO4)2·4H2O, hydroxyapatite, Ca5(PO4)3(OH), and the synthetic salt Cu3(PO4)2 · 2H2O have been used to construct a model for the formation of suites of Zn(II) and Cu(II) phosphate minerals found in the oxidation zone of base metal orebodies. The distributions and modes of occurrence of many natural assemblages of these minerals are readily explained by the model. Particular attention has been focused on deposits at Broken Hill, Zambia, and Saginaw Hill, Arizona, USA.

Stability relations of malachite and azurite are calculated and shown in Eh-pH diagrams, using ΔF (Gibbs free energy) values listed in Garrels and Christ (1965). The malachite/azurite transition is very sensitive to small chemical changes in the environment: equilibrium is reached at PCO2 = 10−3.45 atm., i.e. close to normal values, whereas the precipitation of both minerals from cupric-ion-bearing solutions takes place at pH values between 6 and 8, depending CO2 partial pressures. It is shown that stability relations of these minerals can be better explained in terms of activities of the carbonate and bicarbonate ion.

Azurite can be formed only under relatively acid conditions at relatively high carbonate activities. Since the latter imply mostly basic conditions, this explains why malachite is the more common form of copper carbonate and that azurite can be formed only under rather unusual conditions. It also explains the frequent alteration of azurite into malachite, due to small changes in carbonate/bicarbonate activities. These alterations include pseudomorphs of malachite after azurite.

Specimens of honey-brown to pinkish-brown globular carbonates encrusting concretionary goethite–coronadite from the oxidized zone at Broken Hill, New South Wales, have compositions in the rhodochrosite–smithsonite series. This may be the first extensive natural occurrence of this solid-solution series. Growth of the carbonates occurred in zones which have near uniform composition. The ratio MnCO3/(MnCO3 + ZnCO3) for each zone bears a linear relationship to the measured d spacing for the 104 X-ray reflections. Because cerussite is the only other mineral associated with the Zn-Mn carbonates and because of an absence of detailed locality information, the paragenetic significance of these minerals cannot be determined. The solutions depositing them may have been derived from the near-surface equivalents of the Zinc Lode horizons.

The onset of melting of beryl + H2O was determined experimentally in the P-T range 10–25 kbar, 900 to 1200°C, by synthesis runs on the composition Al2Be3Si6O18. Beryl begins to melt incongruently to chrysoberyl, phenakite, and melt at temperatures slightly above 1000°C. At higher temperatures a divariant stability field exists where beryl, chrysoberyl, phenakite, and melt coexist due to the solubility of H2O in beryl and in the melt. The final disappearance of beryl was bracketed between 1050 and 1100°C at 10 kbar and at 1100°C between 10 and 20 kbar. The phases (analysed for Al and Si by electron microprobe) do not show major deviation from stoichiometric composition.

Ferrierite has been found at Tapu, Coromandel Peninsula, New Zealand, as a mineral vein with calcite in altered hornblende andesite lava of the Miocene Beeson's Island Volcanics. The ferrierite is low in SiO2 (63.67%) and high in Al2O3 (13.75%), MgO (3.48%), and BaO(2.35%). The large a axis and cell volume (a 19.236(4), b 14.162(6), c 7.527(3) Å, V 2050 Å3) are consistent with the low SiO2, high Al2O3, high MgO chemistry. Optical orientation and optical sign (a = Z, b = X, c = Y, 2V(-)55°) of the mineral are different from those of the Lake Kamloops ferrierite reported by Graham (1918). Refractive indices α 1.487, γ 1.489, and density 2.136 were measured. Cleavage observed on (100) is perfect and on (001) is imperfect. Using data from eighteen occurrences so far reported including the Tapu mineral, the crystal chemistry of ferrierite has been studied.

Mineralogical and oxygen isotope analyses have been performed on nine western Indian Ocean core samples in order to distinguish the detrital from authigenic minerals in the sediments. Following the removal of carbonates, organic constituents and Fe and Mn oxides, the residue was separated into five size fractions, the principal minerals present being feldspar, quartz, clinoptilolite, and clay minerals.

Oxygen isotope compositions for two samples reflect an authigenic origin for clinoptilolite by the submarine alteration of volcanic material. Oxygen isotope compositions of two separates (free from feldspar and clays) suggest a detrital origin for the quartz in this area. The same mode of origin is apparent for the other components too, except possibly for some smectite which may have formed authigenically.

Active metamorphism of fine grained sandstone in the c.16000 year old Salton Sea geothermal system has produced a suite of chemically equilibrated coexisting authigenic alkali feldspars and re-equilibrated detrital feldspars in the 250–360°C temperature range. At c.335°C the average compositions, 2 Vs, and (t1o+t1m) and Z ordering parameters of coexisting authigenic feldspars are [Or0.52Ab97.40An2.08, 2Vx = 91.3±4.8, (t1o + t1m) = 0.89±0.05, Z = 0.79±0.09], and [Or94.42 Ab5.10An0.48, 2Vx = 70, (t1o + t1m) = 0.90, Z = 0.81]. At c.360°C authigenic albite becomes more An-rich and less ordered [Or1.21Ab92.83An5.97, 2Vx = 87.5±3.4, (t1o + t1m) = 0.85±0.03, Z = 0.70±0.07] and K-feldspar is no longer stable. Detrital plagioclase (An up to 40%) is preserved metastably to temperatures up to c.190°C in strongly carbonate-cemented sandstone which forms part of a geothermally produced permeability cap. It undergoes rapid alkali exchange at temperatures near 200°C, and by 250°C no plagioclase with An-content over 12% is observed. At > 250°C authigenic and most detrital alkali feldspar compositions are in excellent agreement with the Bachinski and Muller (1971) microcline-low-albite solvus.

Studies of the mafic mineralogy of the Mulanje granite-quartz-syenite-syenite Massif of southern Malawi delineate two mineralogically distinct complexes—the Main complex and the Chambe complex. Each complex is associated with its own trend of pyroxene evolution. The Main complex pyroxenes exhibit initial enrichment in hedenbergite before subsequent enrichment in acmite (i.e. sodic-salite-sodic-hedenbergite-aegirine-hedenbergite-aegirine), whereas the Chambe pyroxenes display constantly increasing acmite content with no significant enrichment in hedenbergite (i.e. sodic-salite-aegirine-augite-aegirine). This phenomenon is also reflected in the more Mg-rich amphiboles and biotites of the Chambe rocks when compared to those of the Main complex.

The general evolutionary trend of the Main complex amphiboles is katophorite → ferroricherite → arfvedsonite which broadly correlates with a change in rock type from syenite to granite. Superimposed on this trend is an essentially similar, yet less extensive trend of the more Mg-rich Chambe amphiboles. The micas of both complexes show a general evolution to more iron-rich compositions with relatively constant Al content. Those of the Main complex, however, display extreme iron enrichment with ultimate formation of essentially pure ferrous annite.

Aenigmatite, astrophyllite, fayalite, chevkinite, yttrofluorite, and unidentified RE minerals are characteristic of the Main complex rocks but totally absent from those of the Chambe complex. Ilmenite constitutes the only iron oxide phase in the Main complex rocks whereas titaniferous magnetite (now unmixed) and ilmenite are both present in the rocks of Chambe.

The differences between the two complexes are explained in terms of oxygen fugacity, silica activity, crystallization interval, and the relative rates of development of peralkalinity. In essence, the Chambe magmas are considered to have crystallized under high fO2 conditions with an earlier development of peralkaline tendencies when compared to those of the Main complex magmas. Moreover, a lower initial silica activity, a smaller alkali to alumina ratio, and a correspondingly smaller crystallization interval could account for the lack of highly evolved granitic magmas in the Chambe complex, whereas such magmas are integral in the evolution of the Main complex.

The Hällefors silver deposit is regarded as a volcanogenic-exhalative iron ore deposit with dispersed amounts of Ag-Pb-Zn (±Cu) which has undergone secondary remobilization leading to the concentration of sulphides and sulphosalts. Based on data from the iron oxides and sulphides, the sulphide-sulphosalt mineralization is believed to have been formed in two stages. The first is characterized by the ranges 573-473 K and 2.25–1.5 kbar, higher gradient of changes of log aS2 with temperature and mostly sulphide precipitation; the second by the ranges 473–443 K, lower gradient of changes of log aS2 and mainly sulphosalt deposition. Assuming the precipitation was from fluids and aqueous solutions, possible conditions of formation of some of the iron minerals have been determined.

Ranciéite occurs as stalactites coated with 10 Å halloysite in an open fissure crossing the Mazzano Romano Mn-impregnated tuffs. Chemical analysis (by EMPA) gave: MnO2 71.9, CaO 6.11, BaO 2.85, MgO 1.53, K2O 0.86, Na2O 0.53 plus minor oxides, total 85.07% (average of sixteen spots). Thermal analysis gave a total loss of ∼ 20 wt% of which 13.9% can be attributed to bonded water. The resulting formula contains 4H2O rather than 3H2O, as in most published references. The loss of water leads to the formation of hausmannite plus unidentified phases, after a complex sequence of reactions. Dehydration is directly followed by an X-ray amorphous stage. The X-ray pattern and IR spectrum indicate a poor structural order, in agreement with the likely formation conditions of the Mazzano ranciéite at atmospheric pressure and very low temperatures (less than 50 °C), from cold water percolating through the main Mn deposit.

Baghdadite, a new calcium zirconium silicate mineral has been found in melilite skarn in contact with banded diorite, from the Qala-Dizeh region, NE Iraq. Electron microprobe analysis yielded: SiO2 = 29.26, ZrO2 = 27.00, TiO2 = 2.11, Fe2O3 = 0.11, Al2O3 = 0.03, MgO = 0.05, CaO = 41.44, Na2O = 0.02, sum = 100.02 wt. %. The mineral contains about 0.16% HfO2. This analysis calculates to Ca3.00(Zr0.89Ti0.11)(Si1.98Fe0.01)O9 which leads to the ideal formula Ca3Zr[O2|Si2O7]. X-ray single crystal study showed it to be monoclinic with space group P21/a. The unit cell dimensions are: a = 10.42(2), b = 10.16(2), c = 7.36(1) Å, β = 91.1°, Z = 4 and cell volume = 779.04 Å3. The seven strongest lines in the powder diffraction pattern are (d,I,hkl): 7.30 (45)(110), 3.23 (80)(130), 3.04 (75)(2̄02), 2.98 (85)(202), 2.88 (70)(320,212), 2.84 (100)(230), 1.702 (40)(522). It is colourless, lustre vitreous, no cleavage and VHN50 = 725–783 kg mm−2 with H ∼ 6. Calculated density = 3.48 g cm−3 which is very close to 3.46 measured density of a synthetic Ca3ZrSi2O9. It is optically biaxial, positive, 2 V ∼ 72°, dispersion indiscernible. The cathodoluminescence colour is dull grey with a greenish tint. Refractive indices: α= 1.652, β = 1.658, γ = 1.670. The crystal habit is stumpy prismatic and a contact twin with b as twinning axis is observed. Optic orientation: α = c, β//b, γ = a.

Protasite, a new barium-containing member of the uranyl oxide hydrate group, occurs as bright orange pseudo-hexagonal platelets associated with uraninite and uranophane on unidentified rock matrix from Shinkolobwe mine, Zaïre. Protasite is monoclinic, Pn with a 12.295(2), b 7.221(1), c 6.9558(8) Å, β 90.40(2)°, and V 617.50(11) Å3. The tabular pseudo-hexagonal crystals are flattened on {010}, 0.1 mm to 0.5 mm wide and up to 0.1 mm thick. They are biaxial negative, 2 V = 60–65°, β and γ 1.79–1.83, and X = b. Sector twinning is common. Microprobe analysis shows BaO 15.0, UO3 78.0, H2O(diff.) 7.0%. The structural formula is Ba[(UO2)3O3(OH)2]. 3H2O, Z = 2, and density(calc.) = 5.827(3) g cm−3. Complete crystal-structure analysis shows protasite to be the simplest model structure of the uranyl oxide hydrate group.

Chenite, a new lead-copper secondary mineral, has been found on specimens from the Leadhills area, Scotland. It is associated with caledonite, linarite, leadhillite, susannite, and other species, on oxidized galena with chalcopyrite. Electron microprobe analysis yielded PbO 74.5, CuO 7.8, SO3 13.3, H2O 4.4 (by difference), sum = 100 wt. %. The empirical formula (based on 14 oxygens) is Pb3.98Cu1.17S1.98O14H5.82; the ideal formula is Pb4Cu(SO4)2(OH)6, which requires PbO 75.2, CuO 6.7, SO3 13.5, H2O 4.6, sum = 100 wt. %.

Infra-red spectroscopy showed the presence of only and OH− ions, with no H2O.

Chenite is triclinic, P1 or P̄, with a = 5.791(1), b = 7.940(1), c = 7.976(1) Å, α = 112.02(1), β = 97.73(1), γ = 100.45(1)°, V = 326.0 Å3, Z = 1. The strongest lines in the X-ray powder diffraction pattern (d, I/Io, hkl) are: 5.55, 7, 100; 4.32, 6, 11; 3.60, 10 002; 3.41, 9, 10; 3.30, 5, 02; 3.00, 5, 111; 2.80, 7, 12; 2.07, 6, 211/21/13; 1.778, 5, 3/23.

Chenite forms minute, singly terminated, transparent to translucent sky-blue crystals from 0.1 to over 1 mm long, elongated approximately [032]. Twenty different forms (pinacoids) have been identified on the four crystals studied. A good cleavage on {100}, and traces of a second on {001}, can be observed. Optically, chenite is biaxial negative, 2 V(measured) = 67±1°, 2 V(calc.) = 68° (Na). The refractive indices are α 1.871±0.005, β 1.909±0.005, γ 1.927±0.005 (Na). Dispersion is strong, r≫v. The mineral is weakly pleochroic. H (Mohs) ∼ 2½. D = 5.98, and calculated Dx = 6.044 g cm−3.

Descloizite, cuprian descloizite, and mottramite from most of the known prospects and mines in the Otavi Mountain Land were sampled and subsequently analysed chemically and by X-ray diffraction. Unit cell parameters were refined with the aid of a computer program. It was found that, contrary to previous opinion, chemical parameters of these vanadates can be deduced from their X-ray powder data according to the equations (correlation coefficients in parenthesis):

ZnO = 75.369c−0.119b−31.177a−456.512(0.9634)

Zn2+ = 369.568c + 236.583b − 146.42a − 3726.344 (0.9642)

CuO = − 74.991c + 0.086b + 29.419a + 486.204 (0.9649)

Cu2+ = − 369.568c − 236.583b + 146.420c + 3826.344 (0.9642).

Samples of granulated slag from Scunthorpe, Humberside, collected over several years, vary somewhat in chemical composition reflecting differences in iron-making practice. All contain some melilite and oldhamite crystals and minor amounts of iron along with the glass. Granulated slag from Usinor, Dunkirk, France, has a little more CaO than the Scunthorpe material with crystals of merwinite and oldhamite. Pelletised slag from Redcar, Teeside, is much more vescicular than the granulated material and contains melilite and oldhamite.

The melilite crystals contain many inclusions of oldhamite and iron. They span a wide range within the akermanite-gehlenite series and are non-stoichiometric in composition. The merwinite may have formed largely by quench crystallization. Oldhamite is probably the first phase to form in all the slags. The silicate mineralogy can be explained in terms of the phase relationships within the CaO-SiO2-Al2O3-MgO quaternary system. The small difference in composition of the French slags is sufficient for them to fall into the primary phase field of merwinite rather than melilite. Assuming that only a minor proportion of crystals is acceptable in slags for use in Portland Blastfurnace Cement, the present low Al (< 11 % Al2O3) British and French slags are approaching an optimum composition.

We show that the structures and phases developed in a variety of polysomatic series, including the biopyroboles, are similar to those predicted by a simple spin model—the Axial Next-Nearest-Neighbour Ising (ANNNI) model in a magnetic field. We argue that the different polysomatic structures can be considered as thermodynamically stable phases, composed of ordered sequences of chemically distinct structural modules. We suggest that the key factors which determine the stability of polysomatic phases are (a) the chemical potential, which controls the proportion of the different structural modules, and (b) the competing interactions between first and second neighbour modules within the structures.