The geochemical evolution of tin-tungsten deposits and their associated sulphides can be discussed in terms of four sequential processes: acquisition of the ore-forming elements (OFEs) by the granitic magma, emplacement of these elements in minerals and residual melt of the crystallizing granite, release of the OFEs to the circulating hydrothermal fluids and transport to the depositional sites, and finally, deposition of ore minerals through interaction of these fluids with the wall rock. Based on their crystallographic behaviour, it is useful to distinguish three principal classes of OFEs, here identified as BOC, LHC, and ALC elements. BOC (bivalent octahedral cation) elements are similar to ferrous iron and here are represented mainly by Zn, Mn, and perhaps Cu. Li also belongs to this class, although it is monovalent. LHC (large highly charged cations) elements encompass As, Nb, Mo, Sn, Sb, Ta, and W and they are similar to ferric iron or titanium in their crystallographic role. ALC (alkali-like cations) are capable of occupying alkali positions and are represented mainly by Pb, Ag, and Hg.

LHCs are rejected from the polymerized silicate liquid network and become enriched in the roof of the acid magma chamber, where more non-bridging oxygens are available. Transport to the roof may be enhanced by the formation of hydrous complexes, as is the pronounced enrichment of Na and Li. BOCs, along with Cl, F, and B, fractionate strongly into the vapour phase during vesiculation. HCl in the ore fluid is crucial for the alteration process and can be produced during boiling by a hydrolysis reaction of the NaCl dissolved or immiscibly present in the silicate magma.

Considerable laboratory information is available concerning release mechanisms of the OFEs to hydrothermal fluids. We can distinguish congruent and incongruent dissolution, both in response to acid buildup, as well as congruent and incongruent exchange not involving HCl. Melt-fluid fractionation is also thought to be important, though the physical mechanisms are not well understood. Any of these release mechanisms may be coupled with reduction or oxidation reactions. LHC, BOC, and ALC elements respond differently to each of these mechanisms, and these differences may in part be responsible for the observed separation of ore minerals in space and time. It is suggested that LHC elements are released preferentially during acid, non-oxidizing conditions typical of early stages, while BOC elements respond more readily to later acid-oxidizing environments, as well as exchange reactions with or without oxidation.

Depositional reactions have been formulated with respect to two contrasting types of country rocks: carbonates and schists. Differences are related to the process of neutralization of the HCl produced by ore deposition: carbonate dissolution on one hand and feldspar-muscovite or biotite-muscovite conversion on the other. In carbonate rocks, evaporite-related sulphates may provide the H2S necessary for sulphide precipitation, while in schists disseminated sulphides and organic matter may be important sulphur reservoirs in addition to the sulphur liberated from the granite. A variety of situations can be envisaged with respect to the sources of the OFEs and the sulphur species required for ore deposition, including granite and wall rocks. Chloride is recognized as the crucial anion for OFE release, transport, and deposition, although F and B play a role yet to be evaluated. Final HCl neutralization is an essential step in the reactions responsible for the deposition of ore minerals.

The ultimate sources of the OFEs must be related to the continental material involved in the process of melt production by partial melting. Oxidized sediments provide sources for LHC and ALC elements in the form of heavy minerals and clastic feldspars and micas. Organic-rich reduced sediments are hosts to BOC and LHC elements as sulphides and ALC elements in organic matter. Remelting of igneous and metamorphic rocks can enrich LHC, BOC, and ALC elements in the melt by extraction from opaques, Fe-Mg silicates, feldspars, and micas.

Short-range order in the oxygen co-ordination shell of the Ca ion in a glass of composition Ca3Mg4Al2Si7O24 is investigated by analysis of the extended X-ray absorption fine structure. The estimate of disorder in the short-range oxygen co-ordination is no greater than that for crystalline samples of diopside and bytownite. An estimate of the oxygen environment of calcium in the particular glass is included.

Two specimens of tremolite and one of richterite, all with nephrite jade texture, have been examined by transmission electron microscopy using ion-thinning for specimen preparation. The specimens contain clusters of very small lath-like crystallites with z-axes approximately parallel but in a range of azimuthal orientations. It is suggested that these clusters which are themselves in varied orientations are the result of post-tectonic recrystallization of strained amphibole crystals, the new crystals inheriting the z-axis orientations of the old. The extreme toughness of nephrite jade is attributed to a number of the sub-microscopic features observed, including the sizes, habits, and orientations of its crystallites, and the nature of its grain boundaries.

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.

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.

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.

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.

Endoskarns formed where a swarm of diorite dykes have intruded calcite marble at Redcap Creek include an inner melilite-dominated, a wollastonite-dominated, and an outer massive tilleyite zone in contact with marble. The massive tilleyite is unusual in that it is coarse-grained (prisms 2–15 cm in length) and its deep grey colour contrasts with the lighter coloured varieties described elsewhere. A chemical analysis gives a formula close to ideal, with only minor substitution of Al, Ti, and Mg. Refined unit cell parameters are in close agreement with those quoted in the literature. The skarns have clearly formed by transport of Si, Mg, Fe, Al, and Ti from the igneous rocks, and Ca in the reverse direction from the marble. Activity diagrams derived from experimental data are most useful in interpreting the zonal sequence of endoskarns, and preliminary results suggest mass transfer at low Xco2 and temperature of the order of 800°C or higher for the formation of the massive tilleyite.

Microprobe analyses of the halogen contents of apatites from two samples of amphibolite-facies schist from Connemara, Ireland, have been used to calculate the fugacity ratios fHCl/fH2O and fHF/fH2O using the experimental data of Korzhinskiy. The results imply fugacities for both acids in the range 0.03 to 0.1 bars, but whereas for the lower grade rock fHF > fHCl, the migmatitic sample gives fHF⋍fHCl. An independent estimate of fHF/fH2O from the biotite composition in one sample is in acceptable agreement with the result obtained from apatite.

Vivianite specimens from various world localities yield X-ray powder patterns of two types: one corresponds with that shown by synthetic Fe3(PO4)2 · 8H2O and is not readily distinguished from that of barićite; the second shows reflections of monoclinic vivianite and triclinic metavivianite along with reflections of a bobierrite-type phase. The triclinic phase occurs as two twin-related lattices with twin plane 110 being the structural equivalent of 010 in the monoclinic phase. The relationship of the bobierrite-type lattice to the other two has not been established. The ternary pattern is produced by some coarse-grained vivianites on natural oxidation. Finer grained vivianites oxidise to an X-ray amorphous state without passing through a triclinic intermediate.

The crystal structure of botallackite, Cu2(OH)3Cl, monoclinic, a = 5.717(1), b = 6.126(1), c = 5.636(1)Å, β = 93.07(1)°, V = 197.06(5)Å3, space group P21/m, Z = 1, has been refined to an R index of 3.8% for 350 observed (4σ) reflections, measured with Mo-Kα X-radiation on an automatic four-circle diffractometer. The structure consists of sheets of edge-sharing Cuϕ6 (ϕ = unspecified anion) octahedra of composition Cu2(OH)3Cl; these sheets are // {100}, and are joined by hydrogen bonding between oxygen and chlorine anions, thus accounting for the perfect {100} cleavage and the platy habit of botallackite.

Junitoite, CaZn2Si2O7·H2O, is orthorhombic, space group Area2, with a = 12.510, b = 6.318, c = 8.561 Å, Z = 4. The structure, determined on the basis of three-dimensional Mo-Kα intensity data for 745 reflections refined to R = 0.10. The structure consists of ZnO4 tetrahedral chains along b joined by Si2O4 groups along a and c to form a three-dimensional network. Ca occurs in distorted CaO5(H2O) octahedra. The structure shows similarities to hemimorphite and Ca-Zn silicates but represents a unique tetrahedral framework.

Electron probe microanalyses of zoisites from high-grade metamorphic rocks in Galicia, NW Spain have been obtained. The elements Na, Mg, P, K, Ti, and Mn were not detected above the 0.1 wt. % level. Assuming all Fe is present as Fe3+, a clear relation is obtained between the Fe content and the optic axial angle. Zoisite with 1.6 wt. % Fe2O3 proves to be uniaxial at 589 nm; uniaxiality in blue light (470 nm) lies at 1.5 wt. % Fe2O3. A change of the optic sign, from positive to negative, is obtained at 2.9 wt. % Fe2O3. The presence of minor elements greatly affects this relation, as is indicated by analyses of sector-zoned Sr-bearing zoisites of a muscovite-zoisite pegmatite from the same region. Under retrograde conditions Fe-rich α-zoisite reacts to form less Fe-rich α-zoisite or β-zoisite and clinozoisite.

Hey's observation of reduction of ferric ion bound to 1,10-phenanthroline in water is explained in terms of the analogy between quaternization of the ligand and its coordination by iron(III).

Pseudomesolite from Carlton Peak, described by Winchell (1900), is shown to be mesolite by means of chemical and X-ray data. A proposal to this effect has been accepted by the International Mineralogical Association's Commission on New Minerals and Mineral Names. Electron microprobe analysis revealed variations in the composition of pseudomesolite and showed the presence of faroelite. The X-ray powder diffraction pattern is similar to that of mesolite. Single-crystal Weissenberg photographs showed a twinning intergrowth which is explained by a 90° rotation of 50% of the unit cells about the c-axis, so that the a- and b-axes of rotated cells coincide with the b- and a-axes respectively of the unrotated cells. This twinning can not be detected optically. Mesolite has recently been proved to be orthorhombic, contrary to the long-held view that it is monoclinic.

Pseudomesolite from Oregon is also shown to be mesolite by single crystal Weissenberg photographs. A wet chemical analysis shows this material to be extremely silica-rich.

Zones of albitization 20 m wide are developed in the peraluminous, undeformed Proterozoic Bastfallshöjden granite, W. Bergslagen, central Sweden. During albitization Na, Si, Mg, Ni, Zn, and Ga are added, while Fe2+, Fe3+, Mn, K, Sc, Rb, Cs, Ba, Pb, U, and F are lost, together with the rare earth elements (REE) in decreasing amounts with increasing atomic number. Ti, Al, P, and Y were immobile. Trace element data for chlorites separated from hydrothermally altered country rocks and from a quartz-chlorite vein in the albitized granite show similar REE patterns indicating a common origin: the most altered granite has a similar REE pattern, probably resulting from interaction with the same hydrothermal fluid which produced the chlorites, in which seawater is thought to have been an important constituent.

Remnants of early Archaean (Akilia) iron-formation occur as enclaves within the c. 3700 Ma Amitsoq gneisses in the eastern Godthåb-Sukkertoppen region of southern West Greenland. Amphibole- and pyroxene-bearing assemblages are preserved respectively in these two areas. The amphibole-facies rocks comprise one, two, and three-amphibole-bearing assemblages, coexisting with magnetite and quartz (and locally garnet). Experimentally determined phase equilibria suggest that the amphibole-bearing types have not exceeded c. 700 °C, while distribution coefficients in the two-pyroxene ironformation indicate a maximum temperature of around 625 °C.

Mg-Fe distribution relationships between the phases are:

and

where the numbers are generalized distribution coefficients and in phase a). Mn distribution is:

and

The distribution coefficients are variable both from one rock to another and internally from one set of grain pairs to another. The development of the observed variable silicate phase assemblages is dependent upon a complex interaction of not only metamorphic grade (P and T) and element availability, but more importantly aH2o and fo2. In particular, the possibility of reactions between observed assemblages containing cummingtonite + actinolite, magnesian actinotite + magnetite and ferrohypersthene+ferrosalite suggest lesser or greater degrees of dehydration under oxidizing or reducing conditions. For example:

and