Mineral data and a brief outline of the structure for zussmanite (ideal formula

KFe13Si17AlO42(OH)14)

have been published previously. This paper describes the determination of the crystal structure and presents and discusses the results. The structure consists of rhombohedrally stacked layers of Fe-(O,OH) octahedra to each side of which are attached rings of six (Si,Al)-O tetrahedra. These composite layers are linked to one another by rings of three (Si,Al)-O tetrahedra, and by potassium atoms, the latter in positions analogous to those in a mica. There is some evidence of disorder of the layer stacking. Interatomic distances and angles, and valency balance, are discussed.

The Mathiatis massive sulphide deposit in Cyprus was a low-grade (0.3% Cu), three million ton ore body of pyrite and minor chalcopyrite occurring within basaltic lavas of the Troodos ophiolite. Cessation of mining in 1987 left a deep open pit surrounded by large heaps of spoil, which are undergoing oxidation and leaching. The aim of this study was to determine the mineralogical controls on the storage and potential remobilization of As, Cu, Pb and Zn within, and from, mine spoil heaps. Most of the spoil samples collected, and related materials (stream sediment, reaction zone between a boulder of massive pyrite and calcareous chert, salt crusts on stream beds), are enriched in As (27—220 ppm), Cu (110—400 ppm), Pb (10—140 ppm) and Zn (290—12,000 ppm) relative to both the basalt and calcareous chert (As 4—10 ppm, Cu 20—76 ppm, Pb 3—6 ppm, Zn 39—200 ppm).

Arsenic, Cu, Pb and Zn in the spoil and related materials are associated with Fe(-Al-S)-O, Fe(-Al-Mg)-S-O, Al(-Mg-Fe)-S-O and Mg(-Al-Fe)-S-O phases (the brackets represent minor components of less than 20 wt.% within the phases). Chemical extraction work using CaCl2 suggests that Cu, Zn and to some extent, As, are potentially more soluble than Pb. This is corroborated by the very high total concentrations of Cu and Zn in both the secondary salt crusts and the reaction zone material, high CaCl2-extractable As, Cu and Zn in the salt crusts, and aqueous data for the Mathiatis mine area collected for a European Union LIFE report. This may have implications for ecosystem health and water quality in the Mathiatis area and areas of similar mineralogy and climate world wide.

Far-from-equilibrium dissolution experiments with diopside and basaltic glass in mixed-flow reactors at 70°C and pH 8.2 show that solute concentrations do not reach steady state over the experimental duration of 45—60 days. Chemical modelling indicates that during the dissolution experiments, solutions have become supersaturated with respect to carbonates in the case of diopside, and carbonates, clay minerals and zeolites in the case of the basaltic glass. Decreasing dissolution is therefore interpreted as a result of secondary surface precipitates blocking the reactive surface area. Calcite formation was supported in both experiments by a significant increase in Ca (and Sr) concentrations as pH was abruptly lowered from 8.2 to 7 because this change increased carbonate solubility and caused all potential carbonate precipitates to re-dissolve. The reduction in pH also led to an increase in Si concentration for diopside and a decrease in Si concentration for basaltic glass. This observation is in accordance with previous experiments on the pH-dependent dissolution rates of pyroxenes and basaltic glass.

There appear to be few published data correlating X-ray powder patterns of chemically analysed plagioclase felspars with composition. Tuttle and Bowen (1950) have examined the powder patterns of low-temperature and high-temperature modifications and find that pure albite from Amelia, Virginia, when heated for ten days at 1050° C., gives a powder pattern identical with that of synthetic albite. They have not given, however, complete data over the whole range from An0Ab100 to An100Ab0. Claisse (1950) selected six reflections from the powder patterns of eight plagioclases of composition extending over the complete range, and plotted line separations against composition determined optically, but did not distinguish between high- or low-temperature forms.

Yoderite occurs as a major constituent in a quartz-kyanite-tale schist, and is a high-pressure phase formed by the reaction Ky + Tc → Yd + Qu. The monoclinic unit-cell, a 8·10 Å., b 5·78 Å., c 7·28 Å., β 106°, space-group P21 or P21m, contains approximately (Mg2·0Ca0·2Fe0·5Al5·3Si4·0O17·6(OH)2·4. The structure appears to be related to that of kyanite, with which the mineral is intergrown; it is not an analogue of staurolite. The three strongest powder lines are 3·50 Å. vvs, 3·03 Å. vs, 2·61 Å. s. Specific gravity 3·39. Subsidiary reflections, similar to those of the intermediate plagioclases, have indices with non-simple fractional values of k. Optical properties are α 1·689 pale Prussian blue, β 1·691 indigo, γ 1·715 light olivegreen, absorption β > α > γ, 2Vγ25°, optic axial plane {010}, γ:[001] ≈ 7° in the obtuse angle β. An interpretation of the colour on the electron-exchange hypothesis Fe2+ ⇌ Fe3+ + e−, is suggested. A kinetic study has been made of the disappearance of the subsidiary reflections in the range 700°C. to 820°C.; further heating to 850°C. produces the metastable appearance of mullite, and at temperatures above 1100°C. the equilibrium anhydrous assemblage indialite + sapphirine appears.

Cathodoluminescence (CL) microscopy and spectroscopy combined with SHRIMP ion probe measurements were carried out on detrital zircons from the Cretaceous Weferlingen quartz sand (Germany) to distinguish and characterize different zircon populations.

Investigations by CL microscopy, SEM-CL and BSE imaging show that there are three main types of zircons (general grain sizes of 100–200 µm): (1) apparently weakly zoned, rounded grains with relict cores, (2) well rounded fragments of optically more or less homogeneous zircon grains showing CL zoning predominantly parallel to the z-axis, and (3) idiomorphic to slightly rounded zircon grains typically showing oscillatory euhedral CL zoning. A fourth type of low abundance is characterized by well-rounded grain fragments with an irregular internal structure showing bright yellow CL.

High-resolution CL spectroscopic analyses reveal that blue CL is mainly caused by an intrinsic emission band centered near 430 nm. Dy3+ is the dominant activator element in all zircons, whereas Sm3+, Tb3+, Nd3+ have minor importance. Yellow CL (emission band between 500 and 700 nm) is probably caused by electron defects localized on the [SiO4] groups (e.g. related to oxygen vacancies) or activation by Yb2+ generated by radiation. Variations of the integral SEM-CL intensity are mainly controlled by the intensity of the broad bands and the Dy3+ peaks.

SHRIMP analysis provides in situ high-resolution U-Pb dating of single zircon grains and confirms different ages for the evaluated different zircon types. The measurements show that the U-Pb ages of the zircons from Weferlingen scatter over a wide range (340 to 1750 Ma), backing up earlier conclusions that the quartz sand from Weferlingen is quite heterogeneous in terms of provenance.

The headwaters of the Río Pilcomayo drain the Cerro Rico de Potosí precious metal-polymetallic tin deposits of southern Bolivia. Mining of these deposits has taken place for around 500 years, leading to severe contamination of the Pilcomayo's waters and sediments for at least 200 km downstream. Communities living downstream of the mines and processing mills rely on the river water for irrigation, washing and occasionally, cooking and drinking, although most communities take their drinking water from springs located in the mountains above their village. This investigation focuses on arsenic exposure in people living in riverside communities up to 150 km downstream of the source. Sampling took place in April–May 2003 (dry season) and was repeated in January–March 2004 (wet season) in five communities: El Molino, Tasapampa, Tuero Chico, Sotomayor and Cota. Cota was the control in 2003 and again in 2004; a nearby city, Sucre, and several locations in the UK were also used as controls in 2004. Drinking, irrigation and river waters, hair and urine samples were collected in each community, digested where appropriate and analysed for As using ICP-MS. Arsenic concentrations in drinking waters ranged 0.2–112 μg 1–1, irrigation water 0.6–329 μg 1–1, river waters 0.9–12,800 μg 1–1, hair 37–2110 μg kg–1 and urine 11–891 μg 1–1. All but one drinking water sample was found to contain As below the World Health Organization recommended guideline of 10 μg 1–1, although a number of irrigation and river water concentrations were above Canadian and Bolivian guidelines. Many As concentrations in the hair and urine samples from this study exceeded published values for non-occupationally exposed subjects. Analysis of mean concentration values for all media types showed that there were no statistically significant differences between the control locations and the communities exposed to known As contamination, suggesting that the source of As may not be mining-related. Arsenic concentration appears to increase as a function of age in hair samples from males and females older than 30 years. Male volunteers over the age of 35 showed increasing urine-As concentrations as a function of age, whereas the opposite was true for the females.

We report in this paper the first occurrence of the rare assemblage corundum + quartz in the high-grade metamorphic zone in the core of the Namaqualand Metamorphic Complex (NMC) (South Africa). The magnetite-bearing rocks hosting the corundum-quartz assemblage are very rare, and occur discontinuous bands a few cm wide, associated with diorite, tonalite and anorthosite within quartzfeldspar ± sillimanite ± biotite ± spinel supracrustal rocks extensively intruded by a foliated granite gneiss. The magnetite-bearing rocks are characterized by the presence of abundant crystals of magnetite together with ilmenite, spinel and large (∽1 cm in diameter) euhedral crystals of corundum both displaying a sharp contact with magnetite and quartz. However, in some micro-domains, spinel and quartz, as well as corundum and quartz, are separated by a thin corona of sillimanite with or without magnetite. These textural features suggest that the following reactions have taken place: quartz + corundum → sillimanite, and quartz + spinel + O2 → sillimanite + magnetite. These reactions are interpreted as occurring at higher, as yet unknown, P-T conditions than previously estimated for the NMC. Whether corundum and quartz were once in equilibrium is worth investigating, as it could constitute a geothermobarometric assemblage for ultra-high T granulites.

A new mineral, eldfellite, was found among fumarolic encrustations collected in 1990 on the Eldfell volcano, Heimaey Island, Iceland. Associated minerals are ralstonite, anhydrite, gypsum, bassanite, hematite, opal and tamarugite, as well as a presumably new mineral with the composition Na3Fe(SO4)3. Along with opal and tamarugite, eldfellite forms soft and fragile aggregates built of thin, platy crystals of micrometre size. The mineral is yellowish-green to greenish-white, with a white streak. The calculated density is 3.062 g/cm3. Eldfellite is monoclinic, C2/m, a 8.043(4) Å, b 5.139(2) Å, c 7.115(4) Å, β 92.13(2)º, Vuc 293.9(2) Å3, Z = 2 and is isostructural with yavapaiite[KFe (SO4)2]. The strongest lines in the powder diffraction diagram are [d (Å), I (relative to 10)]: 3.72, 8; 3.64, 5; 3.43, 5; 2.77, 10; 2.72, 6; 2.57, 3; 2.370, 6; 1.650, 3. Theche mical analysis and theX-ray diffraction data of eldfellite correspond to those of the synthetic compound NaFe(SO4)2.

The major and trace element composition of over 40 wolframites from the Barroca Grande mine of the Panasqueira W-Sn-Cu quartz-vein hosted orebody have been determined by electron probe microanalysis.

The hübnerite content of wolframite is largely uniform (12 to 20 mol. %) throughout most of the mine, suggesting relative uniformity in composition of the main stage ore-forming fluids. However, wolframites show a striking pattern of enrichment in niobium adjacent to major sub-vertical fault zones. Typical wolframite Nb2O5 contents are below 1000 ppm, whilst values greater than 1000, 2000 and 4000 ppm are generally only found in wolframites less than 50, 30, and 10 metres respectively from major sub-vertical faults. This strongly suggests that some of these fault zones acted as major pathways for hydrothermal fluid migration during ore formation. The idea that the greisened cupola at Panasqueira was the sole major pathway for fluid movement is discounted.

Ferrihydrite and goethite are amongst the most important substrates for the sorption of contaminants in soil and other environmental media. Isotopic studies of the transition elements, particularly those that exhibit more than one oxidation state and show pH- and/or redox-sensitive behaviour at low temperatures, have been shown to be potentially useful present-day and past proxies for redox (or palaeoredox) conditions. We have made preliminary investigations of Fe isotope fractionation that take place during the formation of FeIII (oxy)hydroxides (FeIIIox) from an aqueous FeIII(NO3)3 solution (FeIIIaq) under laboratory conditions. We have attempted to keep the chemical system simple by excluding 'vital effects' and major changes in redox through the maintenance of abiotic conditions and use of FeIIIaq. Isotopic measurements (56Fe/54Fe, 57Fe/54Fe) of the FeIII(NO3)3 stock solution, the original ferrihydrite and the mixed ferrihydrite/goethite-supernatant FeIIIaq 'pairs' were carried out using a double focusing multicollector inductively coupled plasma mass spectrometer. The results reveal an apparent systematic variation indicating larger ΔFeIIIaq—FeIIIox with decrease in the ferrihydrite:goethite ratio, which reflects the time allowed for isotopic exchange. These values range from virtually zero (0.03%) after 24 h to 0.30% after 70 h. In each FeIIIox-FeIIIaq 'pair' the lighter Fe isotope is partitioned into the FeIIIox, leaving the FeIIIaq isotopically heavier. The observed fractionation reflects isotopic exchange of Fe between the FeIIIox and FeIIIaq upon at least a two step transition of ferrihydrite to goethite.

The Pendennis minette has an exceptionally high K2O/Na2O ratio and is strongly peralkaline. Its constituent minerals, which are described in detail, are sanidine, biotite, two carbonates (dolomite and ferroan magnesite), two amphiboles (riebeckite and a new variety, potassium magnesio-arfvedsonite), and quartz. The major and trace dement composition of the minette indicates close affinities with the lamproitic lavas.

The sulphide ores from the Julcani mining district (Peru) display many retrograde reactions that may be attributed to solid-state processes accompanying cooling. Fahlores [˜(Cu,Ag)10(Zn,Fe)2(Sb,As)4S13] from the Herminia mine exhibit pronounced downstream enrichments in molar Ag/(Ag+Cu) ratios that are strongly correlated with the abundance of PbS-AgSbS2-AgBiS2 phases. These correlations, discontinuous core to rim Sb/(Sb+As) enrichments in bournonites, and prominent reaction textures involving fahlores, bournonites and galenas provide strong evidence that the fahlores in these ores have been enriched in Ag by the Ag–Cu exchange reaction

which occurred during cooling following mineralization of a PbS-AgSbS2-AgBiS2 galena and has been documented elsewhere. Secondary PbS-AgSbS2-AgBiS2 minerals aramayoite, bismuthian diaphorite [Pb2Ag3(Bi,Sb)3S8], and diaphorite were produced from primary galenas with cooling of ores with high Pb/Cu and Bi/Sb; pyrargyrite formed from the breakdown of the Ag10Zn2Sb4S13 component in the most Ag-rich fahlores, as an exsolution product of galena, and from replacement of aramayoite and galena with the evolution of semimetal sulphides. Based on mineral compositions, phase equilibria, a thermochemical database for sulphides and sulphosalts, and the reintegrated composition for primary grains of Ag-rich PbS-AgSbS2-AgBiS2 phases, we estimate that the primary temperature of hydrothermal mineralization was >320±10°C, that these reactions ceased to affect fahlore Ag/(Ag+Cu) ratios and Bi/(Bi+Sb) ratios of aramayoite and miargyrite after cooling through 220±10°C. Galenas, however, appear to have continued to adjust their compositions to reflect even lower temperatures by continued exsolution of semimetals and production a diverse suite of sulphosalts that occur in fine intergrowths with galena.

Hydroxyl-bastnaesite-(Nd), the Nd- and OH-dominant new member of the bastnaesite group, has been found in the red karstic bauxites near Nikšić, Montenegro. It occurs as whitish, irregular aggregates of crystals usually 100–200 µm in diameter. Hexagonal with the cell dimensions a = 7.191 and c = 9.921 Å, with Z = 6. The strongest lines of the X-ray powder diffraction pattern (d, I, hkl) are: 4.95 80(002); 3.596 79(110); 2.911 100(112); 2.077 29(300); 2.042 51(114); 1.914 30(302). The mineral is uniaxial positive, ω 1.715, ɛ 1.81; Dcalc 4.89 g/cm3.

Electron probe analysis, using garnet, apatite and synthetic glass standards, combined with thermogravimetric and evolved gas analysis, gave Y2O3 0.2, La2O3 27.1, Ce2O3 0.3, Pr2O3 8.5, Nd2O3 31.5, Sm2O3 4.4, Eu2O3 1.3, Gd2O3 1.4, CaO 0.3, F 3.3, H2O 2.26, CO2 20.63, sum 101.19, less O = F 1.39, total 99.80%. This analysis calculates to (Nd0.41La0.36Pr0.11Sm0.06Gd0.02 Eu0.02Ca0.01)Σ0.99(CO3)1.03[(OH)0.55F0.38]Σ0.93, or ideally, (Nd,La)CO3(OH,F), with Nd > La and OH > F.

Eluvial pebbles from the Afu Hills, Nigeria, are largely composed of fluocerite, Ce0.50La0.28Nd0.11 Pr0.04Th0.03Ca0.02F3, with minor monazite. The fluocerite shows two types of alteration, to bastnäsite, and to bastnäsite-(La) with cerianite. Electron microprobe analyses are given for fluocerite, monazite, bastnäsite and bastnäsite-(La). The refined cell parameters of the fluocerite are a = 7.130±0.001, c = 7.2985 ± 0.001 Å. Strongest lines are 3.204 Å (100), 3.65 (45), 2.059 (45), 2.010 (45) and 3.565 (40). Space group P 63/mcm, Z = 6, Dcalc. = 6.12 g cm−3, ω = 1.613, ε = 1.609 both ±0.002, uniaxial negative. For bastnäsite a = 7.131 ± 0.002, c = 9.786±0.004 Å, for cerianite a = 5.460 ± 0.005 Å.

In the Gåsborn area, West Bergslagen, central Sweden, Fe-rich, indium-bearing (0.1–2.0wt.% In) sphalerite is replaced by Fe-poor sphalerite containing minute inclusions of chalcopyrite, roquesite and an unnamed In-Zn-rich phase. Fe-rich, In-bearing sphalerite is primary; indium occurs as a roquesite molecule in solid solution. Fe-poor sphalerite, roquesite, chalcopyrite and the unnamed In-Zn-rich phase were formed from In-bearing sphalerite by secondary processes, characterized by the so-called ‘chalcopyrite disease’.

Kirschsteinite (mainly CaFeSiO4), in association with forsterite-fayalite solid solutions, melilite, clinopyroxene, leucite, nepheline and several minor phases, is reported for the first time in the 290 ka Capo di Bove melilite-leucitite lava flow of the Alban Hills volcanic complex (Italy). Kirschsteinite appears very late in the crystallization sequence, as indicated by textural and chemical evidence (Mg# ≈ 25). It shows significant solid solution towards fayalite, and is found with groundmass phases indicating a relatively low-temperature melt composition more silica-undersaturated than phonolite (i.e. devoid of alkali feldspar). This clearly points to the very silica-undersaturated nature of almost all the Alban Hills volcanic rocks.

Specimens from some forty different localities over the composition range from about 20 % An to about 70 % An have been examined by X-ray single-crystal methods. The majority of these specimens show the normal intermediate plagioclase pattern characterized by weak pairs of subsidiary layer-lines of variable separation. It has been found that the separation of these layer-lines is a linear function of composition over the whole composition range. Further, this range is found to extend to more soda-rich compositions than was formerly believed, whilst the limits of the range are approximately defined by the compositions at which the separations of the subsidiary layer-lines about either the a- or the b-axes become zero.

The anomalous patterns shown by some specimens are discussed, and it is shown that most of these may be interpreted in terms of the previous geological history of the specimens.

A comparison of the present results with those obtained by previous workers in this field is made, and it is shown how the principal points of difference may be resolved. An account of the phase relationships of the low-temperature plagioclase series is given, and the problems arising from the present work are discussed.

The mode of occurrence of uraninite, pitchblende and coffinite at five localities in south-west England is described. Chemical and isotopic analyses of concentrates containing these minerals provide the following 206Pb/238U ages (My.): uraninite, South Crofty, Cornwall, 277 ± 10; uraninite, Geevor, Cornwall, 223 ± 5; pitcbblende-coffinite, King's Wood, Devon, 206 ± 5; pitchblende, Wheal Bray, Cornwall, 165 ± 4; pitchblende, South Terras, Cornwall, 474 ± 2; coffinite, Geevor, Cornwall, c. 45 (chemical analysis only). These results are compatible with geological and mineralogical evidence. Consideration of these and other results indicates that there were at least three periods of uranium mineralization in south-west England, at c. 290 My., c. 225 My., and c. 50 My. Other intermediate ages may also be valid but further work is required to substantiate these.

In earlier analytical work on stony meteorites the analytical results were given in a number of different ways. Not only the principles, but also the methods used in the calculation of the mineral composition as derived from the chemical analyses, were of a different kind in almost every description of a stony meteorite. The same remarks of course apply to a certain extent also to the older descriptions of terrestrial rocks. The publications on the 'Quantitative [(American) system of[ classification of igneous rocks' (1) and some publications by Henry S. Washington, especially a paper on 'The statement of analytical results of rock analyses' (2), contributed greatly to the unifying of the methods of representing the results of chemical analyses of rocks and calculating their mineral composition. Later on other systems for the statement and calculation of rock analyses have been introduced by other petrologists, especially by Paul Niggli, and all this work, taken together, has greatly contributed to clarification of the different ways in which the results of rock analyses can be stated and made use of in the petrological study of rocks.