The advantages of X-ray absorption spectroscopy have been utilized to assess the Cu and Zn ordering in aurichalcite, (Cu5−xZnx)(OH)6(CO3)2. We have examined one hydrozincite sample and three aurichalcite samples in which the Cu:Zn ratios are in the range 1:3 to 2:3. Copper 2p XAS confirms that there is no monovalent copper in aurichalcite and that in each sample the copper might be distributed across more than one metal site. EXAFS, at the Cu and Zn K-edges, shows that the copper atoms preferentially enter the Jahn-Teller elongated, octahedral (M2) and trigonal bipyramidal (M4) sites, with the zinc atoms entering the more regular octahedral (M1) and tetrahedral (M3) site. Substantial solid solution towards the zinc rich region is facilitated by the substitution of copper by zinc on the M2 and M4 sites. This information, not easily obtained by X-ray diffraction, substantially enhances the understanding of the structure of aurichalcite.

Iron minerals influence the environmental redox behaviour and mobility of metals including the long-lived radionuclide technetium. Technetium is highly mobile in its oxidized form pertechnetate (Tc(VII)O4–), however, when it is reduced to Tc(IV) it immobilizes readily via precipitation or sorption. In low concentration tracer experiments, and in higher concentration XAS experiments, pertechnetate was added to samples of biogenic and abiotically synthesized Fe(II)-bearing minerals (bio-magnetite, bio-vivianite, bio-siderite and an abiotically precipitated Fe(II) gel). Each mineral scavenged different quantities of Tc(VII) from solution with essentially complete removal in Fe(II)-gel and bio-magnetite systems and with 84±4% removal onto bio-siderite and 68±5% removal onto bio-vivianite over 45 days. In select, higher concentration, Tc XAS experiments, XANES spectra showed reductive precipitation to Tc(IV) in all samples. Furthermore, EXAFS spectra for bio-siderite, bio-vivianite and Fe(II)-gel showed that Tc(IV) was present as short range ordered hydrous Tc(IV)O2-like phases in the minerals and for some systems suggested possible incorporation in an octahedral coordination environment. Low concentration reoxidation experiments with air-, and in the case of the Fe(II) gel, nitrate-oxidation of the Tc(IV)-labelled samples resulted in only partial remobilization of Tc. Upon exposure to air, the Tc bound to the Fe-minerals was resistant to oxidative remobilization with a maximum of ∼15% Tc remobilized in the bio-vivianite system after 45 days of air exposure. Nitrate mediated oxidation of Fe(II)-gel inoculated with a stable consortium of nitrate-reducing, Fe(II)-oxidizing bacteria showed only 3.8±0.4% remobilization of reduced Tc(IV), again highlighting the recalcitrance of Tc(IV) to oxidative remobilization in Fe-bearing systems. The resultant XANES spectra of the reoxidized minerals showed Tc(IV)-like spectra in the reoxidized Fe-phases. Overall, this study highlights the role that Fe-bearing biogenic mineral phases have in controlling reductive scavenging of Tc(VII) to hydrous TcO2-like phases onto a range of Fe(II)-bearing minerals. In addition, it suggests that on reoxidation of these phases, Fe-bound Tc(IV) may be octahedrally coordinated and is largely recalcitrant to reoxidation over medium-term timescales. This has implications when considering remediation approaches and in predictions of the long-term fate of Tc in the nuclear legacy.

Hydrocarbons (bitumens sensu lato) in sandstones have been recorded in several instances to have partially replaced their host rock, including quartz grains. Many replacive hydrocarbons are uranium-rich: associated non-uraniferous hydrocarbons are not replacive. Uranium is transported as carbonate complexes, which may be decomposed by organic acids to yield UO22+ ions and CO2. The UO22+ will be absorbed onto hydrocarbons before reduction to a mineral phase, generally uraninite; and the CO2 may be aggressive towards the silicate grains of the host sandstone. Accretionary nodules of replacive uraniferous hydrocarbon in red beds (e.g. at the cores of reduction spots) can provide valuable information about petroleum migration. They occur particularly in the vicinity of faults, and may record the interactions between metal-rich groundwaters and hydrocarbons leaking along a fault from an underlying reservoir. A trial study in Devonian sandstones of Easter Ross successfully traced a hydrocarbon-bearing sandstone reservoir from an occurrence of uraniferous hydrocarbon nodules.

A detailed electron microprobe (EMP) and laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) study of zircon from six types of miaskitic and agpaitic alkaline pegmatite from the Larvik Plutonic Complex, Oslo rift valley, Norway, was undertaken to shed light on the pegmatite petrogenesis. Detailed rare earth element (REE) analyses indicate important differences between the zircon from each type of pegmatite. Primary zircon from miaskitic Stavern-, Tvedalen- and Stålaker-type pegmatites has a mean ΣREE = 704 ppm, is depleted in LREE and has a significant positive Ce anomaly (Ce/Ce* = 44–67) and negative Eu anomaly (Eu/Eu* = 0.15–0.18). Secondary Tvedalen-type zircon is REE-enriched (ΣREE = 5035 ppm), with a flatter REE pattern, Ce/Ce* = 0.97 and a Eu anomaly similar to primary Tvedalen-type zircon (Eu/Eu* = 0.21). Secondary zircon from agpaitic Langesundsfjord-type pegmatites display a distinctive flat REE pattern characterized by overall REE enrichment (ΣREE = 967), Ce/Ce* = 1.92, and a minor negative Eu anomaly (Eu/Eu* = 0.37). Zircon from agpaitic Bratthagen-type pegmatites occurs as both altered primary and secondary phases and is strongly enriched in REE relative to other zircon (ΣREE = 4178 and 8388, respectively). Primary Bratthagen-type zircon has a similar REE pattern to miaskitic zircon, with a steeper HREE profile and smaller Ce and Eu anomalies (Eu/Eu* = 0.73; Ce/Ce* = 6.22). Secondary Bratthagen-type zircon is strongly enriched in LREE compared to primary zircon, does not display a positive Ce anomaly and has Eu/Eu* = 0.56. The altered primary and secondary Bratthagen-type zircons have elevated Th/UN ratios, suggesting a different melt source for Bratthagen-type agpaitic pegmatites. Zircon from external pegmatites has trace-element signatures similar to Stavern-, Tvedalen- and Staålaker-type primary zircon with Ce/Ce* = 214 and Nb/Ta and Th/U ratios that are similar to those of secondary Langesundsfjord- and Bratthagen-type zircon. It is suggested that the parental melt of the external pegmatites is the same as the miaskitic pegmatites, but that it has undergone alteration by hydrothermal fluids derived from the host basalt, or by post-magmatic F-rich fluids which mobilize Nb and Th. On the basis of texture, morphology and geochemistry, two populations of zircon can be recognized: (1) primary zircon from miaskitic pegmatites; and (2) secondary zircon from post-magmatic, hydrothermal assemblages. The U–Th–Pb isotope analyses indicate that the secondary and altered zircon are depleted in 238U, and enriched in LREE. Interaction of a post-magmatic hydrothermal fluid with an externally derived meteoric fluid is suggested to have influenced the REE signatures, and in particular the Eu and Ce anomalies of the late-stage zircons.

Some important and interesting data on the O, C and Sr isotopic compositions of rocks associated with the Bayan Obo Fe-Nb-REE deposit have been reported by Le Bas et al. (1997). However, a number of points relating to the interpretation of these data, and also to the terminology adopted, are worthy of further discussion. The essence of this discussion is that some of the geochemical and isotopic signatures found at Bayan Obo are not exclusively consistent with an igneous origin. A replacement hypothesis involving deep-sourced fluids could also explain the pattern of data, if minor carbonatitic intrusions into a sedimentary sequence are considered.

Klajite, MnCu4(AsO4)2(AsO3OH)2(H2O)10, the Mn-Cu-bearing member of the lindackerite group, was found in Jáchymov, Czech Republic, as the second world occurrence. It is associated with ondrušite and other arsenate minerals growing on the quartz gangue with disseminated primary sulfides, namely tennantite and chalcopyrite. Electron-microprobe data showed klajite aggregates to be chemically inhomogeneous at larger scales, varying from Mn-Ca-rich to Cu-rich domains. The chemical composition of the the Mn-rich parts of aggregates can be expressed by the empirical formula (Mn0.46Ca0.22Cu0.07Mg0.02)∑0.77(Cu3.82Mg0.14Ca0.03Zn0.01)∑4.00(As1.94Si0.06)∑2.00O8[AsO2.73(OH)1.27]2(H2O)10 (mean of seven representative spots; calculated on the basis of As + Si + P = 4 a.p.f.u. (atoms per formula unit) and 10 H2O from ideal stoichiometry), showing a slight cationic deficiency at the key Me-site. According to single-crystal X-ray diffraction, klajite from Jáchymov is triclinic, P, with a = 6.4298(8), b = 7.9716(8), c = 10.707(2) Å, α = 85.737(12)°, β = 80.994(13)°, γ = 84.982(10)°, and V = 538.85(14) Å3, Z = 1. The crystal structure was refined to R1 = 0.0628 for 1034 unique observed reflections (with Iobs > 3σ(I)), confirming that klajite (Mn-Cu member) and ondrušite (Ca-Cu member) are isostructural. The current data-set allowed determination of the positions of several hydrogen atoms. Discussion on hydrogen bonding networks in the structure of klajite as well as detailed bond-valence analysis are provided.

Monazite is a light rare-earth element (LREE)-bearing accessory phase common in felsic granitic rocks, and strongly influences LREE concentrations in granites and the chemistry of melts and residues formed during partial melting. Cheralite-rich (high-Th) monazite-(Ce) has been recorded as rims on partially dissolved cores in a suite of granulite-facies migmatites generated by disequilibrium melting. High-Th monazite has previously been recorded only in granitic-pegmatite occurrences. Subidiomorphic monazite-(Ce) from leucosome, melanosome and mesosome consists of complexly zoned cores (up to 300 µm in diameter) containing 5.17–9.87 wt.% ThO2, overgrown by essentially unzoned rims (containing up to 21.4 wt.% ThO2). Uranium contents are average for Th-rich monazite-(Ce) (0.22–3.17 wt.% UO2). Th enrichment (relative to LREE) in monazite-(Ce) rims is ascribed to the presence of fluorine-bearing melts (formed during the incongruent breakdown of biotite to produce a water-undersaturated melt), allowing the formation of REE-fluoride complexes in the melt, coupled with the increased charge balanced substitutions Th4+ + Si4+ ⇌ REE3+ + P5+ and Th4+ + Ca2+ ⇌ 2REE3+ into monazite-(Ce). Fractionation of Th and U (reflected by an increased in Th/U in rims relative to cores) may have occurred due to the removal by a CO2-rich fluid phase in the melt. These interpretations are consistent with elevated CO2 and F contents of granitic liquids produced during the water-undersaturated breakdown of biotite under granulite-facies conditions. Evidence for restricted monazite-(Ce)-melt equilibration and rapid melt removal is provided by the ubiquitous presence of partially embayed cores and unzoned rims.

The S. Domingos abandoned mine is a major source of pollutant-metals contamination. Slags from the 19th-20th century contain the most hazardous material. However, the release of pollutant metals depends on the metal-retention capability of weathering products. This work shows that Zn is not effectively retained by these weathering products while As and Pb are partially stored in sulphates. Copper, on the other hand, has a different behaviour and is the most leachable of the elements studied.

High-pressure-temperature (P-T) experiments were conducted in an attempt to determine the diffusion rates of C atoms in diamond, and the possibility of changes in the isotope compositions of diamond at high P-T in the Earth’s mantle. The starting material consisted of a polished plate of natural diamond (very largely 12C), which had been coated with 13C diamond by chemical-vapourdeposition to form a sharp interface between 12C and 13C diamond. Three experiments were performed at 1800, 2000 and 2300ºC, all at 7.7 GPa, for0.5 –20 h. Isotopic profiles obtained by ion microprobe before and after each experiment showed no evidence of relaxation of the sharp interface between 12C and 13C, and so diffusion must have been on a scale less than the ~32 nm depth resolution for this technique. Using 32 nm as the maximum length scale of diffusion across the interface, the maximum ln D (diffusion coefficient) values for the experiments were calculated to be in the range –38 to –42. Unlike previous experimental data, these results show that changes in the isotopic compositions of diamond on long time scales in the Earth’s upper mantle are unlikely. Furthermore, the results support empirical evidence from mapping of C isotope distributions in natural diamonds that C isotope compositions reflect diamond growth compositions.

Based on nearly 1500 published amphibole analyses the maximum possible Alvi in hornblendes is shown to increase with increase of Aliv. New analyses of hornblendes from amphibole-corundum rocks, with and without anorthite, are given and after critical examination of the available data it is concluded that the maximum verified Alvi-rich calciferous amphibole that approaches the closest to hypothetical tschermakite comes from a kyanite-bearing aluminous high-pressure-crystallized schist from Lukmanier, Switzerland. Pure natural edenite or ferroedenite is unknown, but a new analysis of the nearest known natural edenite, from Mysore, India, agrees with the postulated view that extraordinarily low temperatures are needed for edenite-ferroedenite crystallization, much below that possible in magmas and only rarely achieved in metamorphic rocks containing amphiboles. The limit of the approach of igneous hornblendes to edenite-ferroedenite and tremolite-ferroactinolite is outlined.

At least 1100 °C is required for complete expulsion of water from some amphiboles.

While undergoing 'dry' homogenization at 980°C the 2̄01 X-ray reflections of sodic lowalbite- microcline microperthites show that phase compositions recapitulate (but in a reverse timesense) the unmixing history of ordered feldspars about a solvus with a critical composition near 26 mole per cent KAlSi3O8.

Relict clinopyroxenes from metadolerites of the Early Permian Petroi Metabasalt formation, studied by electron microprobe, show a limited compositional range near the diopside-augite boundary in the pyroxene quadrilateral. Clinopyroxene analyses from three metadolerites, grouped in approximately equal Fs contents, define an overall smooth trend between Fs10 and Fs16. This is typical of clinopyroxenes from mildly alkaline basic magmas. Pyroxene stoichiometry suggests high Fe3+ contents (0.04 to 0.20 a.f.u.), which with high Al (0.10 to 0.31 a.f.u.) and Ti (0.03 to 0.08 a.f.u.) implies that CaTiAl2O6 and CaFe3+AlSiO6 are important ‘other components’. Relative Alz in CaFe3+AlSiO6 decreases and consequently CaTiAl2O6 increases with progressive fractionation. This, with the Fe2+:Fe3+ ratios in the Petroi clinopyroxenes, suggests falling ƒO2 in the magma with fractionation. The ƒO2 controlled entry of Alz, Tiy and Nax into the clinopyroxenes and hence the Petroi clinopyroxene trend.

Kihlmanite-(Ce), Ce2TiO2[SiO4](HCO3)2(H2O), is a new rare-earth titanosilicate carbonate, closely related to tundrite-(Ce). It is triclinic, P, a = 4.994(2), b = 7.54(2), c = 15.48(4) Å, α = 103.5(4), β = 90.7(2), γ = 109.2(2)o , V = 533(1) Å3, Z = 2 (from powder diffraction data) or a = 5.009(5), b = 7.533(5), c = 15.407(5) Å, α = 103.061(5), β = 91.006(5), γ = 109.285(5)°, V = 531.8(7) Å3, Z = 2 (from single-crystal X-ray diffraction data). The mineral was found in the arfvedsonite-aegirine-microcline vein in fenitized metavolcanic rock at the foot of the Mt Kihlman (Chil’man), near the western contact of the Devonian Khibiny alkaline massif and the Proterozoic Imandra-Varzuga greenstone belt. It forms brown spherulites (up to 2 cm diameter) and sheaf-like aggregates of prismatic crystals, flattened on {010} and up to 0.5 mm diameter. Both spherulites and aggregates occur in interstices in arfvedsonite and microcline, in intimate association with golden-green tundrite-(Ce). Kihlmanite-(Ce) is brown, with a vitreous lustre and a pale yellowish-brown streak. The cleavage is perfect on {010}, parting is perpendicular to c and the fracture is stepped. Mohs hardness is ∼3. In transmitted light, the mineral is yellowish brown; pleochroism and dispersion were not observed. Kihlmanite-(Ce) is biaxial (+), α = 1.708(5), β = 1.76(1), γ = 1.82(1) (589 nm), 2Vcalc = 89°. The optical orientation is Y ^ c = 5°, other details are unclear. The calculated and measured densities are 3.694 and 3.66(2) g cm−3, respectively. The mean chemical composition, determined by electron microprobe, is: Na2O 0.13, Al2O3 0.24, SiO2 9.91, CaO 1.50, TiO2 11.04, MnO 0.26, Fe2O3 0.05, Nb2O5 2.79, La2O3 12.95, Ce2O3 27.33, Pr2O3 2.45, Nd2O3 8.12, Sm2O3 1.67, Gd2O3 0.49 wt.%, with CO2 15.0 and H2O 6.0 wt.% (determined by wet chemical and Penfield methods, respectively), giving a total of 99.93 wt.%. The empirical formula calculated on the basis of Si + Al = 1 atom per formula unit is (Ca0.16Na0.11Mn0.02)∑0.29[(Ce0.98La0.47Pr0.09Nd0.29Sm0.06Gd0.02)∑1.91(Ti0.82Nb0.12)∑0.94O2 (Si0.97Al0.03)∑1O4.02(HCO3)2.01](H2O)0.96. The simplified formula is Ce2TiO2(SiO4)(HCO3)2·H2O. The mineral reacts slowly in cold 10% HCl with weak effervescence and fragmentation into separate plates. The strongest X-ray powder-diffraction lines [listed as d in Å(I) (hkl)] are as follows: 15.11(100)(00), 7.508(20)(00), 6.912(12)(01), 4.993(14)(00), 3.563(15)(01), 2.896(15)(1). The crystal structure of kihlmanite-(Ce) was refined to R1 = 0.069 on the basis of 2441 unique observed reflections (MoKα, 293 K). It is closely related to the crystal structure of tundrite-(Ce) and is based upon [Ce2TiO2(SiO4)(HCO3)2] layers parallel to (001). Kihlmanite-(Ce) can be considered as a cationdeficient analogue of tundrite-(Ce). The mineral is named in honour of Alfred Oswald Kihlman (1858–1938), a remarkable Finnish geographer and botanist who participated in the Wilhelm Ramsay expeditions to the Khibiny Mountains in 1891–1892. The mineral name also reflects its occurrence at the Kihlman (Chil’man) Mountain.

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.