First lead isotopic data for cinnabar in the Almadén district (Spain): implications for the genesis of the mercury deposits

The Almadén district constitutes the largest and probably the most intriguing mercury concentration in the world. Two types of mineralization are recognized: 1) stratabound, of Lower Silurian age, well represented by the large Almadén deposit; and 2) fully discordant mercury deposits of minor importance in terms of size, and exemplified by the deposit of Las Cuevas. The latter ones can be found at different positions along the Almadén stratigraphic column. Both types of deposits are always associated with the so-called frailesca rocks (diatremes of alkali basaltic composition). This paper reports the first lead isotope compositions of cinnabar in the district. Whole samples and stepwise leaching cinnabar aliquots display relatively homogeneous isotopic compositions (²⁰⁶Pb/²⁰⁴Pb = 18.112–18.460; ²⁰⁷Pb/²⁰⁴Pb = 15.635–15.705; ²⁰⁸Pb/²⁰⁴Pb = 38.531–38.826). Taken together with Jébrak et al.s (2002) pyrite lead isotope results, the new cinnabar isotopic data define a steep array trend on the ²⁰⁷Pb/²⁰⁴Pb– ²⁰⁶Pb/²⁰⁴Pb diagram, indicating a mixed contribution of lead and probably mercury from different sedimentary sources in the Almadén basin. The Almadén Hg deposits are related to a contemporaneous mafic magmatism that might have provided part of the mercury. Hydrothermal leaching of organic matter from sedimentary rocks and formation of Hg organic complexes enhanced metal solubility, promoting transport from and within the volcanic units.Editorial handling: M. Chiaradia     

Geochemistry of the Kalatongke Ni–Cu–(PGE) sulfide deposit,NW China: implications for the formation of magmatic sulfide mineralization in a postcollisional environment

The Kalatongke (also spelt as Karatungk) Ni–Cu–(platinum-group element, PGE) sulfide deposit, containing 33 Mt sulfide ore with a grade of 0.8 wt.% Ni and 1.3 wt.% Cu, is located in the Eastern Junggar terrane, Northern Xinjiang, NW China. The largest sulfide ore body, which occupies more than 50 vol.% of the intrusion Y1, is dominantly comprised of disseminated sulfide with a massive sulfide inner zone. Economic disseminated sulfides also occur at the base of the intrusions Y2 and Y3. The main host rock types are norite in the lower part and diorite in the upper part of each intrusion. Enrichment in large ion lithophile elements and depletion in heavy rare earth elements relative to mid-ocean ridge basalt indicate that the mafic intrusions were produced from magmas derived from a metasomatized garnet lherzolite mantle. The average grades of the disseminated ores are 0.6 wt.% Ni and 1.1 wt.% Cu, whereas those of the massive ores are 2 wt.% Ni and 8 wt.% Cu. The PGE contents of the disseminated ores (14–69 ppb Pt and 78–162 ppb Pd) are lower than those of the massive ores (120–505 ppb Pt and 30–827 ppb Pd). However, on the basis of 100% sulfide, PGE contents of the massive sulfides are lower than those of the disseminated sulfides. Very high Cu/Pd ratios (>4.5 × 10⁴) indicate that the Kalatongke sulfides segregated from PGE-depleted magma produced by prior sulfide saturation and separation. A negative correlation between the Cu/Pd ratio and the Pd content in 100% sulfide indicates that the PGE content of the sulfide is controlled by both the PGE concentrations in the parental silicate magma and the ratio of the amount of silicate to sulfide magma. The negative correlations between Ir and Pd indicate that the massive sulfides experienced fractionation.     

Mobilization of Ag,heavy metals and Eu from the waste deposit of the Las Herrerias mine (Almería,SE Spain)

We studied the mobility of silver, heavy metals and europium in waste from the Las Herrerías mine in Almería (SE Spain). The most abundant primary mineral phases in the mine wastes are hematite, hydrohematite, barite, quartz, muscovite, anorthite, calcite and phillipsite. The minor phase consisted of primary minerals including ankerite, cinnabar, digenite, magnesite, stannite, siderite and jamesonite, and secondary minerals such as glauberite, szomolnokite, thenardite and uklonscovite. The soils show high concentrations of Ag (mean 21.6 mg kg^–1), Ba (mean 2.5%), Fe (mean 114,000 mg kg^–1), Sb (mean 342.5 mg kg^–1), Pb (mean 1,229.8 mg kg^–1), Zn (mean 493 mg kg^–1), Mn (mean 4,321.1 mg kg^–1), Cd (mean 1.2 mg kg^–1) and Eu (mean 4.0 mg kg^–1). The column experiments showed mobilization of Ag, Al, Ba, Cu, Cd, Eu, Fe, Mn, Ni, Sb, Pb and Zn, and the inverse modelling showed that the dissolution of hematite, hausmannite, pyrolusite and anglesite can largely account for the mobilization of Fe, Mn and Pb in the leaching experiment. The mobility of silver may be caused by the presence of kongsbergite and chlorargyrite in the waste, while the mobility of Eu seems to be determined by Eu(OH)₃, which controls the solubility of Eu in the pH–Eh conditions of the experiments. The mineralogy, pH, Eh and geochemical composition of the mine wastes may explain the possible mobilization of heavy metals and metalloids. However, the absence of contaminants in the groundwater may be caused by the carbonate-rich environment of “host-rocks” that limits their mobility.     

Ages and compositions of primary and secondary allanite from the Lala Fe–Cu deposit,SW China: implications for multiple episodes of hydrothermal events

Numerous Fe–Cu deposits in southwestern China form the Kangdian Iron-Oxide Copper-Gold (IOCG) metallogenic Province. These deposits have a close association of Fe-oxides and Cu-sulfides formed at different stages, which are possibly related to multiple hydrothermal events. In this paper, U–Pb dating and chemical analyses on allanite from different stages of the Lala deposit were used to constrain timing and origin of such events. Allanite occurs as disseminated grains or patches in Fe–Cu ores and is closely associated with chalcopyrite, molybdenite, calcite and minor titanite, postdating magnetite and apatite. High-resolution backscattered electronic (BSE) imaging, electron microprobe compositions and X-ray scanning profiles demonstrate that REE-rich primary allanite was replaced by later, relatively porous and REE-poor secondary allanite. Such a replacement was promoted by interaction between primary allanite and fluid fluxes infiltrating the minerals, following an exchange scheme of REE³⁺ + Fe²⁺ → Ca²⁺ + Al³⁺. The secondary allanite has higher Fe³⁺/(Fe³⁺+Fe²⁺) ratios and U contents, indicating involvement of relatively oxidized fluids during alteration. The alteration has also produced unidentified secondary REE minerals in fractures, indicating re-deposition of some of the removed REEs. The primary and secondary allanites are dated by in situ LA-ICP-MS technique and have U–Pb ages of 1,067 ± 41 Ma and 880–850 Ma, respectively. The ~1.07 Ga primary allanite was contemporaneous with the main Mo–Cu–LREE mineralization with a molybdenite Re–Os age of ~1.08 Ga. The 880–850 Ma secondary allanite is comparable with the Ar–Ar ages (890–830 Ma) of biotite from hosting schists and undeformed sulfide veins occurring throughout the Kangdian Province, suggesting that such an event was possibly syn-deformational and represents a younger hydrothermal event. Occurrences of both primary and secondary allanites suggest that the mineralization may have involved multiple tectonothermal events including the ~1.05–1.1 Ga intra-plate and subsequent 960–740 Ma arc magmatism in the Kangdian region.     

On the possibility of determining rates of removal of uranium from crystalline igneous rocks using U-series disequilibria—2: applicability of a U-leach model to mineral separates

Preliminary U-series data are presented on the disequilibria of mineral separates of surface samples from the Eye-Dashwa lakes granite (Canada). Most analyses of the ferromagnesian, quartz-plus-feldspar, and zircon-plus-sphene grains, show that leaching of U has taken place such that²³⁴U/²³⁹U≤ 1 and ²³⁰Th/²³⁴U 1. The simple leach model presented in a companion paper was used to explain these characteristic ratios. It is suggested that the leach model may be used on zircon and sphere grains to estimate U-leach rates, and this is relevant to the suggestion of using sphene-like hosts as the primary barrier in the safe disposal of nuclear waste. A full analysis of U mobility within a given rock volume was not possible due to our limited data base and to our inability to monitor labile U directly.     

Oxygen isotope signatures in olivines from São Miguel (Azores) basalts: implications for crustal and mantle processes

Oxygen isotope ratios were measured in olivines from eight São Miguel basalt lavas. With one exception (4.57‰), the olivines are indistinguishable from one another with an average δ¹⁸O of 4.92±0.03‰ (1σ). This value is slightly lower than that characteristic of upper mantle peridotite and MORB olivines (5.2±0.2‰). Assimilation of ≥10–20% of high-temperature altered lower oceanic crust or 4–9% hydrothermally altered volcanic edifice rocks could produce the low δ¹⁸O signatures in the São Miguel olivines; both of these assimilation models are permitted by the trace element and radiogenic isotope variations in the São Miguel basalts. However, the limited variation in δ¹⁸O despite eruption of the basalts through compositionally and tectonically variable lithosphere, and the lack of correlation of δ¹⁸O with olivine forsterite content, are more easily explained if the olivine δ¹⁸O signatures are inherited from their mantle source. If the δ¹⁸O signatures reflect mantle source compositions, then the relatively low and uniform δ¹⁸O signatures allow constraints to be placed on the origin of the mantle sources beneath São Miguel. Extreme variations in radiogenic isotope signatures have previously been attributed to two component source mixing between a predominant Azores plume source with mild HIMU-like characteristics, and an EMII-type mantle with very radiogenic Sr. The low δ¹⁸O signatures in the São Miguel basalt olivines suggest that the predominant Azores plume source contains >10% hydrothermally altered recycled oceanic crust. The limited variation in δ¹⁸O is consistent with a component of recycled sediment in the São Miguel EMII-type source, although, unlike the case for other EMII OIB (e.g. Samoa and Society), the relatively low δ¹⁸O signatures in São Miguel restrict any involvement of recycled sediment to <2% of a relatively low δ¹⁸O and very radiogenic Sr or high Rb/Sr sediment. Involvement of several percent metasomatized subcontinental lithospheric mantle could alternatively produce the EMII-type Sr–Nd–Pb isotope signatures without significantly affecting the plume-related low δ¹⁸O signatures. The São Miguel δ¹⁸O data are thus consistent with mixing between a low δ¹⁸O Azores plume source with a component of subducted, hydrothermally altered lower oceanic crust, and either minor recycled sediment or localized EMII-rich delaminated subcontinental lithospheric mantle. The latter could have been introduced into the lithosphere or shallow asthenosphere during opening of the Atlantic ocean basin.     

Compositional variations of olivine from the Jinchuan Ni–Cu sulfide deposit,western China: implications for ore genesis

The Jinchuan Ni–Cu sulfide deposit is hosted by an elongated, olivine-rich ultramafic body that is divided by subvertical strike-slip faults into three segments (central, eastern, and western). The central segment is characterized by concentric enrichments of cumulus olivine crystals and interstitial sulfides (pyrrhotite–pentlandite–chalcopyrite intergrowth), whereas the eastern and western segments are characterized by an increase of sulfides toward the lower contacts. In all segments sulfides are concentrated at the expense of intercumulus silicates. Olivine re-crystallization is found to be associated with actinolite alteration in some samples. The compositional variations of primary olivine from the sulfide-poor samples can be explained by a small degree of olivine crystallization (<5%) from a basaltic magma followed by local re-equilibration of the olivine with up to 30% trapped silicate liquid. In the sulfide-bearing samples the compositions of primary olivine record the results of olivine-sulfide Fe–Ni exchange that occurred after the trapped silicate liquid crystallized. Our olivine data indicate that Ni in the original sulfide liquids increased inward in the central segment and laterally away from the lower contact in the eastern segment. Variations in the compositions of sulfide liquids are thought to result from fractional segregation of immiscible sulfide liquid from a basaltic magma in a staging chamber instead of in situ differentiation. High concentrations of olivine crystals (mostly >50 modal%) and sulfide (averaging ~5 wt%) in the rocks are consistent with the interpretation that the Jinchuan deposit was formed by olivine- and sulfide-laden magma successively ascending through a conduit to a higher, now-eroded, level. Sulfide enrichment toward the center in the central segment and toward the lower contact in the eastern and western segments may have, in part, resulted from flow differentiation and gravitational settling during magma ascent, respectively.Editorial handling: P. Lightfoot     

Structural features of humic acids from a sedimentary sequence in the Guadiana estuary (Portugal–Spain border)

The structural characteristics of humic acids (HAs) from two different depths of a sedimentary sequence representing the last 13 kyr in the valley of Guadiana river estuary (SW Portugal/Spain border) have been approached using a combination of spectroscopic techniques, wet chemical degradation methods (sequential oxidation with sodium persulfate followed by KMnO₄, and oxidation with RuO₄) and analytical pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) in the presence and absence of tetramethylammonium hydroxyde (TMAH). The aim was to obtain complementary information on the sources and alteration of the organic matter (OM) provided by a previous study on the vertical distribution of terrestrial and phytoplankton biogeochemical markers in the sequence. Both the FT-IR (Fourier transformed infrared) and ¹³C NMR (nuclear magnetic resonance) spectra showed a close similarity with the structural characteristics of the HA samples. NMR signals in the alkyl region (0–45 ppm) as well as FT-IR band patterns typical for methoxyl-substituted aromatic rings pointed to the presence of an important aliphatic domain, as well as to lignin-derived compounds. This finding was confirmed using analytical pyrolysis. In addition, the main TMAH thermochemolysis products were typical lignin-derived methoxyphenols with both guaicyl and syringyl nuclei. The detection of methoxyphenol units with three to six carbon atom (C₃–C₆) side chains suggests that lignin and possibly suberin were only partially degraded. Compounds arising from proteins and polysaccharides were also detected, although in lesser and varying amount. The major products from persulfate oxidation were series of n-alkanes (C₁₆–C₃₃ with clear odd/even predominance) and n-fatty acids, both saturated (C₁₀–C₂₆ with strong even/odd predominance) and unsaturated, which may arise from the above aliphatic biomacromolecules. The major products from permanganate oxidation of the persulfate residue were α,ω-diacids (C₆–C₁₁) originating from oxidation of the ether bonds linking the building blocks constituting the core of the HA structure. Aromatic compounds (phenols, methoxy-dimethoxybenzene carboxylic acid and benzene di-, tri-, tetra- and pentacarboxylic acids), most probably derived from the aromatic backbone of the HAs, that may also include lignin moieties as well as other polyphenols (flavonoids and tannins) were also detected. The RuO₄ oxidation also released series of n-alkanes (C₁₆–C₃₃), linear saturated fatty acids (C₁₀–C₂₈) and α,ω-diacids (C₇–C₂₅), as well as traces of benzene polycarboxylic acids. Regarding the usefulness of the various techniques used, they provide complementary information. Indeed, spectroscopic techniques and analytical pyrolysis provide information on the backbone of the HAs, and on their origin, whereas the oxidative degradations provide different information on the structural features of the HA, particularly the nature of the linking between the building blocks. In general, the data support the idea that the HAs still contain information about the signature of aliphatic and aromatic biomacromolecules contributing to the OM deposited. The presence of lignin-derived residues suggests a large input from terrestrial carbon throughout the core.     

Sulfur and lead isotope systematics: Implications for the genesis of the Riópar Zn-(Fe-Pb) carbonate-hosted deposit (Prebetic Zone,SE Spain)

The Zn-(Fe-Pb) deposits of the Riópar area (Prebetic Zone, SE Spain) are hosted by dolostones that replace Berriasian to Valanginian (Upper Jurassic-Lower Cretaceous) limestones. Mineralization consists of hypogene sphalerite, marcasite and galena, and supergene calamine zones. The hypogene ores are associated with a saddle dolomite gangue. The ore bodies occur as discordant and stratiform lenses, ore-cemented breccias, cm- to mm-wide veins and veinlets, disseminations and stylolite porosity filling within the host dolomites. The main ore controls include stratigraphy and/or lithology, tectonics (faults, fractures and breccias) and availability of metals and sulfur. The morphologies and epigenetic character of the hypogene ore bodies are consistent with the classification of this mineralization as a Mississippi Valley-type (MVT) deposit. The Ga/Ge geothermometer in sphalerite yielded a temperature range of 194–252 °C, which represents the temperature of the source region of the ore solution. This value is comparable to the temperature obtained in the ore deposition site, 159 ± 15 °C from the Δ³⁴S geothermometer in sphalerite galena pairs. This similitude points to a hydrothermal fluid that did not cool down significantly during flow from the fluid reservoir area to the precipitation site. δ³⁴S values of base-metal sulfides (−7.5 to +3.5‰) are consistent with thermochemical reduction of Triassic sulfate (seawater and/or derived from dissolution of evaporites) by interaction with organic compounds (e.g., hydrocarbons, methane), which reduced sulfate to sulfide in the deposition site. The lead isotope ratios (²⁰⁶Pb/²⁰⁴Pb = 18.736–18.762; ²⁰⁷Pb/²⁰⁴Pb = 15.629–15.660; ²⁰⁸Pb/²⁰⁴Pb = 38.496–38.595) of galena suggest that Pb, and probably other metals as Zn, is derived from continental crustal rocks. On the other hand, these relations points to a unique metal source probably derived from the Paleozoic basement rocks. The relationship between bedding-parallel stylolites, dolomitization, sulfide precipitation and Alpine tectonic affecting the MVT ore, suggests a relative timing range for the mineralization in the Riópar area of 95–20 Ma (Upper Cretaceous-Tertiary). The sulfide mineralization and the associated dolomitization are thus explained by the contribution of two fluids that mixed in different proportions during dolomitization and mineralization: i) a fluid probably derived from Cretaceous seawater saturating Mesozoic sediments (Fluid A), characterized by being dilute and initially low temperature, which should have contained organic rich compounds in the ore deposition site (e.g., hydrocarbons and CH₄ dissolved gas); and ii) a high salinity hydrothermal brine (Fluid B) rich in both metals and sulfate, circulated through the Paleozoic basement. During the pre-ore dolomitizing stage the fluid phase was dominated by the diluted fluid (Fluid A > Fluid B), whereas in a later fluid pulse, the proportion of the high salinity fluid increased (Fluid A < Fluid B) which allowed sulfide precipitation. MVT exploration in the Prebetic Zone should focus towards the SW of the Riópar mines, in the vicinity of the Alto Guadalquivir-San Jorge fault.     

Sulphur isotope patterns from the Bleiberg deposit (Eastern Alps) and their implications for genetically affiliated lead–zinc deposits

Summary A set of 354 sulphur isotope data from the Bleiberg deposit, the type deposit of Alpine low temperature carbonate hosted Pb–Zn deposits (APT deposits), is critically evaluated applying statistical methods. The sulphur isotope patterns vary significantly among the ore horizons. This suggests a long lasting and polyphase mineralisation system. The sulphur isotope composition of barite corresponds to that of Carnian seawater (i.e. 16 ³⁴S). The ³⁴S values of the iron sulphides correspond to data from sedimentary iron sulphides. Pb and Zn sulphides are characterized by three normally distributed ³⁴S populations with mean values of –6 to –8, –13 to –18, and –25 to –29. Heavy sulphur (>–10 ³⁴S) indicates contribution of sulphide sulphur from epigenetic-hydrothermal fluids, whereas light sulphide sulphur (<–21 ³⁴S) was produced by sulphur – reducing bacteria. The intermediate population is explained by mixing of sulphur derived from these two sources. Other sources of local importance, however, can not be excluded. The isotope populations correspond only partly to the paragenetic ore stages. The sulphur isotope patterns in the APT deposits are regionally different. Data from other low-temperature sediment-hosted Pb–Zn deposits support the proposed interpretation. A comparison demonstrates that the sulphur isotope patterns of APT deposits correspond to patterns of the Irish type deposits, but are different to those of Mississippi Valley type deposits.Supplementary material to this paper is available in electronic form at http://dx.doi.org/10.1007/s00710-004-0071-3     

Magnetite geochemistry of the Longqiao and Tieshan Fe–(Cu) deposits in the Middle-Lower Yangtze River Belt: Implications for deposit type and ore genesis

Magnetite is a common mineral in many ore deposits and their host rocks, and contains a wide range of trace elements (e.g., Ti, V, Mg, Cr, Mn, Ca, Al, Ni, Ga, Sn) that can be used for deposit type fingerprinting. In this study, we present new magnetite geochemical data for the Longqiao Fe deposit (Luzong ore district) and Tieshan Fe–(Cu) deposit (Edong ore district), which are important magmatic-hydrothermal deposits in eastern China.Textural features, mineral assemblages and paragenesis of the Longqiao and Tieshan ore samples have suggested the presence of two main mineralization periods (sedimentary and hydrothermal) at Longqiao, among which the hydrothermal period comprises four stages (skarn, magnetite, sulfide and carbonate); whilst the Tieshan Fe–(Cu) deposit comprises four mineralization stages (skarn, magnetite, quartz-sulfide and carbonate).Magnetite from the Longqiao and Tieshan deposits has different geochemistry, and can be clearly discriminated by the Sn vs. Ga, Ni vs. Cr, Ga vs. Al, Ni vs. Al, V vs. Ti, and Al vs. Mg diagrams. Such difference may be applied to distinguish other typical skarn (Tieshan) and multi-origin hydrothermal (Longqiao) deposits in the MLYRB. The fluid–rock interactions, influence of the co-crystallizing minerals and other physicochemical parameters, such as temperature and fO₂, may have altogether controlled the magnetite trace element contents of both deposits. The Tieshan deposit may have had higher degree of fO₂, but lower fluid–rock interactions and ore-forming temperature than the Longqiao deposit. The TiO₂–Al₂O₃–(MgO + MnO) and (Ca + Al + Mn) vs. (Ti + V) magnetite discrimination diagrams show that the Longqiao Fe deposit has both sedimentary and hydrothermal features, whereas the Tieshan Fe–(Cu) deposit is skarn-type and was likely formed via hydrothermal metasomatism, consistent with the ore characteristics observed.     

Trace elements in pyrite from the Petropavlovsk gold–porphyry deposit (Polar Urals): Results of LA-ICP-MS analysis

The first study of the pyrite composition from gold deposit in the Urals by the LA-ICP-MS method has been carried out. In the pyrite high contents of Au (up to 49 ppm), Ag (105 ppm), and other micronutrients (As (417 ppm), Ag (105 ppm), Co (2825 ppm), Ni (75 ppm), Cu (1442 ppm), and Zn (19 ppm)) were detected. Furthermore, an increase in the concentrations of trace elements from early to later generations of pyrite (from Py-1 to Py-3) Au, Ag, Te, Sn, Te, and Bi and depletion of Co, As, and Ni have been revealed. Gold is mainly concentrated in the pyrite of the second generation (Py-2) and occurs mostly as an “invisible” form with prevalence of nano-sized particles of native Au, similar in composition to electrum AuAg, as well as Au- and Au–Ag tellurides. The presence in the pyrite of admixtures of Cu, Co, Ni, Pb, As, and Te, possibly favors the entrance of Au into it (up to 5–50 ppm), while in common pyrite, poor in the mentioned impurities, the gold content is <1 ppm.     

Age and origin of uranium mineralization in the Camie River deposit (Otish Basin,Québec,Canada)

The Camie River uranium deposit is located in the southeastern part of the Paleoproterozoic Otish Basin (Québec). The uranium mineralization consists of disseminated and vein uraninite and brannerite precipitated close to the unconformity between Paleoproterozoic fluviatile, pervasively altered, sandstones and conglomerates of the Matoush Formation and the underlying sulfide-bearing graphitic schists of the Archean Hippocampe greenstone belt. Diagenetic orange/pink feldspathic alteration of the Matoush Formation consists of authigenic albite cement partly replaced by later orthoclase cement, with the Na₂O content of clastic rocks increasing with depth. Basin-wide green muscovite alteration affected both the Matoush Formation and the top of the basement Tichegami Group. Uraninite with minor brannerite is mainly hosted by subvertical reverse faults in basement graphitic metapelites ± sulfides and overlying sandstones and conglomerates. Uranium mineralization is associated with chlorite veins and alteration with temperatures near 320 °C, that are paragenetically late relative to the diagenetic feldspathic and muscovite alterations. Re-Os geochronology of molybdenite intergrown with uraninite yields an age of 1724.0 ± 4.9 Ma, whereas uraninite yields an identical, although slightly discordant, 1724 ± 29 Ma SIMS U-Pb age. Uraninite has high concentrations in REE with flat REE spectra resembling those of uraninite formed from metamorphic fluids, rather than the bell-shaped patterns typical of unconformity-related uraninite. Paragenesis and geochronology therefore show that the uranium mineralization formed approximately 440 million years after intrusion of the Otish Gabbro dykes and sills at ∼2176 Ma, which constrains the minimum age for the sedimentary host rocks. The post-diagenetic stage of uraninite after feldspathic and muscovite alterations, the paragenetic sequence and the brannerite-uraninite assemblage, the relatively high temperature for the mineralizing event (∼320 °C) following the diagenetic Na- and K-dominated alteration, lack of evidence for brines typical of unconformity-related U deposits, the older age of the Otish Basin compared to worldwide basins hosting unconformity-related uranium deposits, the large age difference between basin fill and mineralization, the older age of the uranium oxide compared to ages for worldwide unconformity-related U deposits, and the flat REE spectra of uraninite do not support the previous interpretation that the Camie River deposit is an unconformity-associated uranium deposit. Rather, the evidence is more consistent with a PaleoProterozoic, higher-temperature hydrothermal event at 1724 Ma, whose origin remains speculative.     

Retrograde formation of NaCl-scapolite in high pressure metaevaporites from the Cordilleras Béticas (Spain)

A Permo-Triassic pelite-carbonate rock series (with interacalated metabasitic rocks) in the Cordilleras Béticas, Spain, was metamorphosed during the Alpine metamorphism at high pressures (P _min near 18 kbar). The rocks show well preserved sedimentary features of evaporites such as pseudomorphs of talc, of kyanite-phengitetalc-biotite, and of quartz after sulfate minerals, and relicts of baryte, anhydrite, NaCl, and KCl, indicating a salt-clay mixture of illite, chlorite, talc, and halite as the original rock. The evaporitic metapelites have a whole rock composition characterized by high Mg/(Mg+Ca) ratios>0.7, variable alkaline and Sr, Ba, contents, but are mostly K₂O rich (<8.8 wt%). The F (<2600 ppm), Cl (<3600 ppm), and P₂O₅ (<0.24 wt%) contents are also high. The pelitic member of this series is a fine grained biotite rock. Kyanite-phengite-talc-biotite aggregates in pseudomorphs developed in the high pressure stage. Albite-rich plagioclase was formed when the rocks crossed the albite stability curve in the early stages of the uplift. Scapolite, rich in NaCl (Ca/(Ca+Na) mol% 24–40) and poor in SO₄, with Cl/(Cl+CO₃) ratios between 0.6 and 0.8, formed as porphyroblasts, sometimes replacing up to 60% of the rock in a late stage of metamorphism (between 10 and 5 kbar, near 600°C). No reaction with albite is observed, and the scapolite formed from biotite by: $$\begin{gathered} Al - biotite + CaCO_3 + NaCl + SiO_2 \hfill \\ = Al - poor biotite + scapolite + MgCO_3 + KCl \hfill \\ + MgCl_2 + H_2 O \hfill \\ \end{gathered}$$ Calculated fluid composition in equilibrium with scapolite indicates varying salt concentrations in the fluid. Distribution of Cl and F in biotite and apatite also indicates varying fluid compositions.     

Uraniferous bitumen nodules in the Talvivaara Ni–Zn–Cu–Co deposit (Finland): influence of metamorphism on uranium mineralization in black shales

In the central part of the Fennoscandian Shield, the Talvivaara Ni–Zn–Cu–Co deposit, hosted by Palaeoproterozoic metamorphosed black schists, contains low uranium concentrations ranging from 10 to 30 ppm. The Talvivaara black schists were deposited 2.0–1.9 Ga ago and underwent subsequent metamorphism during the 1.9–1.79 Ga Svecofennian orogeny. Anhedral uraninite crystals rimmed by bitumen constitute the main host of uranium. U–Pb secondary ion mass spectrometry dating indicates that uraninite crystals were formed between 1,878?±?17 and 1,871?±?43 Ma, during peak metamorphism. Rare earth element patterns and high Th content (average 6.38 wt%) in disseminated uraninite crystals indicate that U was concentrated during high temperature metamorphism (>400 °C). The formation of bitumen rims around uraninite may be explained by two distinct scenarios: (a) a transport of U coincident with the migration of hydrocarbons or (b) post-metamorphic formation of bitumen rims, through radiolytic polymerization of gaseous hydrocarbons at the contact with uraninite.     

Apatite-hosted melt inclusions from the Panzhihua gabbroic-layered intrusion associated with a giant Fe–Ti oxide deposit in SW China: insights for magma unmixing within a crystal mush

The ～?2-km-thick Panzhihua gabbroic-layered intrusion in SW China is unusual because it hosts a giant Fe–Ti oxide deposit in its lower zone. The deposit consists of laterally extensive net-textured and massive Fe–Ti oxide ore layers, the thickest of which is ～?60 m. To examine the magmatic processes that resulted in the Fe enrichment of parental high-Ti basaltic magma and the formation of thick, Fe–Ti oxide ore layers, we carried out a detailed study of melt inclusions in apatite from a ～?500-m-thick profile of apatite-bearing leucogabbro in the middle zone of the intrusion. The apatite-hosted melt inclusions are light to dark brown in color and appear as polygonal, rounded, oval and negative crystal shapes, which range from ～?5 to ～?50 µm in width and from ～?5 to ～?100 µm in length. They have highly variable compositions and show a large and continuous range of SiO₂ and FeO_t with contrasting end-members; one end-member being Fe-rich and Si-poor (40.2 wt% FeO_t and 17.7 wt% SiO₂) and the other being Si-rich and Fe-poor (74.0 wt% SiO₂ and 1.20 wt% FeO_t). This range in composition may be attributed to entrapment of the melt inclusions over a range of temperature and may reflect the presence of µm-scale and immiscible Fe-rich and Si-rich components in different proportions. Simulating results for the motion of Si-rich droplets within a crystal mush indicate that Si-rich droplets would be separated from Fe-rich melt and migrate upward due to density differences in the interstitial liquid when the magma unmixed. Migration of the Si-rich, immiscible liquid component from the interstitial liquid caused the remaining Fe-rich melt in the lower part to react with plagioclase primocrysts (An_59–60), as evidenced by fine-grained lamellar intergrowth of An-rich plagioclase (An_79–84)?+?clinopyroxene in the oxide gabbro of the lower zone. Therefore, magma unmixing within a crystal mush, combined with gravitationally driven loss of the Si-rich component, resulted in the formation of Fe-rich, melagabbro and major Fe–Ti oxide ores in the lower part and Si-rich, leucogabbro in the upper part of the intrusion.     

Mössbauer and ELNES spectroscopy of (Mg,Fe)(Si,Al)O3 perovskite: a highly oxidised component of the lower mantle

(Mg,Fe)(Si,Al)O₃ perovskite samples with varying Fe and Al concentration were synthesised at high pressure and temperature at varying conditions of oxygen fugacity using a multianvil press, and were characterised using ex?situ X-ray diffraction, electron microprobe, Mössbauer spectroscopy and analytical transmission electron microscopy. The Fe³⁺/ΣFe ratio was determined from Mössbauer spectra recorded at 293 and 80?K, and shows a nearly linear dependence of Fe³⁺/ΣFe with Al composition of (Mg,Fe)(Si,Al)O₃ perovskite. The Fe³⁺/ΣFe values were obtained for selected samples of (Mg,Fe)(Si,Al)O₃ perovskite using electron energy-loss near-edge structure (ELNES) spectroscopy, and are in excellent agreement with Mössbauer data, demonstrating that Fe³⁺/ΣFe can be determined with a spatial resolution on the order of nm. Oxygen concentrations were determined by combining bulk chemical data with Fe³⁺/ΣFe data determined by Mössbauer spectroscopy, and show a significant concentration of oxygen vacancies in (Mg,Fe)(Si,Al)O₃ perovskite.