Anhydrite pseudomorphs and the origin of stratiform Cu–Co ores in the Katangan Copperbelt (Democratic Republic of Congo)

The stratiform Cu–Co ore mineralisation in the Katangan Copperbelt consists of dispersed sulphides and sulphides in nodules and lenses, which are often pseudomorphs after evaporites. Two types of pseudomorphs can be distinguished in the nodules and lenses. In type 1 examples, dolomite precipitated first and was subsequently replaced by Cu–Co sulphides and authigenic quartz, whereas in type 2 examples, authigenic quartz and Cu–Co sulphides precipitated prior to dolomite and are coarse-grained. The sulphur isotopic composition of the copper–cobalt sulphides in the type 1 pseudomorphs is between −10.3 and 3.1‰ relative to the Vienna Canyon Diablo Troilite, indicating that the sulphide component was derived from bacterial sulphate reduction (BSR). The generation of during this process caused the precipitation and replacement of anhydrite by dolomite. A second product of BSR is the generation of H₂S, resulting in the precipitation of Cu–Co sulphides from the mineralising fluids. Initial sulphide precipitation occurred along the rim of the pseudomorphs and continued towards the core. Precipitation of authigenic quartz was most likely induced by a pH decrease during sulphide precipitation. Fluid inclusion data from quartz indicate the presence of a high-salinity (8–18 eq. wt.% NaCl) fluid, possibly derived from evaporated seawater which migrated through the deep subsurface. ⁸⁷Sr/⁸⁶Sr ratios of dolomite in type 1 nodules range between 0.71012 and 0.73576, significantly more radiogenic than the strontium isotopic composition of Neoproterozoic marine carbonates (⁸⁷Sr/⁸⁶Sr = 0.7056–0.7087). This suggests intense interaction with siliciclastic sedimentary rocks and/or the granitic basement. The low carbon isotopic composition of the dolomite in the pseudomorphs (−7.02 and −9.93‰ relative to the Vienna Pee Dee Belemnite, V-PDB) compared to the host rock dolomite (−4.90 and +1.31‰ V-PDB) resulted from the oxidation of organic matter during BSR.     

Silicate and salt melts in the genesis of the industrial’noe tin deposit: Evidence from inclusions in minerals

The data obtained on melt and fluid inclusions in minerals of granites, metasomatic rocks, and veins with tin ore mineralization at the Industrial’noe deposit in the southern part of the Omsukchan trough, northeastern Russia, indicate that the melt from which the quartz of the granites crystallized contained globules of salt melts. Silicate melt inclusions were used to determine the principal parameters of the magmatic melts that formed the granites, which had temperatures at 760–1020°C, were under pressures of 0.3–3.6 kbar, and had densities of 2.11–2.60 g/cm³ and water concentrations of 1.7–7.0 wt %. The results obtained on the fluid inclusions testify that the parameters of the mineral-forming fluids broadly varied and corresponded to temperatures at 920–275°C, pressures 0.1–3.1 kbar, densities of 0.70–1.90 g/cm³, and salinities of 4.0–75.0 wt % equiv. NaCl. Electron microprobe analyses of the glasses of twelve homogenized inclusions show concentrations of major components typical of an acid magmatic melt (wt %, average): 73.2% SiO₂, 15.3% Al₂O₃, 1.3% FeO, 0.6% CaO, 3.1% Na₂O, and 4.5% K₂O at elevated concentrations of Cl (up to 0.51 wt %, average 0.31 wt %). The concentrations and distribution of some elements (Cl, K, Ca, Mn, Fe, Cu, Zn, Pb, As, Br, Rb, Sr, and Sn) in polyphase salt globules in quartz from both the granites and a mineralized miarolitic cavity in granite were assayed by micro-PIXE (proton-induced X-ray emission). Analyses of eight salt globules in quartz from the granites point to high concentrations (average, wt %) of Cl (27.5), Fe (9.7), Cu (7.2), Mn (1.1), Zn (0.66), Pb (0.37) and (average, ppm) As (2020), Rb (1850), Sr (1090), and Br (990). The salt globules in the miarolitic quartz are rich in (average of 29 globules, wt %) Cl (25.0), Fe (5.4), Mn (1.0), Zn (0.50), Pb (0.24) and (ppm) Rb (810), Sn (540), and Br (470). The synthesis of all data obtained on melt and fluid inclusions in minerals from the Industrial’noe deposit suggest that the genesis of the tin ore mineralization was related to the crystallization of acid magmatic melts. Original Russian Text@ V.B. Naumov, V.S. Kamenetsky, 2006, published in Geokhimiya, 2006, No. 12, pp. 1279–1289.     

Origin and geochemical reaction paths of sabkha brines: Sabkha Jayb Uwayyid, eastern Saudi Arabia

Sabkhas are ubiquitous geomorphic features in eastern Saudi Arabia. Seven brine samples were taken from Sabkha Jayb Uwayyid in eastern Saudi Arabia. Brine chemistry, saturation state with respect to carbonate and evaporate minerals, and evaporation-driven geochemical reaction paths were investigated to delineate the origin of brines and the evolution of both brine chemistry and sabkha mineralogy. The average total dissolved solids in the sabkha brines is 243 g/l. The order of cation dominance is Na⁺   >>  Mg²⁺ >>  Ca²⁺>K⁺, while anion dominance is Cl⁻ >> SO₄ ²⁻ >> HCO₃ ⁻. Based on the chemical divide principle and observed ion ratios, it was concluded that sabkha brines have evolved from deep groundwater rather than from direct rainfall, runoff from the surroundings, or inflow of shallow groundwater. Aqueous speciation simulations show that: (1) all seven brines are supersaturated with respect to calcite, dolomite, and magnesite and undersaturated with respect to halite; (2) three brines are undersaturated with respect to both gypsum and anhydrite, while three brines are supersaturated with respect to both minerals; (3) anhydrite is a more stable solid phase than gypsum in four brines. Evaporation factors required to bring the brines to the halite phase boundary ranged from 1.016 to 4.53. All reaction paths to the halite phase boundary follow the neutral path as CO₂ is degassed and dolomite precipitates from the brines. On average, a sabkha brine containing 1 kg of H₂O precipitates 7.6 g of minerals along the reaction path to the halite phase boundary, of which 52% is anhydrite, 35.3% is gypsum, and 12.7% is dolomite. Bicarbonate is the limiting factor of dolomite precipitation, and sulfate is the limiting factor of gypsum and anhydrite precipitation from sabkha brines.     

Isotopic composition (H,O, Cl,Sr) of ground brines of the Siberian Platform

New data on the geochemistry and isotopic composition of chloride brines of the Siberian Platform are presented. The distribution of stable isotopes (²H, ¹⁸O, and ³⁷Cl) in brines of the Tunguska, Angara-Lena, western part of the Yakutian and Olenek artesian basins and ⁸⁷Sr/⁸⁶Sr in brines of the western part of the Olenek artesian basin was studied in the context of the problem of genesis of highly mineralized groundwaters. Results of the study and comparative analysis of the geochemical and isotopic peculiarities of the Siberian Platform brines conform to the theory of brine formation through the interaction of connate waters with enclosing rocks.     

Chemical composition of nyerereite and gregoryite from natrocarbonatites of Oldoinyo Lengai volcano,Tanzania

Alkali carbonates nyerereite, ideally Na₂Ca(CO₃)₂ and gregoryite, ideally Na₂CO₃, are the major minerals in natrocarbonatite lavas from Oldoinyo Lengai volcano, northern Tanzania. They occur as pheno- and microphenocrysts in groundmass consisting of fluorite and sylvite; nyerereite typically forms prismatic crystals and gregoryite occurs as round, oval crystals. Both minerals are characterized by relatively high contents of various minor elements. Raman spectroscopy data indicate the presence of sulfur and phosphorous as (SO₄)²⁻ and (PO₄)³⁻ groups. Microprobe analyses show variable composition of both nyerereite and gregoryite. Nyerereite contains 6.1–8.7 wt % K₂O, with subordinate amounts of SrO (1.7–3.3 wt %), BaO (0.3–1.6 wt %), SO₃ (0.8–1.5 wt %), P₂O₅ (0.2–0.8 wt %) and Cl (0.1–0.35 wt %). Gregoryite contains 5.0–11.9 wt % CaO, 3.4–5.8 wt % SO₃, 1.3–4.6 wt % P₂O₅, 0.6–1.0 wt % SrO, 0.1–0.6 wt % BaO and 0.3–0.7 wt % Cl. The content of F is below detection limits in nyerereite and gregoryite. Laser ablation ICP-MS analyses show that REE, Mn, Mg, Rb and Li are typical trace elements in these minerals. Nyerereite is enriched in REE (up to 1080 ppm) and Rb (up to 140 ppm), while gregoryite contains more Mg (up to 367 ppm) and Li (up to 241 ppm) as compared with nyerereite.     

Gold potential of the volcanoplutonic zones in the southeastern Siberian Platform and physicochemical conditions of the deposit formation

Numerous gold deposits and occurrences were recognized in the regions of tectonomagmatic activation in the southeastern Siberian Platform. They are located in four metallogenic zones: the Ket-Kap (skarns, quartz veins, and stockworks; gold-bearing lodes in silicitolites; and argillisite-sericite metasomatites), Ulkan (clayey-micaceous metasomatites, quartz veins), Preddzhugdzhur (quartz veins, skarns, and sericite-hydromicaceous metasomatites), and Uda (sericite-hydromicaceous metasomatites). The skarn mineralization is of Meosozoic age, while the mineralization in the quartz veins, quartz-hydromicaceous metasomatites, and quartz-sulfide veins may have a Meosozoic, Paleozoic, or Late Paleozoic age. The highest temperatures were determined for the ore formation in the Preddzhugdzhur skarns (500–715 °C) and the hydrothermal-metasomatic rocks of the Ket-Kap zone (510–530 °C). The composition of gas-liquid inclusions in the minerals of these rocks is dominated by aqueous Na, K, and Ca chloride solutions with salinity up to 40 wt % NaCl equiv; fluid contains CO₂. Quartz veins and stockworks of the Ket-Kap zone were formed under high (up to 465°C) and moderate temperatures and salinity up to 32 wt % NaCl equiv. Sometimes, the minerals in these rocks contain inclusions of low-density CO₂. The gold-bearing veins of the Preddzhugdzhur zone formed at 225–230°C and salinity of 1–2 wt % NaCl equiv. The ore-bearing solutions in the gold-bearing veins of the Ulkan zone are characterized by a potassium-sodium-chlorine composition and salinity of 2–10 wt % NaCl equiv., and the temperature of their formation was 220–280 °C.     

The role of evaporites in the formation of magnetite–apatite deposits along the Middle and Lower Yangtze River,China: Evidence from LA-ICP-MS analysis of fluid inclusions

Numerous magnetite–apatite deposits occur in the Ningwu and Luzong sedimentary basins along the Middle and Lower Yangtze River, China. These deposits are located in the contact zone of (gabbro)-dioritic porphyries with surrounding volcanic or sedimentary rocks and are characterized by massive, vein and disseminated magnetite–apatite ± anhydrite mineralization associated with voluminous sodic–calcic alteration. Petrologic and microthermometric studies on multiphase inclusions in pre- to syn-mineralization pyroxene and garnet from the deposits at Meishan (Ningwu basin), Luohe and Nihe (both in Luzong basin) demonstrate that they represent extremely saline brines (~ 90 wt.% NaCl_equiv) that were trapped at temperatures of about 780 °C. Laser ablation ICP-MS analyses and Raman spectroscopic studies on the natural fluid inclusions and synthetic fluid inclusions manufactured at similar P–T conditions reveal that the brines are composed mainly of Na (13–24 wt.%), K (7–11 wt.%), Ca (~ 7 wt.%), Fe (~ 2 wt.%), Cl (19–47 wt.%) and variable amounts of SO₄ (3–39 wt.%). Their Cl/Br, Na/K and Na/B ratios are markedly different from those of seawater evaporation brines and lie between those of magmatic fluids and sedimentary halite, suggesting a significant contribution from halite-bearing evaporites. High S/B and Ca/Na ratios in the fluid inclusions and heavy sulfur isotopic signatures of syn- to post-mineralization anhydrite (δ³⁴S_Anh = + 15.2 to + 16.9‰) and pyrite (δ³⁴S_Py = + 4.6‰ to + 12.1‰) further suggest a significant contribution from sedimentary anhydrite. These interpretations are in line with the presence of evaporite sequences in the lower parts of the sedimentary basins.The combined evidence thus suggests that the magnetite–apatite deposits along the Middle and Lower Yangtze River formed by fluids that exsolved from magmas that assimilated substantial amounts of Triassic evaporites during their ascent. Due to their Fe-oxide dominated mineralogy, their association with large-scale sodic–calcic alteration and their spatial and temporal associations with subvolcanic intrusions we interpret them as a special type of IOCG deposits that is characterized by unusually high contents of Na, Ca, Cl and SO₄ in the ore-forming fluids. Evaporite assimilation apparently led to the production of large amounts of high-salinity brine and thus to an enhanced capacity to extract iron from the (gabbro)-dioritic intrusions and to concentrate it in the form of ore bodies. Hence, we believe that evaporite-bearing sedimentary basins are more prospective for magnetite–apatite deposits than evaporite-free basins.     

Geochemistry and stable isotopic signatures,including chlorine and bromine isotopes,of the deep groundwaters of the Siberian Platform,Russia

The chemical composition and the isotopic characteristics of formation waters from the Siberian Platform are presented. The study involved samples of formation brines from depths ranging from 100 to ∼4000 m at five different sites covering a large area of the Siberian Platform. Four water types were identified. The two main water types that were found are: (1) Ca–Cl brines that are believed to be the residual of an evaporated paleoseawater; and (2) Na–Cl brines that are derived mainly from halite dissolution. The origin of a third group of highly saline samples was not determined. However, the chemical and isotopic characteristics of this group of samples suggest that they were produced by various complex scenarios such as metamorphism, water–rock interaction, permafrost freezing and mixing. The last group of samples represents fresh and brackish waters across the area.     

Very low grade metamorphism of the Taveyanne formation of western Switzerland

The andesitic early Oligocene Taveyanne metagreywacke of the Helvetic nappes of western Switzerland shows an increase of metamorphic grade from zeolite facies through lower greenschist facies. Electron microprobe analysis, fluid inclusion thermometry, stable isotope analysis, coal rank, illite and chlorite crystallinity and thermodynamic calculations were carried out to determine metamorphic conditions. Evaluation of all techniques used in this study suggest that only combinations of different parameters yield reliable information to constrain very low-grade metamorphic conditions. Electron microprobe analyses are presented for actinolite, chlorite, epidote, phengite, laumontite, prehnite, pumpellyite, and titanite. With increasing metamorphic grade, chlorite is enriched in tetrahedral Al, pumpellyite becomes poorer in Fe_tot and more homogeneous in chemical composition, and titanite tends to incorporate Ti at the expense of Al and Fe³⁺. Metamorphic P-T conditions were determined by a combination of fluid inclusion microthermobarometry, stable isotope thermometry on quartz-calcite veins, chlorite “geothermometry” and thermodynamic calculations. Peak temperatures range from 210–250 °C for zeolite facies to 270–300 °C for prehnite-pumpellyite facies to 300–360 °C for pumpellyite-actinolite facies. An evaluation of 289 chlorite analyses indicates that the tetrahedral Al content is negatively correlated with the saponite component. Temperatures derived from chlorite “geothermometry” match maximum temperature conditions mentioned above. Illite crystallinity data for shales and slates intercalated with the Taveyanne metagreywacke indicate that the diagenetic zone correlates with the zeolite facies, the upper anchizone with the prehnite-pumpellyite facies, and the lower epizone with the pumpellyite-actinolite facies. A comparison of coal rank and illite crystallinity data (n=12,r=0.91) yielded R _max values of 2.9 and 5.5% for the lower and upper boundary of the anchizone, respectively. Received: 2 August 1996 / Accepted: 16 July 1997     

Experimental study of eclogite melting with participation of the H<Subscript>2</Subscript>O-CO<Subscript>2</Subscript>-KCl fluid at 5 GPa

In order to model the processes of formation of the highly alkaline (potassic) melts during the partial melting of the eclogite nodules in kimberlites, experiments on the melting of the model and natural eclogites in presence of the H₂O-CO₂ and H₂O-CO₂-KCl fluids at 5 GPa and 1200 and 1300°C are performed. A comparative analysis of the phase relations in the systems with H₂O-CO₂ and H₂O-CO₂-KCl demonstrate that KCl in the fluid equilibrated with eclogites intensifies their melting. It is related to both high Cl concentration in the forming silicate melt (2.0–5.5 wt %) and its enrichment in K₂O owing to the K-Na exchange reactions with the immiscible chloride melt. Because of these reactions, the K₂O/Cl ratio in the melts increases with the KCl content in the system and reaches 2.5–3.5 in the silicate melts coexisting with the immiscible chloride liquid. However, the ratio KCl/(H₂O + CO₂ + KCl) in the fluid does not influence on the ratio K₂O/Cl in the melts. Thus, the solubility KCl in the melts, apparently, does not depend on presence of the H₂O-CO₂ fluid, at least, within the concentration range used in the experiments (up to 20 wt %). The experiments show that the deliberated chloride liquid is necessary to form the potassium-rich chlorine-bearing silicate melts during the eclogite melting. It corresponds to the KCl content in the system above 5 wt %.     

Fluid inclusion study of the Wunugetu Cu–Mo deposit,Inner Mongolia,China

Hydrothermal alteration and mineralization at the Wunugetu porphyry Cu–Mo deposit, China, include four stages, i.e., the early stage characterized by quartz, K-feldspar and minor mineralization, followed by a molybdenum mineralization stage associated with potassic alteration, copper mineralization associated with sericitization, and the last Pb–Zn mineralization stage associated with carbonation. Hydrothermal quartz contains three types of fluid inclusions, namely aqueous (W-type), daughter mineral-bearing (S-type) and CO₂-rich (C-type) inclusion, with the latter two types absent in the late stage. Fluid inclusions in the early stage display homogenization temperatures above 510°C, with salinities up to 75.8 wt.% NaCl equivalent. The presence of S-type inclusions containing anhydrite and hematite daughter minerals and C-type inclusions indicates an oxidizing, CO₂-bearing environment. Fluid inclusions in the Mo- and Cu-mineralization stages yield homogenization temperatures of 342–508°C and 241–336°C, and salinities of 8.6–49.4 and 6.3–35.7 wt.% NaCl equivalent, respectively. The presence of chalcopyrite instead of hematite and anhydrite daughter minerals in S-type inclusions indicates a decreasing of oxygen fugacity. In the late stage, fluid inclusions yield homogenization temperatures of 115–234°C and salinities lower than 12.4 wt.% NaCl equivalent. It is concluded that the early stage fluids were CO₂ bearing, magmatic in origin, and characterized by high temperature, high salinity, and high oxygen fugacity. Phase separation occurred during the Mo- and Cu-mineralization stages, resulting in CO₂ release, oxygen fugacity decrease and rapid precipitation of sulfides. The late-stage fluids were meteoric in origin and characterized by low temperature, low salinity, and CO₂ poor.     

Average compositions of igneous melts from main geodynamic settings according to the investigation of melt inclusions in minerals and quenched glasses of rocks

We compiled a database containing more than 480000 determinations for 73 elements in melt inclusions in minerals and quenched glasses of volcanic rocks. These data were used to estimate the mean contents of major, volatile, and trace elements in igneous melts from main geodynamic settings. The following settings were distinguished: (I) oceanic spreading zones (mid-ocean ridges); (II) zones of mantle plume activity on oceanic plates (oceanic islands and plateaus); (III) and (IV) settings related to subduction processes, including (III) zones of island-arc magmatism generated on the oceanic crust and (IV) magmatic zones of active continental margins involving the continental crust into magma generation processes; (V) intracontinental rifts and continental hot spots; and (VI) back-arc spreading centers. The histogram of SiO₂ contents in the natural igneous melts of all geodynamic settings exhibits a bimodal distribution with two maxima at SiO₂ contents of 50–52 wt % and 72–74 wt %. The range 62–64 wt % SiO₂ comprises the minimum number of determinations. Primitive mantle-normalized spidergrams were constructed for average contents of elements in the igneous melts of basic, intermediate, and acidic compositions from settings I–V. The diagrams reflect the characteristic features of melt compositions for each geodynamic setting. On the basis of the analysis of data on the composition of melt inclusions and glasses of rocks, average ratios of incompatible trace and volatile components (H₂O/Ce, K₂O/Cl, Nb/U, Ba/Rb, Ce/Pb, etc.) were estimated for the igneous melts of all of the settings. Variations of these ratios were determined, and it was shown that, in most cases, the ratios of incompatible elements are significantly different between settings. The difference is especially pronounced for the ratios of elements with different degrees of incompatibility (e.g., Nb/Yb) and for some ratios with volatile components (e.g., K₂O/H₂O).     

REE-, Zr-, and Th-rich titanite and associated accessory minerals from a kersantite in the Frankenwald, Germany

Summary The mineral chemistry of a Variscan lamprophyre (kersantite) from the Frankenwald, Germany, has been investigated by electron microprobe. This potassic, Si-saturated, mafic rock contains an assemblage of different generations of titanite and allanite-(Ce), Th-rich zircon, and metamict REE–Ti–Zr–Th silicates. The primary ferroan-ceroan titanite contains unusually high contents of REE₂O₃ (max. (ΣLa to Sm)+Y = 36.8 oxide wt.%), ZrO₂ (max. 5.4 wt.%), and ThO₂ (max. 3.1 wt.%). Its empirical formula averages to (Ca_0.31 La_0.17 Ce_0.30 Pr_0.03 Nd_0.08 Sm_0.01 Y_0.01 Fe²⁺_0.06 Th_0.02 Mn_0.01)_Σ1.00 (Ti_0.60 Fe²⁺_0.22 Al_0.06 Zr_0.07 Mg_0.04 Nb_0.01)_Σ1.00 O_1.00(Si_0.93 Al_0.07)_Σ1.00 O₄. Element correlations reveal operation of the complex substitution Ca²⁺+Ti⁴⁺+Th⁴⁺ ⇔ REE³⁺+Al³⁺+Zr⁴⁺. In comparison to allanite-(Ce), ferroan-ceroan titanite preferentially incorporated the LREE and Th. This finding is inconsistent with previous experimental studies and suggests that both minerals are not cogenetic. High Zr contents in titanite, usually known only from Si-undersaturated alkaline rocks, and the predominance of Fe²⁺ suggest that the ferroan-ceroan titanite crystallized from an alkali-rich, low-fO₂ residual melt.     

Evolution of the trachydacite and pantellerite magmas of the bimodal volcanic association of Dzarta-Khuduk, Central Mongolia: Investigation of inclusions in minerals

Using various methods of melt inclusion investigation, including electron and ion microprobe techniques, we estimated the composition, evolution, and formation conditions of melts producing the trachydacites and pantellerites of the Late Paleozoic bimodal volcanic association of Dzarta-Khuduk, Central Mongolia. Primary crystalline and melt inclusions were detected in anorthoclase from trachydacites and quartz from pantellerites and pantelleritic tuffs. Among the crystalline inclusions, we identified hedenbergite, fluorapatite, and pyrrhotite in the trachydacites and F-arfvedsonite, fluorite, ilmenite, and the rare REE diorthosilicate chevkinite in the pantellerites. Melt inclusions in anorthoclase from the trachydacites are composed of glass, a gas phase, and daughter minerals (F-arfvedsonite, fluorite, villiaumite, and anorthoclase rim on the inclusion wall). Melt inclusions in quartz from the pantellerites are composed of glass, a gas phase, and a fine-grained salt aggregate consisting of Li, Na, and Ca fluorides (griceite, villiaumite, and fluorite). Melt inclusions in quartz crystalloclasts from the pantelleritic tuffs are composed of homogeneous silicate glasses. The phenocrysts of the trachydacites and pantellerites crystallized at temperatures of 1060–1000°C. During thermometric experiments with quartz-hosted melt inclusions from the pantellerites, the formation of immiscible silicate and salt (fluoride) melts was observed at a temperature of 800°C. Homogeneous melt inclusions in anorthoclase from the trachydacites have both trachydacite and rhyolite compositions (wt %): 68–70 SiO₂, 12–13 Al₂O₃, 0.34–0.74 TiO₂, 5–7 FeO, 0.4–0.9 CaO, and 9–12 Na₂O + K₂O. The agpaitic index ranges from 0.92 to 1.24. The glasses of homogenized melt inclusions in quartz from the pantellerites and pantelleritic tuffs have rhyolitic compositions. Compared with the homogeneous glasses trapped in anorthoclase of the trachydacites, quartz-hosted inclusions from the pantellerites show higher SiO₂ (72–78 wt %) and lower Al₂O₃ contents (7.8–10.0 wt %). They also contain 0.14–0.26 wt % TiO₂, 2.5–4.9 wt % FeO, 9–11 wt % Na₂O + K₂O, and 0.9–0.15 wt % CaO and show an agpaitic index of 1.2–2.05. Homogeneous melt inclusions in quartz from the pantelleritic tuffs contain 69–72 wt % SiO₂. The contents of other major components, including TiO₂, Al₂O₃, FeO, and CaO, are close to those in the homogeneous glasses of quartzhosted melt inclusions in the pantellerites. The contents of Na₂O + K₂O are 4–10 wt %, and the agpaitic index is 1.0–1.6. The glasses of melt inclusions from each rock group show distinctive volatile compositions. The H₂O content is up to 0.08 wt % in anorthoclase of the trachydacites, 0.4–1.4 wt % in quartz of the pantellerites, and up to 5 wt % in quartz of the pantelleritic tuffs. The content of F in the glasses of melt inclusions in the phenocrysts of the trachydacites is no higher than 0.67 wt %, and up to 1.4–2.8 wt % in quartz from the pantellerites. The Cl content is up to 0.2 wt % in the glasses of melt inclusions in the minerals of the trachydacites and up to 0.5 wt % in the glasses of quartz-hosted melt inclusions from the pantellerites. The investigation of trace elements in the homogenized glasses of melt inclusions in minerals showed that the trachydacites and pantellerites were formed from strongly evolved rare-metal alkaline silicate melts with high contents of Li, Zr, Rb, Y, Hf, Th, U, and REE. The analysis of the composition of homogeneous melt inclusions in the minerals of the above rocks allowed us to distinguish magmatic processes resulting in the enrichment of these rocks in trace and rare earth elements. The most important processes are the crystallization differentiation and immiscible separation of silicate and fluoride salt melts. It was also shown that all the melts studied evolved in spatially separated magma chambers. This caused the differences in the character of melt evolution between the trachydacites and pantellerites. During the final stages of differentiation, when the magmatic system was saturated with respect to ore elements, Na-Ca fluoride melts were separated and extracted considerable amounts of Li.     

A new finding of Cu-Au alloy in association with rodingite minerals in the Kaa-Khem ophiolitic belt,Tuva

A new Cu-Au alloy occurrence is located at the southeastern flank of the Malye Kopty massif of ultramafic rocks in the Vendian-Early Cambrian Kaa-Khem ophiolitic belt. Lithic clasts with Cu-Au alloy segregations (up to 15 mm in size) intergrown with other minerals were found in alluvium of the Kara-Oss Creek valley, which extends along the fault zone crosscutting ultramafic rocks. Cu-Au alloy occupies the main volume of clasts and fills the network of veinlets in grained aggregates consisting of andradite (2–18% grossular component) and diopside (X _Fe = 0.01–0.05). Cu-Au alloy contains small ingrowths of andradite (up to 43% grossular component), diopside (X _Fe = 0.14–0.19), chlorite (penninite), chalcocite that contains up to 1.5 wt % Au, Cu-bearing greenockite (6.07–13.67 wt % Cu, 0.48–1.56 wt % Zn, and 0.76–1.06 wt % Au), and magnetite. The chemical composition of Cu-Au alloy is nonuniform. The central parts of large Cu-Au alloy segregations consist of Ag-bearing tetraauricupride (AuCu) blocks (3.2–6.4 wt % Ag). They contain veinlet-shaped AuCu zones with 13.3–14.5 wt % Ag. The AuCu blocks are cemented by late Cu-Au alloy, whose composition is close to auricupride (AuCu₃). Taking into account the limits of component miscibility in the Au-Ag-Cu system, the temperature of the Cu-Au alloy formation was estimated at 350–600°C. This temperature corresponds to the formation conditions of garnet-pyroxene rodingite mineral assemblage (Plyusnina et al., 1993). The studied Cu-Au alloy samples from the Malye Kopty massif are very similar to Cu-Au alloy minerals hosted in the Alpine-type ultramafic rocks of the Karabash massif in the southern Urals. This similarity is confirmed by identical chemical compositions of pyroxene, garnet, and chlorite, and similar PT conditions of their formation. The data show that primary ore mineralization of gold-rodingite type occurs in the Kaa-Khem ophiolitic belt.     

Multiple origin of the ‘Kniest feeder zone’ of the stratiform Zn–Pb–Cu ore deposit of Rammelsberg, Germany

The Zn–Pb–Cu ore deposit of Rammelsberg is characterized by a complex fluid flow history. The main phase of ore deposition occurred during the Middle Devonian in the Rhenohercynian basin. The Kniest zone underlying the stratiform ore is interpreted as the feeder zone, along which hydrothermal fluids migrated upward and were expelled on the sea floor. Mineralizing brines possibly had a minimum temperature of 130°C, and salinity ranged between 4.9 and 10.3 eq. wt.% NaCl. The ore and its host rock became folded during the Variscan orogeny, and low salinity fluids (1.0 to 2.3 eq. wt.% NaCl) were mobilized during this tectonic period. Remobilization of the ore took place during the Mesozoic by a high salinity (17.3 to 20.2 eq. wt.% NaCl) H₂O–NaCl–CaCl₂ fluid.     

Storage of F and Cl in the upper mantle: geochemical implications

Electron microprobe analyses yielded mean values of $\text{F}\text{0.43}\text{and}\text{Cl}\text{0.08}\text{wt.}\text{\%}$ for primary-textured phlogopites in coarse, depleted garnet-lherzolite xenoliths from kimberlites. Most secondary-textured phlogopites have too low Cl (0.01–0.08 wt.%) to be metamorphic precursors of primary-textured phlogopites. MARID-suite phlogopites and many megacrysts in kimberlites have low Cl ($\text{～ 0.02}\text{wt.}\text{\%}$), and some but not necessarily all secondary micas may result from infiltration of kimberlite into peridotite xenoliths. A good correlation between P and F in some oceanic basalts and gabbros might suggest that these elements are derived mainly from F-rich apatite inthe mantle, and that whitlockite is not present in the source region. Mantle-derived mica and amphibole have such low Cl that it is necessary to attribute Cl in oceanic basalts and gabbros either to substantial Cl in the source apatite, or to Cl from invading solutions, or both: three apatites from the mantle contain 0.8–1.0 wt.% Cl, and others contain lower amounts. The halogen contents of kimberlitic magmas can be explained by incorporation of Cl-bearing mica and F-rich apatite during melting of peridotites, but compositional constraints are weak.     

Seawater-peridotite interaction at 300°C and 500 bars: implications for the origin of oceanic serpentinites

An experiment has been performed reacting seawater with fresh peridotite (80% olivine, Fo₉₀ and ～- 15% enstatitic orthopyroxene En₉₅ and minor clinopyroxene and spinel) at 300°C, 500 bars and water/rock mass ratio of 20. The duration of the experiment was approximately 1500 hr.Seawater chemistry was appreciably modified during the experiment. Mg, Ca, Sr, SO₄ and H₂O were removed, while H₂S_(aq), Fe, Mn and Zn were added. H₂S_(aq) resulted from the inorganic reduction of seawater SO₄. pH was initially acid (2.8), but then rose slowly to a value of 5.2. The aqueous concentrations of Na, K, Cl and boron (B) changed little from that in seawater prior to reaction. However, as the solution was cooled to room temperature at the end of the experiment, the B concentration decreased. This suggests that the B content of oceanic serpentinites may be the result of retrograde reactions between a previously serpentinized body and ‘cold’ seawater.The primary minerals in the peridotite were replaced to varying degrees by serpentine (lizardite), magnetite. Mg-hydroxysulfate, anhydrite and possibly pyrite and sphalerite. Mg-hydroxysulfate and much anhydrite dissolved on quench.The alteration mineral assemblage generated during this experiment is consistent with that predicted from equilibrium phase relations and is similar in chemical composition, mineralogy and paragenesis to that reported for oceanic serpentinites.     

Evolution of a Carboniferous carbonate-hosted sphalerite breccia deposit,Isle of Man

A newly discovered, extensive sphalerite-bearing breccia (~7.5 wt.% Zn) is hosted in dolomitised Carboniferous limestones overlying Ordovician–Silurian metasedimentary rocks on the Isle of Man. Although base metal sulphide deposits have been mined historically on the island, they are nearly all quartz vein deposits in the metamorphic basement. This study investigates the origin of the unusual sphalerite breccia and its relationship to basement-hosted deposits, through a combination of petrographic, cathodoluminescence, fluid inclusion, stable isotope and hydrogeologic modelling techniques. Breccia mineralisation comprises four stages, marked by episodes of structural deformation and abrupt changes in fluid temperature and chemistry. In stage I, high-temperature (T _h > 300°C), high-salinity (20–45 wt.% equiv. NaCl) fluid of likely basement origin deposited a discontinuous quartz vein. This vein was subsequently dismembered during a major brecciation event. Stages II–IV are dominated by open-space filling sphalerite, quartz and dolomite, respectively. Fluid inclusions in these minerals record temperatures of ~105–180°C and salinities of ~15–20 wt.% equiv. NaCl. The δ³⁴S values of sphalerite (6.5–6.9‰ Vienna-Canyon Diablo troilite) are nearly identical to those of ore sulphides from mines in the Lower Palaeozoic metamorphic rocks. The δ¹⁸O values for quartz and dolomite indicate two main fluid sources in the breccia’s hydrothermal system, local Carboniferous-hosted brines (~0.5–6.0‰ Vienna standard mean ocean water) and basement-involved fluids (~5.5–11.5‰). Ore sulphide deposition in the breccia is compatible with the introduction and cooling of a hot, basement-derived fluid that interacted with local sedimentary brines.     

Origin of CaCl2 brines by basalt-seawater interaction: Insights provided by some simple mass balance calculations

Modern rift zone hydrothermal brines are typically CaCl₂-bearing brines, an unusual chemical signature they share with certain oil field brines, fluid inclusions in ore minerals and a few uncommon saline lakes. Many origins have been suggested for such CaCl₂ brines but in the Reykjanes, Iceland, geothermal system a strong empirical case can be made for a basalt-seawater interaction origin. To examine this mechanism of CaCl₂ brine evolution some simple mass balance calculations were carried out. Average Reykjanes olivine tholeiite was “reacted” with average North Atlantic seawater to make an albite-chlorite-epidotesphene rock using Al₂O₃ as the conservative rock component and Cl as the conservative fluid component. The excess components released by the basalt to the fluid were “precipitated” at 275° C as quartz, calcite, anhydrite, magnetite and pyrite to complete the conversion to greenstone. The resulting fluid was a CaCl₂ brine of seawater chlorinity with a composition remarkably similar to the actual Reykjanes brine at 1750 m depth. Thus, the calculations strongly support the idea that the Reykjanes CaCl₂ brines result from “closed system” oceanic basalt-seawater interaction (albitization — chloritization mechanism) at greenschist facies temperatures. The calculation gives a seawater: basalt mass ratio of 3∶1 to 4∶1 (vol. ratio of 9∶1 to 12∶1), in keeping with experimental results, submarine vent data and with ocean crust cooling calculations. The brine becomes anoxic because there is insufficient dissolved or combined oxygen to balance all the Fe released from the basalt during alteration. Large excesses of Ca are released to the fluid and precipitate out in the form of anhydrite which essentially sweeps the brine free of sulfate leaving an elevated Ca concentration. The calculated rock-water interaction basically involves Na + Mg + SO₄ ? Ca + K, simulating chemical differences observed between oceanic basalts and greenstones from many mid-ocean ridges.