Genesis of the stratiform Zhenzigou PbZn deposit in the North China Craton: RbSr and COSPb isotope constraints

Isotopes (RbSr, C, O, S, and Pb) were investigated from the Zhenzigou PbZn deposit in the Qingchengzi mineral field (QMF) of the North China Craton as an aid to determine the genesis of stratiform PbZn deposits in the Liao-Ji Rift. A step-dissolution RbSr age of 1798 ± 8 Ma with 206Pb/204Pb ratios of 17.7477–17.8527 were obtained from sphalerite. Sulfur isotopic ratios for pyrite (5–14.4‰), sphalerite (2.4–8.6‰), and galena (− 0.3–8.6‰) from Zhenzigou have a narrower range than those from the host Paleoproterozoic Dashiqiao Formation, and granite in the area. Calcite and limestone from ore and wallrocks at the deposit have similar C and O isotope compositions, with δ¹³C_PDB ranging from − 6.0 to − 2.3‰ and δ¹⁸O_SMOW from 9.8 to 13.7‰, which are similar to those of carbonatite and the mantle.Comprehensive analysis of the Pb isotopic composition of the sulfide from the Zhenzigou deposit and PbZn deposits in adjacent area show that the Pb originated from the upper crust and mixed with Pb from the mantle. Sulfur isotopes from Zhenzigou deposit indicate that the mineralization has a volcanic eruption source. The δ¹³C_PDB and δ¹⁸O_SMOW values indicate that the CO₂ originated from a mixed mantle, marine carbonate and organic source.Combined with the study of regional metallogenic background, this paper proposes that deposition of stratiform PbZn mineralization in the QMF began ca. 2052 Ma during development of the Liaoji Rift. The mineralization extended to ca. 1798 Ma prior to deformation associated with the Lvliang Movement, which dismembered the stratiform PbZn mineralization. The veined mineralization in the region cross-cuts the stratiform deposits and represents remobilized and redeposited deposits associated with the emplacement of Triassic plutons such as the Xinling and Shuangdinggou granites.     

Solubility of rare earth elements in carbonatite magmas,indicated by the liquidus surface in CaCO3Ca(OH)2La(OH)3 at 1 kbar pressure

The system CaCO₃Ca(OH)₂(CCCH) represents a synthetic analog to a carbonatite magma. Addition of a light rare earth (RE) component La(OH)₃ (LH) gives a simple analog of a rare earth carbonatite. Liquidus relations for two joins were studied at 1 kbar pressure; CHLH and (CC₅₅CH₄₅)LH. CHLH is binary with a eutectic at CH₇₉LH₂₁ and 710°C. Thejoin CC₅₅ + CH₄₅)LH has a liquidus piercing point between CC and LH, at (CC₅₅CH₄₅)₆₀LH₄₀ and 700°C. Combining the new results with known results for CCCH allows construction of a liquidus diagram for part of the join CCCHLH. A ternary eutectic between the primary liquidus fields for CH, CC and LH occurs near 610°C with estimated composition CC= 33%,CH= 47%,LH= 20%. The solubility of La(OH)₃ in the synthetic carbonatite magma increases with increase of CO₂/H₂O from 20% at the eutectic to 40% at the piercing point on the join (CC₅₅CH₄₅)LH. The solubility of La in synthetic carbonatite is high compared with that of silicates. P₂O₅, and S. The results show that REE can become concentrated to high levels by fractionation of carbonatites, as long as they are not removed by high temperature crystallization of apatite and monazite.     

External sulphur in IOCG mineralization: Implications on definition and classification of the IOCG clan

Although the sources of the ore metals remain problematic in most Iron-oxide Cu and Au (IOCG) deposits, external sulphur, either from surficial basinal brines and seawater (e.g., Central Andean and Carajás deposits) or from formation water and metamorphic fluids (e.g., the Cloncurry deposits), or introduced by magmatic assimilation of metasedimentary units (e.g., Phalaborwa), has been documented in many major Cu-rich IOCG centres. However, only the evaporite-sourced fluids yield diagnostically high δ³⁴S values (i.e., > 10‰), while sedimentary formation water or metamorphic fluids commonly have lower values and are less clearly distinguishable from magmatic fluids, as in the Cloncurry deposits in which the involvement of external fluids is revealed by other evidence, such as noble gas isotopes. On the basis of these arguments, IOCG deposits could be redefined as a clan of Cu (AuAgU) deposits containing abundant hypogene iron oxide (magnetite and/or hematite), in which externally-derived sulphur probably plays an important role for the Cu (AuAgU) mineralization. In this definition, all “Kiruna-type” magnetite deposits, hydrothermal iron deposits (e.g., skarn Fe deposits) and magnetite-rich porphyry CuAu and skarn CuAu deposits are excluded. Two subtypes of IOCG deposits are recognized on the basis of the predominant iron oxide directly associated with the Cu (Au) mineralization, whether magnetite or hematite. Neither magnetite- nor hematite-rich IOCG deposits show any preference for specific host rocks, and both range in age from Neoarchean to Pleistocene, within a broad tectonic environment.     

Zinc and lead isotope signatures of the Zhaxikang PbZn deposit,South Tibet: Implications for the source of the ore-forming metals

Stable Zn isotopes may be applied to trace the source of ore-forming metals in various types of PbZn deposits. To test this application, Zn and Pb isotope systematics for sulfides and associated basement rocks as well as FeMn carbonates (gangue) from the Zhaxikang PbZn deposit in South Tibet have been analyzed. The basement in this region includes metamorphosed mafic to felsic rocks (dolerite, quartz diorite, rhyolite porphyry, pyroclastics and porphyritic monzogranite). These rocks have similar δ⁶⁶Zn values of 0.33 to 0.37‰, with an average value of 0.36 ± 0.03‰ (2σ), except for the more evolved porphyritic monzogranite that has a heavier value of 0.49‰. FeMn carbonates are present as hydrothermal veins and were probably precipitated from magmatic fluids. They have an average δ⁶⁶Zn value of 0.27 ± 0.05‰, which is slightly lighter than the basement rocks, possibly representing δ⁶⁶Zn isotopic compositions of the hydrothermal fluids. Sphalerite and galena have similar Zn isotopic compositions with δ⁶⁶Zn ranging from 0.03 to 0.26‰ and 0.21 to 0.28‰, respectively. Considering the Zn isotope fractionation factor between sphalerite and fluids of − 0.2‰ at ~ 300 °C as reported in literature, hydrothermal fluids from which these sulfides precipitated will have δ⁶⁶Zn values of ca. 0.39 ± 0.10‰, which are consistent with the values of basement rocks and the FeMn carbonates. This similarity supports a magmatic-hydrothermal origin of the Zhaxikang PbZn deposit. Both Pb and S isotopes in these sphalerite and galena show large variations and are consistent with being derived from a mixture of basement and sedimentary rocks in various proportions. Zn isotopic compositions of the sulfides significantly extend the range of regional basement rocks, suggesting that sedimentary rocks (e.g., shales) are also a significant source of Zn. However, the Zn isotopic compositions of sphalerite and galena differ from those of marine carbonates and those of typical SEDEX-type deposits (e.g. Kelley et al., 2009), confirming a magmatic-hydrothermal model. Combined with regional geological observations and the age constraints of ~ 20 Ma (Zheng et al., 2012, 2014), the results of our investigation indicate that the Zhaxikang PbZn deposit is most likely a magmatic-hydrothermal deposit.     

Unveiling growth histories of multi-generational garnet in a single skarn deposit via newly-developed LA-ICP-MS UPb dating of grandite

Although garnet UPb dating method has been reported recently, yet the accurate concordia ²⁰⁶Pb/²³⁸U ages and growth histories of multi generation of garnets based on ages were still lacked. LA-ICP-MS UPb dating on multi-generational grandite (grossular-andradite) garnet from the large Tonglvshan Cu-Fe-Au skarn deposit was applied in this study. Based on petrographic observation, in chronological order, three generation garnets have been distinguished, namely homogeneous Grt1-exo (in the exoskarn zone) and Grt1-endo (in the endoskarn zone), oscillatory zoning Grt2 and vein-type Grt3 cutting magnetite ores. LA-ICP-MS UPb dating on four grandite samples from the Grt1-exo, Grt1-edno, Grt2 and Grt3 yields Tera-Wasserburg lower intercept ²⁰⁶Pb/²³⁸U ages of 139.1 ± 1.0 Ma (2σ, MSWD = 0.79), 134 ± 11 Ma (2σ, MSWD = 2.5), 143.4 ± 8.3 Ma (2σ, MSWD = 2.3) and 140.3 ± 1.4 Ma (2σ, MSWD = 0.95), respectively. More importantly, two concordia ²⁰⁶Pb/²³⁸U ages of 139.2 ± 0.6 Ma (2σ, MSWD = 1.4) and 139.8 ± 1.5 Ma (2σ, MSWD = 0.13) were firstly obtained from the sample of Grt1-exo with highest U concentrations ([U]_avg > 80 ppm) contents. The precision UPb ages of 139–140 Ma from Grt1-exo and Grt3 can be considered as the timing of Cu-Fe-Au skarn mineralization, and consistent with the majority of published zircon UPb ages of the quartz dioritic stock and ⁴⁰Ar³⁹Ar plateau ages of phlogopite at Tonglvshan (142–140 Ma). The precision grandite UPb ages also indicate that the entire metasomatic hydrothermal mineralization activity in the Tonglvshan Cu-Fe-Au skarn deposit occurred within a relatively short time span of <1 (or 2.5 considering errors) Myr. In addition, we found that the grandite garnet is more easily to be enriched in U and can obtain the high-precision concordia UPb ages with higher andradite Mol%, euhedral and larger crystals, and relevant oxidized magmatic rocks or skarns.     

Evolution of unconformity-related MnFeAs vein mineralization,Sailauf (Germany): Insight from major and trace elements in oxide and carbonate minerals

The Sailauf MnFeAs vein mineralization, located in the Spessart district (central Germany), is characterized by complex hydrothermal carbonate and oxide assemblages. The mineralization is hosted by a Permian rhyolite body and is structurally related to the Variscan unconformity that separates Permian sedimentary rocks from the underlying Variscan crystalline basement. The hydrothermal vein system has been studied by optical microscopy, electron-microprobe and LA-ICPMS analysis of major and trace elements (including the REE). Four distinct mineralization stages that are characterized by diagnostic carbonate-oxide assemblages are identified, which are (1) pre-ore stage, (2) ore stage 1, (3) ore stage 2, and (4) the replacement stage. Hydrothermal carbonates show complex compositional trends in CaMn (Fe + Mg) space, and comprise calcite, Mn-calcite, FeMg calcite, Ca-rhodochrosite, and Ca-kutnahorite. Oxide assemblages are dominated by braunite and hematite, with minor amounts of manganite and hausmannite. The mineralization is enriched in a distinct suite of trace elements, including As, W, Pb, Zn and Cu. Analysis of the paragenetic evolution, in conjunction with the major and trace element data, allows to reconstruct the fluid evolution of the hydrothermal system. The first order change in mineralogy between the two main ore stages (Mn oxides and calcite evolving into hematite and Mn-rich calcite) records a pronounced shift in fluid pH and silica activity of the system. This interpretation is also supported by variations in the behavior of Ce in different carbonate generations. The late stage replacement carbonates relate to destabilization of the primary ore assemblages. The distinct geological setting immediately below the Permian unconformity, in conjunction with the mineralogical and chemical data, suggests that dynamic fluid mixing processes involving basement-derived brines and more shallow groundwaters were important in the formation of the Sailauf MnFeAs mineralization. The significant enrichment in the AsWPbZnCu element suite resembles that of other MnFe deposits, and points to felsic lithologies as the main metal source of the mineralization.     

Mineralogical and geochemical characterization of the Riópar non-sulfide Zn-(Fe-Pb) deposits (Prebetic Zone,SE Spain)

The present paper reports the first detailed petrological and geochemical study of non-sulfide Zn–(FePb) deposits in the Riópar area (Prebetic Zone of the Mesozoic Betic Basin, SE Spain), constraining the origin and evolution of ore-forming fluids. In Riópar both sulfide and non-sulfide Zn–(FePb) (“calamine”) ores are hosted in hydrothermally dolomitized Lower Cretaceous limestones. The hypogene sulfides comprise sphalerite, marcasite and minor galena. Calamine ores consist of Zn-carbonates (smithsonite and scarce hydrozincite), associated with abundant Fe-(hydr)oxides (goethite and hematite) and minor Pb-carbonates (cerussite). Three smithsonite types have been recognized: i) Sm-I consists of brown anhedral microcrystalline aggregates as encrustations replacing sphalerite; ii) Sm-II refers to brownish subhedral aggregates of rugged appearance related with Fe oxi-hydroxides in the surface crystals, which replace extensively sphalerite; and iii) Sm-III smithsonite appears as coarse grayish botryoidal aggregates in microkarstic cavities and porosity. Hydrozincite is scarce and appears as milky white botryoidal encrustations in cavities replacing smithsonite. Also, two types of cerussite have been identified: i) Cer-I cerussite consists of fine crystals replacing galena along cleavage planes and crystal surfaces; and ii) Cer-II conforms fine botryoidal crystals found infill porosity. Calcite and thin gypsum encrustations were also recognized. The field and petrographic observations of the Riópar non-sulfide Zn–(FePb) revealed two successive stages of supergene ore formation under meteoric fluid processes: i) “gossan” and “red calamine” formation in the uppermost parts of the ore with deposition of Fe-(hydr)oxides and Zn- and Pb-carbonates (Sm-I, Sm-II and Cer-I), occurring as direct replacements of ZnPb sulfides; and ii) “gray calamine” ore formation with deposition of Sm-III, Cer-II and hydrozincite infilling microkarst cavities and porosity. The stable isotope variation of Riópar smithsonite is very similar to those obtained in other calamine-ore deposits around the world. Their CO isotope data (δ¹⁸O: + 27.8 to + 29.6‰ V-SMOW; δ¹³C: − 6.3 to + 0.4‰ V-PDB), puts constrains on: i) the oxidizing fluid type, which was of meteoric origin with temperatures of 12 to 19 °C, suggesting a supergene weathering process for the calamine-ore formation under a temperate climate; and ii) the carbon source, that resulted from mixing between two CO₂ components derived from: the dissolution of host-dolomite (¹³C-enriched source) and vegetation decomposition (¹³C-depleted component).     

Granulites,CO2 and graphite

Externally derived, pure CO₂ that mixes with a carbon-(under)saturated C-O-H fluid in lower crustal granulites may result in graphite precipitation if the host-rock oxygen fugacity (f_O2^rock) is below the upper f_O2 limit of graphite. The maximum relative amount of graphite that can precipitate varies between a few mol% up to more than 25 mol%, depending on pressure, temperature, and host-rock redox state. The maximum relative amount of graphite that can precipitate from an infiltrating CO₂ fluid into a dry granulite (CO fluid system) varies between zero and a few mol%. Thermodynamic evaluation of the graphite precipitation process shows that CO₂ infiltration into lower crustal rocks does not always result in a carbon (super)saturated fluid. In that case, graphite precipitation is only possible if carbon saturation can be reached as a result of the reaction CO₂ → CO + ½ O₂. Graphite that has been precipitated during granulite facies metamorphic conditions can subsequently be absorbed by a COH fluid during retrograde metamorphism. It is also possible, however, that significant amounts of graphite precipitate from a COH fluid during retrograde metamorphism. This study shows that interpreting the presence or absence of graphite in granulites with respect to CO₂ infiltration requires detailed information on the P–T–f_O2^rock conditions, the relative amount of CO₂ that infiltrates into the rock, and whether H₂O is present or not.     

Large Zn isotope variations in the NiMo polymetallic sulfide layer in the lower Cambrian,South China

In South China, black organic-rich shales in the lower Cambrian Niutitang Formation host a NiMo polymetallic sulfide layer that discontinuously extends over ~1600 km. Seawater and hydrothermal origins are among the many suggested hypotheses and are still under debate. In order to discriminate Zn sources, we report Zn isotopes in NiMo polymetallic sulfide layers and their host shales from the Nayong and Zunyi locations in Guizhou province and the Zhangjiajie section in Hunan province. In each section, host organic-rich shales show homogeneous Zn isotope compositions which likely resulted from quantitative scavenging of dissolved Zn from seawater under euxinic conditions. The difference in the average δ⁶⁶Zn values of organic-rich shales between the two sections in Guizhou (0.76 ± 0.09‰) and one section in Hunan (0.59 ± 0.10‰) might reflect variations of Zn isotope gradient with the depth of seawater. Therefore, the organic-rich sediments need not always represent an isotopically light Zn sink, which is dependent on Zn isotope fractionation in the local basin. However, the δ⁶⁶Zn values in the NiMo polymetallic sulfide layers are different from those of their host shales, indicating that these sulfide layers did not inherit the Zn isotope signal of seawater. Based on the regular increasing trend in δ⁶⁶Zn values from Nayong (0.54 ± 0.06‰) to Zhangjiajie (1.34 ± 0.09‰) and the presence of PbZn mineralization in the Dengying/Doushantuo Formations, we argue that hydrothermal fluids associated with PbZn mineralization could be a major source of Zn in NiMo sulfide layers, especially in the Nayong location. A possible model is that the hydrothermal fluids related to MVT-type mineralization got overprinted on a multiple-sourced synsedimentary sulfide-rich layer. We provide additional evidence that Zn isotopes have great potential as a tracer of metal source and can be applied to similar types of mineralization as e.g., the late Devonian Ni-Zn-PGE Nick deposit (Selwyn Basin, Canada) or elsewhere.     

Multi-stage fluid incursion in the Palaeozoic basement-hosted Saint-Salvy ore deposit (NW Montagne Noire,southern France)

The Saint-Salvy vein-hosted Zn (+Ge) deposit occurs in an E–W fault system which flanks the southern margin of the late Variscan Sidobre granite, and cross-cuts Cambrian black shales of the Palaeozoic basement. Comprehensive mineralogical and geochemical studies of vein samples have revealed four mineralizing events (M1–M4) related to late and post-Variscan tectonic events. A further late-stage event may be related to weathering.M1 (=skarn deposits) and M2 (=patchily mineralized quartz veinlets) are associated with granite emplacement. Quartz contains low salinity, H₂OCO₂(NaCl)-dominated fluids(⩽6wt% NaCl equiv.) of relatively high temperature (300–580°C), trapped under moderate to high pressure. Estimated M1 fluid δD and calculated fluidδ¹⁸O plot within the metamorphic water field. There appears to be no involvement of magmatic fluids.By contrast, M3 (= barren quartz) and M4 (= zinciferous economic mineralization) stages have H₂OCO₂NaClCaCl₂ fluid inclusions with high salinities (23–25 wt% NaCl equiv.) and low temperatures(∼ 80–140°C), which were trapped under low-pressure conditions. The high salinity and NaCl + CaCl₂ content of both M3 and M4 indicates that their parent fluids leached evaporitic salts. M3 fluids are meteoric water dominated, falling close to the meteoric water line (δD andδ¹⁸O averaging −64 and −8‰, respectively). M4 fluids have highly distinctive δD averaging −101‰, and calculated fluidδ¹⁸O varying from−1.2to+7.1‰. The unusually low δD composition of M4 suggests the involvement of “organic” fluids, in which H is derived directly or indirectly from organic matter. The relatively highδ¹⁸O of M4 fluids indicates that considerable isotopic exchange with sedimentary material took place, displacing theδ¹⁸O from the meteoric water line. The data imply interaction of meteoric waters with evaporite and hydrocarbon-bearing sedimentary sequences, most probably the adjacent Aquitain Basin.The main economic mineralization (M4 stage) took place during a tensional event, probably coincident with the Lias-Dogger transition.Calculatedδ³⁴S_H2S of M4 sulphide(+5.4to+8.2‰) is almost identical toδ³⁴S of local Cambrian sulphides(+4.7to+9.4‰) suggesting a genetic link. Abundant siderite associated with M4 sphalerite hasδ¹³C ranging from−2.6to−4.4‰ indicating that carbon was sourced from sedimentary carbonate mobilized by, or equilibrated with the hydrothermal fluid.Late-stage sulphides exhibit extraordinary and highly distinctiveδ³⁴S. Sphalerite has extremely low δ³⁴S(−42.5to−50.5‰), whereas pyrite has an extraordinary large range from−33.2‰to+74.3‰. Closed system sulphate reduction is held to be responsible for the extremely highδ³⁴S: whereas more open system reduction produces the very low values. The coincidence of isotopically lowδ¹³C(−7.6to−11.9‰) for co-genetic calcite suggests the involvement of organic matter in the reduction process.     

Evolution of groundwater chemistry in and around Vaniyambadi Industrial Area: Differentiating the natural and anthropogenic sources of contamination

Groundwaters in the crystalline aquifers are the major source of drinking water in Vaniyambadi area of Vellore district. Geochemical methods in collaboration with statistical methods were applied in this industrial area to understand the natural and anthropogenic influences on groundwater quality. To accomplish this objective, groundwater samples were collected and analyzed for physicochemical parameters and the results showed a dominance in the order of Na⁺ > Mg²⁺ > Ca²⁺ > K⁺ and HCO₃⁻ > Cl⁻ > SO₄²⁻ > NO₃⁻ for anions and cations, respectively. In contrast to this anion dominance were changed to Cl⁻ > HCO₃⁻ > SO₄²⁻ > NO₃⁻ in samples collected near the tannery industries. Groundwater quality evaluation using TDS and TH suggested that 57% of the total samples are hard-brackish type, indicating its unsuitability for drinking purpose. Generally the water type is Na⁺Cl⁻ to Ca²⁺Mg²⁺HCO₃⁻ type with an intermediate Ca²⁺Mg²⁺Cl⁻, suggesting the mixing of fresh groundwater with tannery effluent and cation exchange. Factor analysis and bivariate plots of major ions suggests that both natural and anthropogenic inputs are equally influencing the groundwater quality. Further investigations proved that silicate weathering is the dominant geogenic source of groundwater solute content, whereas tannery effluent is the anthropogenic source. Saline water mixing index (SWMI) and Cl⁻ vs NO₃⁻ bivariate plot were employed to differentiate the tannery contamination from the other anthropogenic inputs such as agricultural fertilizers, municipal sewages, etc. This analysis shows that samples 2, 4, 8 and 9 (located within the tannery cluster) have a SWMI value greater than 1, representing the groundwater–tannery effluent mixing. This study infers that groundwater in the Vaniyambadi area is under serious threat from both natural and anthropogenic contamination. However, the controlling discharge of untreated tannery effluents must be regulated to reduce the further deterioration of this vital resource in this part of the country.     

The Earth as a multiscale quantum-mechanical system

Major features of the Earth's structure and dynamics originate in the contrast between the rigidity of SiO bonds and the softness of SiOSi linkages. Because this contrast results from orbital hybridization, a real understanding of bonding relies on ab initio quantum-mechanical principles. As investigated with first-principles interatomic potentials, the α–β transitions of SiO₂ polymorphs illustrate how soft SiOSi linkages give rise to dynamical structures at rather low temperatures and yield the low melting temperatures of SiO₂-rich minerals that are at the roots of SiO₂ enrichment in magmatic differentiation. The increasing concentration of alkalis throughout this process is another aspect that must also be studied in terms of molecular orbitals in relation with the presence of aluminum in tetrahedral coordination. Finally, calculations of noble gas solubility show that some important features can be treated with “hybrid” calculations when, in addition to quantum-mechanical effects, the energy needed to create a cavity in the silicate melt is dealt with in a classical manner.     

Distribution of reduced inorganic sulfur compounds in lake sediments receiving acid mine drainage

The sediments of Lake Anna, Virginia, act as a major sink for incoming acid mine drainage (AMD) pollutants (Fe, SO₄²⁻, H⁺) due to bacterial sulfate reduction (SR). Acid-volatile sulfide (AVS), elemental S, and pyrite concentrations in the sediments of the polluted arm of the lake are significantly greater than those in unpolluted sections of the lake. Measurements of SR using ³⁵SSO₄²⁻ showed that AVS and S⁰ are the major short-term (48 h) products of SR in these sediments. Inorganic forms of S(AVS, S⁰, and FeS₂) made up from 60 to 100% of the total sediment S concentration. Pyrite concentrations in the sediment were high but decreased exponentially with distance from the AMD source, suggesting that the pyrite was deposited as stream detritus from the abandoned mines. Iron monosulfide and elemental S concentrations were highest at a station 1 km away from the AMD inflow, indicating formation in situ. There was no evidence for the formation of organic S species. The results suggest that in Fe- and S-rich locations such as those contaminated with acid mine drainage, the distribution of end products of SR may vary substantially from those reported for more moderate environments.     

Jurassic–Cretaceous granitoids and related tectono-metallogenesis in the Zapug–Duobuza arc,western Tibet

The Zapug–Duobuza magmatic arc (ZDMA), located along the southern edge of the south Qiangtang terrane in western Tibet, extends east–west for ~ 400 km. Small scattered granite and porphyry intrusions crop out in the ZDMA, but a large amount of granite may be buried by Late Cretaceous to Paleogene thrusting. Two stages of magmatism have been identified, at 170–150 Ma and 130–110 Ma. The widely distributed Middle–Late Jurassic granite intrusions in the ZDMA exhibit SrNd isotopic characteristics similar to those of ore-bearing porphyries in the Duolong giant CuAu deposit, and their εHf(t) values mostly overlap those of other porphyry CuMo deposits in the ZDMA and the Gangdese zone. The SrNdHf isotopic geochemistry suggests variable contributions of mantle and Qiangtang crustal sources, and indicates the presence of two new ore districts with potentials for CuAu, Fe, and PbZn ores, located in the Jiacuo–Liqunshan and Larelaxin–Caima areas. Except for the Duolong ore-forming porphyries, which show significant contributions of mantle components intruded into an accretionary mélange setting, the Early Cretaceous granites in other areas of the belt are of mostly crustal origin, from sources in Qiangtang felsic basement and Permo-Carboniferous strata, indicating the weak ore-forming potential of skarn-type Fe and PbZn deposits. The ephemeral but deep Bangong Co–Nujiang ocean in the Early Jurassic evolved into a shallow compressional marine basin in the Middle–Late Jurassic, possibly transitioning to northward flat subduction of oceanic crust at this time. The subducted slab broke off in the Early Cretaceous, initiating a peak in arc magmatism and metallogenesis at 125–110 Ma.     

Rock–water interactions and pollution processes in the volcanic aquifer system of Guadalajara,Mexico, using inverse geochemical modeling

In order to understand and mitigate the deterioration of water quality in the aquifer system underlying Guadalajara metropolitan area, an investigation was performed developing geochemical evolution models for assessment of groundwater chemical processes. The models helped not only to conceptualize the groundwater geochemistry, but also to evaluate the relative influence of anthropogenic inputs and natural sources of salinity to the groundwater. Mixing processes, ion exchange, water–rock–water interactions and nitrate pollution and denitrification were identified and confirmed using mass-balance models constraint by information on hydrogeology, groundwater chemistry, lithology and stability of geochemical phases. The water–rock interactions in the volcanic setting produced a dominant NaHCO₃ water type, followed by NaMgCaHCO₃ and NaCaHCO₃. For geochemical evolution modeling, flow sections were selected representing recharge and non-recharge processes and a variety of mixing conditions. Recharge processes are dominated by dissolution of soil CO₂ gas, calcite, gypsum, albite and biotite, and Ca/Na exchange. Non-recharge processes show that the production of carbonic acid and Ca/Na exchange are decreasing, while other minerals such as halite and amorphous SiO₂ are precipitated. The origin of nitrate pollution in groundwater are fertilizers in rural plots and wastewater and waste disposal in the urban area. This investigation may help water authorities to adequately address and manage groundwater contamination.     

Origin of formation waters of S-E parts of the Bohemian Massif and the Vienna basin

Deep formation waters were sampled from boreholes on the S-E slopes of the Bohemian Massif. They are NaClHCO₃ waters with TDS in the range 6–52 g L⁻¹. Some of them are associated with gas and oil deposits. The waters are rich in Br and I and their δDandδ¹⁸0 isotope compositions vary from −12 to −77‰ and + 4.6 to −10‰ respectively.The processes of concentration and dilution have been discussed based on deuterium and conservative element contents of the waters. Three regional groups can be identified in the plots Br vs I and Cl vs I: the Vienna Basin samples (VB), southern (S) and northern (N) flanks of the Bohemian Massif (BM). The VB samples have as an end member brackish water with about 7 g L⁻¹ Cl (about 40% marine component) enriched in Br and I. This water has been later diluted by meteoric water of recent isotopic composition. Only 3 VB samples can be considered as derived from the dissolution of evaporites. The salt content of the S and N end members is very close to or higher than sea water with an isotopic composition similar to the brackish water. Subaerial evaporation of diluted sea water is suggested as the process increasing salt content. The evaporative enrichment of primary brackish solution can be estimated from extrapolation of Cl vs I and Br vs I plots to zero I (about 25 mg L⁻¹ Br and 6 g L⁻¹ Cl for the southern flanks of the BM). Evaporated solutions were later diluted by meteoric waters with δD in the range from −50 to −80‰ (southern flanks) and about −80‰ (northern flanks).     

Protoliths and tectonic implications of the newly discovered Triassic Baqing eclogites,central Tibet: Evidence from geochemistry,SrNd isotopes and geochronology

Geochemical, SrNd isotopic and geochronological methods were used to reveal the protoliths and geodynamic implications of the newly discovered Triassic Baqing eclogites, eastern Qiangtang terrane, central Tibet. We assessed the mobility of trace elements, and it turned out that high field strength elements (HFSEs) and rare earth elements (REEs) were immobile in the high-pressure (HP) metamorphic process and reliably employed to discriminate the protoliths of the Baqing eclogites. Whole-rock geochemical data (especially immobile elements) suggested both arc-related (negative NbTa anomalies, high light (L) REEs/heavy (H) REEs ratios) and mid-oceanic ridge basalt (MORB)-related (without negative NbTa anomalies, relatively low REEs contents) characteristics, indicating the contribution of different proportions of subduction material with a backarc basin origin. According to the SrNd isotopic ratios (initial ⁸⁷Sr/⁸⁶Sr ratios: 0.7078–0.7086; ε_Nd(t) values: −0.58 to +1.96), the protoliths of the Baqing eclogites originated from mantle which experienced continental crustal contamination in the subduction zone. Compared with nearby subduction-related magmatic rocks from eastern Qiangtang terrane, backarc basin was the most likely tectonic environment for the Baqing eclogite protoliths. The Jinsha Paleo-Tethyan Ocean southward subduction underneath East Qiangtang block (EQB) and rollback led to the formation of this backarc basin between the Late Permian and Early Triassic, and subsequent northward subduction of the backarc basin formed the Baqing eclogites in early Late Triassic (227–221 Ma).     

Structural characterization of gilsonite bitumen by advanced nuclear magnetic resonance spectroscopy and ultrahigh resolution mass spectrometry revealing pyrrolic and aromatic rings substituted with aliphatic chains

Gilsonite, a naturally occurring asphaltite bitumen, consists of a complex mixture of organic compounds. In the present study, advanced one and two dimensional solid state and solution ¹H, ¹³C and ¹⁵N nuclear magnetic resonance (NMR) and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS) were employed to investigate its composition and structure. ¹³C NMR yielded a carbon aromaticity of 27%. Aromatic moieties in gilsonite were primarily single rings or small clusters of fused rings. Half of the aromatic carbons of gilsonite can be accounted for by pyrroles. ¹⁵N and ¹³C cross polarization-magic angle spinning (CP-MAS) NMR showed that most nitrogen in gilsonite was pyrrolic. The aromatic rings were heavily substituted with alkyl chains, as evidenced by ¹H¹³C correlation spectra. Advanced solid state NMR spectral editing techniques clearly identified specific functional groups such as CCH₃, CCH₂, and CCH₂ (exomethylene). ¹H¹³C wideline separation (WISE) NMR helped identify mobile and non-protonated alkyl carbons. FT-ICR-MS indicated that ∼64% of calculated formulae generated by ESI were aliphatic, while only about 0.8–2.5% of formulae contained possible aromatic rings. All of the assigned formulae contained at least one heteroatom (N, O or S), indicating that ionization by ESI was selective for the polar fraction of gilsonite and potentially less reflective of the overall chemical character of gilsonite than NMR spectroscopy. By combining the information obtained from advanced NMR and ultrahigh resolution MS we propose a structural model for gilsonite as a mixture of many pyrrolic and a few fused aromatic rings highly substituted with and connected by mobile aliphatic chains.     

Composition of olivine,silica activity and oxygen fugacity in kimberlite

Two generations of primary olivine are present in kimberlite, rounded phenocrysts (Fo₉₄Fo₉₁) and euhedral groundmass olivines (Fo₉₁Fo_88-5). Rounded phenocrysts less magnesian than Fo₈₈ are considered to be mantle derived xenocrysts; such crystals comprise up to 40% of the phenocrysts material in kimberlite. Calculated silica activity ranges from 10^?1,5 at 1200 °C, 50 kbs, to between 10^?1,6 and 10^?2.4 at 600 °C, 0.5–1.0 kb. Silica buffers involving olivines, pyroxenes and garnet are considered. Oxygen fugacities on the order of 10^?20 bars indicate that kimberlite magmas are highly reduced at the time of groundmass formation.     

Geochemistry and isotope chemistry of Michigan Basin brines: Devonian formations

Detailed chemical and isotope analysis of 87 formation waters collected from six Devonian-aged units in the Michigan Basin are presented and discussed in terms of the origin of the dissolved components and the water. Total dissolved solids in these waters range from 200,000 to >400,000mg/1. Upper Devonian formations produce dominantly NaCaCl brine, while deeper formations produce CaNaCl water. Ratios of Cl/Br and Na/Br along with divalent cation content (MCl₂), indicate that these brines are derived from evapo-concentrated seawater. Other ion concentrations appear to be extensively modified from seawater values by water-rock reactions. The most important reactions are dolomitization, which explains the Ca content of the brines, and reactions involving aluminosilicate minerals. Stable isotope (δ¹⁸O and δD) compositions indicate that water molecules in the deeper formations are derived from primary concentrated seawater. Isotope enrichment by exchange with carbonates and perhaps gypsum cannot be discounted. Isotope values indicate water in the Upper Devonian formations is a mixture of seawater brine diluted with meteoric-derived water. Dilution has predominantly occurred in basin margins. Two scenarios are presented for the origin of the brines in the Devonian formations: (1) they originated when the Devonian sediments and evaporites were first deposited; or (2) they are residual brine liberated from the deeper Devonian and possibly Silurian salt deposits.