Advanced oxidation of catechol in reverse osmosis concentrate generated in leather wastewater by Cu–graphite electrode

Reverse osmosis (RO) concentrate generated from tannery was treated by advanced electrochemical oxidation using graphite electrodes. Catechol was selected as model organic pollutant in the RO concentrate. The influence of applied current density, catechol concentration, pH, temperature and inner electrode space of electrodes was investigated in electrochemical oxidation system. The optimized conditions were found to be current density (j), 100 mA/cm²; electrolysis time (t _eco), 60 min; pH, 7.0; and temperature, 25 °C at an inner electrode space, 2 cm. The average mass transport coefficient for the removal of catechol as COD was found to be 3.0 × 10^?5 m/s at optimum conditions. Faradic efficiency and specific energy consumption were also calculated for the applied current density. Further, the treatment of catechol was confirmed through Fourier transform infrared spectroscopy. Theoretical evaluation of current density suggested that the removal of catechol was controlled when supplied at above limiting applied current densities and mass transport controlled at lower of limiting current densities.     

Metamorphism,graphite crystallinity,and sulfide anatexis of the Rampura–Agucha massive sulfide deposit,northwestern India

Located adjacent to the Banded Gneissic Complex, Rampura–Agucha is the only sulfide ore deposit discovered to date within the Precambrian basement gneisses of Rajasthan. The massive Zn–(Pb) sulfide orebody occurs within graphite–biotite–sillimanite schist along with garnet–biotite–sillimanite gneiss, calc–silicate gneisses, amphibolites, and garnet-bearing leucosomes. Plagioclase–hornblende thermometry in amphibolites yielded a peak metamorphic temperature of 720–780°C, whereas temperatures obtained from Fe–Mg exchange between garnet and biotite (580–610°C) in the pelites correspond to postpeak resetting. Thermodynamic considerations of pertinent silicate equilibria, coupled with sphalerite geobarometry, furnished part of a clockwise P–T–t path with peak P–T of ∼6.2 kbar and 780°C, attained during granulite grade metamorphism of the major Zn-rich stratiform sedimentary exhalative deposits orebody and its host rocks. Arsenopyrite composition in the metamorphosed ore yielded a temperature [and log f(S ₂)] range of 352°C (−8.2) to 490°C (−4.64), thus indicating its retrograde nature. Contrary to earlier research on the retrogressed nature of graphite, Raman spectroscopic studies on graphite in the metamorphosed ore reveal variable degree of preservation of prograde graphite crystals (490 ± 43°C with a maximum at 593°C). The main orebody is mineralogically simple (sphalerite, pyrite, pyrrhotite, arsenopyrite, galena), deformed and metamorphosed while the Pb–Ag-rich sulfosalt-bearing veins and pods that are irregularly distributed within the hanging wall calc–silicate gneisses show no evidence of deformation and metamorphism. The sulfosalt minerals identified include freibergite, boulangerite, pyrargyrite, stephanite, diaphorite, Mn–jamesonite, Cu-free meneghinite, and semseyite; the last three are reported from Agucha for the first time. Stability relations of Cu-free meneghinite and semseyite in the Pb–Ag-rich ores constrain temperatures at >550°C and <300°C, respectively. Features such as (1) low galena–sphalerite interfacial angles, (2) presence of multiphase sulfide–sulfosalt inclusions, (3) microcracks filled with galena (±pyrargyrite) without any hydrothermal alteration, and (4) high contents of Zn, Ag (and Sb) in galena, indicate partial melting in the PbS–Fe_0.96S–ZnS–(1% Ag₂S ± CuFeS₂) system, which was critical for metamorphic remobilization of the Rampura–Agucha deposit.     

Kinetics of the graphite–diamond transformation in aqueous fluid determined by in-situ X-ray diffractions at high pressures and temperatures

The graphite-diamond transformation was investigated by in situ time-resolved X-ray diffraction experiments using aqueous fluid containing dissolved MgO as the diamond-forming catalyst under conditions of 6.6–8.9 GPa and 1400–1835 °C. The transformed volume fractions of diamond as a function of time under various pressure-temperature conditions were obtained and analyzed using the JMAK rate equation. Variations in the nucleation and growth processes during diamond formation as a function of pressure and temperature were clarified.     

HPLC separation of higher fullerenes in the synthetical “graphite smokes” soot

Higher fullerenes(C84,C90,C92,C94 and C96) were successfully isolated from the Soxhlet extract of the synthetical "Graphote Smokes" soot(GS sample) by using a big Cosmosil Buckysep(Phenomenex) column(250 mm × 10 mm) with a large injection.The fractions isolated have been determined by high performance liquid chro-matography(HPLC) and laser desorption mass spectrometry(LDMS).It is found that there are different fullerenes molecules in different fractions with retention time.The result indicates that fullerenes do exist in GS samples.Also,it excludes the suspicion to some extent that fullerene molecules might be generated by the laser desorption process in the LDMS.In addition,it also provides the experimental basis for the study of natural higher fullerenes and might be helpful to figure out the question if higher fullerenes do exist in the natural samples.     

Apatite recrystallisation during prograde metamorphism,Cooma, southeast Australia: implications for using an apatite – graphite association as a biotracer in ancient metasedimentary rocks

The major patterns in the evolution of life during the Phanerozoic are reviewed. Critical transitions in the evolution of life that reflect increases in ecological complexity are the Cambrian radiation; the Ordovician biodiversification and its subsequent diversification and transition into the Modern Marine Fauna following the Permo-Triassic mass extinction; the colonisation of land, and its subsequent diversification; and the biological colonisation of the atmosphere. This increase in ecological diversity and complexity was often accompanied by increases in morphological complexity, arising, in part, from elaboration of the developmental program. However, it was additionally fuelled by increases in diversification and disparity arising also from morphological simplification in some lineages as developmental program became reduced.     

Origin of epithermal Ag–Au–Cu–Pb–Zn mineralization in Guanajuato, Mexico

The Guanajuato epithermal district is one of the largest silver producers in Mexico. Mineralization occurs along three main vein systems trending dominantly northwest–southeast: the central Veta Madre, the La Luz system to the northwest, and the Sierra system to the east. Mineralization consists dominantly of silver sulfides and sulfosalts, base metal sulfides (mostly chalcopyrite, galena, sphalerite, and pyrite), and electrum. There is a broad zonation of metal distribution, with up to 10 % Cu+Pb+Zn in the deeper mines along the northern and central portions of the Veta Madre. Ore occurs in banded veins and breccias and as stockworks, with gangue composed dominantly of quartz and calcite. Host rocks are Mesozoic sedimentary and intrusive igneous rocks and Tertiary volcanic rocks. Most fluid inclusion homogenization temperatures are between 200 and 300 °C, with salinities below 4 wt.% NaCl equivalent. Fluid temperature and salinity decreased with time, from 290 to 240 °C and from 2.5 to 1.1 wt.% NaCl equivalent. Relatively constant fluid inclusion liquid-to-vapor ratios and a trend of decreasing salinity with decreasing temperature and with increasing time suggest dilution of the hydrothermal solutions. However, evidence of boiling (such as quartz and calcite textures and the presence of adularia) is noted along the Veta Madre, particularly at higher elevations. Fluid inclusion and mineralogical evidence for boiling of metal-bearing solutions is found in gold-rich portions of the eastern Sierra system; this part of the system is interpreted as the least eroded part of the district. Oxygen, carbon, and sulfur isotope analysis of host rocks, ore, and gangue minerals and fluid inclusion contents indicate a hydrothermal fluid, with an initial magmatic component that mixed over time with infiltrating meteoric water and underwent exchange with host rocks. Mineral deposition was a result of decreasing activities of sulfur and oxygen, decreasing temperature, increasing pH, and, in places, boiling.     

Origin of the Yinshan epithermal-porphyry Cu–Au–Pb–Zn–Ag deposit,southeastern China: insights from geochemistry,Sr–Nd and zircon U–Pb–Hf–O isotopes

The Yinshan deposit is a large epithermal-porphyry polymetallic deposit, and the timing and petrogenesis of ore-hosting porphyries have been hotly debated. We present new results from geochemical, whole-rock Sr–Nd and zircon U–Pb–Hf–O isotopic investigations. Zircon U–Pb data demonstrate that the quartz porphyry, dacitic porphyry, and quartz dioritic porphyry formed at ?172.2 ± 0.4 Ma, ?171.7 ± 0.5 Ma, and ?170.9 ± 0.3 Ma, respectively. Inherited zircon cores show significant age spreads from ?730 to ?1390 Ma. Geochemically, they are high-K calc-alkaline or shoshonitic rocks with arc-like trace element patterns. They have similar whole-rock Nd and zircon Hf isotopic compositions, yet an increasing trend in ?_Nd(t) and ?_Hf(t) values typifies the suite. Older (inherited) zircons of the three porphyries display Hf compositions comparable to those of the Jiangnan Orogen basement rocks. In situ zircon oxygen isotopic analyses reveal that they have similar oxygen isotopic compositions, which are close to those of mantle zircons. Moreover, a decreasing trend of δ¹⁸O values is present. We propose that the ore-related porphyries of the Yinshan deposit were emplaced contemporaneously and derived from partial melting of Neoproterozoic arc-derived mafic (or ultra-mafic) rocks. Modelling suggests that the quartz porphyries, dacitic porphyries, and quartz dioritic porphyries experienced ?25%, ?10%, and ?10% crustal contaminations by Shuangqiaoshan rocks. Our study provides important constraints on mantle–crust interaction in the genesis of polymetallic mineralization associated with Mesozoic magmatism in southeastern China.     

水泥–粉煤灰–煤渣–吹填粉细砂混合料强度试验

针对大型堆填场基层结构工程,本着就地取材节约成本的原则,利用吹填砂作为骨料,添加粉煤灰、煤渣和水泥,采用正交试验方法,编制正交设计表,配制不同比例的混合料进行无侧限抗压强度试验。采用方差对不同龄期的混合料抗压强度进行分析,并对混合料加固机理进行研究,给出了混合料最佳质量配比,即水泥20%,粉煤灰15%,煤渣10%,此时混合料的强度最大;其水泥掺量对混合料强度起着关键作用,随着龄期的增长粉煤灰与煤渣对混合料强度影响程度逐渐增强,不过煤渣对混合料初期强度影响不及粉煤灰。      

Formation of gold–silver sulfides and native gold in Fe–Ag–Au–S system

We carried out experiments on crystallization of Fe-containing melts FeS₂Ag_0.1–0.1xAu_0.1x (x = 0.05, 0.2, 0.4, and 0.8) with Ag/Au weight ratios from 10 to 0.1. Mixtures prepared from elements in corresponding proportions were heated in evacuated quartz ampoules to 1050 ºC and kept at this temperature for 12 h; then they were cooled to 150 ºC, annealed for 30 days, and cooled to room temperature. The solid-phase products were studied by optical and electron microscopy and X-ray spectroscopy. The crystallization products were mainly from iron sulfides: monoclinic pyrrhotite (Fe_0.47S_0.53 or Fe₇S₈) and pyrite (Fe_0.99S_2.01). Gold–silver sulfides (low-temperature modifications) are present in all synthesized samples. Depending on Ag/Au, the following sulfides are produced: acanthite (Ag/Au = 10), solid solutions Ag_2–xAu_xS (Ag/Au = 10, 2), uytenbogaardtite (Ag/Au = 2, 0.75), and petrovskaite (Ag/Au = 0.75, 0.12). They contain iron impurities (up to 3.3 wt.%). Xenomorphic micro- (<1–5 μm) and macrograins (5–50 μm) of Au–Ag sulfides are localized in pyrite or between the grains of pyrite and pyrrhotite. High-fineness gold was detected in the samples with initial ratio Ag/Au ≤ 2. It is present as fine and large rounded microinclusions or as intergrowths with Au–Ag sulfides in pyrite or, more seldom, at the boundary of pyrite and pyrrhotite grains. This gold contains up to 5.7 wt.% Fe. Based on the sample textures and phase relations, a sequence of their crystallization was determined. At ~1050 ºC, there are probably iron sulfide melt L₁ (Fe,S ? Ag,Au), gold–silver sulfide melt L₂ (Au,Ag,S ? Fe), and liquid sulfur L_S. On cooling, melt L₁ produces pyrrhotite; further cooling leads to the crystallization of high-fineness gold (macrograins from L₁ and micrograins from L₂) and Au–Ag sulfides (micrograins from L₁ and macrograins from L₂). Pyrite crystallizes after gold–silver sulfides by the peritectic reaction FeS + L_S = FeS₂ at ~743 ºC. Elemental sulfur is the last to crystallize. Gold–silver sulfides are stable and dominate over native gold and silver, especially in pyrite-containing ores with high Ag/Au ratios.     

Metallogeny of the northeastern Gangdese Pb–Zn–Ag–Fe–Mo–W polymetallic belt in the Lhasa terrane,southern Tibet

The northeastern Gangdese Pb–Zn–Ag–Fe–Mo–W polymetallic belt (NGPB), characterized by skarn and porphyry deposits, is one of the most important metallogenic belts in the Himalaya–Tibetan continental orogenic system. This belt extends for nearly four hundred kilometers along the Luobadui–Milashan Fault in the central Lhasa subterrane, and contains more than 10 large ore deposits with high potential for development. Three major types of mineralization system have been identified: skarn Fe systems, skarn/breccia Pb–Zn–Ag systems, and porphyry/skarn Mo–Cu–W systems. In this study, we conducted a whole-rock geochemical, U–Pb zircon geochronological, and in situ zircon Hf isotopic study of ore-forming rocks in the NGPB, specifically the Jiangga, Jiaduopule, and Rema skarn Fe deposits, and the Yaguila Pb–Zn–Ag deposit. Although some of these deposits (porphyry Mo systems) formed during the post-collisional stage (21–14 Ma), the majority (these three systems) developed during the main (‘soft collision’) stage of the India–Asia continental collision (65–50 Ma). The skarn Fe deposits are commonly associated with granodiorites, monzogranites, and granites, and formed between 65 and 50 Ma. The ore-forming intrusions of the Pb–Zn–Ag deposits are characterized by granite, quartz porphyry, and granite porphyry, which developed in the interval of 65–55 Ma. The ore-forming porphyries in the Sharang Mo deposit, formed at 53 Ma. The rocks from Fe deposits are metaluminous, and have relatively lower SiO₂, and higher CaO, MgO, FeO contents than the intrusions associated with Mo and Pb–Zn–Ag mineralization, while the Pb–Zn–Ag deposits are peraluminous, and have high SiO₂ and high total alkali concentrations. They all exhibit moderately fractionated REE patterns characterized by lower contents of heavy REE relative to light REE, and they are enriched in large-ion lithophile elements and relatively depleted in high-field-strength elements. Ore-forming granites from Fe deposits display ⁸⁷Sr/⁸⁶Sr_(i) = 0.7054–0.7074 and ε_Nd(t) = − 4.7 to + 1.3, whereas rocks from the Yaguila Pb–Zn–Ag deposit have ⁸⁷Sr/⁸⁶Sr_(i) = 0.7266–0.7281 and ε_Nd(t) = − 13.5 to − 13.3. In situ Lu–Hf isotopic analyses of zircons from Fe deposits show that ε_Hf(t) values range from − 7.3 to + 6.6, with T_DM(Hf)^C model ages of 712 to 1589 Ma, and Yaguila Pb–Zn–Ag deposit has ε_Hf(t) values from − 13.9 to − 1.3 with T_DM(Hf)^C model ages of 1216 to 2016 Ma. Combined with existing data from the Sharang Mo deposit, we conclude that the ore-forming intrusions associated with the skarn Fe and porphyry Mo deposits were derived from partial melting of metasomatized lithospheric mantle and rejuvenated lower crust beneath the central Lhasa subterrane, respectively. Melting of the ancient continental material was critical for the development of the Pb–Zn–Ag system. Therefore, it is likely that the source rocks play an important role in determining the metal endowment of intrusions formed during the initial stage of the India–Asia continental collision.     

LA–ICP–MS U–Pb定年技术相关问题探讨

LA–ICP–MS U–Pb定年技术是地质科学中被广泛应用的重要手段。发展至今，该技术已相对成熟，但在实际工作中仍需要注意一些关键问题。笔者就该技术的样品准备、定年结果的取舍、铅丢失问题、普通铅问题和定年结果投图与解释等5个方面进行简要探讨。研究认为，对于复杂矿物进行U–Pb定年研究建议不分选出单矿物，而是采用矿物识别定位手段和LA–ICP–MS仪器相结合的技术手段，直接在岩石光片或探针片上进行原地原位微区定年分析，但要注意样品准备过程中可能存在的铅污染问题。在碎屑矿物定年结果选择方面，对于大于1.5Ga的定年测点，笔者建议采用₂₀₇Pb/₂₀₆Pb年龄代表该颗粒的结晶年龄，而对于小于1.5 Ga的定年测点则应采用₂₀₆Pb/₂₃₈U年龄。对沉积岩最大沉积年龄的判断和选择主要依靠统计学方法，必要时需要结合地球化学数据和地质背景信息作为辅助判断依据。对于连续分布在谐和线上的年轻样品要提高警惕，需要采用谐和图、加权平均图、CL图像和元素含量等多种手段识别是否存在铅丢失不一致线。针对普通铅校正问题，笔者重...     

The Fe–C–O–H–N system at 6.3–7.8 GPa and 1200–1400 °C: implications for deep carbon and nitrogen cycles

Interactions in a Fe–C–O–H–N system that controls the mobility of siderophile nitrogen and carbon in the Fe⁰-saturated upper mantle are investigated in experiments at 6.3–7.8 GPa and 1200–1400 °C. The results show that the γ-Fe and metal melt phases equilibrated with the fluid in a system unsaturated with carbon and nitrogen are stable at 1300 °C. The interactions of Fe₃C with an N-rich fluid in a graphite-saturated system produce the ε-Fe₃N phase (space group P6₃/mmc or P6₃22) at subsolidus conditions of 1200–1300 °C, while N-rich melts form at 1400 °C. At IW- and MMO-buffered hydrogen fugacity (fH₂), fluids vary from NH₃- to H₂O-rich compositions (NH₃/N₂?>?1 in all cases) with relatively high contents of alkanes. The fluid derived from N-poor samples contains less H₂O and more carbon which mainly reside in oxygenated hydrocarbons, i.e., alcohols and esters at MMO-buffered fH₂ and carboxylic acids at unbuffered fH₂ conditions. In unbuffered conditions, N₂ is the principal nitrogen host (NH₃/N₂?≤?0.1) in the fluid equilibrated with the metal phase. Relatively C- and N-rich fluids in equilibrium with the metal phase (γ-Fe, melt, or Fe₃N) are stable at the upper mantle pressures and temperatures. According to our estimates, the metal/fluid partition coefficient of nitrogen is higher than that of carbon. Thus, nitrogen has a greater affinity for iron than carbon. The general inference is that reduced fluids can successfully transport volatiles from the metal-saturated mantle to metal-free shallow mantle domains. However, nitrogen has a higher affinity for iron and selectively accumulates in the metal phase, while highly mobile carbon resides in the fluid phase. This may be a controlling mechanism of the deep carbon and nitrogen cycles.     

Melting of Fe–Ni–Si and Fe–Ni–S alloys at megabar pressures: implications for the core–mantle boundary temperature

High pressure melting behavior of three Fe-alloys containing 5 wt% Ni and (1) 10 wt% Si, (2) 15 wt% Si or (3) 12 wt% S was investigated up to megabar pressures by in situ X-ray diffraction and laser-heated diamond anvil cell techniques. We observe a decrease in melting temperature with increasing Si content over the entire investigated pressure range. This trend is used to discuss the melting curve of pure Fe. Moreover, our measurements of eutectic melting in the Fe–Fe₃S system show a change in slope around 50 GPa concomitant with the fcc–hcp phase transition in pure solid iron. Extrapolations of our melting curve up to the core–mantle boundary pressure yield values of 3,600–3,750 K for the freezing temperature of plausible outer core compositions.     

Metallogenesis and ore-forming time of the Changtuxili Mn–Ag–Pb–Zn deposit in Inner Mongolia: Evidence from C–O–S isotopes and U–Pb geochronology

This paper reports new geochronological (U–Pb) and isotope (C, O, and S) data to investigate the timing of mineralization and mode of ore genesis for the recently discovered Changtuxili Mn–Ag–Pb–Zn deposit, located on the western slopes of the southern Great Hinggan Range in NE China. The mineralization is hosted by intermediate–acidic lavas and pyroclastic rocks of the Baiyingaolao Formation. Three stages of mineralization are identified: quartz–pyrite (Stage I), galena–sphalerite–tetrahedrite–rhodochrosite (Stage II), and quartz–pyrite (Stage III). δ¹³C and δ¹⁸O values for carbonate from the ore vary from −8.51‰ to −4.96‰ and 3.97‰ to 15.90‰, respectively, which are indicative of a low-temperature alteration environment. δ³⁴S_V-CDT values of sulfides range from −1.77‰ to 4.16‰ and show a trend of equilibrium fractionation (δ³⁴S_Py ​> ​δ³⁴S_Sp ​> ​δ³⁴S_Gn). These features indicate that pyrite, sphalerite, and galena precipitated during the period of mineralization. The alteration mineral assemblage and isotope data indicate that the weakly acidic to weakly alkaline ore-forming fluid was derived largely from meteoric water and the ore-forming elements C and S originated from magma. During the mineralization, a geochemical barrier was formed by changes in the pH of the ore-forming fluid, leading to the precipitation of rhodochrosite. On the basis of the mineralization characteristics, new isotope data, and comparison with adjacent deposits, we propose that the Changtuxili Mn–Ag–Pb–Zn deposit is an intermediate-to low-sulfidation epithermal deposit whose formation was controlled by fractures and variability in the pH of the ore-forming fluid. The surrounding volcanic rocks yield zircon U–Pb ages of 160−146 ​Ma (Late Jurassic), indicating that the mineralization is younger than 146 ​Ma.     

The molar volume of FeO–MgO–Fe2O3–Cr2O3–Al2O3–TiO2 spinels

We define and calibrate a new model of molar volume as a function of pressure, temperature, ordering state, and composition for spinels in the supersystem (Mg, Fe²⁺)(Al, Cr, Fe³⁺)₂O₄ ? (Mg, Fe²⁺)₂TiO₄. We use 832 X-ray and neutron diffraction measurements performed on spinels at ambient and in situ high-P, T conditions to calibrate end-member equations of state and an excess volume model for this system. The effect on molar volume of cation ordering over the octahedral and tetrahedral sites is captured with linear dependence on Mg²⁺, Al³⁺, and Fe³⁺ site occupancy terms. We allow standard-state volumes and coefficients of thermal expansion of the end members to vary within their uncertainties during extraction of the mixing properties, in order to achieve the best fit. Published equations of state of the various spinel end members are analyzed to obtain optimal values of the bulk modulus and its pressure derivative, for each explicit end member. For any spinel composition in the supersystem, the model molar volume is obtained by adding excess volume and cation order-dependent terms to a linear combination of the five end-member volumes, estimated at pressure and temperature using the high-T Vinet equation of state. The preferred model has a total of 9 excess volume and order-dependent parameters and fits nearly all experiments to within 0.02 J/bar/mol, or better than 0.5 % in volume. The model is compared to the current MELTS spinel model with a demonstration of the impact of the model difference on the estimated spinel-garnet lherzolite transition pressure.     

Nd–Sr–Hf–O isotope provinciality in the northernmost Arabian–Nubian Shield: implications for crustal evolution

Multi-isotope study including whole-rock Nd–Sr, single zircon Hf, and SIMS δ¹⁸O analyses of zircons sheds light on magma sources in the northernmost Arabian–Nubian Shield (ANS) during ~820–570 Ma. Reconnaissance initial Nd and Sr isotope data for the older rocks (~820–740 Ma) reaffirms previous estimates that early crustal evolution in this part of the shield involved some crustal contamination by pre-ANS material. Prominent isotope provinciality is displayed by post-collisional calc-alkaline and alkaline igneous rocks of ~635–570 Ma across a NW-SE transect across basement of the Sinai Peninsula (Egypt) and southern Israel. Silicic rocks of the NW-region are characterized by lower εNd(T)–εHf(T) and higher Sr_i and δ¹⁸O compared with rocks of the SE-region, and the transition between the regions is gradual. Within each region isotope ratios are independent of the extent of magma fractionation, and zircon cores and rims yield similar δ¹⁸O values. Comparison with southern segments of the ANS shows that the source for most ~635–570 Ma rocks can be modeled as the isotopically aged lower-intermediate crust in the ANS core (SE-region) and its northern, more contaminated ANS margins (NW-region). Nevertheless, Nd–Sr isotope enrichment of the lithospheric mantle is indicated by some basic magmas of the NW-region displaying the most enriched Nd–Sr isotope compositions. Comparison of Nd and Hf depleted mantle model ages for rocks of the SE-region may indicate that crustal formation events in the ANS geographical core took place at 1.1–1.2 Ga and were followed by crustal differentiation starting at ~0.9 Ga.     

The origin of the Dapingzhang volcanogenic Cu–Pb–Zn ore deposit,Yunnan province,SW China: Constraints from host rock geochemistry and ore Os–Pb–S–C–O–H isotopes

The Dapingzhang volcanogenic Cu–Pb–Zn sulfide deposit is located in the Lancangjiang tectonic zone within the Sanjiang region, Yunnan province of southwestern China. The deposit occurs within a felsic volcanic dome belonging to a mid-Silurian volcanic belt stretching for more than 100 km from Dapingzhang to Sandashan. The mineralized volcanic rocks are predominantly keratophyre and quartz keratophyre with subordinate spilite. The Dapingzhang deposit is characterized by well-developed vertical zonation with stockwork ores in the bottom, disseminated sulfide ores in the middle, and massive sulfide ores in the top, overlain by a thin layer of chemical sedimentary exhalative rocks (chert and barite). The Re–Os age of the pyrites from the deposit is 417 ± 23 Ma, indistinguishable from the age of the associated felsic volcanic rocks. The associated felsic volcanic rocks are characterized by negative Nb–Ta anomalies and positive ε_Nd(t) values (+ 4.4–+6.5), similar to the coeval calc-alkaline volcanic rocks in the region. This observation supports the interpretation that the felsic volcanic rocks associated with the Dapingzhang deposit are the derivatives of arc basaltic magma by extensive fractional crystallization. The δ³⁴S values of the sulfides from the deposit vary from − 1.24 to + 4.32‰, indicating a predominantly magmatic source for the sulfur. The sulfides are also characterized by homogeneous and relatively low radiogenic Pb isotope compositions (²⁰⁶Pb/²⁰⁴Pb = 18.310–18.656, ²⁰⁷Pb/²⁰⁴Pb = 15.489–15.643 and ²⁰⁸Pb/²⁰⁴Pb = 37.811–38.662), similar to the Pb isotopic compositions of the associated volcanic rocks. The Pb isotopic data indicate that mantle-derived Pb is more prevalent than crust-derived Pb in the deposit. The S–Pb isotopic data indicate that the important ore-forming materials were mainly derived from the associated volcanic rocks. The δ¹³C_PDB and δ¹⁸O_SMOW values of the associated hydrothermal calcite crystals vary from − 2.3‰ to + 0.27‰ and from + 14.6 to + 24.4‰, respectively. These values are between the mantle and marine carbonate values. The narrow range of the δ¹³C_PDB values for the calcite indicates that carbon-bearing species in the hydrothermal fluids were primarily derived from marine carbonates. The δ¹⁸O values for the hydrothermal fluids, calculated from the measured values for quartz, are between − 2.1‰ and + 3.5‰. The corresponding δD values for the fluids range from − 59‰ to − 84‰. The O–H isotopic data indicate mixing between magmatic fluids and seawater in the ore-forming hydrothermal system. Similar to a typical volcanogenic massive sulfide (VMS) deposit, the ore-forming fluids contained both magmatic fluids and heated seawater; the ore metals and regents were derived from the underlying magma as well as felsic country rocks.     

Multistage growth of Fe–Mg–carpholite and Fe–Mg–chloritoid,from field evidence to thermodynamic modelling

We provide new insights into the prograde evolution of HP/LT metasedimentary rocks on the basis of detailed petrologic examination, element-partitioning analysis, and thermodynamic modelling of well-preserved Fe–Mg–carpholite- and Fe–Mg–chloritoid-bearing rocks from the Afyon Zone (Anatolia). We document continuous and discontinuous compositional (ferromagnesian substitution) zoning of carpholite (overall X _Mg = 0.27–0.73) and chloritoid (overall X _Mg = 0.07–0.30), as well as clear equilibrium and disequilibrium (i.e., reaction-related) textures involving carpholite and chloritoid, which consistently account for the consistent enrichment in Mg of both minerals through time, and the progressive replacement of carpholite by chloritoid. Mg/Fe distribution coefficients calculated between carpholite and chloritoid vary widely within samples (2.2–20.0). Among this range, only values of 7–11 correlate with equilibrium textures, in agreement with data from the literature. Equilibrium phase diagrams for metapelitic compositions are calculated using a newly modified thermodynamic dataset, including most recent data for carpholite, chloritoid, chlorite, and white mica, as well as further refinements for Fe–carpholite, and both chloritoid end-members, as required to reproduce accurately petrologic observations (phase relations, experimental constraints, Mg/Fe partitioning). Modelling reveals that Mg/Fe partitioning between carpholite and chloritoid is greatly sensitive to temperature and calls for a future evaluation of possible use as a thermometer. In addition, calculations show significant effective bulk composition changes during prograde metamorphism due to the fractionation of chloritoid formed at the expense of carpholite. We retrieve P–T conditions for several carpholite and chloritoid growth stages (1) during prograde stages using unfractionated, bulk-rock XRF analyses, and (2) at peak conditions using compositions fractionated for chloritoid. The P–T paths reconstructed for the Kütahya and Afyon areas shed light on contrasting temperature conditions for these areas during prograde and peak stages.