Trace element compositions of pyrite and stibnite:implications for the genesis of antimony mineralization in the Yangla Cu skarn deposit,Northwestern Yunnan,China

The Yangla Cu skarn deposit is located in the central part of the Jinshajiang Suture Zone,southwest China,with a total reserve of 150 Mt Cu@1.03%.The newly discovered antimony orebodies at the depth of Yangla are strictly controlled by the stratum,structure,and lithology,which are lenticular and vein-like within the marble fracture zone,which can provide a window into multistage miner-alization and ore genesis at Yangla.Mineralization can be divided into three types,Cu–Pb–Zn(skarn)pyrite,galena,and sphalerite,Cu(porphyry)chalcopyrite and pyrite,and Sb(hydrothermal)stibnite and pyrite.The mineral assem-blages were stibnite+pyrite+calcite+quartz±minor scheelite in antimony ores.This study presents quantitative measurements of the trace element compositions of pyrite and stibnite from the Yangla antimony ores.Analysis of pyrite with electron probe microanalysis(EPMA)showed enrichment in Co,Ni,Sb,As,and Mo,and deficit in its S and Fe contents when compared to the stoichiometric con-centrations of S and Fe in pyrite.The Sb-related pyrite may belong to sedimentary-reworked genesis and may be modi-fied by hydrothermalfluids,thereby presenting a certain dif-ference(i.e.,crystal morphology,texture,and chemical com-position)compared to the skarn and porphyry Cu-related pyrite in the Yangla Cu skarn deposit.Analysis of stibnite with EPMA and inductively coupled plasma-mass spectrom-etry showed enrichment in As,Pb,Sn,Pb,Cu,and Zn,and presented much higher Sb contents and slightly lower S con-tents when compared to the stoichiometric concentrations of Sb and S in stibnite.Statistical analysis of the stibnite trace elements showed correlations for the elemental pairs Cu–Pb,As–Sb,and Sn–Pb,and the coupled substitution equations Sb^(3+)↔Cu^(+)+Pb^(2+),Sb^(3+)↔As^(3+),and Sn^(2+)↔Pb^(2+)may be the major factors governed the incorporating Cu,Pb,As and Sn within the stibnite.Moreover,this study preliminary shows that the antimony mineralization may belong to a car-bonate replacement hydrothermal genesis at Yangla.

The Yanshanian Granites and Associated Mo-Polymetallic Mineralization in the Xiangcheng-Luoji Area of the Sanjiang-Yangtze Conjunction Zone in Southwest China

The Xiangcheng-Luoji area is located in the conjunction of the southern part of the ＂Sanjiang＂ mineralization belt and the west margin of Yangtze craton. The geological studies were carried out to know the Indosinian large porphyry Cu polymetallic deposits. Recent studies revealed that the area existed in the superposition of Late Yanshanian acidic intrusive rock belt and developed Mo-Cu polymetallic mineralization where promising exploration results have been achieved. Through the systematic study of geochronology, formation age of the Renlin Mo-minieralization monzogranite is 81.7±1.1 Ma. Re-Os dating results concentrate on 82.34±1.2–88.27±1.23 Ma for the model ages of molbdenite of Tongchanggou Mo deposits, average age is 85 ± 2 Ma where seven data points constitute a good isochron which shows that they were the same period products of mineralization. Geochemical features shown that the rocks have a high content of SiO 2（66.59–77.36wt%）, alkaline-rich（K2O=2.68–6.08wt%; Na2O=0.50–4.91wt%; K2O/Na2 O ratios are 0.71–5.56, where average ratio of 1.89） and have aluminum–rich features（Al2O3 10.38–15.15wt%） with σ values less than 3.3. Which indicate that they belong to the high-K calc-alkali to shoshonite series. Geochemistry of Yanshanian intrusions shows that rocks are enrich in LREE with obvious negative δEu anomalies, enrichment of trace elements like, LILE elements（Rb, Th, Ba） with a relative loss of Ba, and loss of high field strength elements（Nb, Ta, P, Ti） and HREE elements. The granite genetic classification diagram shows that the granites belong to A-type granite and formatted in syn-collision tectonic environment. Meanwhile, the Yanshanian granites also inherited the characteristics of island arc environment which formed in the process of crustal melting caused by upwelling of asthenospheric substances in the extensional tectonic background. The process of partial melting existed substances from the deep（lower crust or upper mantle） which have been added. In the Xiangcheng-Luoji area, monzogranite and granodiorite porphyry bodies are widely developed Mo polymetallic mineralization, the deep porphyry mineralization have great potential for geological prospecting.

Re–Os Dating of Bitumen from Paleo–Oil Reservoir in the Qinglong Antimony Deposit, Guizhou Province, China and Its Geological Significance

Abundant organic inclusions are present in the Qinglong antimony deposit. However, the source rocks of these organic matters have not been reliably identified. Recently, a paleo--oil reservoir was found in the Qinglong antimony deposit. In view of similar components of gaseous hydrocarbon, we propose that the organic matters observed in inclusions in Qinglong antimony deposit would come from this paleo-oil reservoir. We used the Re-Os dating method to determine the age of the bitumen from this paleo-oil reservoir, and obtained an isochron age of 254.3~2.8 Ma. The age indicates that the oil- generation from source rock occurred in the early Late Permian, earlier than the Sb mineralization age （-148~8.5 Ma） in the Qinglong antimony deposit area. After oil generation from Devonian source rock, first and secondary migration, the crude oil have probably entered into the fractures and pores of volcanic rocks and limestone and formed a paleo-oil reservoir in the western wing of Dachang anticline. As burial process deepened, the crude oil has turned into natural gas, migrates into the core of Dachang anticline and formed a paleo-gas reservoir. The hydrocarbons （including CH4） in the reservoirs can serve as reducing agent to provide the sulfur required for Sb mineralization through thermal chemical reduction of sulfates. Therefore, the formation of oil-gas in the area is a prerequisite for the Sb mineralization in the Qinglong antimony deposit.

Selective depression action of taurine in flotation separation of specularite and chlorite

Chlorite,as the most representative gangue mineral associated with specularite,of which the separation of these two minerals is difficult.This paper investigated the depression effect of taurine on specularite/chlorite separation via flotation experiments,adsorption tests,contact angle measurements,Zeta potential detection,FT-IR measurements,and XPS analyses.The results of single mineral flotation indicated that chlorite could be depressed selectively by taurine with the recovery of less than 30%,but the floatability of specularite remains high with recovery rate of 81.77%at pH 10.The artificial mixed mineral flotation results confirmed the effectiveness of taurine as a depressant.Surface adsorption,contact angle,and Zeta potential detection revealed taurine primarily adsorbs on the chlorite surface,which hampered the DDA’s subsequent adsorption and results in the chlorite’s poor floatability.The FT-IR spectra and XPS analyses provided further proof that taurine adsorbed on chlorite surface as an electron donor,and part of the electrons transferred from the sulfonic acid group of taurine to metal ions during the adsorption process.In addition,the hydrogen bond between amino-group of taurine and O ions in chlorite surface was also formed in the adsorption process.Finally,optimized adsorption configurations of taurine on chlorite surfaces were proposed.

Petrogenesis and Tectonic Significance of the Xiuwacu Two-Period Magmatism in Geza Arc of Yunnan Province： Constraints from Lithogeochemistry, Zircon U-Pb Geochronology and Hf isotopic Compositions

Objective The Late Cretaceous Xiuwacu ore-bearing porphyry is located in the Geza area of southern Yidun arc, SW China. In this area, the rock mass is mainly composed of three lithofacies： biotite granite porphyry, monzonitic granite and light alkali feldspar granite. As a part of the Yidun arc, the Geza arc has common structure and temporal- spatial evolution with the ~idun arc, which has experienced three stages of oceanic crust subduction, collision orogeny and intracontinent convergence stages. The molybdenite ores in the area are mainly hosted in monzonitic granite-porphyry and structural fracture zone, and the ore bodies are strictly controlled by faults. In recent years, great geological prospecting results have been achieved in Xiuwacu, and the deposit has reached a medium scale. However, there are few researches on the metallogenic porphyry. Based on the previous research, we determined the rock-forming and ore-forming age of the porphyry, and found that there were two stages of magmatism intrusion in Xiuwacu： Indosinian and Yanshanian. We also discussed the geochemical characteristics and source area of the rocks in the area.

Petrogenesis of the Langdu High-K Calc-Alkaline Intrusions in Yunnan Province: Constraints from Geochemistry and Sr-Nd Isotopes

The Langdu high-K calc-alkaline intrusions are located in the Zhongdian area, which is the southern part of the Yidun island arc. These intrusive rocks consist mainly of monzonite porphyry, granodiorite, and diorite porphyry. The K20 content of majority of these rocks is greater than 3%, and, in the K20-SiO2 diagram, all the samples fall into the high-K calc-alkaline to shoshonitic fields. They are enriched in light rare earth elements （LREEs） and depleted in heavy rare earth elements （HREEs; LaN/YbN = 14.3-21.2）, and show slightly negative Eu anomalies （6Eu = 0.77-1.00）. These rocks have high K, Rb, Sr, and Ba contents; moderate to high enrichment of compatible elements （Cr = 36.7-79.9 ppm, Co = 9.6-16.4 ppm, and MgO = 2.2%-3.4%）; low Nb, Ta, and Ti contents, and characteristic of low high field strength elements（HFSEs） versus incompatible elements ratios （Nb/Th = 0.75, Nb/La = 0.34） and incompatible elements ratios （Nb/U = 3.0 and Ce/Pb = 5.1, Ba/Rb = 12.0）. These rocks exhibit restricted Sr and Nd isotopic compositions, with （87Sr/S6Sr）i values ranging from 0.7044 to 0.7069 and ENd（t） values from -2.8 to -2.2. The Sr-Nd isotope systematic and specific trace element ratios suggest that Langdu high-K calc-alkaline intrusive rocks derived from a metasomatized mantle source. The unique geochemical feature of intrusive rocks can be modeled successfully using different members of a slightly enriched mantle, a slab-derived fluid, and terrigenous sediments. It can be inferred that the degree of partial melting and the presence of specific components are temporally related to the tectonic evolution of the Zhongdian island arc. Formation of these rocks can be explained by the various degrees of melting within an ascending region of the slightly enriched mantle, triggered by the subduction of the Garz^--Litang ocean, and an interaction between the slab-derived fluid and the terrigenous sediments.

The Late Cretaceous Crustal Magmatism of the Geza Arc Metallogenic Belt in Yunnan Province,and Zircon Ages and Hf Isotopic Evidence of the Porphyry Cu-Mo Mineralization

Objective The Geza arc in Yunnan Province,located in the southern Yidun arc,is an important part of the Sanjiang tectonic-magmatic belts in southwestern China and is a newly discovered copper polymetallic ore-concentrating district.Recent studies show that the newly discovered Yanshanian porphyry Cu-Mo polymetallic mineralization superimposed in the Indosinian porphyry copper belt in this area.

Silver sulfide leaching with a copper-thiosulfate solution in the absence of ammonia

Leaching from silver sulfide.using a copper-thiosulfate solution in the absence of ammonia was investigated. It is found that silver sulfide could be effectively dissolved in the copper-thiosulfate system without ammonia. The effects of thiosulfate concentration, cop- per-to-thiosulfate ratio, agitation vigorousness, pH values, and dissolved gases on the leaching of silver sulfide with the copper-thiosulfate solution were studied. A maximum extraction of 95.1% was achieved with the 0.12 mol/L thiosulfate and the 0.048 rnol/L copper sulfate. It is shown that copper-to-thiosulfate ratio is an important factor in silver sulfide dissolution and oxygen is not needed to leach silver sulfide, which leads to the instability of the leaching system at high copper-to-thiosulfate ratio. On the other hand, the silver extraction is not affected by the pulp pH values.

Chemical compositions of sulfides in the porphyry Cu ores,Yangla Cu deposit,Yunnan,China:implication for ore genesis

The Yangla Cu deposit is the largest ore deposit in the Jinshajiang polymetallic metallogenic belt,northwest Yunnan,China.There is no consensus on the genesis of the ore deposit owing to the limited studies on the chemical compositions of sulfides.This study used an electron probe micro-analyzer to constrain the chemical compositions of pyrite,chalcopyrite,molybdenite,and sphalerite in the porphyry Cu ore of the Yangla Cu deposit and compared them with the chemical compositions of sulfides in the skarn Cu ore.The trace element contents and their occurrences were used to estimate the metallogenic temperature and infer the genesis of the Yangla deposit.The results show that the sulfides in the porphyry Cu ores have variations of ore element concentrations relative to their theoretical values.Pyrite is depleted in S but elevated in Fe;chalcopyrite is depleted in Cu,Fe,and S;and molybdenite and sphalerite are enriched in S whilst depleted in Mo and Zn.The concentrations of the main metallogenic elements Cu,Fe,Mo,Zn,and S in the porphyry are generally lower than those in skarn,suggesting that the porphyry ore was formed in a moderate to moderate-high temperature metallogenic environment.The formation time may also be slightly later than that of the skarn Cu ore.Elements such as As,Co,Cu.Pb,Zn,Mo,Cd,and Ni mainly exist as isomorphic replacements and mineral inclusions in the sulfides of both porphyry and skarn Cu ores.The trace element features of sulfides in the two ore bodies show that the Yangla Cu deposit may be a composite super imposed ore deposit,and让s formation has undergone the process of exhalative-sedimentary to skarnporphyry mineralization.

Zircon U-Pb Ages of the Muchang Alkali Granites in Zhenkang Block, Western Yunnan: Implication for the Time Limit on Tectono-Magmatic Activities

Objective The Luziyuan super-large Pb-Zn-Fe polymetallic ore district is located in the southern section of the Baoshan-Zhenkang block,which is an important part of the Pb-Zn-Cu-Fe-Sn-Au polymetallic metallogenic belt,SW China.

Utilization of DTAB as a collector for the reverse flotation separation of quartz from fluorapatite

Reverse flotation desilication is an indispensable step for obtaining high-grade fluorapatite. In this work, dodecyltrimethylammoni- um bromide (DTAB) is recommended as an efficient collector for the reverse flotation separation of quartz from fluorapatite. Its collectivity for quartz and selectivity for fluorapatite were also compared with figures corresponding to the conventional collector dodecylamine hydrochlor- ide (DAC) via microflotation experiments. The adsorption behaviors of DTAB and DAC on minerals were systematically investigated with surface chemical analyses, such as contact angle determination, zeta potential detection, and adsorption density measurement. The results re- vealed that compared to DAC, DTAB displayed a similar and strong collectivity for quartz, and it showed a better selectivity (or worse col- lectivity) for fluorapatite, resulting in a high-efficiency separation of the two minerals. The surface chemical analysis results showed that the adsorption ability of DTAB on the quartz surface was as strong as that of DAC, whereas the adsorption amount of DTAB on the fluorapatite surface was much lower than that of DAC, which is associated with the flotation performance. During the floatation separation of the actual ore, 8wt% fluorapatite with a higher grade can be obtained using DTAB in contrast to DAC. Therefore, DTAB is a promising collector for the high-efficiency purification and sustainable utilization of valuable fluorapatite recourses.

Carbon–oxygen isotopic covariations of calcite from Langdu skarn copper deposit, China: implications for sulfide precipitation

The Langdu skarn copper deposit in the Zhongdian area, Yunnan Province, China, has an average Cu grade of 6.49 %. The deposit is related to a porphyry intrusion(*216 Ma), which was emplaced in the Upper Triassic sedimentary rocks of the Tumugou and Qugasi Formations.At the Langdu skarn copper deposit, carbon and oxygen isotope ratios of fresh limestones(d18O = 3.0–5.6 % relative to V-SMOW; d13 C = 24.5–25.7 % relative to PDB)and partly altered limestones(d18O = 27–7.2 to-1.9 %;d13C = 11.8–15.2 %) indicated that the deposit was a typical marine carbonate source. Oxygen and carbon isotope values for calcites formed at different hydrothermal stages are-9.1 to 0.2 and 10.1–16.3 %, respectively. Moreover,the carbon–oxygen isotopic composition of an ore-forming fluid(d18O = 5.0–9.5 %, d13 C =-7.3 to-5.3 %) suggested the presence of magmatic water, which most likely came from the differentiation or melting of a homologous magma chamber. The deposition of Calcite I may arise from metasomatism in an open system with a progressively decreasing temperature.Later, the minerals chalcopyrite, pyrrhotite, quartz and Calcite II were precipitated due to immiscibility. Water–rock interaction could potentially be responsible for Calcite III precipitation in the post-ore stage.

Slime coating of kaolinite on chalcopyrite in saline water flotation

In saline water flotation, the salinity can cause a distinguishable slime coating of clay minerals on chalcopyrite particles through its effect on their electrical double layers in aqueous solutions. In this work, kaolinite was used as a representative clay mineral for studying slime coating during chalcopyrite flotation. The flotation of chalcopyrite in the presence and absence of kaolinite in tap water, seawater, and gypsum-saturated water and the stability of chalcopyrite and kaolinite particles in slurries are presented. Zeta-potential distributions and scanning electron microscopy images were used to characterize and explain the different slime coating degrees and the different flotation performances. Kaolinite particles induced slime coating on chalcopyrite surfaces and reduced chalcopyrite floatability to the greatest extent when the p H value was in the alkaline range. At 0.24 wt% of kaolinite, the chalcopyrite floatability was depressed by more than 10% at alkaline p H levels in tap water. Salinity in seawater and gypsum-saturated water compressed the electrical double layers and resulted in extensive slime coating.

Improved flotation performance of hematite fines using citric acid as a dispersant

In this study, citric acid was used as a dispersant to improve the flotation performance of hematite fines. The effect and mechanism of citric acid on the reverse flotation of hematite fines were investigated by flotation tests, sedimentation experiments, scanning electron microscopy（SEM）, zeta-potential measurements, and X-ray photoelectron spectroscopy（XPS）. The results of SEM analysis and flotation tests reveal that a strong heterocoagulation in the form of slime coating or coagulation in hematite fine slurry affects the beneficiation of hematite ores by froth flotation. The addition of a small amount of citric acid（less than 300 g/t） favorably affects the reverse flotation of hematite fines by improving particle dispersion. The results of sedimentation experiments, zeta-potential measurements, and XPS measurements demonstrate that citric acid adsorbs onto hematite and quartz surfaces via hydrogen bonding, thereby reducing the zeta potentials of mineral surfaces, strengthening the electrical double-layer repulsion between mineral particles, and dispersing the pulp particles.

Applicability of large-ion lithophile and high field strength element basalt discrimination diagrams

Basalt discriminant diagrams have been used to identify the tectonic setting of basaltic magmatism since the 1970s and have played an important role in reconstructing paleotectonic environments.However,the significant increase in the availability of geochemical data has led to a reassessment of these diagrams,suggesting that some of the tectonic settings indicated by these diagrams are not accurate.Here,we use a database of global ocean island basalt(OIB),mid-ocean ridge basalt(MORB),and island arc basalt(IAB)geochemistry to propose a series of new tectonic discriminant diagrams based on the ratios of large-ion lithophile elements(LILEs)to high field strength elements(HFSEs).These new diagrams indicate that the LILE can be used to differentiate OIB,MORB,and IAB samples,meaning that LILE/HFSE ratios can discriminate between these basalts that form in different tectonic settings.Our new diagrams can correctly assign samples to OIB,MORB,and IAB categories more than 85%of the time,with the discrimination between OIB and MORB having an accuracy of slightly less than 85%.

Role of oxygen and ammonium ions in silver leaching with thiosulfate–ammonia–cupric ions

The dissolution of silver with thiosulfate and copper ions was studied in a batch-stirred reactor at 25 °C in the absence and presence of various ammonium ions and oxygen concentrations in the aqueous solution. Leaching silver with 4 mg L-1oxygen in the aqueous solution requires high concentration of ammonium and thiosulfate ions. High silver dissolution is achieved at pH of high cupric tetraamine concentration, around pH 9.8, but a high degradation of thiosulfate ions is resulted from their oxidation by the presence of oxygen. When the oxygen concentration is below 1 mg L-1, dissolved silver thiosulfate species are fairly stable and the degradation of thiosulfate ions in the aqueous solution is low. Under these conditions,high silver dissolution is attained using low thiosulfate concentration. At the oxygen concentration of 4 mg L-1,dissolved silver thiosulfate species precipitate out of the aqueous solution significantly affecting silver dissolution.Precipitation of dissolved silver thiosulfate species occurs because of oxidation of the thiosulfate bonding to the silver.

Comparative study of big data of global adakites and mineralization-related granite in the Geza arc metallogenic belt, northwest Yunnan, Southwest China

The Geza arc is an important part of the Sanjiang tectono-magmatic belt and is a newly discovered copper polymetallic ore concentration area in northwest Yunnan province,Southwest China.The area comprises numerous metal ore deposits,including one super-largedeposit,three large deposits,etc.The formation of these deposits was closely related to intermediate–acidic magmatic intrusions.Based on previous studies,the“big data”analysis technique was used for a comparative study of large geochemical datasets of granite related to ore-formation in the Geza porphyry copper deposit and global adakites.As a result,1313 element combinations and 127,765 overlap ratios were obtained.The results show that the Geza porphyry has similar geochemical characteristics to global adakites(the ratios of REE and Ga to major elements are in the range of global adakites).However,theCu,Mo,and Zn contents of the porphyry are significantly higher than those of global adakites,and the porphyry may,therefore,represent an end-member of the global range of adakite composition.In addition,the geochemistry of adakites associated with the porphyry copper deposits overlaps in part with that of global adakites,although most of the data lie outside of the range of global adakites(i.e.lowMn/Cu,Sr/Cu,Na/Cu,and Zr/Cu values,and high Th/Cu,Ba/Cu,Na/Mo,Rb/Mo,Th/Mo,Ta/Mo,Ba/Mo,Mn/Zn,and Ba/Znvalues).The samples with characteristics that deviate significantly from the geochemistry of global adakites show more advanced mineralization and alteration,and a stronger relationship with Cu and Momineralization.The results of geochemical data mining can be used as a prospecting indicator,and provide a new scientific basis for geological prospecting of the deep levels and per-iphery of the Geza Cu polymetallic ore belt.

Collectorless flotation of marmatite with pine oil

The interaction between pine oil and marmatite without collectors and activators was investigated by flotation,scanning electron microscope and energy-dispersive spectrometer（SEM-EDS）,infrared（IR） spectroscopy,Zeta potential,and first-principle theory calculations.The flotation results show that marmatite exhibits considerable floatability with the addition of pine oil.SEM-EDS results show that carbon atomic ratios on the surface are significantly high,which suggests that the flotation of marmatite is caused by the adsorption of pine oil.Further evidence of the adsorption mechanism was given by IR,and Zeta potential examining pine oil depends on the physical adsorption on the surface independently.The first-principle theory calculations indicate that pine oil molecule adsorbs on Zn and Fe atom surfaces by ionic bond and covalent bond of adsorption energies of-1.23and-1.51 eV,respectively.P orbital of O atom,s orbital of Zn atom,and d orbital of Fe are the major participants.

Big data:new methods and ideas in geological scientific research

Big data research is a developing field that is bringing change to people’s lives.Big data is an inevitable outcome of the development of science:scientific research has resulted in the accumulation of a large amount of data and conventional methods cannot handle such massive amounts of data.Therefore,alternatives such as big data,cloud computing,artificial intelligence,and blockchain have emerged.