In situ U-Pb dating and trace elements of magmatic rutile from Mujicun Cu-Mo deposit,North China Craton:Insights into porphyry mineralization

Porphyry Cu(Mo-Au)deposit is one of the most important types of copper deposit and usually formed under magmatic arc-related settings,whilst the Mujicun porphyry Cu-Mo deposit in North China Craton uncommonly generated within intra-continental settings.Although previous studies have focused on the age,origin and ore genesis of the Mujicun deposit,the ore-forming age,magma source and tectonic evolution remain controversial.Here,this study targeted rutile(TiO_(2))in the ore-hosting diorite porphyry from the Mujicun Cu-Mo deposit to conduct in situ U-Pb dating and trace element composition studies,with major views to determine the timing and magma evolution and to provide new insights into porphyry Cu-Mo metallogeny.Rutile trace element data show flat-like REE patterns characterized by relatively enrichment LREEs and depleted HREEs,which could be identified as magmatic rutile.Rutile U-Pb dating yields lower intercept ages of 139.3–138.4 Ma,interpreted as post magmatic cooling timing below about 500℃,which are consistent or slightly postdate with the published zircon U-Pb ages of diorite porphyry(144.1–141.7 Ma)and skarn(146.2 Ma;139.9 Ma)as well as the molybdenite Re-Os ages of molybdenum ores(144.8–140.0 Ma).Given that the overlap between the closure temperature of rutile U-Pb system and ore-forming temperature of the Mujicun deposit,this study suggests that the ore-forming ages of the Mujicun deposit can be constrained at 139.3–138.4 Ma,with temporal links to the late large-scale granitic magmatism at 138–126 Ma in the Taihang Orogen.Based on the Mg and Al contents in rutile,the magma of ore-hosting diorite porphyry was suggested to be derived from crust-mantle mixing components.In conjunction with previous studies in Taihang Orogen,this study proposes that the far-field effect and the rollback of the subducting Paleo-Pacific slab triggered lithospheric extension,asthenosphere upwelling,crust-mantle interaction and thermo-mechanical erosion,which jointly facilitated the formation of dioritic magmas during the Early Cretaceous.Subsequently,the dioritic magmas carrying crust-mantle mixing metallic materials were emplaced and precipitated at shallow positions along NNE-trending ore-controlling faults,eventually resulting in the formation of the Mujicun Cu-Mo deposit within an intracontinental extensional setting.

Radiological and X-Ray Diffraction Characterization of Bauxite and Rutile Ore Contaminated Environment in Kanam and Wase Mineral Exploration Sites, Plateau State-Nigeria

Two non-destructive analytical techniques (gamma spectrometer and X-ray diffractometer) were employed in the analysis of bauxite and rutile ore and their vicinity soil and control sourced within the Kanam and Wase mineral exploration sites. The activity concentrations of natural radionuclides 238U, 232Th, and 40K in the soil samples received from bauxite and rutile mineral mining vicinities revealed high concentrations of 238U, 232Th, and 40K compared to the control soil samples sourced 500 m away from the mineral exploration vicinities. Radiological detriments RLI, AUI, Hin and Hex unveiled values exceeding the radiation standard concentration (>1) for soil. X-ray diffraction characterization of bauxite ore revealed the interlocking minerals of Bauxite (18)%, Albite (11)%, Garnet (15)%, Illite (6)% and Muscovite (43)% in various proportions obtained within the 2θ range (9.18 to 64.4) and a peak value (intensity, cps) of 3400. Pure bauxite percentage in the ore meets metallurgical grade (15 - 25)%. X-ray diffraction of rutile ore revealed the minerals of rutile (40)%, quartz (21.4)%, ilmenite (27)% and garnet (11.8)% found within the 2θ range (27.5 to 35.6) and a peak value intensity of 31.1 - 100.0 cps also meeting the metallurgical grade of 15% - 25%. The major environmental concern associated with the mineral-sands industry is the radiation hazards, pollution of ground-water sources from heavy metals, mineral transport with heavy equipment’s, dredging operations in fragile coastal area and clearing of vegetation.

Identifying the effect of photo-generated carriers on the phonons in rutile TiO_(2) through Raman spectroscopy

Investigating lattice vibrations through Raman spectroscopy is a crucial method for studying crystalline materials.Carriers can interact with lattices and influence lattice vibrations;thus,it is feasible to study the effect of photo-generated carriers on phonons by analyzing changes in the Raman spectra of semiconductors.Rutile is one of the predominant crystalline phases of TiO_(2),which is a widely utilized metal oxide semiconductor.In this work,rutile TiO_(2) is coated on a thinned optical fiber to concentrate ultraviolet light energy within the material,thereby enhancing the generation of carriers and amplifying the changes in the Raman spectra.A Raman detection laser with a wavelength of 532 nm is utilized to collect the Raman spectra of rutile TiO_(2) during irradiation.Using this setup,the impact of photo-generated carriers on the phonons corresponding to Raman vibrational modes is researched.The localization and non-radiative recombination of photo-generated carriers contribute to a reduction in both the frequencies and lifetimes of phonons.This work provides a novel approach to researching the effect of carriers on phonons.

Time-resolved photoluminescence of anatase/rutile TiO_2 phase junction revealing charge separation dynamics

Junctions are an important structure that allows charge separation in solar cells and photocatalysts. Here, we studied the charge transfer at an anatase/rutile TiO2 phase junction using time-resolved photoluminescence spectroscopy. Visible （-S00 nm） and near-infrared （NIR, -830 nm） emissions were monitored to give insight into the photoinduced charges of anatase and rutile in the junction, respectively, New fast photoluminescence decay components appeared in the visible emission of futile-phase dominated TiO2 and in the NIR emission of many mixed phase TiO2samples. The fast decays confirmed that the charge separation occurred at the phase junction. The visible emission intensity from the mixed phase TiO2 increased, revealing that charge transfer from rutile to anatase was the main pathway. The charge separation slowed the microsecond time scale photolumines- cence decay rate for charge carriers in both anatase and rutile. However, the millisecond decay of the charge carriers in anatase TiO2 was accelerated, while there was almost no change in the charge carrier dynamics of rutile TiO2. Thus, charge separation at the anatase/rutile phase junction caused an increase in the charge carrier concentration on a microsecond time scale, because of slower electron-hole recombination. The enhanced photocatalytic activity previously observed at ana- tase/rutile phase junctions is likely caused by the improved charge carrier dynamics we report here. These findings may contribute to the development of improved photocatalytic materials.

Flotation Separating Rutile from Calcium and Silicon Gangue Minerals

Rutile separation from calcite, apatite and quartz by flotation was investigated. The results show that the rutile separation from calcium and silicon gangue minerals can be realized with alkyl-imino-bismethylene phosphoric acid (TF112) as a collector and sodium hexametaphosphate (SH) as a regulator.

Rutile to Titanite Transformation in Eclogites and its Geochemical Consequences:An Example from the Sumdo Eclogite,Tibet

The formation of titanite coronae after rutile is common in retrograde high-to ultrahigh-pressure meta-mafic rocks,which provides a good opportunity to address the geochemical behavior of HFSE in crustal environments.In the Sumdo eclogite,titanite occurs either as a corona around rutile grains or as semi-continuous veins cross-cutting the major foliation,whereas rutile grains occur either as inclusions in garnet or omphacite or as a relict core surrounded by titanite.Textural relationships and trace elements characteristics of rutile and titanite with different occurrences indicate that both minerals preferentially incorporate Nb and Hf over Ta and Zr in aqueous fluid.Moreover,the breakdown of omphacite and epidote could release substantial amounts of aqueous fluids enriched in Ca,Si,Fe and REE,which would react with rutile to form titanite coronae and veins.During this process,water-insoluble elements,like HFSE and HREE,behave like mobile elements,but they do not migrate substantially out of the system,instead,tending to react in situ.This suggests that the aqueous fluids released during the retrograde metamorphic reactions in mafic rocks could not substantially transfer fluidimmobile elements into the overlying mantle wedge in subduction environments.

The discovery of TiO_(2)-Ⅱ,the α-PbO_(2)-structured high-pressure polymorph of rutile,in the Suizhou L6 chondrite

We report the discovery of TiO_(2)-Ⅱ in the unmelted rock of the shocked Suizhou L6 chondrite.Natural TiO_(2)-Ⅱ was previously found in ultrahigh-pressure metamorphic and mantle-derived rocks,terrestrial impact structures,and tektite.Our microscopic,Raman spectroscopic,electron microprobe and transmission electron microscopic investigations have revealed:(1) All observed TiO_(2)-Ⅱ grains are related with ilmenite and pyrophanite;(2) TiO_(2)-Ⅱ occurs as needle-and leaf-shaped inclusions in llmenite and patch-,tape-shaped body in pyrophanite;(3)The composition of TiO_(2)-Ⅱ is identical with that of its precursor rutile;(4) The Raman spectrum of TiO_(2)-Ⅱ is in good agreement with that of natural and synthesized α-PbO_(2)-type TiO_(2);(5) TiO_(2)-Ⅱ occurs mainly in the form of well-ordered nano-domains and small mis-orientation among the domains can be observed.(6) All electron diffraction reflections from TiO_(2)-Ⅱ can be indexed to α-PbO_(2)structure in space group Pbcn with lattice parameters of a=4.481 ?,b=5.578 A and c=4.921 A;(7) The exsolution inclusions of rutile from host ilmenite are mostly connected with an alternation process along the lamellar twinning plane of ilmenite induced by shockinduced high pressure and high temperature;(8) The P-T regime of 20-25 GPa and 1000 ℃ estimated for the Suizhou unmelted rock is suitable for phase transition of rutile into TiO_(2)-Ⅱ phase.

Mineral cleavage nature and surface energy: Anisotropic surface broken bonds consideration

The population of surface broken bonds of some typical sulfide, oxide and salt-type minerals which may belong to cubic, tetragonal, hexagonal, or orthorhombic system, were calculated. In terms of the calculation results, the cleavage natures of these minerals were analyzed, and the relationship between surface broken bonds density and surface energy was also established. The results show that the surface broken bonds properties could be used to predict the cleavage nature of most of minerals, and the predicted cleavage planes agree well with those reported in previous literature. Moreover, this work explored a rule that, surface broken bonds density is directly related to surface energy with determination coefficient（R2） of over 0.8, indicating that the former is a dominant factor to determine the latter. Therefore, anisotropic surface broken bonds density can be used to predict the stability of mineral surface and the reactivity of surface atoms.

Fluidized-bed chlorination thermodynamics and kinetics of Kenya natural rutile ore

Natural rutile and gaseous chlorine with carbon as reductant were used to prepare titanium tetrachloride. Thermodynamics and kinetics of chlorination of Kenya natural rutile particles in a batch-type fluidized bed were studied at 1173-1273 K. Thermodynamic analysis of this system revealed that the equation of producing CO was dominant at high temperatures. Based on the gas-solid multi-phase reaction theory and a two-phase model for the fluidized bed, the mathematical description for the chlorination reaction of rutile was proposed. The reaction parameters and the average concentration of gaseous chlorine in the emulsion phase were estimated. The average concentration of emulsion phase in the range of fluidized bed was calculated as 0.3 mol/m^3. The results showed that the chlorination of natural rutile proceeded principally in the emulsion phase, and the reaction rate was mainly controlled by the surface reaction.

Synthesis of rutile from high titania slag by pyrometallurgical route

A new technique was developed for the conversion of high titania slag,containing 70%-75% TiO2 and with MgO,FeO,CaO,Al2O3 and SiO2 as main impurities,into a synthetic rutile,90%-95% TiO2,which satisfies the requirements for fluidizing chlorination process with respect to impurity contents.After a pre-oxidation at around 1 042 ℃ and a heat-treatment above 1 510 ℃,the Ti components in high titania slag can be enriched into the rutile phase which can precipitate and grow,and can be separated with dilute hydrochloric and sulfuric acid,respectively.The results show that the average crystal size of rutile phase is over 25 μm,and the synthetic rutile containing more than 95% TiO2 can be produced by selective leaching.

Bio-desilication of rutile concentrate and analysis of community structure in bio-desilication reactor

The original strain HY-7 was isolated from the bauxite mine drainage（BMD） taken from a reservoir in Sanmenxia Mine,Henan Province,China.The optimum temperature and pH for the growth of strain HY-7 were 30 ℃ and 7.0,respectively.The optimum UV radiating time was 20 s and the positive mutation rate was 23.0%.The growth curves show that strain HY-7 needs144 h to reach the stationary phase after its mutagenesis,which is 24 h earlier than that of the original strain.Sequence homology analysis indicated that this community consisted of mainly two branches：one sharing high homology with Paenibacillus stellifer and the other sharing high homology with Sporolactobacillus laevolacticus.The experimental results showed that the TiO2 grade of mtile concentrate increased from 78.21%to 91.80%and the recovery of TiO2 reached 95.24%after 7 d of bioleaching.The bio-desilication process can not only effectively improve the TiO2 grade of rutile concentrate but also meet the requirements of environmental protection.

Adsorption behavior and mechanism of Bi(Ⅲ) ions on rutile-water interface in the presence of nonyl hydroxamic acid

The adsorption behavior and mechanism of Bi（Ⅲ） ions on the rutile-water interface were investigated through micro-flotation, Zeta potential measurement, adsorption amount measurement and X-ray photoelectron spectroscopy（XPS）. According to the results of micro-flotation, Bi（Ⅲ） ions could largely improve the rutile flotation recovery（from 62% to 91%）, and they could increase the activating sites and reduce the competitive adsorption between nonyl hydroxamic acid negative ions and OH-ions, which determined that Bi（Ⅲ） ions were capable of activating rutile flotation. The adsorption of Bi（Ⅲ） ions onto the rutile surface led to the shift of Zeta potential into the positive direction, which was good for the adsorption of nonyl hydroxamic acid anions. In addition, the results of XPS indicated that the chemical environment around Ti atom had not changed before and after the adsorption of Bi（Ⅲ） ions. Based on the adsorption mechanism of Bi（Ⅲ） ions, it was deduced that firstly Bi（Ⅲ） ions occupied the vacancies of the original Ca^2＋, Mg^2＋ and Fe^2＋ ions on the rutile surface; secondly Bi（Ⅲ） ions covered on the rutile surface in the form of hydroxides.

水对甲醇在Rutile-TiO_2(110)-(1×1)表面光催化解离的影响(英文)

采用程序升温脱附方法研究了甲醇分子吸附在真空退火后的二氧化钛(110)表面的光催化过程,对比分析了单独吸附甲醇分子以及甲醇分子与水分子共吸附情况下的光催化解离过程.结果表明,在二氧化钛(110)表面吸附的甲醇分子对共吸附水分子的光催化解离过程并没有直接的帮助作用.共吸附状态下的水分子也同样没有影响到甲醇的光致解离过程,但是水分子的存在抑制了甲醇光解产物甲醛的光致脱附过程,同时促进了甲酸甲酯的形成.

Hydrophobic flocculation flotation of rutile fines in presence of styryl phosphonic acid

The hydrophobic flocculation flotation of rutile fines in the presence of styryl phosphonic acid（SPA） was investigated by flotation tests, zeta-potential measurement, optical microscope observation, laser-based particle size analysis, adsorption measurements and DLVO theory. The flotation tests indicated that rutile fines could be flocculated by SPA, and pH, shear force（stirring speed） and stirring time played significant roles in flocculation. The isoelectric point（IEP） and zeta-potential in whole range all moved to negative values as SPA was added according to the results from zeta-potential measurement. It was demonstrated that the primary reason for above was chemical adsorption. The laser-based particle size results showed the particle size at a stirring speed of 1800 r/min and 1000 mg/L SPA was the largest in all experiments. Furthermore, using the optical microscope observation and flotation tests, it was important for flotation of rutile fines to produce the flocculant. In the light of above-mentioned facts, floc flotation of rutile fines could be induced in the form of chemical adsorption by SPA to increase particle size. The data calculated from DLVO theory also indicated that chemical adsorption was the main reason for the formation of flocculant.

Nitrate-group-grafting-induced assembly of rutile TiO2 nanobundles for enhanced photocatalytic hydrogen evolution

In this study,an acid-induced assembly strategy for a rutile TiO2 photocatalyst was proposed on the basis of the treatment of lamellar protonated titanate with a concentrated HNO3 solution.Nitrate groups were successfully grafted onto a TiO2 surface and induced the assembly of rutile TiO2 nanorods into uniform spindle-like nanobundles.The resulting TiO2 product achieved a photocatalytic hydrogen evolution rate of 402.4μmol h^?1,which is 3.1 times higher than that of Degussa P25-TiO2.It was demonstrated that nitrate group grafting caused the rutile TiO2 surface to become negatively charged,which is favorable for trapping positive protons and improving charge carrier separation,thereby enhancing photocatalytic hydrogen production.Additionally,surface charges were crucial to structural stability based on electrostatic repulsion.This study not only developed a facile surface modification strategy for fabricating efficient H2 production photocatalysts but also identified an influence mechanism of inorganic acids different from that reported in the literature.

Adsorption mechanism of sodium oleate and styryl phosphonic acid on rutile and amphibole surfaces

A reagent combination of sodium oleate(NaOl)and salicyl hydroximic acid was employed as the roughing and scavenging collectors,whereas styryl phosphoric acid(SPA)and octanol were employed as the cleaning collectors.Results of bench-scale flotation demonstrate that the dosage of SPA can be reduced by about 80%,and that a better flotation index can be obtained using the proposed reagent system.The results of adsorption amount and contact angle measurements indicate that the rutile surface adsorbed not only a large amount of residual NaOl but also SPA and a small amount of NaOl remained on the amphibole surface in strong acidic solution.The hydrophobic difference between rutile and amphibole surfaces was therefore amplified in cleaning,and their further separation became much easier consequently.

Effect of rutile crystal shapes on its settlement

The effect of rutile crystal shapes on its settlement in a modified slag was studied by theoretical analysis,FactSage simulation,X-ray diffraction and scanning electron microscopy.The results show that the settling velocities of spherical rutile crystals are faster than those of other shapes of rutile crystals under the same volume conditions,and the shape transformation of rutile crystals from rod to sphere can be achieved by adding titanium slag to Ti-bearing blast furnace slag.The volume fractions of the rutile crystals in the upper and lower parts of the modified slag are 30%and 71%when the added titanium slag increases to 278 g,indicating that rutile settling is obvious.Due to the rutile settling,half shaker sorting task is saved,and the recovery rate of TiO2 is significantly increased.The TiO2 content of rutile is greater than 93%,and the total content of CaO and MgO is less than 0.4%,meeting the requirements for the raw materials of titanium white in the chloride process.

Depressing effect of sodium hexametaphosphate on apatite in flotation of rutile

The separation of rutile from apatite by flotation and the mechanism of depressing the apatite of sodium hexametaphosphate were studied. The results showed that rutile and apatite could be separated by using alkyl-imino-bismethylene phosphoric acid and sodium hexametaphosphate as a collector and a regulator, respectively. Sodium hexametaphosphate could selectively dissolve calcium ions on the apatite surface, and make calcium ions break away from lattice binding through combining.

Preparation of synthetic rutile via selective sulfation of ilmenite with(NH4)2SO4 followed by targeted removal of impurities

This paper describes a novel, facile chemical pathway for preparing synthetic rutile from ilmenite. The pathway consists of two primary units, i.e., selectively sulfating ilmenite, which was realized via roasting ilmenite with(NH_4)_2SO_4followed by selective thermal decomposition of the sulfated ilmenite, and targeted leaching of the impurities. The effects of the process parameters were systematically investigated. The results showed that the optimum sulfation conditions were a mass ratio of(NH_4)_2SO_4to ilmenite of 14, temperature of 360 °C, and time of 120 min with a sulfation ratio of ~ 95%. The optimum thermal decomposition conditions were480 °C in N_2 atmosphere, and nearly all Ti OSO_4 were decomposed with co-decomposition of Fe SO_4 of 23%. For acid leaching, the optimum conditions were 2.5 wt% HCl, 98 °C and 120 min. Under those conditions, 94.2% iron was removed with a Ti O_2 dissolution loss b 1%. For alkali leaching, 67% Si O_2 was removed in 5 wt% Na OH at102 °C for 1 h. A synthetic rutile with a Ti O_2 content N 92 wt% and total Mg O + Ca O b 1.5 wt% was obtained.Based on these results, a schematic flowsheet was proposed. Additionally, it was found that the decomposition of Fe SO_4 mixed with Ti OSO_4 under N_2was inhibited due to its oxidation to a higher thermal stability Fe_2(SO_4)_3by oxygen emitted from the decomposition of Ti OSO_4. At the same time, Ti OSO_4 decomposition was promoted due to the immediate in situ consumption of oxygen by Fe SO_4. The synergetic effect might be responsible for the enhanced selectivity of sulfated ilmenite thermal decomposition.

Influence of rutile(TiO_2) content on wear and microhardness characteristics of aluminium-based hybrid composites synthesized by powder metallurgy

The effect of rutile（TiO_2） content on the wear and microhardness properties of aluminium（Al）-based hybrid composites was explored. The proposed content of TiO_2（0, 4%, 8%, 12%, mass fraction） was blended to Al-15% SiC composites through powder metallurgy（P/M） process. Wear test was conducted using pin-on-disc apparatus under dry sliding conditions. Fabricated preforms were characterized using X-ray diffractometer（XRD）, scanning electron microscope（SEM） and energy-dispersive X-ray spectrometer（EDS）. Optical micrographs of the composite preforms display uniform distribution of TiO_2 throughout the matrix. Quantitative results indicate that wear resistance and microhardness increase with the increase of TiO_2 content. SEM images unveil that high wear resistance is attributed to high dislocation density of deformed planes and high hardness of TiO_2. SEM images of wear debris display gradual reduction in mean size of debris when TiO_2 content increases. EDS spectra confirm the presence of oxide layer which obviously reduces the effective area of contact between the sliding surfaces thereby lowers the wear loss of composites. The observation concludes that delamination and adhesive wear are the predominant mechanisms.