Primary Sn-rich titianite in the Qitianling granite, Hunan Province, southern China: An important type of tin-bearing mineral and its implications for tin exploration

The Qitianling calc-alkaline granite in Hunan Province (South China) has attracted much attention since the discovery of the Furong super-large tin deposit. The present study provides new mineralogical data to address their implications for exploration of tin deposits. In the Taoxiwo granite in the southeastern part of the Qitianling granite body, Sn-rich titanite was identified as an important type of Sn-bearing mineral. The titanite commonly occurs with biotite as euhedral crystals, exhibiting typical envelope-like shape and sector-zoning texture. These indicate that the titanite most likely crystallized in the magmatic stage. Electron-microprobe analyses show that the titanite is enriched in tin up to 1.12 wt% SnO₂, with an average of 0.43 wt%. With the crystallization of the granite, primary minerals undertook hydrothermal alteration by magma-derived fluids. Subsequently, in the hydrothermal stage, the primary Sn-bearing titanite was altered (at least partially), but still preserved its typical envelope-shaped outline. Micro-scale cassiterite is a representative product of such alteration; other secondary minerals include fluorite, ilmenite, Sn-bearing rutile and quartz. Therefore, the titanite, commonly present in the calcalkaline granites, can be treated as an important Sn-carrying mineral in the Qitianling granite, reflecting the primary magmatic environment with tin enrichment. The hydrothermal alteration of the primary titanite and subsequent crystallization of cassiterite recorded a process of leaching and accumulation of tin in magmatic-hydrothermal evolution of the Sn-bearing granite. Thus, this titanite has important implications for tin exploration. Supported by National Natural Science Foundation of China (Grant Nos. 40730423 and 40221301) and Project of China Geological Survey (Grant No. 1212010632100)     

Morphologic characteristics and growth interface stability of nano-micron FeS2 whiskers

Micromorphology is further studied on the basis of our previous researches concerned with the nano-micron FeS2 whisker. There are obvious differences in the intensive degree, diameter and micro- morphology among the FeS2 whiskers growing in different stages. From the early to late stage, the intensive degree increases, the diameter decreases, and the surface micro-morphology changes following the regularity： protrusive nodulation → coarse → smooth → flat. According to the theory of crystal growth, the geological setting and processes of whisker formation, we discuss the stability and evolution of crystal growth interface of FeS2 whisker occurring in Gengzhuang gold deposit （Shanxi Province, China）. The results suggest that the negative temperature gradient and the supercooling appear in the early stage of the whisker growth, whereas the positive temperature gradient of reposeful state appears in the late stage. In the whisker growth stage, the component concentration changes through the three stages： severely nonhomogeneous in the early stage, relatively homogeneous in the middle stage, more homogeneous in the late stage. The general changing process of the interfacial state is from unstable to stable. Micromorphology of FeS2 whisker in Gengzhuang is the result of synergism of temperature, component concentration and stability of crystal interface phase in hydrothermal system. The micromorphology not only reflects the physical and chemical characteristics of the hydrothermal system during the whisker growth, but also indicates the stability characteristics of the interface phase and records the changing process of the whisker growth.     

Sr-rich apatite from the Dangzishan leucitite-ijolite xenoliths （Heilongjiang Province）： Mineralogy and mantle-fluid metasomatism

Abundant apatite grains with elevated SrO content were found in leucitite-ijolite xenoliths in the Dangzi Mountain,Heilongjiang Province.Morphological and mineralogical associations,and compositional analysis of the Sr-rich apatite,were carried out using an electron microprobe.Two principal types of apatite were distinguished.One type occurs as short-prismatic crystals with Sr-rich rims,while another type with acicular or finely columnar shapes constitutes Sr-rich apatite element maps and systematic quantitative analysis of apatite revealed great variations in SrO content (0.42%-26.79%).The calculated structural formula of the measured Sr-rich apatite is:(Ca3.15-4.963Sr0.019-1.510Ba0.00-0.030Na0.006-0.108REE0.106-0.153) (P2.84-3.028Si0.009-0.094)O12(F0.675-1.079,Cl0.000-0.256,OH0.084-0.297).Mineralogical textures of apatite implied a replacement mechanism for the Sr-rich apatite.Sr-rich rims of apatite are suggested to have formed after metasomatism (isomorphic replacement) of early fluorapatite in a Sr-,light rare-earth elements (LREE),lithophile light elements (LILE)-and volatile-rich residual melt during late magmatism.However,the acicular apatite probably directly crystallized from a Sr-rich residual melt.The Sr-Nd isotopic composition of the apatite was distinctive from that of leucitite-ijolite and its host rock.These differences,combined with mineralogical features of apatite,imply that Sr-LREE-LILE-volatile-rich components in the residual melt were derived from deep in the asthenosphere,and subsequently were enriched at a late stage in magma evolution.     

Zircon U-Pb dating confirms existence of a Caledonian scheelite-bearing aplitic vein in the Penggongmiao granite batholith, South Hunan

Granite at Penggongmiao is a large batholith in the Nanling Range, with an outcrop area of over 900 km 2 . There are many scheelite-quartz veins around the granite. LA-ICP-MS U-Pb dating was carried out for zircons from the granite. The middlecoarse-grained biotite granite has U-Pb ages of 435 to 436 Ma. Ages of 426.5±2.5 Ma were obtained for aplitic dyke cross-cutting the granite. The scheelite of magmatic origin in the aplite dyke was identified from petrographic investigation. This demonstrates that W-bearing granites of Early Paleozoic (corresponding to the Caledonian orogensis in the traditional sense) occur in the Nanling Range. This finding has important implications for the ore-forming potential of Paleozoic granites and on the extent of Mesozoic mineralization. Thus it merits performing an intensive study of Paleozoic granites in South China. The occurrences of aplite or microgranite may be an indicative of the Caledonian tungsten granites and associated W mineralization.     

Highly Zn, Mn-rich calcite in calcareous tufa from the Qixiashan Pb-Zn Mine, Nanjing: a possible candidate for Zn-Mn removal from mining impacted waters

The exploitation of metallic mines may cause serious environmental problems. The removal of the heavy metals from the contaminated mining environments has become an urgent issue. In this paper, the occurrence and distribution of heavy metals in the calcareous tufa collected from the mining laneway of the Qixiashan Pb-Zn Mine in Nanjing were investigated by using multiple mineralogical techniques. Examination by X-ray diffraction spectrum (XRD) shows that calcite is the major component of the calcareous tufa. Several heavy metals such as Mn, Zn, Mg, Fe and Pb are detected in calcite by means of electron microprobe analysis. Although the heavy metal contents in the hostrock and the formation water are significantly low, the contents of Mn, Zn, Mg, Fe and Pb in the tufa calcite are as high as 23.65 wt%, 9.6 wt%, 0.76 wt%, 4.44 wt% and 0.66 wt%, respectively. The back-scattered electron image shows complex compositional zoning texture in the tufa, which is linked directly to variations in heavy metals, particularly in Mn and Zn. In addition, we also observed floccule and helical precipitations, which may be derived from the metabolism of the microbe. It is deduced that the occurrence and high concentration of heavy metals in tufa may be controlled by the activities of microbes. The results presented in this work suggest that calcite will be an important candidate for the remediation of the heavy metal contamination in mining areas. Supported by National Basic Research Program of China (Grant No. 2007CB815603), National Natural Science Foundation of China (Grant No. 40573001) and the Ph.D. Programs Foundation of Ministry of Education of China (Grant No. 20050284044)     

Finding of ancient materials in Cathaysia and implication for the formation of Precambrian crust

U-Pb dating for fifty-six detrltsl zircons from a paragneiss in Nanxiong area, northern Guangdong Province, Indicates that the latest Neoproterozoic sediments in Cathaysia hinterland are composed of numerous Grenvillian and Necerchaean clasUc materials, as well as some Mesoproterozolc detritus. Minor Paleoarchaean （3.76 Ga） and Mesoarchaean （3.0-3.2 Ga） zircons, which are the oldest zircons In South China, also are firstly found in the sediments, suggesting that the Cathaysia Block may contsln very old materials. The Hf isotope compositions of thirty-seven zircons reveal that these clastlc materials have different origins. Minor zircons crystslllzed from magma generated from relatively juvenile crust, while the parental magma of most zircons was derived from ancient crust. Integration of U-Pb dating and Hf Isotope analysis of these zircons suggests that the generation of juvenile crust in the Cathaysia block mainly occurred at 2.5-2.6 Ga. Mesoarchaean （3.0-3.3 Ga）, late Paleoproterozolc （-1.8 Ga） and Paleoarchaean （-3.7 Ga） may also be important episodes of crustal growth. Grenvllllan magmatism is extremely Intense, but it mainly involved recycling of ancient crustal components with little formation of Juvenile crust. The marked presence of -2.1 Ga Hf model ages and the absence of the zircons with crystsllizatlon ages at -2.1 Ga suggest that the parental magma of many zircons was probably derived from the mixed source consisting of Neoarchaean and late Paleoproterozoic materlals.     

Timing of hydrothermal activity associated with the Douzhashan uranium-bearing granite and its significance for uranium mineralization in northeastern Guangxi, China

The Miaoershan uranium(U)ore field in northeastern Guangxi is one of the important granite-related U deposits in south China and is closely related to the Douzhashan U-bearing granite.The Douzhashan granite contains primary U-rich accessory minerals,including monazite(UO2=0.98-1.75 wt%)and xenotime(UO2=1.48-6.14 wt%).Primary monazite and xenotime yield chemical ages of 231±28 Ma and 230±38 Ma by electron microprobe analysis and U-Pb isotopic ages of 220±6 Ma and 211±7 Ma by laser ablation-inductively coupled-mass spectrometry respectively.These ages demonstrate that the Douzhashan granite formed during the period of Indosinian magmatic activity.Back scattered electron imaging shows that monazite and xenotime are commonly altered to assemblages of low-U synchisite and apatite,which was associated with loss of U to hydrothermal fluids.U-Th-Pb analyses of secondary apatite yielded a chemical age of 136±17 Ma,which corresponds to the timing of Cretaceous-Tertiary crustal extension in south China.We suggest that the heat and CO2required for mineralization was the result of Yanshanian crustal extension,and that this triggered the breakdown of U-rich accessory minerals in the Douzhashan U-bearing granite.Uranium remobilization from the Douzhashan granite provided materials for mineralization within the granite and/or surrounding country rocks.Therefore,a combination of Indosinian compression and Yanshanian extensional overprint produced the hydrothermal U deposits associated with the Douzhashan granite.     

Mantle metasomatism by P- and F-rich melt/fluids： evidence from phosphate glass in spinel Iherzolite xenolith in Keluo, Heilonsjiang Province

Spinel Iherzolite xenoliths were found in phonoliUc alkaline basalt in the Keluo area, Heilongjiang Province. Detailed electron-microprobe study revealed abundant phosphates and associated metasomatic minerals between primary phases in xenolith. The phosphates are considered special residual phases （coagulation） of P- and F-rich mantle melt/fluid, most of which were identified as glass phases based on Raman spectroscopic analyses. Such melt/fluid also further metasomatized primary minerals, thus leading to formation of reaction rims successively composed of Cr-spinel symplecUUc zone and olivine ＋ diopside zone. Therefore, the P- and F-rich melt/fluid played an important role in the upper-mantle metasomatism in the Keluo area. It is suggested that this kind of metasomstism may occur in some other places of eastern China. The present results may also have significance in studying types of metasomatic melt/fluid and its evolution in the lithospheric mantle beneath eastern China.