Trace Elements of Multi-stage Minerals and Titanite U-Pb Dating for the Gneisses from Liansan Island,Sulu UHPM Belt

Gneisses with anatectic characteristics from the Liansan island in the Sulu UHPM(ultra-high pressure metamorphic)belt were studied for petrography,titanite U-Pb dating and mineral geochemistry.Three origins of garnets are distinguished:metamorphic garnet,peritectic garnet and anatectic garnet,which are formed in the stages of peak metamorphism,retrograde anatexis and melt crystallization,respectively.The euhedral titanite has a high content of REE and high Th/U ratios,which is interpreted as indicating that it was newly-formed from an anatectic melt.The LA-ICP-MS titanite U-Pb dating yields 214-217 Ma ages for the titanite(melt)crystallization.The distribution of trace elements varies in response to the different host minerals at different stages.At the peak metamorphic stage,Y and HREE are mainly hosted by garnet,Ba and Rb by phengite,Sr,Nb,Ta,Pb,Th,U and LREE by allanite and Y,U and HREE by zircon.During partial melting,Y,Pb,Th,U and REE are released into the melt,which causes a dramatic decline of these element contents in the retrograde minerals.Finally,titanite absorbs most of the Nb,U,LREE and HREE from the melt.Therefore,the different stages of metamorphism have different mineral assemblages,which host different trace elements.

Advance in Matrix Effect Study of LA-MC-ICPMS U-Pb Dating on U-Bearing Oxide Minerals

Objective With the development of analytic technologies, in-situ dating on U-bearing oxide minerals （e.g., cassiterite, rutile and baddeleyite） has been widely used in geological chronological researches and has attracted remarkable attention to explore evolution of the earth and obtain age information of various geological processes. Matrix effect related studies are especially important during in-situ U- Pb dating based on Laser Ablation Multiple Collector Inductively Coupled Plasma Mass Spectrometry （LA-MC- ICPMS）. However, to our knowledge, only few thorough and systematical matrix effect study of U-bearing oxide minerals has been reported. In this study, we systematically analyzed the matrix effect of U-bearing oxide minerals in order to take place the standards which are difficult to prepare with available standards.

SHRIMP zircon U-Pb dating of the mafic and felsic intrusive rocks of the Saza area in the Lupa goldfields, southwestern Tanzania: Implication for gold mineralization

The Lupa Goldfield (LGF) is one of the eight structural terranes in the NW – SE striking Ubendian Belt of SW Tanzania. The LGF is comprised of granitic gneisses with bands of amphibolites which are intruded by mafic intrusions including gabbros, granodiorites, diorites;and various granites as well as metavol-canics. These rocks are cross-cut by narrow mafic dykes and aplites. SHRIMP zircon U-Pb data are presented for the granodiorite and a mafic dyke that cross-cut the granodiorites in the Saza area of the LGF, with the aim of constraining the mafic and felsic magmatism and their implication to gold mineralization. The zircon U-Pb data shows that the Saza granodiorites were emplaced at 1924 ± 13 Ma (MSWD = 2.6) whereas the cross-cutting mafic dyke yielded a zircon U-Pb age of 1758 ± 33 Ma (MSWD = 0.88). The dated granodiorite sample was in sheared contact with an altered mafic intrusive rock, most likely a diorite, along which an auriferous quartz vein occurs. The 1924 ± 13 Ma age of granodiorites is within error of the reported molybdenite Re-Os age of 1937 Ma determined for the gold mineralization event in Lupa Goldfields. Although auriferous quartz veins are younger than the granodiorites, the more or less similar ages between the emplacement of granodiorites and the mineralizing event indicate that the granodiorites might be the heat source (or driver) of hydrothermal fluids responsible for gold mineralization in the Lupa goldfields. This would further suggest that gold mineralization in the LGF is intrusion-related type. The mafic dykes represent the youngest rocks to have been emplaced in the area and hence the 1758 ± 33 Ma age of the mafic dykes conclude the magmatic evolution in the Lupa goldfields during the Palaeoproterozoic.

Early Mineralization Age of the Hengjian Uranium Deposit: Constraints from Zircon SIMS U-Pb Dating

Objective The Hengjian uranium deposit is a typical hydrothermal deposit in the Xiangshan uranium ore field.The uranium mineralization ages of the Xiangshan deposits are poorly constrained,and only a few mineralization ages using the pitchblende U–Pb method have been published.These ages are commonly discordant and dispersed for abundant inclusions and an open U–Pb system.Zircon grains after strong hydrothermal alteration are usually characterized by high common Pb contents,and their U–Pb isochron ages recorded the hydrothermal alteration event without interference of common Pb components.The Hengjian gray/grayish-green granite porphyry experienced strong alteration by hydrothermal fluids during the pervasive uranium mineralization in the Xiangshan uranium ore field.Uranium mineralization in the Hengjian deposit may had different stages,and strong hydromicatization alteration occurred at a relatively early stage.Their altered zircon U–Pb isochron ages possibly represent relatively early mineralization age of the Xiangshan uranium deposits.Altered zircon grains from the Hengjian granite porphyry were analyzed using the secondary ion mass spectrometry(SIMS)U-Pb method in this study,and U–Pb isochron ages were measured to constrain the relatively early mineralization age of the Hengjian uranium deposit.

The dating and temperature measurement technologies for carbonate minerals and their application in hydrocarbon accumulation research in the paleouplift in central Sichuan Basin, SW China

A new method for reconstructing the geological history of hydrocarbon accumulation is developed, which are constrained by U-Pb isotope age and clumped isotope((35)47) temperature of host minerals of hydrocarbon-bearing inclusions. For constraining the time and depth of hydrocarbon accumulation by the laser in-situ U-Pb isotope age and clumped isotope temperature, there are two key steps:(1) Investigating feature, abundance and distribution patterns of liquid and gaseous hydrocarbon inclusions with optical microscopes.(2) Dating laser in-situ U-Pb isotope age and measuring clumped isotope temperature of the host minerals of hydrocarbon inclusions. These technologies have been applied for studying the stages of hydrocarbon accumulation in the Sinian Dengying gas reservoir in the paleo-uplift of the central Sichuan Basin. By dating the U-Pb isotope age and measuring the temperature of clumped isotope((35)47) of the host minerals of hydrocarbon inclusions in dolomite, three stages of hydrocarbon accumulation were identified:(1) Late Silurian: the first stage of oil accumulation at(416±23) Ma.(2) Late Permian to Early Triassic: the second stage of oil accumulation between(248±27) Ma and(246.3±1.5) Ma.(3) Yanshan to Himalayan period: gas accumulation between(115±69) Ma and(41±10) Ma. The reconstructed hydrocarbon accumulation history of the Dengying gas reservoir in the paleo-uplift of the central Sichuan Basin is highly consistent with the tectonic-burial history, basin thermal history and hydrocarbon generation history, indicating that the new method is a reliable way for reconstructing the hydrocarbon accumulation history.

Petrogenesis and Mineralization of Two-Stage A-Type Granites in Jiuyishan,South China:Constraints from Whole-rock Geochemistry, Mineral Composition and Zircon U-Pb-Hf Isotopes

The Jiuyishan complex massif,located in the northern section of the Nanling region,is a combination of five plutons,namely,the Xuehuading,Jinjiling,Pangxiemu,Shaziling and Xishan plutons.Whole-rock geochemistry,Imineral electron microprobe analysis,zircon U-Pb dating and Hf isotope analysis were carried out for the Jinjiling and Pangxiemu plutons.The zircon U-Pb dating yields weighted mean ages of 152.9±0.9 Ma for the Jinjiling pluton and 151.7±1.5 Ma for the Pangxiemu pluton,with a narrow gap between them.The Jinjiling and Pangxiemu plutons both have geochemical characteristics of high SiO2,Al2 O3,Na2 O,K2 O and low TiO2,MgO,CaO,P2 O5 contents,with intense depletions in Sr,Ba,Ti,Eu and enrichments in Ga,FeoOT and HFSE,and these characteristics reflect an A-type affinity.From the Jinjiling to the Pangxiemu plutons,the mineral composition of mica changes from lepidomelane to zinnwaldite,with increases in F,Li2 O and Rb2 O contents.The mineral composition of zircon changes from low Zr/Hf to high Zr/Hf,with increasing HfO2,P2 O5 and UO2+ThO2+Y2 O3 contents.The mineral compositions of feldspar indicate that the Pangxiemu pluton contains more alkali feldspar than the Jinjiling pluton.The whole-rock geochemistry and mineral compositions reveal a higher degree of differentiation for the Pangxiemu pluton.The nearly uniformεHf(t)indicates the same source region for the two plutons:both were derived from partial melting of the lower crust,with small contributions of mantle materials.In addition,higher F,lower Nb/Ta and Zr/Hf ratios in the Pangxiemu Pluton suggest a closer relationship with the rare metal mineralization than for the Jinjiling pluton.

Redetermination of the Depositional Age of the Haerdaban Group in the Northern Margin of the Yili Block,Western Tianshan,NW China:Implications for Regional Tectonics and Pb-Zn Mineralization

The Yili Block in the Western Tianshan orogen is a key area for understanding the early crustal formation and evolution of the Central Asian orogenic belt,due to the widely-distributed Precambrian rocks.Also,it hosts a lot of medium–to large-scale sedimentary exhalative(SEDEX)Pb-Zn deposits that mainly occur in Proterozoic metamorphosed clasticcarbonate rocks.In this study,LA-ICP-MS U-Pb analyses were carried out on detrital zircons in siltstones of the Precambrian Haerdaban Group in the Haerdaban Pb-Zn deposit and magmatic zircons in the diorite dyke that cuts through the strata and orebodies.The maximum depositional age of the siltstones was determined to be about 604 Ma,the diorite having formed at approximately 500 Ma.As such,the Haerdaban Group was most likely formed in the Neoproterozoic Sinian,rather than the previously considered Mesoproterozoic Changchengian.Detrital materials of the Haerdaban Group were mostly derived from the Nanhua–Sinian mafic dykes and granitic rocks around Lake Sayram at the northern margin of the Yili Block.It is proposed that the Yili Block,together with the Kazakhstan and Central Tianshan blocks and the Tarim Craton,might all pertain to the same Rodinia supercontinent,which has great potential for targeting large to super-large SEDEX Pb-Zn deposits.

Multiple and prolonged porphyry Cue Au mineralization and alteration events in the Halasu deposit, Chinese Altai, Xinjiang,northwestern China

The Halasu area is located in the southeastern margin of the Chinese Altai in Xinjiang, China. It is part of the Altaid orogenic collage where a number of porphyry-type Cue Moe Au deposits have been discovered in recent years. Geological mapping and drilling indicate the presence of various mineralized porphyritic intrusions in the Halasu Cue Au deposit, which is currently under exploration. Ue Pb dating of zircon crystals from four different mineralized porphyries reveals three significantly different ages of magmatic intrusion, i.e., ca. 372e382 Ma granodioritic porphyry and porphyritic granite, ca. 266 Ma quartz monzonitic porphyry, and ca. 216 Ma quartz dioritic porphyry. Ree Os dating of molybdenite from veinletdissemination ores in the granodioritic porphyry yields an age of mineralization of ca. 377 Ma, and Ar e Ar dating of K-feldspar from K-feldsparequartzechalcopyrite veins produces ages of ca. 269 and ca.198 Ma. The mineralization（and alteration） ages correspond broadly to the three episodes of magmatic intrusion, suggesting three overprinting porphyry mineralization events that are significantly separated in time. The first episode of porphyry intrusion and mineralization may be related to the magmatic arc being above a plate subduction zone, and the second was formed in a late-collisional environment during the closing of the Junggar Ocean, whereas the third episode of mineralization took place in the postcollisional stage. This case study suggests that in orogens where major porphyry deposits have been found in magmatic arc environments, the potential of discovering late- to post-collisional porphyry deposits cannot be neglected; conversely, in orogens where most porphyry deposits have late- to postcollisional ages, more attention should be paid to porphyries that were formed earlier in magmatic arc environments.

High-reliability zircon separation for hunting the oldest material on Earth： An automatic zircon separator with image-processing/microtweezers-manipulating system and double-step dating

Despite the recent development in radiometric dating of numerous zircons by LA-ICPMS, mineral separation still remains a major obstacle, particularly in the search for the oldest material on Earth. To improve the efficiency in zircon separation by an order of magnitude, we have designed/developed a new machine-an automatic zircon separator（AZS）. This is designed particularly for automatic pick-up of100 μm-sized zircon grains out of a heavy mineral fraction after conventional separation procedures. The AZS operates in three modes：（1） image processing to choose targeted individual zircon grains out of all heavy minerals spread on a tray,（2） automatic capturing of the individual zircon grains with microtweezers, and（3） placing them one-by-one in a coordinated alignment on a receiving tray. The automatic capturing was designed/created for continuous mineral selecting without human presence for many hours. This software also enables the registration of each separated zircon grain for dating, by recording digital photo-image, optical（color） indices, and coordinates on a receiving tray. We developed two new approaches for the dating; i.e.（1） direct dating of zircons selected by LA-ICPMS without conventional resin-mounting/polishing,（2） high speed U-Pb dating, combined with conventional sample preparation procedures using the new equipment with multiple-ion counting detectors（LA-MIC-ICPMS）.With the first approach, Pb-Pb ages obtained from the surface of a mineral were crosschecked with the interior of the same grain after resin-mounting/polishing. With the second approach, the amount of time required for dating one zircon grain is ca. 20 s, and a sample throughput of 〉150 grains per hour can be achieved with sufficient precision（ca. 0.5%）.We tested the practical efficiency of the AZS, by analyzing an Archean Jack Hills conglomerate in Western Australia with the known oldest（〉4.3 Ga） zircon on Earth. Preliminary results are positive; we were able to obtain more than 194 zircons that are over 4.0 Ga out of ca. 3800 checked grains, and 9 grains were over 4300 Ma with the oldest at 4371 ± 7 Ma. This separation system by AZS, combined with the new approaches, guarantees much higher yield in the hunt for old zircons.

Mineral inclusions in zircon domains and geological significance of SHRIMP U-Pb dating for coesite-bearing zircons of paragneiss in Sulu terrane, eastern China

Laser Raman spectroscopy and cathodoluminescence (CL) image reveal that zircons separated from paragneisses in the southwestern Sulu terrane (eastern China) preserve multi-stage mineral assemblages in different zircon domains. In the same paragneiss zircon sample, some zircon grains retain inherited (detrital) cores with abundant low-pressure mineral inclusions of Qtz + Phe + Ap + impurities and Qtz + Phe + impurities. The ultrahigh-pressure (UHP) metamorphic overgrowths mantles of these zircons preserve Coe, Coe + Phe and other UHP mineral inclusions, indicating that these inherited (detrital) zircons from protoliths experienced metamorphic recrystallization during the Sulu UHP metamorphic event. However, other zircon grains preserve UHP mineral inclusions of Coe, Coe + Ap and Coe + Phe in the cores and mantles, whereas the outmost rims contain quartz (Qtz) and other low-pressure mineral inclusions. These phenomena prove that the second group zircons were crystallized at UHP metamorphic stage and overprinted by the late retrogressive metamorphism related to the Sulu terrane exhumation. SHRIMP U-Pb dating reveals that zircons separated from the paragneisses recorded complicated geochronological traces. Some zircons retain inherited cores with the 206Pb/238U ages of 284-754 Ma, indicating the complexity of the detrital zircons in protoliths. Coesite-bearing zircon domains recorded 238-266 Ma (with the average age of 245(14 Ma) for the UHP metamorphic event. The retrogressive rims of zircons recorded 213-223 Ma (with the average age of 217(15 Ma) for the late-stage amphibolite facies metamorphic event, indicating that the rapid exhumation time for the Sulu UHP terrane is about 220 Ma.

Sequence structure, sedimentary evolution and their controlling factors of the Jurassic Lianggaoshan Formation in the East Sichuan Basin, SW China

Based on the data of outcrops, seismic sections, thin sections, heavy mineral assemblages and detrital zircon U-Pb dating, the sedimentary characteristics, lake level fluctuation and provenance characteristics of the Middle Jurassic Lianggaoshan Formation(J_(2)l) in eastern Sichuan Basin, SW China, were investigated to reveal the control of tectonic movements of the surrounding orogenic belts on the sedimentary systems. The J_(2)lmainly developed a delta–lake sedimentary system, which contained a complete third-order sequence that was subdivided into four lake level up-down cycles(fourth-order sequence).The lake basins of cycles Ⅰ and Ⅱ were mainly distributed in eastern Sichuan Basin, while the lake basins of cycles Ⅲ and Ⅳ migrated to central Sichuan Basin, resulting in the significant difference in sedimentary characteristics between the north and the south of eastern Sichuan Basin. The provenance analysis shows that there were three types of provenances for J_(2)l. Specifically, the parent rocks of Type Ⅰ were mainly acidic igneous rocks and from the proximal northern margin of the Yangtze Plate;the parent rocks of Type Ⅱ were intermediate-acid igneous rocks and metamorphic rocks and from the central parts of the southern and northern Qinling orogenic belts;the parent rocks of Type Ⅲ were mainly metamorphic rocks followed by intermediate–acid igneous rocks, and from the North Daba Mountain area. It is recognized from the changes of sedimentary system and provenance characteristics that the sedimentary evolution of J_(2)lin eastern Sichuan Basin was controlled by the tectonic compression of the Qinling orogenic belt. In the early stage, the lake basin was restricted to the east of the study area, and Type Ⅰ provenance was dominant. With the intensifying north-south compression of the Qinling orogenic belt, the lake basin expanded rapidly and migrated northward, and the supply of Type Ⅱ provenance increased. In the middle and late stages, the uplift of the North Daba Mountain led to the lake basin migration and the gradual increase in the supply of Type Ⅲ provenance.

FS-ICPMS和TIMS联用法测定微粒铀矿物的年龄

A method for age dating of uranium mineral particles by double focusing magnetic sector inductively coupled mass spectrometry (FS-ICPMS) and thermal ionization mass spectrometry (TIMS) was presented. Pb/U ratio in uranium mineral particles was measured by FS-ICPMS without any chemical separation procedure. Pb isotope composition in uranium mineral particles was determined by TIMS associated with micro column anion exchange resin method. Due to simplified chemical procedure and minimum use of reagents, the full procedure blank was reduced to 230 pg Pb, leading to the successful age dating of uranium mineral particles with relative standard deviation less than 2%.

Ultrahigh-pressure and Retrograde Metamorphic Ages for Paleozoic Protolith of Paragneiss in the Main Drill Hole of the Chinese Continental Scientific Drilling Project(CCSD-MH),SW Sulu UHP Terrane

Laser Raman spectroscopy and cathodoluminescence （CL） images show that most zircon crystals separated from paragneiss in the main drill hole of the Chinese Continental Scientific Drilling Project （CCSD-MH） at Maobei, southwestern Sulu terrane, contain low-pressure mineral-bearing detrital cores, coesite-bearing mantles and quartz-bearing or mineral inclusion-free rims. SHRIMP U-Pb dating on these zoned zircons yield three discrete and meaningful age groups. The detrital cores yield a large age span from 659 to 313 Ma, indicating the protolith age for the analyzed paragnelss is Paleozoic rather than Proterozoic. The coesite-bearing mantles yield a weighted mean age of 228 ± 5 Ma for the UHP event. The quartz-bearing outmost rims yield a weighted mean age of 213 ± 6 Ma for the retrogressive event related to the regional amphibolite facies metamorphism in the Sulu UHP terrane. Combined with previous SHRIMP U-Pb dating results from orthogneiss in CCSD-MH, it is suggested that both Neoproterozoic granitic protolith and Paleozoic sedimentary rocks were subducted to mantle depths in the Late Triassic. About 15 million years later, the Sulu UHP metamorphic rocks were exhumed to mid-crustal levels and overprinted by an amphibolite-facies retrogressive metamorphism. The exhumation rate deduced from the SHRIMP data and metamorphic P-T conditions is about 6.7 km/Ma. Such a fast exhumation suggests that the Sulu UHP paragnelss and orthogneiss returned towards the surface as a dominant part of a buoyant sliver, caused as a consequence of slab breakoff.

A study on the Dushiling tungsten-copper deposit in the Miao＇ershan-Yuechengling area, Northern Guangxi, China：Implications for variations in the mineralization of multi-aged composite granite plutons

The polymetallic Dushiling W-Cu deposit is a large, altered, skarn-type deposit, located in the northeastern part of the Miao'ershan-Yuechengling pluton, China. Two types of granite have been identified in the deposit: a medium-grained porphyritic biotite granite, and a medium- to fine-grained biotite granite. Both are spatially and temporally related to ore bodies, suggesting they may be the source of mineralization in the deposit. A medium- to fine-grained porphyritic biotite granite is exposed at the surface in the region of mineralization. U-Pb dating of zircons yielded magmatic ages of 423 Ma for the medium-grained porphyritic biotite granite and 421 Ma for the medium- to fine-grained porphyritic biotite granite, while a younger age(217 Ma) obtained for surface samples indicates later diagenesis. Thus, magmatism occurred during the Caledonian and Indosinian, respectively. The petrological and geochemical characteristics of the two Caledonian granites show that both are calc-alkaline and peraluminous.They are moderately enriched in Cs, Rb, U, and REE, and strongly depleted in Sr,Ba,P,and Ti; they show similar REE behavior,including negative Eu anomalies. These geochemical similarities suggest that the two granites were derived from the same source,although they were emplaced during different stages of the evolution of the magma. Furthermore, the granites are associated with mineralization, suggesting they were the source of mineralization in the Dushiling W-Cu deposit. Sm-Nd ages of scheelite from the Dushiling W-Cu deposit indicate that metallogenesis occurred at 417±35 Ma, while the two types of titanite, intergrown with scheelite, yield U-Pb ages of 423–425 Ma(in altered granite sample) and 218 Ma(in skarn sample). These ages place the main mineralization event in the late Caledonian, and later magmatic-hydrothermal activity occurred in the Indosinian. The ages obtained for the Dushiling W-Cu deposit in the western Nanling Range, northern Yuechengling, together with the occurrence and ages of the Niutangjie W deposit in southern Yuechengling, provide insight into the process of ore concentration during the Caledonian and Indosinian.

Geochronology and Geochemistry of the Granites from the Longtoushan Hydrothermal Gold Deposit in the Dayaoshan Area,Guangxi:Implication for Petrogenesis and Mineralization

The gold mineralization in the Longtoushan hydrothermal gold deposit is concentrated within the contact zone of the granitic complex. Whole rock geochemistry and in-situ U-Pb and Hf isotopic data were used to constrain the genesis and age of the granites and related Cu-Au mineralization in the Longtoushan Deposit. The granites mainly consist of the granite porphyry, rhyolite porphyry, porphyritic granite and quartz porphyry. LA-ICP-MS U-Pb dating of zircons from the granite porphyry, rhyolite porphyry and quartz porphyry indicates that they intruded from ca. 94 to 97 Ma. These intrusions exhibit similar trace element characteristics, i.e., right-dipping REE patterns, depletion of Ba, Sr, P and Ti, and enrichment of Th, U, Nd, Zr and Hf. The εHf(t) values of zircons from the granite porphyry, rhyolite porphyry and quartz porphyry range from-26.81 to-8.19,-8.12 to-5.33, and-8.99 to-5.83, respectively, suggesting that they were mainly derived from the partial melting of the Proterozoic crust. The Cu-Au mineralization is mainly related to the rhyolite porphyry and porphyritic granite, respectively. The Longtoushan granites were most likely formed in a post-collisional extensional environment, and the deposit is a part of the Late Yanshanian magmatism related mineralization in the Dayaoshan area and its adjacent areas.

Geochemistry and geochronology of multi-generation garnet:New insights on the genesis and fluid evolution of prograde skarn formation

Origin of garnet in skarn(magmatic vs.hydrothermal)and the prograde skarn fluid evolution are still controversial.Two generations of garnet(Grt1,Grt2)were identified at the Tongshankou deposit:Grt1 is anisotropic with oscillatory zoning and resorbed boundary,whilst Grt2 grew around Grt1 and formed oscillatory rims.In-situ LA-ICP-MS U-Pb dating of Grt1 and Grt2 yielded a lower intercept^(206)Pb/^(238)U age of 142.4±2.8 Ma(n=57;MSWD=1.16)and 142.3±9.6 Ma(n=60;MSWD=1.06),respectively,coeval with the ore formation and ore-related granodiorite emplacement.Positive Eu anomaly,non-CHARAC Y/Ho value and low TiO_(2)content,together with the mineral assemblages indicate that both Grtl and Grt2 have a hydrothermal origin.The existence of melt and melt-fluid inclusions in Grt1,together with similar LREE-enriched patterns to the granodiorite,further indicate that Grt1 may have formed in the magmatic-hydrothermal transition.Higher U contents and LREE-enriched patterns of Grt1 indicate that fluid I is mildly acidic pH and low fO_(2).The inner gray Grt2 rims(Grt2A)is HREE-enriched with low U contents,indicating that fluid II has nearly neutral pH and high fO_(2).The wider Y/Ho range and LREE-enriched patterns of the outer light-gray Grt2 rims(Grt2B)show that the evolved magmatic fluidⅡhad mixed with an external fluid,characterized by being mildly acidic pH and with high fO_(2)·Our results suggest that the prograde skarn-forming fluids can be multistage at Tongshankou,and the mixing of meteoric water may have been prominent in the prograde skarn stage.