Consistency between apatite and zircon petrochronology supports robustness of apatite in fingerprinting igneous processes in porphyry systems

Consistency between apatite and zircon petrochronology supports robustness of apatite in fingerprinting igneous processes in porphyry systems | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Consistency between apatite and zircon petrochronology supports robustness of apatite in fingerprinting igneous processes in porphyry systems Hongying Qu, Julie Rowland, Jingwen Mao, Evan Orovan, Michael Rowe, and 1 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4524703/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Apatite low-temperature thermochronology can be double or even triple dated allowing for a reconstruction of the thermal history of rock from ~ 550 o C to near-surface temperatures. Even though it has disadvantageous U–Th–Pb contents (high Pb contents and low U and Th contents) and an unstable nature, apatite is still regarded to have the same robustness in fingerprinting igneous processes in porphyry systems as zircon, so far as to be replace zircon. Hence, we systematically studied characteristics of morphology, geochronology and geochemistry of apatite hosted in syenogranite and monzogranite intrusive rocks in the large Hutouya skarn deposit, in order to corroborate its potential thermochronological monitoring capabilities like zircon in fingerprinting igneous processes in porphyry systems. In this study, apatite grains can be subdivided into two types, FI-free Apatite I formed in the early less fractionated magma and FI-rich Apatite II crystallized in the late highly fractionated magma stage. We obtained ages of 229.0 ± 6.6 Ma in syenogranite and 224.3 ± 4.5 Ma / 223.7 ± 3.9 Ma in monzogranite from Apatite I of magmatic origins. Zircon grains in the two granites can be classified into three types. Zircon I is characterized by transparent and bright zones, Zircon II by dark and metamict features, and Zircon III by mineral inclusions. Zircon I grains with a magmatic texture of well-developed bright oscillatory zones, are most likely primary magmatic zircon that crystallized early in the evolution of granitic magma, dating results of which are 224.70 ± 0.61 Ma in syenogranite intrusions and 225.75 ± 0.66 Ma / 226.31 ± 0.78 Ma in monzogranite, respectively. The apatite–zircon timing is coincident. Furthermore, apatite trace rare earth element contents in the syenogranite and monzogranite intrusions display a negative-slope chondrite-normalized distribution from La to Lu with strong negative Eu anomalies and weak positive Ce anomalies, with major element contents that are statistically identical with enriched F but poor Cl. Zircon trace element compositions in the two intrusions show consistent and steeply increasing chondrite-normalized REE diagrams from La to Lu with negative Eu anomalies and strong positive Ce anomalies. Accordingly, apatite U–Pb dates and the corresponding in-situ trace element compositions and isotopes can test precise constraints on rock formation ages, temperature, oxygen fugacity, material source, and tectonic background, which can be relatively more robust when used as proxies for magma oxidation state. Robustness of apatite zircon petrochronology in-situ multi-element analysis porphyry–skarn system Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Figure 11 Figure 12 1. Introduction The determination of rock-forming and mineralizing ages is critical to understanding mineral deposit genesis. Zircon, as is stable, has a high sealing temperature, and high U and low common Pb concentrations, making it the most commonly used imeral for U–Pb dating; however, zircon may be absence, or may not represent the timing of mineralization in some mineral deposits. Recently, developed highly sensitive analytical techniques, most notably, laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS) age dating of U-rich minerals (e.g., apatite, epidote, cassiterite, magnetite, garnet, titanite, rutile, calcite, wolframite, scheelite, etc.), has allowed researchers to not solely rely on zircon for dating hydrothermal events in mineral deposits (Andersson et al., 2019 ; Glorie et al., 2020; Mao et al., 2016 ; Pan et al., 2016 ; Qu et al., 2019b ). It is worth mentioning that apatite, being a common accessory mineral in magmatic rocks and hydrothermal deposits, is generally employed in low-temperature thermochronology research (Chew and Spikings, 2015 ; Prowatke and Klemme, 2006 ; Webster et al., 2009 ). Due to its relatively low U–Th–Pb isotope sealing temperature (~ 550–350 o C), apatite dating can provide age information for P–T–t trajectory research for metamorphic rocks with complex evolutionary and thermal histories. Apatite can be double or even triple dated (U–Pb, fission track, and U–Th–Sm/He), allowing a reconstruction of a thermal history of a rock from ~ 550 o C to near-surface temperatures (Carrapa et al., 2009 ; Glorie et al., 2019 ; Jepson et al., 2018 ). Although apatite LA–ICP–MS dating has advantages, such as in-situ rapid age determinations, there are significant problems for samples with high Pb and low U and Th contents. Also, apatite is unstable in acidic groundwaters and weathering profiles and has only limited mechanical stability in sedimentary transport systems (Morton and Hallsworth, 1999 ). In contrast, zircon have a much more stable nature than apatite. Like zircon, apatite trace element compositions can be used to interpret characteristics of the melt from which it was derived, e.g., its compositional evolution, degree of assimilation and fractionation, oxidation state, and even determination of paragenetic separation from the parental magma (Ballard et al., 2002 ; Liang et al., 2006 ; Odlum et al., 2022 ; Zhang et al., 2017 ). This is possible because the apatite mineral structure, Ca 5 (PO 4 ) 3 (F,Cl,OH), can incorporate a variety of transition metals, rare earth elements (REE), and other cations. For example, Sr 2+ , Mn 2+ , Fe 2+ , REE, and Na + can be substituted in the Ca 2+ and Si 4+ sites, and As 5+ and S 6+ can be substituted in the P 5+ site (Hughes and Rakovan, 2002 ). In this study, we evaluate the consistency between apatite and zircon petrochronology from rocks that are proximal to a skarn deposit to test the robustness of apatite in fingerprinting igneous processes in porphyry systems. We used LA–ICP–MS to obtain U–Pb ages of apatite and zircon for Middle–Late Triassic intrusions of the Hutouya skarn deposit, NW China, and determined their in-situ trace element compositions. Through comparisons with global trace element compositions of apatite from fertile intrusions in the porphyry systems, we concluded that a similar robustness in fingerprinting igneous processes in porphyry systems as zircon, and that apatite thermochronology can test complementary information on magma evolutions and ore-forming fluids that are not available from zircon alone. 2. Regional geological setting China has one of the widest distribution of skarn deposits in the world, providing for the domestic industrial demand of 70% tin, 60% tungsten, 30% copper, 23% molybdenum, 20% gold, and 11% iron (Zhao et al., 2013 ). However, distributions of skarn deposits in China are irregular, with the vast majority (over 95%) of large and medium-sized deposits occurring in East China (i.e., Pacific Rim metallogenic domain), especially Fe–Cu skarns, which occur in the middle and lower reaches of the Yangtze River and the Yanliao Cu–Fe–Mo polymetallic mineralization belt. In recent years, there has been an increased discovery rate of large- and medium-sized polymetallic skarn deposits in the Qiman Tagh Metallogenic Belt (QMB) of the East Kunlun Mountains, forming the most profile polymetallic skarn belt in the northwest region (Feng et al., 2011 , 2010 ). The QMB is in the western portion of the East Kunlun Orogenic Belt (EKOB) along the northern part of the Qinghai–Tibet Plateau (QTP), between the Qaidam Basin and Kumukuri Basin in NW China (Feng et al., 2010 ). It is an important exploration target area for porphyry- and skarn-related Fe–Cu–Pb–Zn deposits (Feng et al., 2012 ; Zhao et al., 2013 ; Zhong et al., 2021 ). At present, skarn-related Fe–Cu–Pb–Zn deposits are the main prospecting targets in the belt, and many economically-mineable skarn deposits have been discovered, including the Kendekeke Fe (Xiao et al., 2013 ), Hutouya Cu–Pb–Zn–Fe (Feng et al., 2011 ; Qu et al., 2019a ), Kaerqueka Cu (Wang et al., 2009 ), Galinge Fe (Yu et al., 2015 ), and Yemaquan Fe deposits (Gao et al., 2014 ). The QMB is associated with the Qiman Tagh Orogen, which was constructed through protracted accretion and collision of a collage of terranes during the subduction and closure of the Qiman Tagh Ocean, a branch of the Paleo-Tethys Ocean from the Neoproterozoic to Early Mesozoic (Wang et al., 2009 ; Yu et al., 2017 ). The early Neoproterozoic (ca. 1000–820 Ma) ages for this orogen suggests a link with the formation of the Rodinia supercontinent (He et al., 2016 ; Meng et al., 2015 ). The Qiman Tagh Terrane was tectonically and chronologically separated into the North Qiman Tagh Terrane (NQT) and South Qiman Tagh Terrane (SQT), which was tectonically clipped by the Adatan fault in the east and Baiganhu fault in the west (Wang et al., 2009 ; Yu et al., 2017 ) (Fig. 1 A). The NQT was an active continental margin containing abundant Paleozoic granitoids, which possibly formed through melting of old basement (Li et al., 2013 ; Wang et al., 2014 ). In contrast, the SQT was an exotic terrane that had intra-oceanic subduction, where supra-subduction zone (SSZ) type ophiolites were documented together with island arc tholeiite and calc–alkaline lavas, in a primary oceanic island arc environment during the Early Paleozoic (Meng et al., 2015 ). In addition, the SQT developed abundant Late Paleozoic and Early Mesozoic granitoids (Chen et al., 2006 ; Yao et al., 2016 ) (Fig. 1 B, C). The collision between the SQT and NQT occurred probably in the Late Silurian (ca. 422 Ma) and continued to ca. 398 Ma (Chen et al., 2006 ; Yao et al., 2016 ), as evidenced by ages of abundant within-plate granitic magmatism in the NQT that formed after 398 Ma (Yao et al., 2016 ). The final closure of the Paleo Tethyan Qiman Tagh Ocean might have occurred in the Late Permian, and resulted in the accretion of the Kumukuri microcontinent followed by significant Triassic magmatism (Chen et al., 2005; Feng et al., 2012 ). A series of calc–alkaline and alkaline granitoids generated through mantle–crustal mixing were linked with transitions from post-collision to within-plate settings (Yu et al., 2015 ). 3. Geology of the Hutouya skarn The Hutouya skarn, located at the center of the QMB (Fig. 1 D), hosts a Cu–Pb–Zn resource of 0.85 million tones (Mt) at an average grade of 2.05% Cu, 5.79% Pb, and 4.46% Zn and an Fe resource of 200 Mt at an average grade of 28.82% Fe (Zhao et al., 2013 ). It comprises both magnesian and calcic skarns carrying Fe–Sn–Cu–Co mineralization in the inner zone and Pb–Zn mineralization in the outer zone, and locally contains W–Mo–Ag–Bi–Sn mineralization, and substantial pyrrhotite-bearing iron ores. Skarn alteration and Fe–Cu–Pb–Zn–W–Mo–Ag–Co–Bi–Sn mineralization is developed at the contacts between carbonate rocks and granitic intrusions. The ore is typically hosted by E–W trending Lower Carboniferous Dagangou marble and limestone and Upper Carboniferous Di’aosu Formation marble, calcsilicate hornfels, and dolomitic limestone with thinly-bedded limestone (Fig. 2 ). Mesoproterozoic Langyashan Formation of the Jixian Group, Ordovician–Silurian Qiman Tagh Group, and Upper Triassic Elashan Formation are also exposed in the district. All Paleozoic sedimentary rocks in the Hutouya deposit are extensively faulted and folded along E–W trends related to compressive fracture zones. These structures appear to be important in ore localization. More detailed descriptions can be found in Qu et al. ( 2019a ). Indosinian Permo–Triassic intermediate to felsic intrusions in the Hutouya deposit area include red syenogranite, light buff-colored monzogranite, and gray granodiorite, and diorite (Fig. 3 ). The syenogranite and monzogranite intrusions are spatially associated with mineralization in Ore Belt III (Fig. 4 A) and show an intrusive contact relationship (Fig. 4 B). The syenogranite is widespread in the center of the ore district and occurs as a 1.4 km 2 stock intruding the Di'aosu Formation, the Qiman Tagh Group, and Dagangou in the northern, western, and southern part of the district, respectively (Fig. 2 ). The monzogranite only crops out sporadically in the south of the Ore Belt II (Fig. 2 ). The irregularly-shaped monzogranite stock has an exposed area of 9 km 2 , and contains large amounts of mafic microgranular enclaves (MMEs) (Fig. 4 C, D). The intrusion has a contact with the underlying Di'aosu Formation where thick magnetite-rich skarn formed. The Hutouya deposit includes 51 skarn ore bodies in seven ore belts. These include three Cu–Pb–Zn ore bodies, and several medium-sized Fe ore bodies locally associated with W–Mo–Ag–Bi–Sn mineralization (Fig. 2 ). Ore belts I, II, and III contain Cu and Mo as an “inner contact” skarn with minor Fe and Sn. These skarns developed on and near contacts of syenogranite and monzogranite with carbonate-rich strata of the Lower Carboniferous Dagangou and Upper Carboniferous Di'aosu Formations. At the inner contact zone with the intrusions, the syenogranite displays strong endoskarn, alteration, and radial and meshed skarn veins (Fig. 4 E). However, the monzogranite shows a sharp contact relationship with the skarn and syenogranite intrusions in Ore belt III, which indicates that the monzogranite was probably emplaced after the syenogranite and skarn alteration (Fig. 4 F). Some of the meshed skarn veins occurr in the surrounding marble and are interpreted as the metasomatized front. The geometry and extent of these ore bodies are controlled by structures along the intrusive contact zone. Chalcopyrite, pyrite, and magnetite hosted in banded and massive skarns are the dominant ore minerals in these ore belts (Liu et al., 2013 ), with lesser pyrrhotite, arsenopyrite, and minor stannite (Zou et al., 2017 ). Ore belts IV–VII host Pb–Zn “outer contact” skarns with subordinate copper mineralization. The Pb–Zn ore bodies occor mainly in fracture zones and are largely strata bound sphalerite- and galena-bearing skarn bodies selectively replacing carbonate layers of the Di'aosu Formation, Qiman Tagh Group, and Langyashan Formation. Chalcopyrite and magnetite also occur in those ores. The ore belts and ore bodies appear to be both structurally- and stratigraphically-controlled. Skarn bodies range a few meters to tens of meters in width, and discontinuously extend to more than two km in length. Metal contents of skarns in the deposit are zoned from innermost Mo-bearing ores nearest intrusive contacts progressively outward to Fe–Sn–Cu–Co, Cu–Mo–(Pb–Zn), and outermost Pb–Zn zones. In a broad sense, silicate mineralogy in the skarn zones from innermost garnet-rich skarn near potassic-altered igneous rock grades progressively outward to diopside-, epidote-, tremolite- / actinolite-, and chlorite-rich minerals, surrounded by a peripheral zone of recrystallized marble with local massive sulfides. This zoning is complicated by late-stage quartz–sulfide and phlogopite-rich retrograde alteration that crosscuts early prograde skarn. Liu et al. ( 2013 ) suggested that fluids responsible for retrograde alteration played an important role in concentrating sphalerite in the Pb–Zn ores. 4. Sampling and analytical methods 4.1. Sampling There three representative rock samples from the Hutouya deposit were selected for petrographic examination, as well as U–Pb in-situ trace element analysis. Sample HT1901 was taken from the quartz-rich syenogranite and Sample HT1903 (which was divided into two subsamples) was selected from the porphyritic monzogranite. The samples are all from the Cu–Mo “inner contact” zone of Ore belt III. Zircon grains were separated using magnetic and heavy liquid separation. Approximately, 1000 zircon grains from each sample were mounted and polished in 25-mm epoxy discs. The 400 apatite grains used in this study were not separated by standard mineral separation techniques; rather, they were selected by employing optical and back-scattered electron (BSE) microscopy from polished thin sections. This approach combines detailed textural relationships, allowing for a more precise interpretation of apatite compositions. Individual apatite and zircon grains show conspicuous euhedral to subhedral columnar shapes in BSE (Fig. 5 ) and cathodoluminescence (CL) (Fig. 6 ), and there are no obvious cracks on the surface. 4.2. Analytical methods 4.2.1. BSE and CL imaging BSE imaging of apatite was performed by electron-probe microanalysis (EPMA) at the MNR Key Laboratory of Metallogeny and Mineral Assessment, using a JEOL JXA-8800 instrument with a 2 to 5 µm beam. Internal zonation patterns of zircon crystals were observed in CL images at the MNR Key Laboratory of Metallogeny and Mineral Assessment, Institute of Mineral Resources, Chinese Academy of Geological Sciences (CAGS), Beijing, China. Using a combination of CL imaging and optical microscopy, the clearest and least fractured zircon crystals were selected as suitable targets for laser ablation. 4.2.2. U–Pb dating and in-situ multi-element analysis of apatite and zircon U–Pb dating and in-situ multi-element composition analysis of apatite and zircon was performed using an ASI RESOLution S-155 ablation system with Coherent Compex Pro 110 Ar-F excimer laser operating at a 193 nm wavelength and pulse width of 20ns coupled to an Agilent 7900 quadrupole ICP–MS. Detailed analytical conditions are described in Thompson et al. ( 2016 ). All instrumentation is housed at the Centre for Ore Deposit and Earth Sciences (CODES) Analytical Laboratory at the University of Tasmania (UTAS), Hobart, Australia. Analyses comprise a 30s blank gas measurement followed by a further 30s of ablation when the laser is switched on using a 29 µm spot size, firing at a frequency of 5 Hz and beam energy density of 2.0 J/cm 2 for zircon and 3.5 J/cm 2 for apatite. All analyses have a pre-ablation of 5 laser shots to remove any surface contamination. Ablation was performed in a pure He atmosphere flowing at 0.35 L/min and immediately mixed with Ar, flowing at a rate of 1.05 L/min after ablation. The mass of each isotope (e.g., 23 Na, 31 P, 43 Ca, 51 V, 56 Fe, 88 Sr, etc.) was measured every ~ 2 ms with longer counting times on the Pb and U isotopes. Data reduction in apatite was done using the method outlined in Thompson et al ( 2016 ) and references therein, where a common Pb correction was performed on the calibration standard. The downhole fractionation, instrument drift and mass bias correction factors for Pb/U ratios were calculated using values of the OD306 apatite from Thompson et al ( 2016 ). The calibration of the U–Pb ages was monitored using several apatite reference materials: 401 apatite (Thompson et al., 2016 ), Durango apatite (McDowell et al. 2005 ) and the McClure Mountain apatite (Schoene and Bowring 2006 ). Ages are calculated using Concordia intercept with Stacey and Kramer’s (Stacey and Kramer, 1975) model Pb composition at the age of the apatite, unless there was enough spread on the isochron to negate the need for the assumption of common Pb composition. In zircon, U–Pb dating was based on the method outlined in Thompson et al ( 2018 ) and Halpin et al. ( 2014 ). For each analysis, a subset of data that closely matches a concordant composition was selected for quantification. The downhole fractionation, instrument drift, and mass bias correction factors for Pb/U ratios were calculated from analyses of the 91500-zircon using the values of Wiendenbeck et al. (1995). A calibration of U–Pb ages was performed by comparing measured analyses of the Temora zircon (Black et al. 2004 ) and the Plesovice zircon (Slama et al. 2008 ) with published values. Trace element abundances measured in the 91500 zircon were within the range of reported values from the GeoReM website ( http://georem.mpch-mainz.gwdg.de/ ). All common Pb corrections were done using Stacey and Kramer’s (Stacey and Kramer, 1975) model Pb composition at the age of the zircon, unless independent common Pb compositions existed for a sample. In both routines, instrument drift and mass bias correction factors of the 207 Pb/ 206 Pb ratio (ages) were determined using the Pb isotopic values of the NIST610 glass determined by Baker et al. ( 2004 ). Trace element abundances were calibrated on the NIST610 glass from values of Jochum et al. ( 2011 ) and using secondary standard corrections based on the composition of the glasses BCR-2G and GSD-1G (GeoReM preferred values). Quantification was performed using 43 Ca as an internal standard element in apatite and 91 Zr in zircon and normalizing all measured cations to stoichiometric concentrations of these elements in each respective mineral. The calibration standards and the NIST610, BCR-2G and GSD-1G glasses were analyzed in duplicate at the beginning, end and every 60 minutes throughout the analytical session. All data was processed using the program LADR (v1.1.01; Norris and Danyushevsky, 2018 ). 4.2.3. Apatite major element analysis Major element analysis of apatite was performed using EPMA at the UTAS using a JEOL JXA-8800 instrument with a 2 to 5 µm beam. F, Na, and Cl were analyzed with a 4 nA beam current and 10 kV accelerating voltage in the first instrumental pass; the remaining elements were measured utilizing a 20 nA beam current and 20 kV accelerating potential in the second instrumental pass. Natural minerals and synthetic oxides were used as standards, and the ZAF software provided by JEOL was used to correct matrix effects. The accuracy of the analytic results is 1–5% depending on the abundance of the element. 5. Results 5.1. U–Pb ages of apatite and zircon Typical BSE images of apatite from both intrusives are shown in Fig. 5 . Age data of apatite are summarized in Table S1 and Fig. 7 . Apatite from both intrusives can be categorized into two types: FI-free Apatite I and FI-rich Apatite II (Fig. 8 ). In this study, we present dating results of Apatite I. Most apatite from the two intrusives are euhedral, elongate, and tabular crystals about 100 × 40 µm to 200 × 60 µm in size without prominent zonation patterns (Fig. 5 ). The apatite age of sample HT1901 (syenogranite) yielded a lower intercept age of 229.0 ± 6.6 Ma, (MSWD = 1.15, n = 51), and samples HT1903-1 and HT1903-2 (monzogranite) yielded lower intercept ages of 224.3 ± 4.5 Ma (MSWD = 3.5, n = 27) and 223.7 ± 3.9 Ma (MSWD = 1.4, n = 40) (Fig. 7 ). Typical CL images of zircon are shown in Fig. 6 , and U–Pb data are summarized in Table S2 and Fig. 9 . According to size, color, texture, and morphology, zircon crystals from the two intrusives can be classified into Zircon I with transparent and bright zones, Zircon II with dark and metamict features, and Zircon III with mineral inclusions (Fig. 8 ). In this study, we present dating results of Zircon I. The zircon grains are clear to pale, euhedral to subhedral, nearly granular (normally 100 to 200 µm in size) and display concentric zonation patterns in CL. Zircon U–Pb ages of the two intrusives show a grouping with lower intercept ages in Tera–Wasserburg Concordia diagrams. The zircon age from sample HT1901 (syenogranite) yielded a lower intercept age of 224.70 ± 0.61 Ma (MSWD = 1.3, n = 24) (Fig. 9 ), and samples HT1903-1 and HT1903-2 (monzogranite) yielded lower intercept ages of 225.75 ± 0.66 Ma (MSWD = 1.15, n = 23) and 226.31 ± 0.78 Ma (MSWD = 1.4, n = 16) (Fig. 9 ), respectively. U–Pb ages of apatite–zircon from the two intrusives (monzogranite and syenogranite) in the Hutouya deposit are consistent within error. These ages likely represent the time of emplacement of the intrusives. 5.2. In-situ trace element compositions of zircon and apatite Trace element contents of apatite (Apatite I) are summarized in Table S3 and Fig. 10 . V, Pb, Th, and U concentrations of the apatite range from − 1 ppm to 10s ppm and do not show systematic variations from between the two intrusive. In contrast, Sr contents are much higher, ranging from 10s ppm to 100s ppm. REE concentrations range from 1,000s ppm to over 1 wt% in both intrusives. In the chondrite-normalized REE diagrams (Fig. 10 ), results have a negative slope from La to Lu, strong negative Eu anomalies with similar (Eu/Eu*) N , and weak positive Ce anomalies with similar (Ce/Ce*) N values (Fig. 11 ). Trace element compositions of zircon are listed in Table S4. Syenogranite (HT1901) and monzogranite (HT1903-1 and HT1903-2) have average REE contents of 732 ppm, 756 ppm, and 992 ppm, respectively. Th and U contents range from 10s ppm to 1,000s ppm. Hf concentrations are 1,000s ppm, with average values of 10,195 ppm for syenogranite, and 9,771 ppm and 10,069 ppm for the monzogranite samples. Chondrite-normalized REE diagrams for zircon show a consistent and steeply increasing trend diagrams from La to Lu with strongly positive Ce anomalies and negative Eu anomalies (Fig. 10 ). According to the (Ce/Ce*) N calculation method proposed by CODES on the basis of a lattice-strain model for mineral-melt partitioning of Ce 4+ and Ce 3+ cations, the relationships of Ce and Eu anomalies among different intrusions at Hutouya are examined. Calculated zircon (Ce/Ce*) N and (Eu/Eu*) N values are listed in Table S4, where the subscript indicates chondrite normalization. Zircon all display higher (Ce/Ce*) N values, ranging from 6 to 421 (average: 119) in the syenogranite and 15 to 309 (average: 84) and 1 to 245 (average: 62) in the monzogranite samples. The (Eu/Eu*) N values do not show noticeable differences between the intrusives, with most values ranging from 0.05 to 0.52 (Fig. 12 ). 5.3. Apatite major element compositions Analytical data of major elements for apatite from syenogranite (HT1901) and monzogranite (HT1903-1 and HT1903-2) are summarized in Table S5. The consistency of the results and previous published studies for the secondary standards suggests that the major element compositions for apatite are robust and reliable. The low analytical totals in some of the analyses are likely related to: 1) OH not being analysed, 2) elements present in the mineral but not captured in the routine, 3) the laser crater is adjacent to the EPMA spot in a sufficiently small grain, such that the interaction volume either overlaps with the crater or with epoxy, 4) charging effects due to insufficient coating of the crater next to the EPMA spot, and 5) there could be beam damage,since apatite are very susceptive to it. Major element contents of apatite from syenogranite and monzogranite intrusives are statistically identical. All apatite samples are fluorapatite, enriched in F but have low Cl contents. 6. Discussion 6.1. Robustness of apatite petrochronology in fingerprinting porphyry systems Accurate chronological constraints are critical for establishing the timing of mineralization, deciphering mineralization processes, and developing mineral exploration models. Geochronological and geochemical fingerprints of mineralization processes can be preserved by apatite and zircon. Zircon has characteristics of high stability and sealing temperatures, and high U and low common Pb contents, and therefore is one of the most suitable minerals for U–Pb dating. However, zircon may be absent in some ore systems or may not directly represent mineralization. Therefore, in recent years, the development of LA–ICP–MS dating of other U-rich minerals that form in hydrothermal fluids or related intrusives has become a powerful method to determine the age of mineral deposits. Apatite, a common accessory mineral in magmatic rocks and hydrothermal deposits, stands out due to it already being widely employed in low temperature thermochronology research (Chew and Spikings, 2015 ; Prowatke and Klemme, 2006 ; Webster et al., 2009 ). Apatite can be U–Pb dated (Tc = 550–350 o C), fission track dated (Tc = 110–60 o C), and U–Th–Sm/He dated (Tc = 80–40 o C), forming a medium- to low-temperature continuous thermochronology that can comprehensively and continuously analyze tectono–thermochronological history (Carrapa et al., 2009 ; Glorie et al., 2019 ; Jepson et al., 2018 ). Furthermore, apatite can accommodate a variety of elements (e.g., S, Sr, U, Th, REE, etc.) and has high volatile contents, such as F, OH and Cl, making it an ideal mineral for both geological dating and tracing (Chu et al., 2009 ; Piccoli and Candela, 1994 ). In this study, we selected apatite and zircon grains from the syenogranite and monzogranite in the Hutouya deposit to study thermochronology and in-situ trace element compositions, with the aim to test the consistency between apatite and zircon for petrochronology and fingerprinting of igneous processes in a porphyry–skarn system. Apatite grains in the two intrusives can be categorized into two types (FI-free Apatite I and FI-rich Apatite II; Fig. 8 ). The variations of textures and geochemical compositions in the two types of apatite are indicative of changing crystallization environments. The euhedral grains of Apatite I might be crystallized from a volatile-undersaturated magma. Conversely, Apatite II with lower Cl and higher F contents are only distributed in the more highly fractionated granite (Table S5, Fig. 8 ) and formed under a volatile-oversaturated stage demonstrated by the rich fluid inclusion contents (Andersson et al., 2019 ; Glorie et al., 2020; Mao et al., 2016 ; Pan et al., 2016 ; Qu et al., 2019b ). Lower Cl and higher F contents of Apatite II could be attributed to the segregation of isolated fluid phase in the late aqueous magma (Chu et al., 2009 ; Doherty et al., 2014 ; Mathez and Webster, 2005 ; Sha and Chappell, 1999; Webster et al., 2009 ). Zircon grains in the two granites can be classified into Zircon I with transparent and bright zones, Zircon II with dark and metamict features, and Zircon III with mineral inclusions (Fig. 8 ) in the CL images, indicating that they were formed under different physicochemical conditions during the magmatic-hydrothermal evolution. Zircon I grains have a magmatic texture of well-developed bright oscillatory zones, and are most likely primary magmatic zircon that crystallized early in the evolution of granitic magma. The low Th and U contents and higher Zr/Hf ratios of Zircon I (Table S4) indicate they crystallized from volatileundersaturated anhydrous magma (Erdmann et al., 2013; Qu et al., 2019b ; Zeng et al., 2016 ). Zircon II occurring as individual grains or overgrowth with the Zircon I might be of a successive later origin than the Zircon I (Fig. 8 ). Notably, high Th and U contents of Zircon II may be its crystallization from a volatile-enriched aqueous magma (Nasdala et al., 2001 ; Claiborne et al., 2006 ; Bacon et al., 2007 ; Geisler et al., 2007 ; Erdmann et al., 2013). Zircon III grains full of numerous hydrothermal mineral inclusions might be of the product of fluid interaction with previous Zircon II in a volatile-oversaturated environment, indicative of hydrothermal crystallization or hydrothermal alteration (Breiter and Skoda, 2012 ; Erdmann et al., 2013; Hoskin, 2005 ; Hoskin and Schaltegger, 2003 ). Collectively, apatite and zircon from the syenogranite and monzogranite in the Hutouya deposit experienced a prolonged crystallization process and were altered by late-stage exsolved fluids. The well-developed euhedral apatite and oscillatory primary magmatic zircon represent an early-crystallized phase from a least fractionated granite. Metamict zircon occurs as individual grains or overgrowth with the magmatic zircon formed under volatile–saturated aqueous magma during the magmatic-hydrothermal transition stage. Some formed zircon was altered by exsolved magmatic fluids in the most fractionated granite, indicating a volatile oversaturated environment. Meanwhile, apatite with abundant fluid inclusions and high F/Cl ratios from the most fractionated granite crystallized in this subsolidus stage. Apatite I and Zircon I are interpreted to be of magmatic origins, and their ages therefore represent the time of magma emplacement. The apatite LA–ICP–MS U–Pb ages range from 235–220 Ma, which is consistent with the zircon U–Pb ages that range from 227–224 Ma. These ages are indistinguishable within error and indicate that the magmas were emplaced over a short time span, and cooled rapidly, given the closure temperature of apatite (~ 620 o C) and zircon (900 o C). As hydrothermal activities and mineralization in porphyry–skarn systems are intimately tied to the emplacement of ore-forming intrusions (Razique et al. 2014 ), the associated hydrothermal and mineralization events at Hutouya probably have similar short durations of just a few million years or less (Zhong et al., 2018 ). At the regional scale, magmatism at Hutouya coincides with that in the other porphyry and skarn deposits in the QMB (Fig. 1 C). For instance, Kaerqueka porphyry–skarn in the QMB formed circa 227 Ma (Feng et al., 2012 ), 224 Ma at Yazigou Cu–Mo deposits (Li et al., 2008 ), and 229.4 Ma at Kendekeke Fe deposits (Xiao et al., 2013 ). The granitoids associated with skarns in the area formed during the same period, including the ages at Hutouya (this study), 225 Ma at Galinge Fe skarn deposits (Zhao et al., 2013 ), and 227 Ma at Tawenchahan Fe skarn deposits (Feng et al., 2012 ). It should be noted that geochemical compositions of apatite can be regarded as a tool to identify magmatic mineralization potentials. The magmatic oxygen fugacity is a key factor to fertile magmas of porphyry deposits (Lehmann, 1990 ; Sun et al., 2015 , 2013; Wittenbrink et al., 2009 ; Zhang et al., 2017 ; Zhong et al., 2017 ). Oxidized magmas are more likely to form Cu porphyry deposits than reduced magmas (Imai, 2002 ; Li et al., 2017a ; Liang et al., 2006 ; Lu et al., 2016 ), considering that under the high oxygen fugacity, sulfur in magmas mainly exists in the form of sulfate (SO 4 2− ) which has a much higher solubility in silicate melts than sulfide, that is, sulfide is difficult to reach saturation then precipitate during the magmatic stage thus facilitating metal accumulations in the late stage of magmatic evolutions (Ballard et al., 2002 ; Richards, 2003 ). Skarn and porphyry deposits have similar magmatic origins and evolution processes (Li et al., 2017b ), so it is also applicable to Cu (–Pb–Zn) skarn deposits in controlling of the oxygen fugacity to fertil magmas of Cu porphyry deposits. Zircon (Eu/Eu*) N and (Ce/Ce * ) N values are effective indicators for evaluating the magmatic oxygen fugacity (Ballard et al., 2002 ; Gardiner et al., 2017 ; Trail et al., 2012 ). In the Hutouya Fe–Cu–Pb–Zn skarn deposit, the syenogranite and monzogranite have similar (Eu/Eu * ) N and (Ce/Ce * ) N values in zircon, (Table S4; Fig. 12 ). According to the Weibao Cu–Pb–Zn skarn deposit in the QMB, fertile intrusions have higher Ce 4+ /Ce 3+ values than those of non-fertile intrusions (Zhong et al., 2018 ). We can draw a conclusion that parental magmas with the higher oxygen fugacity from fertile intrusions in Cu skarn deposits tend to form Cu mineralization. However, Pb and Zn are not easily controlled by oxygen fugacity and behave as incompatible elements. This means that magmas related to the Pb–Zn mineralization can be either high oxygen fugacity or low oxygen fugacity. Many studies have shown that both S-type granite (low oxygen fugacity magmas) and I-type granite (high oxygen fugacity magmas) can form Pb–Zn skarn deposits (Fu et al., 2017 ; Niu et al., 2017 ), which also supports that Pb-Zn mineralization is independent of magmatic oxygen fugacity conditions. In other words, the oxidation state is not a controlling factor for Pb–Zn mineralization within the Hutouya deposit. Apatite Eu and Ce anomalies may be more easily affected by other factors unlike zircon Eu and Ce anomalies which are mainly controlled by oxygen fugacity conditions, therefore the relationship between apatite Eu and Ce anomalies and magmatic oxygen fugacity is not so similar (Piccoli and Candela, 1994 ). Nevertheless, if the physical conditions (specifically temperature and pressure) and concentrations of these elements in magma are relatively stable, apatites crystallizing from more oxidized magma will have higher Eu 3+ /Eu 2+ but lower Ce 4+ /Ce 3+ than reduced magma owing to ion substitution in the apatite structure, which results in apatites having strong negative Eu and positive Ce anomalies (Cao et al., 2012; Sha and Chappell, 1999). In this study, we further confirm that magmatism in the Hutouya deposit is similar to other skarn deposits in the QMB. Notwithstanding, this work shows that the fertile intrusions at Hutouya can be well defined by (Eu/Eu * ) N and (Ce/Ce * ) N parameters, that is strong negative Eu anomalies and weak positive Ce in apatite. Hence, apatite Ce anomalies including (Ce/Ce * ) N , Ce 4+ /Ce 3+ , and Ce/Nd values are relatively more robust as proxies for magma oxidation state (Loader et al., 2017 ). The parameter (Eu/Eu * ) N , although affected by many magmatic processes, can still reflect the magma redox state to some degree (Dilles et al., 2015 ). Moreover, previous studies found that Mn contents are significantly controlled by the oxygen fugacity with high apatite Mn contents in reduced magmas while low apatite Mn contents in oxidized magmas, which can be explained by the substitution of Ca 2+ by Mn 2+ . Compared with Mn 3+ and Mn 4+ , Mn 2+ is more easily enriched in apatite, because the ionic radius of Mn 2+ is close to that of Ca 2+ (Belousova et al., 2002 ). Mn mainly exists as Mn 2+ at low oxygen fugacity with high Mn contents in apatite, while Mn mainly exists as Mn 3+ and Mn 4+ at the high oxygen fugacity with low Mn contents. In the Weibao deposit, apatite within two ore-forming intrusions exhibits much lower Mn concentrations than within the barren diorite porphyry. Apatite Mn contents of the two fertile intrusions in the Hutouya deposit are similar to the fertile intrusions in the Webao deposit (Zhong et al., 2018 ). Notwithstanding, halogen contents of magmas (especially F and Cl contents) in apatite can also be regarded as an important indicator to evaluate productive magmas since halogens can effectively complex and transport metal elements (Coulson et al., 2001 ; Pan et al. 2016 ; Piccoli and Candela, 1994 ; Webster et al., 2004 ). A previous study showed that apatite, occurring as inclusions within biotite and hornblende, was one of the early crystal phases that appeared during crystallization (Tang et al., 2021 ), and thus the F and Cl partitioning between the apatite and the melt seems unlikely to be influenced by the crystallization of biotite and hornblende. Therefore, the contents of chlorine and fluorine in the melt predominantly affected by their magmatic sources can be evaluated from the concentrations of chlorine and fluorine in apatite. In this study, the fluorine contents of apatite is much higher than chlorine contents, because the partition coefficient of fluorine between apatite and melt is much higher than those of chlorine (Mathez and Webster, 2005 ). In addition, the chlorine contents of the two fertile intrusions in this study remain almost invariable, because the apatite/melt ratio is approximately constant at low Cl contents, but when the melt becomes saturated in Cl both partition coefficients increase rapidly as Cl content of the bulk system increases (Doherty et al., 2014 ). Furthermore, magmas formed by partial melting of lower crust materials usually show relatively stronger enrichment of F and depletion of Cl than those formed by dehydration melting in slab subduction environments (Ding et al., 2015; Jiang et al., 2018 ; Kendrick et al., 2011 ; Xu et al., 2022 ). Therefore, the volatile components of the parent magmas of syenogranite and monzogranite are mainly related to lower crustal melting. 6.2. Implication for regional exploration The QMB region experienced two important tectonic evolutionary processes of the Proto-Tethys Ocean and the Paleo-Tethys Ocean, corresponding to two magmatic cycles of the Early Paleozoic and Late Paleozoic to Early Mesozoic (Feng et al., 2012 ; Mo et al., 2007 ; Yang et al., 2003 ; Yu et al., 2017 ). The Proto-Tethys Ocean began to form and expand in the Early Cambrian (Feng et al., 2010 ; Yang et al., 1996 ), the subduction gradually weakened in the Silurian and began to transition to a collisional orogeny stage (Liu et al., 2013 ; Ren et al., 2009 ), and changed from a syn-collision compressional environment to a post-collision extensional environment in the Devonian (Meng et al., 2015 ; Qi et al., 2016 ; Zhao et al., 2008 ). The Paleo-Tethys Ocean was in a subduction stage during the Late Permian-Early Triassic (Yao et al., 2020 ), and entered collision and post-collision stages during the Middle–Late Triassic (Feng et al., 2012 ). The Middle–Late Triassic is a very important metallogenic period in the QMB (Gao et al., 2014 ; Wang et al., 2018 ; Zhang et al., 2010 ). At this stage, the QMB evolution changed from a compressional and transpressional to an extensional environment, which resulted in asthenosphere upwelling and strong crust–mantle interaction (Yao et al., 2017 ). As consequence, extensive partial melting of lower crust caused widespread development of magmatic intrusions in the upper crust. Thus, it provided favorable conditions for polymetallic mineralization in this area, and ore-forming ages of skarn polymetallic deposits are concentrated in a range of 230–224 Ma (Qu et al., 2023 ), consistent with the apatite and zircon aged determinations in this study. 7. Conclusion Apatite from the two fertile intrusives (syenogranite and monzogranite) in the Hutouya skarn deposit can be divided into FI-free Apatite I and FI-rich Apatite II, meanwhile, zircon can be classified into three sub-types: Zircon I with transparent and bright zones, Zircon II with dark and metamict features, and Zircon III with mineral inclusions. They syenogranite and monzogranite were emplaced between 235 to 220 Ma (apatite ages), which is similar to their zircon ages (227 to 224 Ma). These ages are coincident with other fertile intrusives in QMB. These ages are coincident with other fertile intrusives in the QMB. They also have similar magmatic oxygen fugacity coefficients and apatite halogen contents as other fertile intrusives in the QMB, indicating that apatite trace element compositions can be used as robust proxies for magma oxidation state in porphyry-skarn systems. Declarations CRediT authorship contribution statement Hongying Qu : data curation, funding acquisition, investigation, writing original draft, and writing review and editing. Julie Rowland : supervision and writing review and editing. Jingwen Mao : conceptualization, supervision, and writing review and editing. Evan Orovan : data curation, methodology, and writing review and editing. Michael Rowe : formal analysis and methodology. Shihua Zhong : conceptualization and formal analysis Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Acknowledgments This study was financially supported by the China Geological Survey Program (Grant number: DD20240117). Prof. Chengyou Feng and Dr. Miaoyu, Hui Wang, and Jiannan Liu are acknowledged for their assistance during the fieldwork. We are thankful for assistance from Prof. David Cooke and Leonid Danyushevsky and Dr. Lejun Zhang for LA–ICP–MS analyses. References Andersson, S.S., Wagner, T., Jonsson, E., Fusswinkel, T., Whitehouse, M.J., 2019. Apatite as a tracer of the source, chemistry and evolution of ore-forming fluids: The case of the Olserum–Djupedal REE-phosphate mineralization, SE Sweden. Geochimica et Cosmochimica Acta 255, 163–187. Bacon, C.R., Sisson, T.W., Mazdab, F.K., 2007. 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The Evidence of Intrusive Rocks about Collision-orogenyduring Early Devonian in Eastern Kunlun Area. Geological Review 47–56 (in Chinese with English abstract). Zhong, S.H., Li, S.Z., Feng, C.Y., Liu, Y.J., Santosh, M., He, S.Y., Qu, H.Y., Liu, G.Y., Seltmann, R., Lai, Z.Q., Wang, X.H., Song, Y.X., Zhou, J., 2021. Porphyry copper and skarn fertility of the northern Qinghai–Tibet Plateau collisional granitoids. Earth–Science Reviews 214, 103524. Zhong, S.H., Feng, C.Y., Seltmann, R., Li, D.X., Dai, Z.H., 2018. Geochemical contrasts between Late Triassic ore-bearing and barren intrusions in the Weibao Cu–Pb–Zn deposit, East Kunlun Moutains, NW China: constraints from accessory minerals (zircon and apatite). Mineralium Deposita 53, 855–870. Zhong, S.H., Seltmann, R., Shen, P., 2017. Two different types of granitoids in the Suyunhe large porphyry Mo deposit, NW China and their genetic relationships with molybdenum mineralization. Ore Geology Reviews 88, 116-139. Zou, Y.H., Liu, Y., Dai, T.G., Mao, X.C., Lei, Y.B., Lai, J.Q., Tian, H.L., 2017. Finite difference modeling of metallogenic processes in the Hutouya Pb–Zn deposit, Qinghai, China: Implications for hydrothermal mineralization. Ore Geology Reviews 91, 463–476. Additional Declarations No competing interests reported. Supplementary Files SupplementaryTablelegends.docx TableS14.xlsx TableS5.xlsx Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-4524703","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":316213511,"identity":"cb46bda0-431a-455f-9eab-46a8f62f461c","order_by":0,"name":"Hongying Qu","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA0UlEQVRIiWNgGAWjYBACAwTJfODAhwrStLAlHpxxhmgtYMBjfJi3hQgt5uy9h1/zFNyx67uR8+EAbwODPL/YAfxaLHvOpVnzGDxLnnkjd8MByR0MhjNnJxBw2I0cM2Meg8PJBiAthmcYEgxuE68l58GBxDbitBg/BmqxAzIYDhwkSsuZM2aMcwwOJ0ieeWZwsOGMBBF+Od5j/OHNn8P2fMeTH3/+U2Ejzy9NQAsQsEnxMDAkNhwAcyQIKgcB5o8/GBjsGQ4QpXgUjIJRMApGIgAA6iFPUiDqJZ8AAAAASUVORK5CYII=","orcid":"","institution":"Institute of Mineral Resources, CAGS","correspondingAuthor":true,"prefix":"","firstName":"Hongying","middleName":"","lastName":"Qu","suffix":""},{"id":316213512,"identity":"24a1036d-a278-4279-a162-f587f594a706","order_by":1,"name":"Julie Rowland","email":"","orcid":"","institution":"University of Auckland","correspondingAuthor":false,"prefix":"","firstName":"Julie","middleName":"","lastName":"Rowland","suffix":""},{"id":316213513,"identity":"500a855c-6017-4f6a-8da5-a38e36558b40","order_by":2,"name":"Jingwen Mao","email":"","orcid":"","institution":"Institute of Mineral Resources, CAGS","correspondingAuthor":false,"prefix":"","firstName":"Jingwen","middleName":"","lastName":"Mao","suffix":""},{"id":316213514,"identity":"503f53f9-7575-40c9-8a38-096aaa1ef7d1","order_by":3,"name":"Evan Orovan","email":"","orcid":"","institution":"British Columbia Geological Survey","correspondingAuthor":false,"prefix":"","firstName":"Evan","middleName":"","lastName":"Orovan","suffix":""},{"id":316213515,"identity":"2e915b49-e102-4cb7-82f6-64fb5c987466","order_by":4,"name":"Michael Rowe","email":"","orcid":"","institution":"University of Auckland","correspondingAuthor":false,"prefix":"","firstName":"Michael","middleName":"","lastName":"Rowe","suffix":""},{"id":316213516,"identity":"67fd9410-2504-4894-9372-0bbe8241265a","order_by":5,"name":"Shihua Zhong","email":"","orcid":"","institution":"Ocean University of China","correspondingAuthor":false,"prefix":"","firstName":"Shihua","middleName":"","lastName":"Zhong","suffix":""}],"badges":[],"createdAt":"2024-06-04 02:45:54","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-4524703/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-4524703/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":58925873,"identity":"3bc56025-e2f4-4418-8b50-edb2d49da54c","added_by":"auto","created_at":"2024-06-24 08:13:24","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":3950059,"visible":true,"origin":"","legend":"\u003cp\u003e(A) Tectonic outline of the Tibet Plateau showing the locations of the main suture zones. The satellite image of the East Kunlun showing major tectonic units. (B) Tectonic–magmatic sketch map of the Qiman Tagh showing tectonic subdivisions, South Qiman Tagh magma belt and North Qiman Tagh magma belt. They are bordered by the Adatan thrust fault in the east and Baiganhu thrust fault in the west. (C) Frequency plot of the U–Pb ages for the intrusions from the North Qiman Tagh Belt and South Qiman Tagh Belt. (D) The age data sources are referred in the text. Ages that are in ~200 Ma are colored blue, ~300 Ma are black, and ~400 Ma are red. Italic characters: SHRIMP; standard character: LA–ICP–MS.\u003c/p\u003e","description":"","filename":"floatimage1.png","url":"https://assets-eu.researchsquare.com/files/rs-4524703/v1/5c140bfde86179c0f3dfd300.png"},{"id":58924678,"identity":"0f4c9965-dc34-49d9-992e-7dd43cf21aad","added_by":"auto","created_at":"2024-06-24 07:57:25","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":1191635,"visible":true,"origin":"","legend":"\u003cp\u003eGeological sketch map of the Hutouya deposit in Qiman Tagh, Qinghai Province (modified after Feng et al., 2011), showing sample locations in this study (triangles).\u003c/p\u003e","description":"","filename":"floatimage2.png","url":"https://assets-eu.researchsquare.com/files/rs-4524703/v1/efa870a561681e0c84e2a0bc.png"},{"id":58924687,"identity":"f2dd4dd2-99f0-4c7a-9a0b-019539be5f7e","added_by":"auto","created_at":"2024-06-24 07:57:25","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":31745995,"visible":true,"origin":"","legend":"\u003cp\u003eMicrograph of syenogranite and monzogranite (cross-polarized light).\u003c/p\u003e","description":"","filename":"floatimage3.png","url":"https://assets-eu.researchsquare.com/files/rs-4524703/v1/463d44dd8df431c03cfaea6b.png"},{"id":58924676,"identity":"c3ed09f6-d083-4705-8999-4bf1306f7c67","added_by":"auto","created_at":"2024-06-24 07:57:24","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":3910852,"visible":true,"origin":"","legend":"\u003cp\u003eField photographs of Ore Belt III in the Hutouya skarn deposit. (A) Contact relationship between Ore Belt III and intrusions; (B) intrusive relationship between monzogranite and syenogranite; (C, D) MMEs hosted by monzogranite; (E) endoskarn showing strong alteration of syenogranite; (F) monzogranite intruded into altered syenogranite and skarn.\u003c/p\u003e","description":"","filename":"floatimage4.png","url":"https://assets-eu.researchsquare.com/files/rs-4524703/v1/6fbf9deee4e103a75ffce1d2.png"},{"id":58925240,"identity":"f4630ef9-85b0-4b02-9901-638f118af22a","added_by":"auto","created_at":"2024-06-24 08:05:25","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":879290,"visible":true,"origin":"","legend":"\u003cp\u003eRepresentative BSE images of apatite for syenogranite and monzogranite in the Hutouya deposit. The analytical spots and dating results are shown.\u003c/p\u003e","description":"","filename":"floatimage5.png","url":"https://assets-eu.researchsquare.com/files/rs-4524703/v1/cfde99da161ad4633917aac9.png"},{"id":58925241,"identity":"7ad453ac-fe70-4c66-9d01-d120cdcae047","added_by":"auto","created_at":"2024-06-24 08:05:25","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":777818,"visible":true,"origin":"","legend":"\u003cp\u003eRepresentative CL images of zircon for syenogranite and monzogranite in the Hutouya deposit. The analytical spots and dating results are shown.\u003c/p\u003e","description":"","filename":"floatimage6.png","url":"https://assets-eu.researchsquare.com/files/rs-4524703/v1/4f09e1c4d5b5e7dd6855765b.png"},{"id":58925238,"identity":"de926e47-3f14-4339-ac4e-853b1888ce4e","added_by":"auto","created_at":"2024-06-24 08:05:25","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":953797,"visible":true,"origin":"","legend":"\u003cp\u003eDiagrams of apatite U–Pb dating for syenogranite and monzogranite in the Hutouya deposit.\u003c/p\u003e","description":"","filename":"floatimage7.png","url":"https://assets-eu.researchsquare.com/files/rs-4524703/v1/560060daffc39ec90801af9e.png"},{"id":58924680,"identity":"d03bf8eb-0a21-47db-9470-5168369affe2","added_by":"auto","created_at":"2024-06-24 07:57:25","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":3079232,"visible":true,"origin":"","legend":"\u003cp\u003eA schematic illustration of the zircon and apatite recording the magmatic\u003cstrong\u003e–\u003c/strong\u003ehydrothermal evolution process (modified after Qu et al., 2019b). The variations of the zircon types (I, II, and III) and apatite types (I and II) on morphology, textures and geochemical compositions reflecting the progressive evolution of the granitic melt from volatile-undersaturated to oversaturated conditions.\u003c/p\u003e","description":"","filename":"floatimage8.png","url":"https://assets-eu.researchsquare.com/files/rs-4524703/v1/4dbc3d8b1eaf0bdb346b4746.png"},{"id":58924681,"identity":"09d8543d-dc4c-412d-b057-a80e6ff279e8","added_by":"auto","created_at":"2024-06-24 07:57:25","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":1134268,"visible":true,"origin":"","legend":"\u003cp\u003e1) Diagrams of zircon U–Pb dating for syenogranite and monzogranite in the Hutouya deposit, and 2) histograms on ages and numbers.\u003c/p\u003e","description":"","filename":"floatimage9.png","url":"https://assets-eu.researchsquare.com/files/rs-4524703/v1/3217f0ebd9b8089b85a34ce8.png"},{"id":58924684,"identity":"7bc92e03-74e2-489c-bfff-e395c8b704a8","added_by":"auto","created_at":"2024-06-24 07:57:25","extension":"png","order_by":10,"title":"Figure 10","display":"","copyAsset":false,"role":"figure","size":1465280,"visible":true,"origin":"","legend":"\u003cp\u003eChondrite-normalized REE diagrams of zircon and apatite for syenogranite and monzogranite in the Hutouya deposit.\u003c/p\u003e","description":"","filename":"floatimage10.png","url":"https://assets-eu.researchsquare.com/files/rs-4524703/v1/ff8666673595c04c79640258.png"},{"id":58925239,"identity":"78d15a4d-c78d-40af-a660-ee1ed4a58d3e","added_by":"auto","created_at":"2024-06-24 08:05:25","extension":"png","order_by":11,"title":"Figure 11","display":"","copyAsset":false,"role":"figure","size":17583,"visible":true,"origin":"","legend":"\u003cp\u003eApatite (Eu/Eu\u003csup\u003e*\u003c/sup\u003e)\u003csub\u003eN\u003c/sub\u003e versus (Ce/Ce\u003csup\u003e*\u003c/sup\u003e)\u003csub\u003eN\u003c/sub\u003e diagram for syenogranite and monzogranite in the Hutouya deposit.\u003c/p\u003e","description":"","filename":"11.png","url":"https://assets-eu.researchsquare.com/files/rs-4524703/v1/edd6673ed6e2e4dec97facdf.png"},{"id":58924683,"identity":"33ff6235-6ada-4b63-be0c-e3cff0653ffa","added_by":"auto","created_at":"2024-06-24 07:57:25","extension":"png","order_by":12,"title":"Figure 12","display":"","copyAsset":false,"role":"figure","size":20394,"visible":true,"origin":"","legend":"\u003cp\u003eZircon (Eu/Eu\u003csup\u003e*\u003c/sup\u003e)\u003csub\u003eN\u003c/sub\u003e versus (Ce/Ce\u003csup\u003e*\u003c/sup\u003e)\u003csub\u003eN\u003c/sub\u003e diagram for syenogranite and monzogranite in the Hutouya deposit.\u003c/p\u003e","description":"","filename":"12.png","url":"https://assets-eu.researchsquare.com/files/rs-4524703/v1/b2f9953ff9f053312364c100.png"},{"id":81928454,"identity":"39ee5922-9900-4958-9d45-2c305a597d56","added_by":"auto","created_at":"2025-05-05 04:32:01","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":56415127,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4524703/v1/cedbf725-0c81-4bde-8e0d-4d665deef948.pdf"},{"id":58924674,"identity":"bf801a9b-a642-48a5-ba50-04d13311e15b","added_by":"auto","created_at":"2024-06-24 07:57:24","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":29718,"visible":true,"origin":"","legend":"","description":"","filename":"SupplementaryTablelegends.docx","url":"https://assets-eu.researchsquare.com/files/rs-4524703/v1/88f7bbb3bdfaded4cd3ab4c8.docx"},{"id":58924688,"identity":"c0ae2845-2646-43b3-bf81-70fa919edbb4","added_by":"auto","created_at":"2024-06-24 07:57:25","extension":"xlsx","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":126021,"visible":true,"origin":"","legend":"","description":"","filename":"TableS14.xlsx","url":"https://assets-eu.researchsquare.com/files/rs-4524703/v1/4dc3423931d382c8d9d69d03.xlsx"},{"id":58925236,"identity":"0c57b281-1a6e-41b3-9678-49465a0e09d1","added_by":"auto","created_at":"2024-06-24 08:05:24","extension":"xlsx","order_by":3,"title":"","display":"","copyAsset":false,"role":"supplement","size":15451,"visible":true,"origin":"","legend":"","description":"","filename":"TableS5.xlsx","url":"https://assets-eu.researchsquare.com/files/rs-4524703/v1/3ed52ee4b13270246b7c1372.xlsx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Consistency between apatite and zircon petrochronology supports robustness of apatite in fingerprinting igneous processes in porphyry systems","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eThe determination of rock-forming and mineralizing ages is critical to understanding mineral deposit genesis. Zircon, as is stable, has a high sealing temperature, and high U and low common Pb concentrations, making it the most commonly used imeral for U\u0026ndash;Pb dating; however, zircon may be absence, or may not represent the timing of mineralization in some mineral deposits. Recently, developed highly sensitive analytical techniques, most notably, laser ablation inductively coupled plasma mass spectrometry (LA\u0026ndash;ICP\u0026ndash;MS) age dating of U-rich minerals (e.g., apatite, epidote, cassiterite, magnetite, garnet, titanite, rutile, calcite, wolframite, scheelite, etc.), has allowed researchers to not solely rely on zircon for dating hydrothermal events in mineral deposits (Andersson et al., \u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e2019\u003c/span\u003e; Glorie et al., 2020; Mao et al., \u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e2016\u003c/span\u003e; Pan et al., \u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e2016\u003c/span\u003e; Qu et al., \u003cspan citationid=\"CR60\" class=\"CitationRef\"\u003e2019b\u003c/span\u003e). It is worth mentioning that apatite, being a common accessory mineral in magmatic rocks and hydrothermal deposits, is generally employed in low-temperature thermochronology research (Chew and Spikings, \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e2015\u003c/span\u003e; Prowatke and Klemme, \u003cspan citationid=\"CR56\" class=\"CitationRef\"\u003e2006\u003c/span\u003e; Webster et al., \u003cspan citationid=\"CR75\" class=\"CitationRef\"\u003e2009\u003c/span\u003e). Due to its relatively low U\u0026ndash;Th\u0026ndash;Pb isotope sealing temperature (~\u0026thinsp;550\u0026ndash;350 \u003csup\u003eo\u003c/sup\u003eC), apatite dating can provide age information for P\u0026ndash;T\u0026ndash;t trajectory research for metamorphic rocks with complex evolutionary and thermal histories. Apatite can be double or even triple dated (U\u0026ndash;Pb, fission track, and U\u0026ndash;Th\u0026ndash;Sm/He), allowing a reconstruction of a thermal history of a rock from ~\u0026thinsp;550 \u003csup\u003eo\u003c/sup\u003eC to near-surface temperatures (Carrapa et al., \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e2009\u003c/span\u003e; Glorie et al., \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e2019\u003c/span\u003e; Jepson et al., \u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). Although apatite LA\u0026ndash;ICP\u0026ndash;MS dating has advantages, such as in-situ rapid age determinations, there are significant problems for samples with high Pb and low U and Th contents. Also, apatite is unstable in acidic groundwaters and weathering profiles and has only limited mechanical stability in sedimentary transport systems (Morton and Hallsworth, \u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e1999\u003c/span\u003e). In contrast, zircon have a much more stable nature than apatite. Like zircon, apatite trace element compositions can be used to interpret characteristics of the melt from which it was derived, e.g., its compositional evolution, degree of assimilation and fractionation, oxidation state, and even determination of paragenetic separation from the parental magma (Ballard et al., \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e2002\u003c/span\u003e; Liang et al., \u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e2006\u003c/span\u003e; Odlum et al., \u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e2022\u003c/span\u003e; Zhang et al., \u003cspan citationid=\"CR89\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). This is possible because the apatite mineral structure, Ca\u003csub\u003e5\u003c/sub\u003e(PO\u003csub\u003e4\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e(F,Cl,OH), can incorporate a variety of transition metals, rare earth elements (REE), and other cations. For example, Sr\u003csup\u003e2+\u003c/sup\u003e, Mn\u003csup\u003e2+\u003c/sup\u003e, Fe\u003csup\u003e2+\u003c/sup\u003e, REE, and Na\u003csup\u003e+\u003c/sup\u003e can be substituted in the Ca\u003csup\u003e2+\u003c/sup\u003e and Si\u003csup\u003e4+\u003c/sup\u003e sites, and As\u003csup\u003e5+\u003c/sup\u003e and S\u003csup\u003e6+\u003c/sup\u003e can be substituted in the P\u003csup\u003e5+\u003c/sup\u003e site (Hughes and Rakovan, \u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e2002\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eIn this study, we evaluate the consistency between apatite and zircon petrochronology from rocks that are proximal to a skarn deposit to test the robustness of apatite in fingerprinting igneous processes in porphyry systems. We used LA\u0026ndash;ICP\u0026ndash;MS to obtain U\u0026ndash;Pb ages of apatite and zircon for Middle\u0026ndash;Late Triassic intrusions of the Hutouya skarn deposit, NW China, and determined their in-situ trace element compositions. Through comparisons with global trace element compositions of apatite from fertile intrusions in the porphyry systems, we concluded that a similar robustness in fingerprinting igneous processes in porphyry systems as zircon, and that apatite thermochronology can test complementary information on magma evolutions and ore-forming fluids that are not available from zircon alone.\u003c/p\u003e"},{"header":"2. Regional geological setting","content":"\u003cp\u003eChina has one of the widest distribution of skarn deposits in the world, providing for the domestic industrial demand of 70% tin, 60% tungsten, 30% copper, 23% molybdenum, 20% gold, and 11% iron (Zhao et al., \u003cspan citationid=\"CR90\" class=\"CitationRef\"\u003e2013\u003c/span\u003e). However, distributions of skarn deposits in China are irregular, with the vast majority (over 95%) of large and medium-sized deposits occurring in East China (i.e., Pacific Rim metallogenic domain), especially Fe\u0026ndash;Cu skarns, which occur in the middle and lower reaches of the Yangtze River and the Yanliao Cu\u0026ndash;Fe\u0026ndash;Mo polymetallic mineralization belt. In recent years, there has been an increased discovery rate of large- and medium-sized polymetallic skarn deposits in the Qiman Tagh Metallogenic Belt (QMB) of the East Kunlun Mountains, forming the most profile polymetallic skarn belt in the northwest region (Feng et al., \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e2011\u003c/span\u003e, \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e2010\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eThe QMB is in the western portion of the East Kunlun Orogenic Belt (EKOB) along the northern part of the Qinghai\u0026ndash;Tibet Plateau (QTP), between the Qaidam Basin and Kumukuri Basin in NW China (Feng et al., \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e2010\u003c/span\u003e). It is an important exploration target area for porphyry- and skarn-related Fe\u0026ndash;Cu\u0026ndash;Pb\u0026ndash;Zn deposits (Feng et al., \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e2012\u003c/span\u003e; Zhao et al., \u003cspan citationid=\"CR90\" class=\"CitationRef\"\u003e2013\u003c/span\u003e; Zhong et al., \u003cspan citationid=\"CR92\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). At present, skarn-related Fe\u0026ndash;Cu\u0026ndash;Pb\u0026ndash;Zn deposits are the main prospecting targets in the belt, and many economically-mineable skarn deposits have been discovered, including the Kendekeke Fe (Xiao et al., \u003cspan citationid=\"CR79\" class=\"CitationRef\"\u003e2013\u003c/span\u003e), Hutouya Cu\u0026ndash;Pb\u0026ndash;Zn\u0026ndash;Fe (Feng et al., \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e2011\u003c/span\u003e; Qu et al., \u003cspan citationid=\"CR59\" class=\"CitationRef\"\u003e2019a\u003c/span\u003e), Kaerqueka Cu (Wang et al., \u003cspan citationid=\"CR74\" class=\"CitationRef\"\u003e2009\u003c/span\u003e), Galinge Fe (Yu et al., \u003cspan citationid=\"CR85\" class=\"CitationRef\"\u003e2015\u003c/span\u003e), and Yemaquan Fe deposits (Gao et al., \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e2014\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eThe QMB is associated with the Qiman Tagh Orogen, which was constructed through protracted accretion and collision of a collage of terranes during the subduction and closure of the Qiman Tagh Ocean, a branch of the Paleo-Tethys Ocean from the Neoproterozoic to Early Mesozoic (Wang et al., \u003cspan citationid=\"CR74\" class=\"CitationRef\"\u003e2009\u003c/span\u003e; Yu et al., \u003cspan citationid=\"CR86\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). The early Neoproterozoic (ca. 1000\u0026ndash;820 Ma) ages for this orogen suggests a link with the formation of the Rodinia supercontinent (He et al., \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e2016\u003c/span\u003e; Meng et al., \u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e2015\u003c/span\u003e). The Qiman Tagh Terrane was tectonically and chronologically separated into the North Qiman Tagh Terrane (NQT) and South Qiman Tagh Terrane (SQT), which was tectonically clipped by the Adatan fault in the east and Baiganhu fault in the west (Wang et al., \u003cspan citationid=\"CR74\" class=\"CitationRef\"\u003e2009\u003c/span\u003e; Yu et al., \u003cspan citationid=\"CR86\" class=\"CitationRef\"\u003e2017\u003c/span\u003e) (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e1\u003c/span\u003eA). The NQT was an active continental margin containing abundant Paleozoic granitoids, which possibly formed through melting of old basement (Li et al., \u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e2013\u003c/span\u003e; Wang et al., \u003cspan citationid=\"CR72\" class=\"CitationRef\"\u003e2014\u003c/span\u003e). In contrast, the SQT was an exotic terrane that had intra-oceanic subduction, where supra-subduction zone (SSZ) type ophiolites were documented together with island arc tholeiite and calc\u0026ndash;alkaline lavas, in a primary oceanic island arc environment during the Early Paleozoic (Meng et al., \u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e2015\u003c/span\u003e). In addition, the SQT developed abundant Late Paleozoic and Early Mesozoic granitoids (Chen et al., \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2006\u003c/span\u003e; Yao et al., \u003cspan citationid=\"CR84\" class=\"CitationRef\"\u003e2016\u003c/span\u003e) (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e1\u003c/span\u003eB, C). The collision between the SQT and NQT occurred probably in the Late Silurian (ca. 422 Ma) and continued to ca. 398 Ma (Chen et al., \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2006\u003c/span\u003e; Yao et al., \u003cspan citationid=\"CR84\" class=\"CitationRef\"\u003e2016\u003c/span\u003e), as evidenced by ages of abundant within-plate granitic magmatism in the NQT that formed after 398 Ma (Yao et al., \u003cspan citationid=\"CR84\" class=\"CitationRef\"\u003e2016\u003c/span\u003e). The final closure of the Paleo Tethyan Qiman Tagh Ocean might have occurred in the Late Permian, and resulted in the accretion of the Kumukuri microcontinent followed by significant Triassic magmatism (Chen et al., 2005; Feng et al., \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e2012\u003c/span\u003e). A series of calc\u0026ndash;alkaline and alkaline granitoids generated through mantle\u0026ndash;crustal mixing were linked with transitions from post-collision to within-plate settings (Yu et al., \u003cspan citationid=\"CR85\" class=\"CitationRef\"\u003e2015\u003c/span\u003e).\u003c/p\u003e"},{"header":"3. Geology of the Hutouya skarn","content":"\u003cp\u003eThe Hutouya skarn, located at the center of the QMB (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e1\u003c/span\u003eD), hosts a Cu\u0026ndash;Pb\u0026ndash;Zn resource of 0.85\u0026nbsp;million tones (Mt) at an average grade of 2.05% Cu, 5.79% Pb, and 4.46% Zn and an Fe resource of 200 Mt at an average grade of 28.82% Fe (Zhao et al., \u003cspan citationid=\"CR90\" class=\"CitationRef\"\u003e2013\u003c/span\u003e). It comprises both magnesian and calcic skarns carrying Fe\u0026ndash;Sn\u0026ndash;Cu\u0026ndash;Co mineralization in the inner zone and Pb\u0026ndash;Zn mineralization in the outer zone, and locally contains W\u0026ndash;Mo\u0026ndash;Ag\u0026ndash;Bi\u0026ndash;Sn mineralization, and substantial pyrrhotite-bearing iron ores. Skarn alteration and Fe\u0026ndash;Cu\u0026ndash;Pb\u0026ndash;Zn\u0026ndash;W\u0026ndash;Mo\u0026ndash;Ag\u0026ndash;Co\u0026ndash;Bi\u0026ndash;Sn mineralization is developed at the contacts between carbonate rocks and granitic intrusions. The ore is typically hosted by E\u0026ndash;W trending Lower Carboniferous Dagangou marble and limestone and Upper Carboniferous Di\u0026rsquo;aosu Formation marble, calcsilicate hornfels, and dolomitic limestone with thinly-bedded limestone (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e2\u003c/span\u003e). Mesoproterozoic Langyashan Formation of the Jixian Group, Ordovician\u0026ndash;Silurian Qiman Tagh Group, and Upper Triassic Elashan Formation are also exposed in the district. All Paleozoic sedimentary rocks in the Hutouya deposit are extensively faulted and folded along E\u0026ndash;W trends related to compressive fracture zones. These structures appear to be important in ore localization. More detailed descriptions can be found in Qu et al. (\u003cspan citationid=\"CR59\" class=\"CitationRef\"\u003e2019a\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eIndosinian Permo\u0026ndash;Triassic intermediate to felsic intrusions in the Hutouya deposit area include red syenogranite, light buff-colored monzogranite, and gray granodiorite, and diorite (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e3\u003c/span\u003e). The syenogranite and monzogranite intrusions are spatially associated with mineralization in Ore Belt III (Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e4\u003c/span\u003eA) and show an intrusive contact relationship (Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e4\u003c/span\u003eB). The syenogranite is widespread in the center of the ore district and occurs as a 1.4 km\u003csup\u003e2\u003c/sup\u003e stock intruding the Di'aosu Formation, the Qiman Tagh Group, and Dagangou in the northern, western, and southern part of the district, respectively (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e2\u003c/span\u003e). The monzogranite only crops out sporadically in the south of the Ore Belt II (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e2\u003c/span\u003e). The irregularly-shaped monzogranite stock has an exposed area of 9 km\u003csup\u003e2\u003c/sup\u003e, and contains large amounts of mafic microgranular enclaves (MMEs) (Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e4\u003c/span\u003eC, D). The intrusion has a contact with the underlying Di'aosu Formation where thick magnetite-rich skarn formed.\u003c/p\u003e \u003cp\u003eThe Hutouya deposit includes 51 skarn ore bodies in seven ore belts. These include three Cu\u0026ndash;Pb\u0026ndash;Zn ore bodies, and several medium-sized Fe ore bodies locally associated with W\u0026ndash;Mo\u0026ndash;Ag\u0026ndash;Bi\u0026ndash;Sn mineralization (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e2\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eOre belts I, II, and III contain Cu and Mo as an \u0026ldquo;inner contact\u0026rdquo; skarn with minor Fe and Sn. These skarns developed on and near contacts of syenogranite and monzogranite with carbonate-rich strata of the Lower Carboniferous Dagangou and Upper Carboniferous Di'aosu Formations. At the inner contact zone with the intrusions, the syenogranite displays strong endoskarn, alteration, and radial and meshed skarn veins (Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e4\u003c/span\u003eE). However, the monzogranite shows a sharp contact relationship with the skarn and syenogranite intrusions in Ore belt III, which indicates that the monzogranite was probably emplaced after the syenogranite and skarn alteration (Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e4\u003c/span\u003eF). Some of the meshed skarn veins occurr in the surrounding marble and are interpreted as the metasomatized front. The geometry and extent of these ore bodies are controlled by structures along the intrusive contact zone. Chalcopyrite, pyrite, and magnetite hosted in banded and massive skarns are the dominant ore minerals in these ore belts (Liu et al., \u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e2013\u003c/span\u003e), with lesser pyrrhotite, arsenopyrite, and minor stannite (Zou et al., \u003cspan citationid=\"CR95\" class=\"CitationRef\"\u003e2017\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eOre belts IV\u0026ndash;VII host Pb\u0026ndash;Zn \u0026ldquo;outer contact\u0026rdquo; skarns with subordinate copper mineralization. The Pb\u0026ndash;Zn ore bodies occor mainly in fracture zones and are largely strata bound sphalerite- and galena-bearing skarn bodies selectively replacing carbonate layers of the Di'aosu Formation, Qiman Tagh Group, and Langyashan Formation. Chalcopyrite and magnetite also occur in those ores. The ore belts and ore bodies appear to be both structurally- and stratigraphically-controlled.\u003c/p\u003e \u003cp\u003eSkarn bodies range a few meters to tens of meters in width, and discontinuously extend to more than two km in length. Metal contents of skarns in the deposit are zoned from innermost Mo-bearing ores nearest intrusive contacts progressively outward to Fe\u0026ndash;Sn\u0026ndash;Cu\u0026ndash;Co, Cu\u0026ndash;Mo\u0026ndash;(Pb\u0026ndash;Zn), and outermost Pb\u0026ndash;Zn zones. In a broad sense, silicate mineralogy in the skarn zones from innermost garnet-rich skarn near potassic-altered igneous rock grades progressively outward to diopside-, epidote-, tremolite- / actinolite-, and chlorite-rich minerals, surrounded by a peripheral zone of recrystallized marble with local massive sulfides. This zoning is complicated by late-stage quartz\u0026ndash;sulfide and phlogopite-rich retrograde alteration that crosscuts early prograde skarn. Liu et al. (\u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e2013\u003c/span\u003e) suggested that fluids responsible for retrograde alteration played an important role in concentrating sphalerite in the Pb\u0026ndash;Zn ores.\u003c/p\u003e"},{"header":"4. Sampling and analytical methods","content":"\u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e4.1. Sampling\u003c/h2\u003e \u003cp\u003eThere three representative rock samples from the Hutouya deposit were selected for petrographic examination, as well as U\u0026ndash;Pb in-situ trace element analysis. Sample HT1901 was taken from the quartz-rich syenogranite and Sample HT1903 (which was divided into two subsamples) was selected from the porphyritic monzogranite. The samples are all from the Cu\u0026ndash;Mo \u0026ldquo;inner contact\u0026rdquo; zone of Ore belt III.\u003c/p\u003e \u003cp\u003eZircon grains were separated using magnetic and heavy liquid separation. Approximately, 1000 zircon grains from each sample were mounted and polished in 25-mm epoxy discs. The 400 apatite grains used in this study were not separated by standard mineral separation techniques; rather, they were selected by employing optical and back-scattered electron (BSE) microscopy from polished thin sections. This approach combines detailed textural relationships, allowing for a more precise interpretation of apatite compositions.\u003c/p\u003e \u003cp\u003eIndividual apatite and zircon grains show conspicuous euhedral to subhedral columnar shapes in BSE (Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e5\u003c/span\u003e) and cathodoluminescence (CL) (Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e6\u003c/span\u003e), and there are no obvious cracks on the surface.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e4.2. Analytical methods\u003c/h2\u003e \u003cdiv id=\"Sec7\" class=\"Section3\"\u003e \u003ch2\u003e4.2.1. BSE and CL imaging\u003c/h2\u003e \u003cp\u003eBSE imaging of apatite was performed by electron-probe microanalysis (EPMA) at the MNR Key Laboratory of Metallogeny and Mineral Assessment, using a JEOL JXA-8800 instrument with a 2 to 5 \u0026micro;m beam.\u003c/p\u003e \u003cp\u003eInternal zonation patterns of zircon crystals were observed in CL images at the MNR Key Laboratory of Metallogeny and Mineral Assessment, Institute of Mineral Resources, Chinese Academy of Geological Sciences (CAGS), Beijing, China. Using a combination of CL imaging and optical microscopy, the clearest and least fractured zircon crystals were selected as suitable targets for laser ablation.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec8\" class=\"Section3\"\u003e \u003ch2\u003e4.2.2. U\u0026ndash;Pb dating and in-situ multi-element analysis of apatite and zircon\u003c/h2\u003e \u003cp\u003eU\u0026ndash;Pb dating and in-situ multi-element composition analysis of apatite and zircon was performed using an ASI RESOLution S-155 ablation system with Coherent Compex Pro 110 Ar-F excimer laser operating at a 193 nm wavelength and pulse width of 20ns coupled to an Agilent 7900 quadrupole ICP\u0026ndash;MS. Detailed analytical conditions are described in Thompson et al. (\u003cspan citationid=\"CR70\" class=\"CitationRef\"\u003e2016\u003c/span\u003e). All instrumentation is housed at the Centre for Ore Deposit and Earth Sciences (CODES) Analytical Laboratory at the University of Tasmania (UTAS), Hobart, Australia.\u003c/p\u003e \u003cp\u003eAnalyses comprise a 30s blank gas measurement followed by a further 30s of ablation when the laser is switched on using a 29 \u0026micro;m spot size, firing at a frequency of 5 Hz and beam energy density of 2.0 J/cm\u003csup\u003e2\u003c/sup\u003e for zircon and 3.5 J/cm\u003csup\u003e2\u003c/sup\u003e for apatite. All analyses have a pre-ablation of 5 laser shots to remove any surface contamination. Ablation was performed in a pure He atmosphere flowing at 0.35 L/min and immediately mixed with Ar, flowing at a rate of 1.05 L/min after ablation. The mass of each isotope (e.g., \u003csup\u003e23\u003c/sup\u003eNa, \u003csup\u003e31\u003c/sup\u003eP, \u003csup\u003e43\u003c/sup\u003eCa, \u003csup\u003e51\u003c/sup\u003eV, \u003csup\u003e56\u003c/sup\u003eFe, \u003csup\u003e88\u003c/sup\u003eSr, etc.) was measured every\u0026thinsp;~\u0026thinsp;2 ms with longer counting times on the Pb and U isotopes.\u003c/p\u003e \u003cp\u003eData reduction in apatite was done using the method outlined in Thompson et al (\u003cspan citationid=\"CR70\" class=\"CitationRef\"\u003e2016\u003c/span\u003e) and references therein, where a common Pb correction was performed on the calibration standard. The downhole fractionation, instrument drift and mass bias correction factors for Pb/U ratios were calculated using values of the OD306 apatite from Thompson et al (\u003cspan citationid=\"CR70\" class=\"CitationRef\"\u003e2016\u003c/span\u003e). The calibration of the U\u0026ndash;Pb ages was monitored using several apatite reference materials: 401 apatite (Thompson et al., \u003cspan citationid=\"CR70\" class=\"CitationRef\"\u003e2016\u003c/span\u003e), Durango apatite (McDowell et al. \u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e2005\u003c/span\u003e) and the McClure Mountain apatite (Schoene and Bowring \u003cspan citationid=\"CR64\" class=\"CitationRef\"\u003e2006\u003c/span\u003e). Ages are calculated using Concordia intercept with Stacey and Kramer\u0026rsquo;s (Stacey and Kramer, 1975) model Pb composition at the age of the apatite, unless there was enough spread on the isochron to negate the need for the assumption of common Pb composition.\u003c/p\u003e \u003cp\u003eIn zircon, U\u0026ndash;Pb dating was based on the method outlined in Thompson et al (\u003cspan citationid=\"CR69\" class=\"CitationRef\"\u003e2018\u003c/span\u003e) and Halpin et al. (\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e2014\u003c/span\u003e). For each analysis, a subset of data that closely matches a concordant composition was selected for quantification. The downhole fractionation, instrument drift, and mass bias correction factors for Pb/U ratios were calculated from analyses of the 91500-zircon using the values of Wiendenbeck et al. (1995). A calibration of U\u0026ndash;Pb ages was performed by comparing measured analyses of the Temora zircon (Black et al. \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e2004\u003c/span\u003e) and the Plesovice zircon (Slama et al. \u003cspan citationid=\"CR65\" class=\"CitationRef\"\u003e2008\u003c/span\u003e) with published values. Trace element abundances measured in the 91500 zircon were within the range of reported values from the GeoReM website (\u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttp://georem.mpch-mainz.gwdg.de/\u003c/span\u003e\u003cspan address=\"http://georem.mpch-mainz.gwdg.de/\" targettype=\"URL\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e). All common Pb corrections were done using Stacey and Kramer\u0026rsquo;s (Stacey and Kramer, 1975) model Pb composition at the age of the zircon, unless independent common Pb compositions existed for a sample.\u003c/p\u003e \u003cp\u003eIn both routines, instrument drift and mass bias correction factors of the \u003csup\u003e207\u003c/sup\u003ePb/\u003csup\u003e206\u003c/sup\u003ePb ratio (ages) were determined using the Pb isotopic values of the NIST610 glass determined by Baker et al. (\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e2004\u003c/span\u003e). Trace element abundances were calibrated on the NIST610 glass from values of Jochum et al. (\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e2011\u003c/span\u003e) and using secondary standard corrections based on the composition of the glasses BCR-2G and GSD-1G (GeoReM preferred values). Quantification was performed using \u003csup\u003e43\u003c/sup\u003eCa as an internal standard element in apatite and \u003csup\u003e91\u003c/sup\u003eZr in zircon and normalizing all measured cations to stoichiometric concentrations of these elements in each respective mineral. The calibration standards and the NIST610, BCR-2G and GSD-1G glasses were analyzed in duplicate at the beginning, end and every 60 minutes throughout the analytical session. All data was processed using the program LADR (v1.1.01; Norris and Danyushevsky, \u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e2018\u003c/span\u003e).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec9\" class=\"Section3\"\u003e \u003ch2\u003e4.2.3. Apatite major element analysis\u003c/h2\u003e \u003cp\u003eMajor element analysis of apatite was performed using EPMA at the UTAS using a JEOL JXA-8800 instrument with a 2 to 5 \u0026micro;m beam. F, Na, and Cl were analyzed with a 4 nA beam current and 10 kV accelerating voltage in the first instrumental pass; the remaining elements were measured utilizing a 20 nA beam current and 20 kV accelerating potential in the second instrumental pass. Natural minerals and synthetic oxides were used as standards, and the ZAF software provided by JEOL was used to correct matrix effects. The accuracy of the analytic results is 1\u0026ndash;5% depending on the abundance of the element.\u003c/p\u003e \u003c/div\u003e \u003c/div\u003e"},{"header":"5. Results","content":"\u003cdiv id=\"Sec11\" class=\"Section2\"\u003e \u003ch2\u003e5.1. U\u0026ndash;Pb ages of apatite and zircon\u003c/h2\u003e \u003cp\u003eTypical BSE images of apatite from both intrusives are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e5\u003c/span\u003e. Age data of apatite are summarized in Table S1 and Fig.\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e7\u003c/span\u003e. Apatite from both intrusives can be categorized into two types: FI-free Apatite I and FI-rich Apatite II (Fig.\u0026nbsp;\u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e8\u003c/span\u003e). In this study, we present dating results of Apatite I. Most apatite from the two intrusives are euhedral, elongate, and tabular crystals about 100 \u0026times; 40 \u0026micro;m to 200 \u0026times; 60 \u0026micro;m in size without prominent zonation patterns (Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e5\u003c/span\u003e). The apatite age of sample HT1901 (syenogranite) yielded a lower intercept age of 229.0\u0026thinsp;\u0026plusmn;\u0026thinsp;6.6 Ma, (MSWD\u0026thinsp;=\u0026thinsp;1.15, n\u0026thinsp;=\u0026thinsp;51), and samples HT1903-1 and HT1903-2 (monzogranite) yielded lower intercept ages of 224.3\u0026thinsp;\u0026plusmn;\u0026thinsp;4.5 Ma (MSWD\u0026thinsp;=\u0026thinsp;3.5, n\u0026thinsp;=\u0026thinsp;27) and 223.7\u0026thinsp;\u0026plusmn;\u0026thinsp;3.9 Ma (MSWD\u0026thinsp;=\u0026thinsp;1.4, n\u0026thinsp;=\u0026thinsp;40) (Fig.\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e7\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eTypical CL images of zircon are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e6\u003c/span\u003e, and U\u0026ndash;Pb data are summarized in Table S2 and Fig.\u0026nbsp;\u003cspan refid=\"Fig12\" class=\"InternalRef\"\u003e9\u003c/span\u003e. According to size, color, texture, and morphology, zircon crystals from the two intrusives can be classified into Zircon I with transparent and bright zones, Zircon II with dark and metamict features, and Zircon III with mineral inclusions (Fig.\u0026nbsp;\u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e8\u003c/span\u003e). In this study, we present dating results of Zircon I. The zircon grains are clear to pale, euhedral to subhedral, nearly granular (normally 100 to 200 \u0026micro;m in size) and display concentric zonation patterns in CL. Zircon U\u0026ndash;Pb ages of the two intrusives show a grouping with lower intercept ages in Tera\u0026ndash;Wasserburg Concordia diagrams. The zircon age from sample HT1901 (syenogranite) yielded a lower intercept age of 224.70\u0026thinsp;\u0026plusmn;\u0026thinsp;0.61 Ma (MSWD\u0026thinsp;=\u0026thinsp;1.3, n\u0026thinsp;=\u0026thinsp;24) (Fig.\u0026nbsp;\u003cspan refid=\"Fig12\" class=\"InternalRef\"\u003e9\u003c/span\u003e), and samples HT1903-1 and HT1903-2 (monzogranite) yielded lower intercept ages of 225.75\u0026thinsp;\u0026plusmn;\u0026thinsp;0.66 Ma (MSWD\u0026thinsp;=\u0026thinsp;1.15, n\u0026thinsp;=\u0026thinsp;23) and 226.31\u0026thinsp;\u0026plusmn;\u0026thinsp;0.78 Ma (MSWD\u0026thinsp;=\u0026thinsp;1.4, n\u0026thinsp;=\u0026thinsp;16) (Fig.\u0026nbsp;\u003cspan refid=\"Fig12\" class=\"InternalRef\"\u003e9\u003c/span\u003e), respectively.\u003c/p\u003e \u003cp\u003eU\u0026ndash;Pb ages of apatite\u0026ndash;zircon from the two intrusives (monzogranite and syenogranite) in the Hutouya deposit are consistent within error. These ages likely represent the time of emplacement of the intrusives.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec12\" class=\"Section2\"\u003e \u003ch2\u003e5.2. In-situ trace element compositions of zircon and apatite\u003c/h2\u003e \u003cp\u003eTrace element contents of apatite (Apatite I) are summarized in Table S3 and Fig.\u0026nbsp;\u003cspan refid=\"Fig13\" class=\"InternalRef\"\u003e10\u003c/span\u003e. V, Pb, Th, and U concentrations of the apatite range from \u0026minus;\u0026thinsp;1 ppm to 10s ppm and do not show systematic variations from between the two intrusive. In contrast, Sr contents are much higher, ranging from 10s ppm to 100s ppm. REE concentrations range from 1,000s ppm to over 1 wt% in both intrusives. In the chondrite-normalized REE diagrams (Fig.\u0026nbsp;\u003cspan refid=\"Fig13\" class=\"InternalRef\"\u003e10\u003c/span\u003e), results have a negative slope from La to Lu, strong negative Eu anomalies with similar (Eu/Eu*)\u003csub\u003eN\u003c/sub\u003e, and weak positive Ce anomalies with similar (Ce/Ce*)\u003csub\u003eN\u003c/sub\u003e values (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e11\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eTrace element compositions of zircon are listed in Table S4. Syenogranite (HT1901) and monzogranite (HT1903-1 and HT1903-2) have average REE contents of 732 ppm, 756 ppm, and 992 ppm, respectively. Th and U contents range from 10s ppm to 1,000s ppm. Hf concentrations are 1,000s ppm, with average values of 10,195 ppm for syenogranite, and 9,771 ppm and 10,069 ppm for the monzogranite samples. Chondrite-normalized REE diagrams for zircon show a consistent and steeply increasing trend diagrams from La to Lu with strongly positive Ce anomalies and negative Eu anomalies (Fig.\u0026nbsp;\u003cspan refid=\"Fig13\" class=\"InternalRef\"\u003e10\u003c/span\u003e). According to the (Ce/Ce*)\u003csub\u003eN\u003c/sub\u003e calculation method proposed by CODES on the basis of a lattice-strain model for mineral-melt partitioning of Ce\u003csup\u003e4+\u003c/sup\u003e and Ce\u003csup\u003e3+\u003c/sup\u003e cations, the relationships of Ce and Eu anomalies among different intrusions at Hutouya are examined. Calculated zircon (Ce/Ce*)\u003csub\u003eN\u003c/sub\u003e and (Eu/Eu*)\u003csub\u003eN\u003c/sub\u003e values are listed in Table S4, where the subscript indicates chondrite normalization. Zircon all display higher (Ce/Ce*)\u003csub\u003eN\u003c/sub\u003e values, ranging from 6 to 421 (average: 119) in the syenogranite and 15 to 309 (average: 84) and 1 to 245 (average: 62) in the monzogranite samples. The (Eu/Eu*)\u003csub\u003eN\u003c/sub\u003e values do not show noticeable differences between the intrusives, with most values ranging from 0.05 to 0.52 (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e12\u003c/span\u003e).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec13\" class=\"Section2\"\u003e \u003ch2\u003e5.3. Apatite major element compositions\u003c/h2\u003e \u003cp\u003eAnalytical data of major elements for apatite from syenogranite (HT1901) and monzogranite (HT1903-1 and HT1903-2) are summarized in Table S5. The consistency of the results and previous published studies for the secondary standards suggests that the major element compositions for apatite are robust and reliable. The low analytical totals in some of the analyses are likely related to: 1) OH not being analysed, 2) elements present in the mineral but not captured in the routine, 3) the laser crater is adjacent to the EPMA spot in a sufficiently small grain, such that the interaction volume either overlaps with the crater or with epoxy, 4) charging effects due to insufficient coating of the crater next to the EPMA spot, and 5) there could be beam damage,since apatite are very susceptive to it.\u003c/p\u003e \u003cp\u003eMajor element contents of apatite from syenogranite and monzogranite intrusives are statistically identical. All apatite samples are fluorapatite, enriched in F but have low Cl contents.\u003c/p\u003e \u003c/div\u003e"},{"header":"6. Discussion","content":"\u003cdiv id=\"Sec15\" class=\"Section2\"\u003e \u003ch2\u003e6.1. Robustness of apatite petrochronology in fingerprinting porphyry systems\u003c/h2\u003e \u003cp\u003eAccurate chronological constraints are critical for establishing the timing of mineralization, deciphering mineralization processes, and developing mineral exploration models. Geochronological and geochemical fingerprints of mineralization processes can be preserved by apatite and zircon. Zircon has characteristics of high stability and sealing temperatures, and high U and low common Pb contents, and therefore is one of the most suitable minerals for U\u0026ndash;Pb dating. However, zircon may be absent in some ore systems or may not directly represent mineralization. Therefore, in recent years, the development of LA\u0026ndash;ICP\u0026ndash;MS dating of other U-rich minerals that form in hydrothermal fluids or related intrusives has become a powerful method to determine the age of mineral deposits. Apatite, a common accessory mineral in magmatic rocks and hydrothermal deposits, stands out due to it already being widely employed in low temperature thermochronology research (Chew and Spikings, \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e2015\u003c/span\u003e; Prowatke and Klemme, \u003cspan citationid=\"CR56\" class=\"CitationRef\"\u003e2006\u003c/span\u003e; Webster et al., \u003cspan citationid=\"CR75\" class=\"CitationRef\"\u003e2009\u003c/span\u003e). Apatite can be U\u0026ndash;Pb dated (Tc\u0026thinsp;=\u0026thinsp;550\u0026ndash;350 \u003csup\u003eo\u003c/sup\u003eC), fission track dated (Tc\u0026thinsp;=\u0026thinsp;110\u0026ndash;60 \u003csup\u003eo\u003c/sup\u003eC), and U\u0026ndash;Th\u0026ndash;Sm/He dated (Tc\u0026thinsp;=\u0026thinsp;80\u0026ndash;40 \u003csup\u003eo\u003c/sup\u003eC), forming a medium- to low-temperature continuous thermochronology that can comprehensively and continuously analyze tectono\u0026ndash;thermochronological history (Carrapa et al., \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e2009\u003c/span\u003e; Glorie et al., \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e2019\u003c/span\u003e; Jepson et al., \u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). Furthermore, apatite can accommodate a variety of elements (e.g., S, Sr, U, Th, REE, etc.) and has high volatile contents, such as F, OH and Cl, making it an ideal mineral for both geological dating and tracing (Chu et al., \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e2009\u003c/span\u003e; Piccoli and Candela, \u003cspan citationid=\"CR55\" class=\"CitationRef\"\u003e1994\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eIn this study, we selected apatite and zircon grains from the syenogranite and monzogranite in the Hutouya deposit to study thermochronology and in-situ trace element compositions, with the aim to test the consistency between apatite and zircon for petrochronology and fingerprinting of igneous processes in a porphyry\u0026ndash;skarn system. Apatite grains in the two intrusives can be categorized into two types (FI-free Apatite I and FI-rich Apatite II; Fig.\u0026nbsp;\u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e8\u003c/span\u003e). The variations of textures and geochemical compositions in the two types of apatite are indicative of changing crystallization environments. The euhedral grains of Apatite I might be crystallized from a volatile-undersaturated magma. Conversely, Apatite II with lower Cl and higher F contents are only distributed in the more highly fractionated granite (Table S5, Fig.\u0026nbsp;\u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e8\u003c/span\u003e) and formed under a volatile-oversaturated stage demonstrated by the rich fluid inclusion contents (Andersson et al., \u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e2019\u003c/span\u003e; Glorie et al., 2020; Mao et al., \u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e2016\u003c/span\u003e; Pan et al., \u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e2016\u003c/span\u003e; Qu et al., \u003cspan citationid=\"CR60\" class=\"CitationRef\"\u003e2019b\u003c/span\u003e). Lower Cl and higher F contents of Apatite II could be attributed to the segregation of isolated fluid phase in the late aqueous magma (Chu et al., \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e2009\u003c/span\u003e; Doherty et al., \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e2014\u003c/span\u003e; Mathez and Webster, \u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e2005\u003c/span\u003e; Sha and Chappell, 1999; Webster et al., \u003cspan citationid=\"CR75\" class=\"CitationRef\"\u003e2009\u003c/span\u003e). Zircon grains in the two granites can be classified into Zircon I with transparent and bright zones, Zircon II with dark and metamict features, and Zircon III with mineral inclusions (Fig.\u0026nbsp;\u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e8\u003c/span\u003e) in the CL images, indicating that they were formed under different physicochemical conditions during the magmatic-hydrothermal evolution. Zircon I grains have a magmatic texture of well-developed bright oscillatory zones, and are most likely primary magmatic zircon that crystallized early in the evolution of granitic magma. The low Th and U contents and higher Zr/Hf ratios of Zircon I (Table S4) indicate they crystallized from volatileundersaturated anhydrous magma (Erdmann et al., 2013; Qu et al., \u003cspan citationid=\"CR60\" class=\"CitationRef\"\u003e2019b\u003c/span\u003e; Zeng et al., \u003cspan citationid=\"CR87\" class=\"CitationRef\"\u003e2016\u003c/span\u003e). Zircon II occurring as individual grains or overgrowth with the Zircon I might be of a successive later origin than the Zircon I (Fig.\u0026nbsp;\u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e8\u003c/span\u003e). Notably, high Th and U contents of Zircon II may be its crystallization from a volatile-enriched aqueous magma (Nasdala et al., \u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e2001\u003c/span\u003e; Claiborne et al., \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e2006\u003c/span\u003e; Bacon et al., \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2007\u003c/span\u003e; Geisler et al., \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e2007\u003c/span\u003e; Erdmann et al., 2013). Zircon III grains full of numerous hydrothermal mineral inclusions might be of the product of fluid interaction with previous Zircon II in a volatile-oversaturated environment, indicative of hydrothermal crystallization or hydrothermal alteration (Breiter and Skoda, \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e2012\u003c/span\u003e; Erdmann et al., 2013; Hoskin, \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e2005\u003c/span\u003e; Hoskin and Schaltegger, \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e2003\u003c/span\u003e). Collectively, apatite and zircon from the syenogranite and monzogranite in the Hutouya deposit experienced a prolonged crystallization process and were altered by late-stage exsolved fluids. The well-developed euhedral apatite and oscillatory primary magmatic zircon represent an early-crystallized phase from a least fractionated granite. Metamict zircon occurs as individual grains or overgrowth with the magmatic zircon formed under volatile\u0026ndash;saturated aqueous magma during the magmatic-hydrothermal transition stage. Some formed zircon was altered by exsolved magmatic fluids in the most fractionated granite, indicating a volatile oversaturated environment. Meanwhile, apatite with abundant fluid inclusions and high F/Cl ratios from the most fractionated granite crystallized in this subsolidus stage.\u003c/p\u003e \u003cp\u003eApatite I and Zircon I are interpreted to be of magmatic origins, and their ages therefore represent the time of magma emplacement. The apatite LA\u0026ndash;ICP\u0026ndash;MS U\u0026ndash;Pb ages range from 235\u0026ndash;220 Ma, which is consistent with the zircon U\u0026ndash;Pb ages that range from 227\u0026ndash;224 Ma. These ages are indistinguishable within error and indicate that the magmas were emplaced over a short time span, and cooled rapidly, given the closure temperature of apatite (~\u0026thinsp;620 \u003csup\u003eo\u003c/sup\u003eC) and zircon (900 \u003csup\u003eo\u003c/sup\u003eC).\u003c/p\u003e \u003cp\u003eAs hydrothermal activities and mineralization in porphyry\u0026ndash;skarn systems are intimately tied to the emplacement of ore-forming intrusions (Razique et al. \u003cspan citationid=\"CR61\" class=\"CitationRef\"\u003e2014\u003c/span\u003e), the associated hydrothermal and mineralization events at Hutouya probably have similar short durations of just a few million years or less (Zhong et al., \u003cspan citationid=\"CR93\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). At the regional scale, magmatism at Hutouya coincides with that in the other porphyry and skarn deposits in the QMB (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e1\u003c/span\u003eC). For instance, Kaerqueka porphyry\u0026ndash;skarn in the QMB formed circa 227 Ma (Feng et al., \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e2012\u003c/span\u003e), 224 Ma at Yazigou Cu\u0026ndash;Mo deposits (Li et al., \u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e2008\u003c/span\u003e), and 229.4 Ma at Kendekeke Fe deposits (Xiao et al., \u003cspan citationid=\"CR79\" class=\"CitationRef\"\u003e2013\u003c/span\u003e). The granitoids associated with skarns in the area formed during the same period, including the ages at Hutouya (this study), 225 Ma at Galinge Fe skarn deposits (Zhao et al., \u003cspan citationid=\"CR90\" class=\"CitationRef\"\u003e2013\u003c/span\u003e), and 227 Ma at Tawenchahan Fe skarn deposits (Feng et al., \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e2012\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eIt should be noted that geochemical compositions of apatite can be regarded as a tool to identify magmatic mineralization potentials. The magmatic oxygen fugacity is a key factor to fertile magmas of porphyry deposits (Lehmann, \u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e1990\u003c/span\u003e; Sun et al., \u003cspan citationid=\"CR67\" class=\"CitationRef\"\u003e2015\u003c/span\u003e, 2013; Wittenbrink et al., \u003cspan citationid=\"CR77\" class=\"CitationRef\"\u003e2009\u003c/span\u003e; Zhang et al., \u003cspan citationid=\"CR89\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; Zhong et al., \u003cspan citationid=\"CR94\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). Oxidized magmas are more likely to form Cu porphyry deposits than reduced magmas (Imai, \u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e2002\u003c/span\u003e; Li et al., \u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e2017a\u003c/span\u003e; Liang et al., \u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e2006\u003c/span\u003e; Lu et al., \u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e2016\u003c/span\u003e), considering that under the high oxygen fugacity, sulfur in magmas mainly exists in the form of sulfate (SO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2\u0026minus;\u003c/sup\u003e) which has a much higher solubility in silicate melts than sulfide, that is, sulfide is difficult to reach saturation then precipitate during the magmatic stage thus facilitating metal accumulations in the late stage of magmatic evolutions (Ballard et al., \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e2002\u003c/span\u003e; Richards, \u003cspan citationid=\"CR63\" class=\"CitationRef\"\u003e2003\u003c/span\u003e). Skarn and porphyry deposits have similar magmatic origins and evolution processes (Li et al., \u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e2017b\u003c/span\u003e), so it is also applicable to Cu (\u0026ndash;Pb\u0026ndash;Zn) skarn deposits in controlling of the oxygen fugacity to fertil magmas of Cu porphyry deposits.\u003c/p\u003e \u003cp\u003eZircon (Eu/Eu*)\u003csub\u003eN\u003c/sub\u003e and (Ce/Ce\u003csup\u003e*\u003c/sup\u003e)\u003csub\u003eN\u003c/sub\u003e values are effective indicators for evaluating the magmatic oxygen fugacity (Ballard et al., \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e2002\u003c/span\u003e; Gardiner et al., \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; Trail et al., \u003cspan citationid=\"CR71\" class=\"CitationRef\"\u003e2012\u003c/span\u003e). In the Hutouya Fe\u0026ndash;Cu\u0026ndash;Pb\u0026ndash;Zn skarn deposit, the syenogranite and monzogranite have similar (Eu/Eu\u003csup\u003e*\u003c/sup\u003e)\u003csub\u003eN\u003c/sub\u003e and (Ce/Ce\u003csup\u003e*\u003c/sup\u003e)\u003csub\u003eN\u003c/sub\u003e values in zircon, (Table S4; Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e12\u003c/span\u003e). According to the Weibao Cu\u0026ndash;Pb\u0026ndash;Zn skarn deposit in the QMB, fertile intrusions have higher Ce\u003csup\u003e4+\u003c/sup\u003e/Ce\u003csup\u003e3+\u003c/sup\u003e values than those of non-fertile intrusions (Zhong et al., \u003cspan citationid=\"CR93\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). We can draw a conclusion that parental magmas with the higher oxygen fugacity from fertile intrusions in Cu skarn deposits tend to form Cu mineralization. However, Pb and Zn are not easily controlled by oxygen fugacity and behave as incompatible elements. This means that magmas related to the Pb\u0026ndash;Zn mineralization can be either high oxygen fugacity or low oxygen fugacity. Many studies have shown that both S-type granite (low oxygen fugacity magmas) and I-type granite (high oxygen fugacity magmas) can form Pb\u0026ndash;Zn skarn deposits (Fu et al., \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; Niu et al., \u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e2017\u003c/span\u003e), which also supports that Pb-Zn mineralization is independent of magmatic oxygen fugacity conditions. In other words, the oxidation state is not a controlling factor for Pb\u0026ndash;Zn mineralization within the Hutouya deposit.\u003c/p\u003e \u003cp\u003eApatite Eu and Ce anomalies may be more easily affected by other factors unlike zircon Eu and Ce anomalies which are mainly controlled by oxygen fugacity conditions, therefore the relationship between apatite Eu and Ce anomalies and magmatic oxygen fugacity is not so similar (Piccoli and Candela, \u003cspan citationid=\"CR55\" class=\"CitationRef\"\u003e1994\u003c/span\u003e). Nevertheless, if the physical conditions (specifically temperature and pressure) and concentrations of these elements in magma are relatively stable, apatites crystallizing from more oxidized magma will have higher Eu\u003csup\u003e3+\u003c/sup\u003e/Eu\u003csup\u003e2+\u003c/sup\u003e but lower Ce\u003csup\u003e4+\u003c/sup\u003e/Ce\u003csup\u003e3+\u003c/sup\u003e than reduced magma owing to ion substitution in the apatite structure, which results in apatites having strong negative Eu and positive Ce anomalies (Cao et al., 2012; Sha and Chappell, 1999). In this study, we further confirm that magmatism in the Hutouya deposit is similar to other skarn deposits in the QMB. Notwithstanding, this work shows that the fertile intrusions at Hutouya can be well defined by (Eu/Eu\u003csup\u003e*\u003c/sup\u003e)\u003csub\u003eN\u003c/sub\u003e and (Ce/Ce\u003csup\u003e*\u003c/sup\u003e)\u003csub\u003eN\u003c/sub\u003e parameters, that is strong negative Eu anomalies and weak positive Ce in apatite. Hence, apatite Ce anomalies including (Ce/Ce\u003csup\u003e*\u003c/sup\u003e)\u003csub\u003eN\u003c/sub\u003e, Ce\u003csup\u003e4+\u003c/sup\u003e/Ce\u003csup\u003e3+\u003c/sup\u003e, and Ce/Nd values are relatively more robust as proxies for magma oxidation state (Loader et al., \u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). The parameter (Eu/Eu\u003csup\u003e*\u003c/sup\u003e)\u003csub\u003eN\u003c/sub\u003e, although affected by many magmatic processes, can still reflect the magma redox state to some degree (Dilles et al., \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e2015\u003c/span\u003e). Moreover, previous studies found that Mn contents are significantly controlled by the oxygen fugacity with high apatite Mn contents in reduced magmas while low apatite Mn contents in oxidized magmas, which can be explained by the substitution of Ca\u003csup\u003e2+\u003c/sup\u003e by Mn\u003csup\u003e2+\u003c/sup\u003e. Compared with Mn\u003csup\u003e3+\u003c/sup\u003e and Mn\u003csup\u003e4+\u003c/sup\u003e, Mn\u003csup\u003e2+\u003c/sup\u003e is more easily enriched in apatite, because the ionic radius of Mn\u003csup\u003e2+\u003c/sup\u003eis close to that of Ca\u003csup\u003e2+\u003c/sup\u003e (Belousova et al., \u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e2002\u003c/span\u003e). Mn mainly exists as Mn\u003csup\u003e2+\u003c/sup\u003e at low oxygen fugacity with high Mn contents in apatite, while Mn mainly exists as Mn\u003csup\u003e3+\u003c/sup\u003e and Mn\u003csup\u003e4+\u003c/sup\u003e at the high oxygen fugacity with low Mn contents. In the Weibao deposit, apatite within two ore-forming intrusions exhibits much lower Mn concentrations than within the barren diorite porphyry. Apatite Mn contents of the two fertile intrusions in the Hutouya deposit are similar to the fertile intrusions in the Webao deposit (Zhong et al., \u003cspan citationid=\"CR93\" class=\"CitationRef\"\u003e2018\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eNotwithstanding, halogen contents of magmas (especially F and Cl contents) in apatite can also be regarded as an important indicator to evaluate productive magmas since halogens can effectively complex and transport metal elements (Coulson et al., \u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e2001\u003c/span\u003e; Pan et al. \u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e2016\u003c/span\u003e; Piccoli and Candela, \u003cspan citationid=\"CR55\" class=\"CitationRef\"\u003e1994\u003c/span\u003e; Webster et al., \u003cspan citationid=\"CR76\" class=\"CitationRef\"\u003e2004\u003c/span\u003e). A previous study showed that apatite, occurring as inclusions within biotite and hornblende, was one of the early crystal phases that appeared during crystallization (Tang et al., \u003cspan citationid=\"CR68\" class=\"CitationRef\"\u003e2021\u003c/span\u003e), and thus the F and Cl partitioning between the apatite and the melt seems unlikely to be influenced by the crystallization of biotite and hornblende. Therefore, the contents of chlorine and fluorine in the melt predominantly affected by their magmatic sources can be evaluated from the concentrations of chlorine and fluorine in apatite. In this study, the fluorine contents of apatite is much higher than chlorine contents, because the partition coefficient of fluorine between apatite and melt is much higher than those of chlorine (Mathez and Webster, \u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e2005\u003c/span\u003e). In addition, the chlorine contents of the two fertile intrusions in this study remain almost invariable, because the apatite/melt ratio is approximately constant at low Cl contents, but when the melt becomes saturated in Cl both partition coefficients increase rapidly as Cl content of the bulk system increases (Doherty et al., \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e2014\u003c/span\u003e). Furthermore, magmas formed by partial melting of lower crust materials usually show relatively stronger enrichment of F and depletion of Cl than those formed by dehydration melting in slab subduction environments (Ding et al., 2015; Jiang et al., \u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e2018\u003c/span\u003e; Kendrick et al., \u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e2011\u003c/span\u003e; Xu et al., \u003cspan citationid=\"CR78\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). Therefore, the volatile components of the parent magmas of syenogranite and monzogranite are mainly related to lower crustal melting.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec16\" class=\"Section2\"\u003e \u003ch2\u003e6.2. Implication for regional exploration\u003c/h2\u003e \u003cp\u003eThe QMB region experienced two important tectonic evolutionary processes of the Proto-Tethys Ocean and the Paleo-Tethys Ocean, corresponding to two magmatic cycles of the Early Paleozoic and Late Paleozoic to Early Mesozoic (Feng et al., \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e2012\u003c/span\u003e; Mo et al., \u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e2007\u003c/span\u003e; Yang et al., \u003cspan citationid=\"CR80\" class=\"CitationRef\"\u003e2003\u003c/span\u003e; Yu et al., \u003cspan citationid=\"CR86\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). The Proto-Tethys Ocean began to form and expand in the Early Cambrian (Feng et al., \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e2010\u003c/span\u003e; Yang et al., \u003cspan citationid=\"CR81\" class=\"CitationRef\"\u003e1996\u003c/span\u003e), the subduction gradually weakened in the Silurian and began to transition to a collisional orogeny stage (Liu et al., \u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e2013\u003c/span\u003e; Ren et al., \u003cspan citationid=\"CR62\" class=\"CitationRef\"\u003e2009\u003c/span\u003e), and changed from a syn-collision compressional environment to a post-collision extensional environment in the Devonian (Meng et al., \u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e2015\u003c/span\u003e; Qi et al., \u003cspan citationid=\"CR57\" class=\"CitationRef\"\u003e2016\u003c/span\u003e; Zhao et al., \u003cspan citationid=\"CR91\" class=\"CitationRef\"\u003e2008\u003c/span\u003e). The Paleo-Tethys Ocean was in a subduction stage during the Late Permian-Early Triassic (Yao et al., \u003cspan citationid=\"CR82\" class=\"CitationRef\"\u003e2020\u003c/span\u003e), and entered collision and post-collision stages during the Middle\u0026ndash;Late Triassic (Feng et al., \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e2012\u003c/span\u003e). The Middle\u0026ndash;Late Triassic is a very important metallogenic period in the QMB (Gao et al., \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e2014\u003c/span\u003e; Wang et al., \u003cspan citationid=\"CR73\" class=\"CitationRef\"\u003e2018\u003c/span\u003e; Zhang et al., \u003cspan citationid=\"CR88\" class=\"CitationRef\"\u003e2010\u003c/span\u003e). At this stage, the QMB evolution changed from a compressional and transpressional to an extensional environment, which resulted in asthenosphere upwelling and strong crust\u0026ndash;mantle interaction (Yao et al., \u003cspan citationid=\"CR83\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). As consequence, extensive partial melting of lower crust caused widespread development of magmatic intrusions in the upper crust. Thus, it provided favorable conditions for polymetallic mineralization in this area, and ore-forming ages of skarn polymetallic deposits are concentrated in a range of 230\u0026ndash;224 Ma (Qu et al., \u003cspan citationid=\"CR58\" class=\"CitationRef\"\u003e2023\u003c/span\u003e), consistent with the apatite and zircon aged determinations in this study.\u003c/p\u003e \u003c/div\u003e"},{"header":"7. Conclusion","content":"\u003cp\u003eApatite from the two fertile intrusives (syenogranite and monzogranite) in the Hutouya skarn deposit can be divided into FI-free Apatite I and FI-rich Apatite II, meanwhile, zircon can be classified into three sub-types: Zircon I with transparent and bright zones, Zircon II with dark and metamict features, and Zircon III with mineral inclusions.\u003c/p\u003e \u003cp\u003eThey syenogranite and monzogranite were emplaced between 235 to 220 Ma (apatite ages), which is similar to their zircon ages (227 to 224 Ma). These ages are coincident with other fertile intrusives in QMB. These ages are coincident with other fertile intrusives in the QMB. They also have similar magmatic oxygen fugacity coefficients and apatite halogen contents as other fertile intrusives in the QMB, indicating that apatite trace element compositions can be used as robust proxies for magma oxidation state in porphyry-skarn systems.\u003c/p\u003e "},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eCRediT authorship contribution statement\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eHongying Qu\u003c/strong\u003e: data curation, funding acquisition, investigation, writing original draft, and writing review and editing. \u003cstrong\u003eJulie Rowland\u003c/strong\u003e: supervision and writing review and editing. \u003cstrong\u003eJingwen Mao\u003c/strong\u003e: conceptualization, supervision, and writing review and editing. \u003cstrong\u003eEvan Orovan\u003c/strong\u003e: data curation, methodology, and writing review and editing. \u003cstrong\u003eMichael Rowe\u003c/strong\u003e: formal analysis and methodology. \u003cstrong\u003eShihua Zhong\u003c/strong\u003e: conceptualization and formal analysis\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eDeclaration of competing interest\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAcknowledgments \u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis study was financially supported by the China Geological Survey Program (Grant number: DD20240117). Prof. Chengyou Feng and Dr. Miaoyu, Hui Wang, and Jiannan Liu are acknowledged for their assistance during the fieldwork. We are thankful for assistance from Prof. David Cooke and Leonid Danyushevsky and Dr. Lejun Zhang for LA\u0026ndash;ICP\u0026ndash;MS analyses.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eAndersson, S.S., Wagner, T., Jonsson, E., Fusswinkel, T., Whitehouse, M.J., 2019. Apatite as a tracer of the source, chemistry and evolution of ore-forming fluids: The case of the Olserum\u0026ndash;Djupedal REE-phosphate mineralization, SE Sweden. Geochimica et Cosmochimica Acta 255, 163\u0026ndash;187.\u003c/li\u003e\n\u003cli\u003eBacon, C.R., Sisson, T.W., Mazdab, F.K., 2007. Young cumulate complex beneath veniaminof caldera, aleutian arc, dated by zircon in erupted plutonic blocks. Geology 35, 491\u0026ndash;494.\u003c/li\u003e\n\u003cli\u003eBaker, T., Van Achterberg, E., Ryan, C.G., Lang, J.R., 2004. Composition and evolution of ore fluids in a magmatic-hydrothermal skarn deposit. Geology 32(2), 117\u0026ndash;120.\u003c/li\u003e\n\u003cli\u003eBallard, J.R., Palin, M.J., Campbell, I.H., 2002. Relative oxidation states of magmas inferred from Ce(IV)/Ce(III) in zircon: application to porphyry copper deposits of northern Chile. Contrib Mineral Petrol 144(3), 347\u0026ndash;364.\u003c/li\u003e\n\u003cli\u003eBelousova, E.A., Griffin, W.L., O\u0026apos;Reilly, S.Y., Fisher, N.I., 2002. Apatite as an indicator mineral for mineral exploration: trace-element compositions and their relationship to host rock type. J Geochem Explor 76(1), 45\u0026ndash;69.\u003c/li\u003e\n\u003cli\u003eBlack, L.P., Kamos, L., Allen, C.M., Davis, D.W., Aleinikoff, J.N., Valley, J.W., Mundil, R., Campbell, I.H., Korsch, R.J., Williams, I.S., Foudoulis, C., 2004. Improved \u003csup\u003e206\u003c/sup\u003ePb/\u003csup\u003e25\u003c/sup\u003e8U microprobe geochronology by the monitoring of trace-element-related matrix effect: SHRIMP, ID-TIMS, ELA\u0026ndash;ICP\u0026ndash;MS and oxygen isotope documentation for a series of zircon standards. Chemical Geology 205(1\u0026ndash;2), 115\u0026ndash;140.\u003c/li\u003e\n\u003cli\u003eBreiter, K., Skoda, R., 2012. Vertical zonality of fractionated granite plutons reflected in zircon chemistry: the Cinovec A-type versus the Beauvoir S-type suite. Geol Carpath 63, 383\u0026ndash;398.\u003c/li\u003e\n\u003cli\u003eCarrapa, B., DeCelles, P.G., Reiners, P.W., Gehrels, G.E., Sudo, M., 2009. Apatite triple dating and white mica \u003csup\u003e40\u003c/sup\u003eAr/\u003csup\u003e39\u003c/sup\u003eAr thermochronology of syntectonic detritus in the Central Andes: a multiphase tectonothermal history. Geology 37, 407\u0026ndash;410.\u003c/li\u003e\n\u003cli\u003eChen, H.W., Luo, Z.H., Mo, X.X., Zhang, X.T., Wang, J., Wang, B.Z., 2006. SHRIMP ages of Kayakedengt age complex in the East Kunlun Mountains and their geological implications. Acta Petrologica et Mineralogica 25(1), 25\u0026ndash;32.\u003c/li\u003e\n\u003cli\u003eChew, D.M., Spikings, R.A., 2015. Geochronology and thermochronology using apatite: time and temperature, lower crust to surface. Elements 11, 189\u0026ndash;194.\u003c/li\u003e\n\u003cli\u003eChu, M.F., Wang, K.L., Griffin, W.L., Chung, S.L., O\u0026rsquo;Reilly, S.Y., Pearson, N.J., Iizuka, Y., 2009. Apatite composition: tracing petrogenetic processes in Transhimalayan Granitoids. J. Petrol. 50, 1829\u0026ndash;1855.\u003c/li\u003e\n\u003cli\u003eClaiborne, L.L., Miller, C.F., Walker, B.A., Wooden, J.L., Mazdab, F.K., Bea, F., 2006. Tracking magmatic processes through Zr/Hf ratios in rocks and Hf and Ti zoning in zircons: an example from the Spirit Mountain batholith, Nevada. Mineral. Mag. 70, 517\u0026ndash;543.\u003c/li\u003e\n\u003cli\u003eCoulson, I.M., Dipple, G.M., Raudsepp, M., 2001. Evolution of HF and HCl activity in magmatic volatiles of the gold-mineralized Emerald Lake pluton, Yukon Territory, Canada. Mineral Deposita 36(6), 594\u0026ndash;606.\u003c/li\u003e\n\u003cli\u003eDilles, J.H., Kent, A.J.R., Wooden, J.L., Tosdal, R.M., Koleszar, A., Lee, R.G., Farmer, L.P., 2015. Zircon compositional evidence for sulfurdegassing from ore-forming arc magmas. Econ Geol 110, 241\u0026ndash;251.\u003c/li\u003e\n\u003cli\u003eDing, L.R., 2006. Petroleum geological characteristics and resource potential of Alay Basin in Central Asia. Offshore Oil 26 (4), 29\u0026ndash;33 (in Chinese with English abstract).\u003c/li\u003e\n\u003cli\u003eDoherty, A.L., Webster, J.D., Goldoff, B.A., Piccoli, P.M., 2014. Partitioning behavior of chlorine and fluorine in felsic meltefluid (s)eapatite systems at 50MPa and 850\u0026ndash;950 \u003csup\u003eo\u003c/sup\u003eC. Chem. Geol. 384, 94\u0026ndash;111.\u003c/li\u003e\n\u003cli\u003eFeng, C.Y., Wang, S., Li, G.C., Ma, S.C., Li, D.S., 2012. Middle to late Triassic granitoids in the Qimantage area, Qinghai Province, China: Chronology, geochemistry and metallogenic significance. Acta Petrologica Sinica 28(2), 665\u0026ndash;678 (in Chinese with English abstract).\u003c/li\u003e\n\u003cli\u003eFeng, C.Y., Wang, X.P., Shu, X.F., Zhang, A.K., Xiao, Y., Liu, J.N., Ma, S.C., Li, G.C., Li, D.X., 2011. Isotopic chronology for Hutouya skarn-type lead\u0026ndash;zinc polymetallic metallogenic district in the Qimantage area, Qinghai Province, and its geological significance. Journal of Jilin University (Earth Science Edition) 41(6), 1806\u0026ndash;1817 (in Chinese with English abstract).\u003c/li\u003e\n\u003cli\u003eFeng, C.Y., Li, D.S., Wu, Z.S., Li, J.H., Zhang, Z.Y., Zhang, A.K., Shu, X.F., Su, S.S., 2010. Major types\u0026rsquo; time\u0026ndash;space distribution and metallogenesis of polymetallic deposits in the Qimantage metallogenic belt, eastern Kunlun area. Northwestern Geology 43(4), 10\u0026ndash;17 (in Chinese with English abstract).\u003c/li\u003e\n\u003cli\u003eFu, Q., Xu, B., Zheng, Y., Yang, Z., Hou, Z., Huang, K., Liu, Y., Zhang, C., Zhao, L., 2017. Two episodes of mineralization in the Mengya\u0026rsquo;a deposit and implications for the evolution and intensity of Pb\u0026ndash;Zn\u0026ndash;(Ag) mineralization in the Lhasa terrane, Tibet. Ore Geol Rev 90, 877\u0026ndash;896.\u003c/li\u003e\n\u003cli\u003eGao, Y.B., Li, W.Y., Qian, B., Li, K., Li, D.S., He, S.Y., Zhang, Z.W., Zhang, J.W., 2014. Geochronology, geochemistry and Hf isotopic compositions of the granitic rocks related with iron mineralization in Yemaquan deposit, East Kunlun, NW China. Acta Petrol Sin 30, 1647\u0026ndash;1665 (in Chinese with English abstract).\u003c/li\u003e\n\u003cli\u003eGardiner, N.J., Hawkesworth, C.J., Robb, L.J., Whitehouse, M.J., Roberts, N.M., Kirkland, C.L., Evans, N.J., 2017. Contrasting granite metallogeny through the zircon record: a case study from Myanmar. Sci Rep 7(1), 748.\u003c/li\u003e\n\u003cli\u003eGeisler, T., Schaltegger, U., Tomaschek, F., 2007. Re-equilibration of zircon in aqueous fluids and melts. Elements 3, 43\u0026ndash;50.\u003c/li\u003e\n\u003cli\u003eGlorie, S., Jepson, G., Konopelko, D., Mirkamalov, R., Meeuws, F., Gilbert, S., Gillespie, J., Collins, A.S., Xiao, W.J., Dewaele, S., De Grave, J., 2019. Thermochronological and geochemical footprints of post-orogenic fluid alteration recorded in apatite: implications for mineralisation in the Uzbek Tian Shan. Gondwana Res. 71, 1\u0026ndash;15.\u003c/li\u003e\n\u003cli\u003eHalpin, J.A., Jensen, T., McGoldrick, P., Meffre, S., Berry, R.F., Everard, J.L., Calver, C.R.., Thompson, J., Goemann, K., Whittaker, J.M., 2014. Authigenic monazite and detrital zircon dating from the Proterozoic Rocky Cape Group, Tasmania: Links to the Belt-Purcell Supergroup, North America. Precambrian Research 250, 50\u0026ndash;67.\u003c/li\u003e\n\u003cli\u003eHe, D.F., Dong, Y.P., Zhang, F.F., Yang, Z., Sun, S.S., Cheng, B., Zhou, B., Liu, X.M., 2016. The 1.0 Ga S-type granite in the East Kunlun Orogen, Northern Tibetan Plateau: Implication for the Meso- to Neoproterozoic tectonic evolution. Journal of Asian Earth Sciences 130, 46\u0026ndash;59.\u003c/li\u003e\n\u003cli\u003eHoskin, P.W.O., 2005. Trace-element composition of hydrothermal zircon and the alteration of hadean zircon from the Jack Hills, Australia. Geochim. Cosmochim. Acta 69, 637\u0026ndash;648.\u003c/li\u003e\n\u003cli\u003eHoskin, P.W.O., Schaltegger, U., 2003. The composition of zircon and igneous and metamorphic petrogenes. Rev. Mineral. Geochem. 53, 27\u0026ndash;62.\u003c/li\u003e\n\u003cli\u003eHughes, J.M., Rakovan, J., 2002. The Crystal Structure of Apatite, Ca\u003csub\u003e5\u003c/sub\u003e(PO\u003csub\u003e4\u003c/sub\u003e)\u003csup\u003e3\u003c/sup\u003e(F, OH, Cl). Phosphates\u0026ndash;Geochemical, Geobiological and Materials Importance, Reviews in Mineralogy and Geochemistry. Edited by Kohn, M.J., Rakovan, J., Hughes, J.M., Mineralogical Society of America, Washington DC, 48: 1-12.\u003c/li\u003e\n\u003cli\u003eImai, A., 2002. Metallogenesis of porphyry Cu deposits of the western Luzon arc, Philippines: K-Ar ages, SO\u003csub\u003e3\u003c/sub\u003e contents of microphenocrystic apatite and significance of intrusive rocks. Resour Geol 52(2), 147\u0026ndash;161.\u003c/li\u003e\n\u003cli\u003eJepson, G., Glorie, S., Konopelko, D., Gillespie, J., Danisik, M., Evans, N.J., Mamadjanov, Y., Collins, A.S., 2018. Thermochronological insights into the structural contact between the Tian Shan and Pamirs, Tajikistan. Terra Nova 30, 95\u0026ndash;104.\u003c/li\u003e\n\u003cli\u003eJiang, X.Y., Li, H., Ding, X., Wu, K., Guo, J., Liu, J.Q., Sun, W.D., 2018. Formation of A-type granites in the Lower Yangtze River Belt: A perspective from apatite geochemistry. Lithos 304\u0026ndash;307, 125\u0026ndash;134.\u003c/li\u003e\n\u003cli\u003eJochum, K.P., Weis, U., Stoll, B., Kuzmin, D., Yang, Q., Raczek, I., Jacob, D.E., Stracke, A., Birbaum, K., Frick, D.A., Gunther, D., Enzweiler, J., 2011. Determination of Reference Values for NIST SRM 610\u0026ndash;617 Glasses Following ISO Guidelines. Geostandards and Geoanalytical Research 35, 397\u0026ndash;429.\u003c/li\u003e\n\u003cli\u003eKendrick, M.A., Scambelluri, M., Honda, M., Phillips, D., 2011. High abundances of noble gas and chlorine delivered to the mantle by serpentinite subduction. Nature Geoscience 4(11), 807\u0026ndash;812.\u003c/li\u003e\n\u003cli\u003eLehmann, B., 1990. Metallogeny of tin. Lecture Notes in Earth Sciences. Springer Verlag, Berlin, p 32.\u003c/li\u003e\n\u003cli\u003eLi, C.Y., Hao, X.L., Liu, J.Q., Ling, M.X., Ding, X., Zhang, H., Sun, W.D., 2017a. The formation of Luoboling porphyry Cu\u0026ndash;Mo deposit: constraints fromzircon and apatite. Lithos 272\u0026ndash;273, 291\u0026ndash;300.\u003c/li\u003e\n\u003cli\u003eLi, J.W., Zhao, X.F., Zhou, M.F., Vasconcelos, P., Ma, C.Q., Deng, X.D., Zhao, Y.X., Wu, G., 2008. Origin of the Tongshankou porphyry\u0026ndash;skarn Cu\u0026ndash;Mo deposit, eastern Yangtze craton, Eastern China: Geochronological, geochemical, and Sr\u0026ndash;Nd\u0026ndash;Hf isotopic constraints. Mineralium Deposita 43, 319\u0026ndash;336.\u003c/li\u003e\n\u003cli\u003eLi, W., Neubauer, F., Liu, Y.J., Genser, J., Ren, S.M., Han, G.Q., Liang, C.Y., 2013. Paleozoic evolution of the Qimantagh magmatic arcs, Eastern Kunlun Mountains: Constraints from zircon dating of granitoids and modern river sands. Journal of Asian Earth Sciences 77, 183\u0026ndash;202.\u003c/li\u003e\n\u003cli\u003eLi, X.Y., Chi, G.X., Zhou, Y.Z., Deng, T., Zhang, J.R., 2017b. Oxygen fugacity of Yanshanian granites in South China and implications for metallogeny. Ore Geology Reviews 88, 690\u0026ndash;701.\u003c/li\u003e\n\u003cli\u003eLiang, H.Y., Campbell, I.H., Allen, C., Sun, W.D., Liu, C.Q., Yu, H.X., Xie, Y.W., Zhang, Y.Q., 2006. Zircon Ce\u003csup\u003e4+\u003c/sup\u003e/Ce\u003csup\u003e3+\u003c/sup\u003e ratios and ages for Yulong orebearing porphyries in eastern Tibet. Mineral Deposita 41(2), 152\u0026ndash;159.\u003c/li\u003e\n\u003cli\u003eLiu, J.N., Feng, C.Y., Zhao, Y.M., Li, D.X., Xiao, Y., Zhou, J.H., Ma, Y.T., 2013. Characteristics of intrusive rock, metasomatites, mineralization, and alteration in Yemaquan skarn Fe\u0026ndash;Zn polymetallic deposit, Qinghai Province. Mineral Deposit 32(1), 77\u0026ndash;93 (in Chinese with English abstract).\u003c/li\u003e\n\u003cli\u003eLoader, M.A., Wilkinson, J.J., Armstrong, R.N., 2017. The effect of titanite crystallisation on Eu and Ce anomalies in zircon and its implications for the assessment of porphyry Cu deposit fertility. Earth Planet Sci Lett 472, 107\u0026ndash;119.\u003c/li\u003e\n\u003cli\u003eLu, Y.J., Loucks, R.R., Fiorentini, M., McCuaig, T.C., Evans, N.J., Yang, Z.M., Hou, Z.Q., Kirkland, C.L., Parra-Avila, L.A., Kobussen, A., 2016. Zircon compositions as a pathfinder for porphyry Cu\u0026plusmn;Mo\u0026plusmn;Au deposits. Econ Geol Spec Pub 19, 329\u0026ndash;347.\u003c/li\u003e\n\u003cli\u003eMao, M., Rukhlov, A.S., Rowins, S.M., Spence, J., Coogan, L.A., 2016. Apatite trace element compositions: A robust new tool for mineral exploration. Economic Geology 111, 1187\u0026ndash;1222.\u003c/li\u003e\n\u003cli\u003eMathez, E.A., Webster, J.D., 2005. Partitioning behavior of chlorine and fluorine in the system apatite-silicate melt-fluid. Geochim Cosmochim Acta 69(5), 1275\u0026ndash;1286.\u003c/li\u003e\n\u003cli\u003eMcDowell, F.W., McIntosh, W.C., Farley, K.A., 2005. A precise \u003csup\u003e40\u003c/sup\u003eAr\u0026ndash;\u003csup\u003e39\u003c/sup\u003eAr reference age for the Durango apatite (U\u0026ndash;Th)/He and fission-track dating standard. Chemical Geology 214, 249\u0026ndash;263.\u003c/li\u003e\n\u003cli\u003eMeng, F.C., Cui, M.H., Wu, X.K., Ren, Y.F., 2015. 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Petrol. 141, 125\u0026ndash;144. \u003c/li\u003e\n\u003cli\u003eNiu, S.D., Li, S.R., Huizenga, J.M., Santosh, M., Zhang, D.H., Zeng, Y.J., Li, Z.D., Zhao, W.B., 2017. Zircon U\u0026ndash;Pb geochronology and geochemistry of the intrusions associated with the Jiawula Ag\u0026ndash;Pb\u0026ndash;Zn deposit in the Great Xing\u0026rsquo;an Range, NE China and their implications for mineralization. Ore Geology Reviews 86, 35\u0026ndash;54.\u003c/li\u003e\n\u003cli\u003eNorris, A., Danyushevsky, L., 2018. Towards Estimating the Complete Uncertainty Budget of Quantified Results Measured by LA-ICP-MS. Goldschmidt, Boston, 2018-08-12.\u003c/li\u003e\n\u003cli\u003eOdlum, M.L., Levy, D.A., Stockli, D.F., Stockli, L.D., DesOrmeau, J.W., 2022. Deformation and metasomatism recorded by single-grain apatite petrochronology. Geology 50 (6), 697\u0026ndash;703.\u003c/li\u003e\n\u003cli\u003ePan, L.C., Hu, R.Z., Wang, X.S., Bi, X.W., Zhu, J.J., Li, C., 2016. Apatite trace element and halogen compositions as petrogenetic-metallogenic indicators: examples from four granite plutons in the Sanjiang region, SW China. Lithos 254\u0026ndash;255, 118\u0026ndash;130.\u003c/li\u003e\n\u003cli\u003ePiccoli, P.M., Candela, P.A., 1994. Apatite in felsic rocks; a model for the estimation of initial halogen concentrations in the Bishop Tuff (Long Valley) and Tuolumne Intrusive Suite (Sierra Nevada Batholith) magmas. Am J Sci 294(1), 92\u0026ndash;135.\u003c/li\u003e\n\u003cli\u003eProwatke, S., Klemme, S., 2006. Trace element partitioning between apatite and silicate melts. Geochim. Cosmochim. Acta 70, 4513\u0026ndash;4527.\u003c/li\u003e\n\u003cli\u003eQi, X.P., Fan, X.G., Yang, J., Cui, J.T., Wang, B.Y., Fan, Y.Z., Yang, G.X., Li, Z., Chao, W.D., 2016. The discovery of Early Paleozoic eclogite in the upper reaches of Langmuri in eastern East Kunlun Mountains and its significance. Geological Bulletin of China 35, 1771\u0026ndash;1783 (in Chinese with English abstract).\u003c/li\u003e\n\u003cli\u003eQu, H.Y., Zhang, B.W., Friehauf, K., Wang, H., Feng, C.Y., Dick, J.M., 2023. Apatite as a record of ore-forming processes Magmtic-hydrothermal evolution of the Hutouya Cu\u0026ndash;Fe\u0026ndash;Pb\u0026ndash;Zn ore district in the Qiman Tagh Metallogenic Belt, NW China. Ore Geology Reviews 154, 105343.\u003c/li\u003e\n\u003cli\u003eQu, H.Y., Friehauf, K., Santosh, M., Pei, R.F., Li, D.X., Liu, J.N., Zhou, S.M., Wang, H., 2019a. Middle\u0026ndash;Late Triassic magmatism in the Hutouya Fe\u0026ndash;Cu\u0026ndash;Pb\u0026ndash;Zn deposit, East Kunlun Orogenic Belt, NW China Implications for geodynamic setting and polymetallic mineralization. Ore Geology Reviews 113, 103088.\u003c/li\u003e\n\u003cli\u003eQu, P., Li, N.B., Niu, H.C., Yang, W.B., Shan, Q., Zhang, Z.Y., 2019b. Zircon and apatite as tools to monitor the evolution of fractionate I-type granites from the central Great Xing\u0026rsquo;an Range, NE China. Lithos 348\u0026ndash;349, 105207.\u003c/li\u003e\n\u003cli\u003eRazique, A., Tosdal, R.M., Creaser, R.A., 2014. Temporal evolution of the western porphyry Cu\u0026ndash;Au systems at Reko Diq, Balochistan, western Pakistan. Econ Geol 109(7), 2003\u0026ndash;2021.\u003c/li\u003e\n\u003cli\u003eRen, J.H., Liu, Y.Q., Feng, Q., Han, W.Z., Zhou, D.W., 2009. LA\u0026ndash;ICP\u0026ndash;MS U\u0026ndash;Pb zircon dating and geochemical characteristics of diabase-dykes from the Qingshuiquan area, eastern Kunlun orogenic belt. Acta Petrologica Sinica 25, 1135\u0026ndash;1145 (in Chinese with English abstract).\u003c/li\u003e\n\u003cli\u003eRichards, J.P., 2003. Tectono-magmatic precursors for porphyry Cu\u0026ndash;(Mo\u0026ndash;Au) deposit formation. Econ Geol 98(8), 1515\u0026ndash;1533.\u003c/li\u003e\n\u003cli\u003eSchoene, B., Bowring, S.A., 2006. U\u0026ndash;Pb systematics of the McClure Mountain syenite: thermochronological constraints on the age of the\u003csup\u003e 40\u003c/sup\u003eAr/\u003csup\u003e39\u003c/sup\u003eAr standard MMhb. Contributions to Mineralogy and Petrology 151, 615\u0026ndash;630.\u003c/li\u003e\n\u003cli\u003eSlama, J., Kosler, J., Condon, D.J., Crowley, J.L., Gerdes, A., Hanchar, J.M., Horstwood, M.S.A., Morris, G.A., Nasdala, L., Norberg. N., Schaltegger, U., Schoene, B., Tubrett, M.N., Whitehouse, M.J., 2008. Plesovice zircon \u0026ndash; A new natural reference material for U\u0026ndash;Pb and Hf isotopic microanalysis. Chem Geology 249, 1-35.\u003c/li\u003e\n\u003cli\u003eStacey, J.S., Kramers, J.D., 1975. Approximation of terrestrial lead isotope evolution by a two-stage model. Earth and Planetary Science Letters 26, 207\u0026ndash;221.\u003c/li\u003e\n\u003cli\u003eSun, W.D., Huang, R.F., Li, H., Hu, Y.B., Zhang, C.C., Sun, S.J., Zhang, L.P., Ding, X., Li, C.Y., Zartman, R.E., Ling, M.X., 2015. Porphyry deposits and oxidized magmas. Ore Geology Reviews 65, 97\u0026ndash;131.\u003c/li\u003e\n\u003cli\u003eTang, P., Tang, J.X., Wang, Y., Lin, B., Leng, Q.F., Zhang, Q.Z., He, L., Zhang, Z.B., Sun, M., Wu, C.N., Qi, J., Li, Y.X., Dai, S.J., 2021. Genesis of the Lakang\u0026apos;e porphyry Mo (Cu) deposit, Tibet: Constraints from geochemistry, geochronology, Sr\u0026ndash;Nd\u0026ndash;Pb\u0026ndash;Hf isotopes, zircon and apatite. Lithos 380\u0026ndash;381, 105834. \u003c/li\u003e\n\u003cli\u003eThompson, J.M., Meffre, S., Danyushevsky, L., 2018. Impact of air, laser pulse width and fluence on U\u0026ndash;Pb dating of zircons by LA-ICPMS. Journal of Analytical Atomic Spectrometry 33, 221\u0026ndash;230.\u003c/li\u003e\n\u003cli\u003eThompson, J., Meffre, S., Maas, R., Kamenetsky, V., Kamenetsky, M., Goemann, K., Ehrig, K., Danyushevsky, L., 2016. Matrix effects in Pb/U measurements during LA\u0026ndash;ICP\u0026ndash;MS analysis of the mineral apatite. Journal of Analytical Atomic Spectrometry 31, 1206\u0026ndash;1215.\u003c/li\u003e\n\u003cli\u003eTrail, D., Bruce Watson, E., Tailby, N.D., 2012. Ce and Eu anomalies in zircon as proxies for the oxidation state of magmas. Geochim Cosmochim Acta 97, 70\u0026ndash;87.\u003c/li\u003e\n\u003cli\u003eWang, C., Liu, L., Xiao, P., Cao, Y., Yu, H., Meert, J.G., Liang, W., 2014. Geochemical and geochronologic constraints for Paleozoic magmatism related to the orogenic collaps in the Qimantagh\u0026ndash;South Altyn region, northwestern China. Lithos 202, 1\u0026ndash;20.\u003c/li\u003e\n\u003cli\u003eWang, H., Feng, C.Y., Li, R.X., Li, D.X., 2018. Geological characteristics, metallogenesis, and tectonic setting of porphyry-skarn Cu deposits in East Kunlun Orogen. Geol. J. 53, 58\u0026ndash;76.\u003c/li\u003e\n\u003cli\u003eWang, S., Feng, C.Y., Li, S.J., Jiang, J.H., Li, D.S., Su, S.S., 2009. Zircon SHRIMP U\u0026ndash;Pb dating of granodiorite in the Kaerqueka polymetallic ore deposit, Qimantage Mountain, Qinghai Province, and its geological implication. Geology in China 36(1), 74\u0026ndash;84 (in Chinese with English abstract).\u003c/li\u003e\n\u003cli\u003eWebster, J.D., Tappen, C.M., Mandeville, C.W., 2009. Partitioning behavior of chlorine and fluorine in the system apatiteemeltefluid. II: felsic silicate systems at 200MPa. Geochim. Cosmochim. Acta 73, 559e\u0026ndash;581 \u003c/li\u003e\n\u003cli\u003eWebster, J., Thomas, R., F\u0026ouml;rster, H.J., Seltmann, R., Tappen, C., 2004. Geochemical evolution of halogen-enriched granite magmas and mineralizing fluids of the Zinnwald tin-tungsten mining district, Erzgebirge, Germany. Mineral Deposita 39, 452\u0026ndash;472.\u003c/li\u003e\n\u003cli\u003eWittenbrink, J., Lehmann, B., Wiedenbeck, M., Wallianos, A., Dietrich, A., Palacios, C., 2009. Boron isotope composition of melt inclusions from porphyry systems of the Central Andes: a reconnaissance study. Terra Nova 21(2), 111\u0026ndash;118.\u003c/li\u003e\n\u003cli\u003eXu, B., Hou, Z., Griffin, W.L., Yu, J., Long, T., Zhao, Y., Wang, T., Fu, B., Belousova, E., O\u0026apos;Reilly, S.Y., 2022. Apatite halogens and SrO and zircon HfO isotopes: Recycled volatiles in Jurassic porphyry ore systems in southern Tibet. Chemical Geology 120924.\u003c/li\u003e\n\u003cli\u003eXiao, Y., Feng, C.Y., Liu, J.N., Yu, M., Zhou, J.H., Li, D.X., Zhao, Y.M., 2013. 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Origin of the Late Permian gabbros and Middle Triassic granodiorites and their mafic microgranular enclaves from the Eastern Kunlun Orogen Belt: Implications for the subduction of the Palaeo-Tethys Ocean and continent\u0026ndash;continent collision. Geol. J. 55, 147\u0026ndash;172.\u003c/li\u003e\n\u003cli\u003eYao, L., L\u0026uuml;, Z., Zhao, C., Pang, Z., Yu, X., Yang, T., Li, Y., Liu, P., Zhang, M., 2017. Zircon U\u0026ndash;Pb geochronological, trace element, and Hf isotopic constraints on the genesis of the Fe and Cu skarn deposits in the Qiman Tagh area, Qinghai Province, Eastern Kunlun Orogen, China. Ore Geology Reviews 91, 387\u0026ndash;403.\u003c/li\u003e\n\u003cli\u003eYao, L., Yu, X.F., Xue, J.L., Zhang, Z.H., Zhang, M.C., Zhen, S.M., Jia, R.Y., 2016. Geochemical features of Triassic igneous rocks, Qiman Tagh area, Qinghai Province: Implications for prospecting of the Triassic polymetallic deposits. 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Ore Geology Reviews 88, 116-139.\u003c/li\u003e\n\u003cli\u003eZou, Y.H., Liu, Y., Dai, T.G., Mao, X.C., Lei, Y.B., Lai, J.Q., Tian, H.L., 2017. Finite difference modeling of metallogenic processes in the Hutouya Pb\u0026ndash;Zn deposit, Qinghai, China: Implications for hydrothermal mineralization. Ore Geology Reviews 91, 463\u0026ndash;476.\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Robustness of apatite, zircon, petrochronology, in-situ multi-element analysis, porphyry–skarn system","lastPublishedDoi":"10.21203/rs.3.rs-4524703/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4524703/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eApatite low-temperature thermochronology can be double or even triple dated allowing for a reconstruction of the thermal history of rock from ~\u0026thinsp;550 \u003csup\u003eo\u003c/sup\u003eC to near-surface temperatures. Even though it has disadvantageous U\u0026ndash;Th\u0026ndash;Pb contents (high Pb contents and low U and Th contents) and an unstable nature, apatite is still regarded to have the same robustness in fingerprinting igneous processes in porphyry systems as zircon, so far as to be replace zircon. Hence, we systematically studied characteristics of morphology, geochronology and geochemistry of apatite hosted in syenogranite and monzogranite intrusive rocks in the large Hutouya skarn deposit, in order to corroborate its potential thermochronological monitoring capabilities like zircon in fingerprinting igneous processes in porphyry systems. In this study, apatite grains can be subdivided into two types, FI-free Apatite I formed in the early less fractionated magma and FI-rich Apatite II crystallized in the late highly fractionated magma stage. We obtained ages of 229.0\u0026thinsp;\u0026plusmn;\u0026thinsp;6.6 Ma in syenogranite and 224.3\u0026thinsp;\u0026plusmn;\u0026thinsp;4.5 Ma / 223.7\u0026thinsp;\u0026plusmn;\u0026thinsp;3.9 Ma in monzogranite from Apatite I of magmatic origins. Zircon grains in the two granites can be classified into three types. Zircon I is characterized by transparent and bright zones, Zircon II by dark and metamict features, and Zircon III by mineral inclusions. Zircon I grains with a magmatic texture of well-developed bright oscillatory zones, are most likely primary magmatic zircon that crystallized early in the evolution of granitic magma, dating results of which are 224.70\u0026thinsp;\u0026plusmn;\u0026thinsp;0.61 Ma in syenogranite intrusions and 225.75\u0026thinsp;\u0026plusmn;\u0026thinsp;0.66 Ma / 226.31\u0026thinsp;\u0026plusmn;\u0026thinsp;0.78 Ma in monzogranite, respectively. The apatite\u0026ndash;zircon timing is coincident. Furthermore, apatite trace rare earth element contents in the syenogranite and monzogranite intrusions display a negative-slope chondrite-normalized distribution from La to Lu with strong negative Eu anomalies and weak positive Ce anomalies, with major element contents that are statistically identical with enriched F but poor Cl. Zircon trace element compositions in the two intrusions show consistent and steeply increasing chondrite-normalized REE diagrams from La to Lu with negative Eu anomalies and strong positive Ce anomalies. Accordingly, apatite U\u0026ndash;Pb dates and the corresponding in-situ trace element compositions and isotopes can test precise constraints on rock formation ages, temperature, oxygen fugacity, material source, and tectonic background, which can be relatively more robust when used as proxies for magma oxidation state.\u003c/p\u003e","manuscriptTitle":"Consistency between apatite and zircon petrochronology supports robustness of apatite in fingerprinting igneous processes in porphyry systems","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-06-24 07:57:20","doi":"10.21203/rs.3.rs-4524703/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"c6c563d7-7022-463e-a7a2-a6be1d923fb0","owner":[],"postedDate":"June 24th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2025-05-05T04:23:27+00:00","versionOfRecord":[],"versionCreatedAt":"2024-06-24 07:57:20","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-4524703","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4524703","identity":"rs-4524703","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}