Asynchronous transfer of magmas and mineralizing fluids in a plutonic-subvolcanic-volcanic plumbing system

Asynchronous transfer of magmas and mineralizing fluids in a plutonic-subvolcanic-volcanic plumbing system | 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 Article Asynchronous transfer of magmas and mineralizing fluids in a plutonic-subvolcanic-volcanic plumbing system Gabriele Paoli, Andrea Dini, Simone Vezzoni, Maria Ovtcharova, and 1 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5689469/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 05 Dec, 2025 Read the published version in Scientific Reports → Version 1 posted 12 You are reading this latest preprint version Abstract The geochronological-geochemical interplay between magma transfer and mineralizing fluid is studied at Campiglia igneous complex, Tuscany. Here, crustal and mantle-derived magmas were emplaced at plutonic, subvolcanic, and volcanic level (5.4 to 4.4 Ma), and were quickly exhumed, thus allowing U-Pb CA-ID-TIMS zircon dating with error of ka to tens of ka. The igneous activity is intertwined with the genesis of Cu-Pb-Zn(-Ag) ore deposits. A two-cycle scenario is reconstructed. In the first cycle, a bimodal deep reservoir remained in melt-present condition for ~ 500 ka. In this time interval, a peraluminous pluton is emplaced, followed by generation of skarn with related Zn-Pb(-Ag) sulfide ore. Fe-Cu ore is then generated in association with mantle-derived mafic dykes, and a peraluminous rhyolite eruption terminates the cycle. These crust- or mantle-derived igneous units show limited evidence for interaction. Early-crystallized, antecrystic zircons were recycled within portions of melts sequentially extracted from the reservoir. In the second cycle, during the following 500 ka, an independent reservoir freshly fed by interacting crustal and mantle melts gave eventually way to eruption of a hybrid rhyolite. Timescales of the Campiglia complex reveal significant asynchrony between magma feeding of the plutonic-subvolcanic-volcanic plumbing system and the mineralizing activity of igneous fluids. Figures Figure 1 Figure 2 Figure 3 Figure 4 INTRODUCTION Timescales are key to understanding the genetic link between plutonic and volcanic realms in igneous plumbing systems. High-precision zircon geochronology by CA-ID-TIMS (chemical abrasion isotope dilution thermal ionization mass spectrometry) is pivotal in estimating timescales for magma extraction, emplacement, and fluxes (Caricchi et al., 2016 ; Leuthold et al., 2012 ; Schaltegger et al., 2015 ). Zircon geochronology is supporting the idea of prolonged periods of zircon crystallization in felsic magmas (Barboni and Schoene, 2014 ; Casalini et al., 2017 ; Wotzlaw et al., 2013 ). Intrusive bodies can show cumulative time intervals of zircon crystallization significantly longer than the time required for the complete solidification of a single pulse of magma, suggesting a multistage, pulsed, growth history (Menand et al., 2011 ). Moreover, zircon grains found in subvolcanic and volcanic bodies can originate in and be withdrawn from partly crystallized magma mushes before or during an eruption (Caricchi et al., 2014 ; Miller et al., 2007 ), either as isolated crystals or in mobilized residual melt pockets (Cashman and Giordano, 2014 ), thus providing key information on otherwise inaccessible portions of igneous systems (Caricchi et al., 2016 ). Finally, combining timescales of events with petrochemical and isotopic data contributes to resolve the duration of processes at different levels of the plumbing system (Deering et al., 2016 ) as well as the nature of magma source(s). Timescale issues have been successfully addressed for rhyolite eruptions in volcanic arcs, deriving from either large-volume silicic magmas evolving as open systems assimilating older crust, or extended crystal fractionation at mid- to upper-crustal level of mantle-derived magmas (Bachmann et al., 2007a ; Payacán et al., 2023 ; Wotzlaw et al., 2014 ; Wotzlaw et al., 2013 ). Recently, timescales of such systems have also been proven as critical clues for the understanding the interplay between magmatic and hydrothermal processes in the generation of porphyry-related ore deposits in subduction systems (Large et al., 2021 ; Large et al., 2024 ; Large et al., 2020 ). On the other hand, igneous plumbing systems fed by post-collisional crustal and mantle magmas and related to ore deposits are receiving comparatively little attention in terms of their timescale evolution, and even less for their relationships with magmatic-to-hydrothermal ore deposits. To contribute to fill this gap, we investigated the Miocene-Pliocene Campiglia Marittima igneous complex, Tuscany (Paoli et al., 2019b ). This complex is in many respects a unique example of a plumbing system where (i) crustal and mantle magmas did interact to generate a complete range of crustal, mantle and hybrid magmas, (ii) these magmas were emplaced at plutonic, subvolcanic, and volcanic levels over a time span of c. 1 Ma, (iii) a serendipitous quick exhumation of the intrusive bodies occurred here (Vezzoni et al., 2018 ), thus exposing young plutonic and subvolcanic rocks as well as to their volcanic counterpart to which apply high-precision U-Pb CA-ID-TIMS zircon dating, obtaining uncertainties smaller than the duration of processes internal to the plumbing system -also for intrusive rocks, and (iv) skarn and ore genesis occurred amidst magma emplacement/eruption events. This unveils processes internal to the plumbing system such as magma recharge-interaction in prolonged melt-present conditions, and zircon cannibalism by younger magma batches at the expense of older ones. Finally, the interleaving of igneous events with skarn/ore formation opens a window on the understanding of the link between magmatism, activity of mineralizing fluid and their timing and timescales, revealing an asynchrony between feeding processes and magma emplacement/eruption. THE CAMPIGLIA IGNEOUS COMPLEX The Miocene-Quaternary Tuscan Magmatic Province is characterized by crustal peraluminous magmas, minor mantle-derived products, and volumetrically significant hybrid products (Poli and Peccerillo, 2016 ). Magmatic centers were activated by post-collisional extension, as the crust of the Northern Apennines fold-and-thrust belt was progressively thinned to 20–25 km and heated by asthenosphere upwelling during the eastward roll-back of the subducting Adria Plate (Dini et al., 2002 ). Some of the igneous complexes are characterized by a simple intrusive history, while multiple batches of crustal, mantle and hybrid magmas were emplaced in western-central Elba Island (8.4–6.9 Ma), Campiglia Marittima (5.4–4.4 Ma) and Larderello (3.8–1.6 Ma) (Dini et al., 2005 ; Farina et al., 2018 ). The Campiglia Marittima igneous complex (Fig. 1 ) is made of the Botro ai Marmi granite pluton, several subvolcanic mafic and felsic porphyry dykes, and the rhyolitic volcanic complex of San Vincenzo. The intrusive sequence started with the emplacement of the Botro ai Marmi granite magma into a Jurassic limestone sequence at shallow depth (∼0.10–0.15 GPa) (Leoni and Tamponi, 1991 ), producing a N-S elongated thermal aureole (Vezzoni et al., 2016 ). The top of the granite body crops out for as little as ∼ 0.1 km 2 , with a buried roof extending over ~ 18 km 2 (Vezzoni et al., 2018 ). The pluton has peraluminous monzo-syenogranite composition (SiO 2 = 68–72 wt%, ASI = 1.1–1.3) and is made of a light grey facies with pristine igneous features (minor) and a metasomatized white-pinkish facies (dominant). The primary paragenesis consists of quartz, K-feldspar, plagioclase, biotite, and cordierite along with accessory apatite, zircon and late-magmatic tourmaline. The metasomatized granite is characterized by replacement of oligoclase and biotite by K-feldspar and phlogopite plus titanite, respectively (Paoli et al., 2019b ). Skarn occur as minor proximal masses (Paoli et al., 2019b ) and large distal bodies associated with Zn-Pb(-Ag) and Cu-Fe ore deposits (Vezzoni et al., 2016 ). The Temperino mafic porphyry (Vezzoni et al., 2016 ) occurs as small-volume, isolated dykelets emplaced into distal skarn bodies. The porphyry consists of phenocrysts of plagioclase, biotite, clinopyroxene, orthopyroxene and olivine, commonly replaced by actinolite, epidote, chlorite and carbonates, along with a significant xenocryst cargo of coarse-grained sanidine and quartz, all set in a fine-grained groundmass completely recrystallized to K-feldspar, quartz and chlorite. Accessory minerals are chromite, apatite, zircon, monazite, and ilmenite. The felsic porphyry dykes are found as three main lithological types (Di Vincenzo et al., 2022 ; Vezzoni et al., 2016 ). The Coquand porphyry consists of two dykes, ~ 2 km-long, and carrying dm-sized mafic enclaves. The Ortaccio porphyry consists of a ~ 8 km-long dyke crosscutting the Coquand dykes and is characterized by abundant cm-sized K-feldspar phenocrysts and scattered small mafic enclaves. The Monticino porphyry is K-feldspar-phyric. The San Vincenzo rhyolite covers ~ 10 km 2 as viscous lava flows/domes with a mean thickness around 100 m, for a total preserved volume of about 1 km 3 . Petrographic (Ridolfi et al., 2016 ) and geochemical-isotopic features distinguish the rhyolites into two types (Ferrara et al., 1989 ). Type-A have vitrophyric texture hosting phenocrysts of quartz, sanidine, plagioclase, biotite, cordierite, along with accessory apatite, monazite, zircon and ilmenite. Type-B are distinguished for the occurrence of fine-grained enclaves of latite composition, scattered ortho- and clinopyroxene xenocrysts, and lower Sr and higher Mg contents with respect to Type-A rhyolite. The igneous units of the Campiglia complex cover the whole range of Sr-Nd isotope systematics of the Tuscan Magmatic Province (Table 1SM, Fig. 2 ). Therefore, they have significantly variable petrochemical origins, ranging from purely crustal magmas to (purely) mantle-derived magmas with hybrid magmas in between. The Botro ai Marmi granite samples have the highest 87 Sr/ 86 Sr t (0.72555–0.72643) and the lowest 143 Nd/ 144 Nd t (0.51206–0.512123) of the whole Tuscan Magmatic Province, standing as typical representatives of crust-derived magmas (Supplemental Table 1, Fig. 2 ). On the other hand, the latite enclaves in San Vincenzo rhyolites have the lowermost 87 Sr/ 86 Sr t (0.70790–0.70918) and the highest 143 Nd/ 144 Nd t (0.51236–0.512520) of the whole Tuscan Magmatic Province, thus representing the composition closest to a mantle end-member (Dini et al., 2002 ). The Type-A San Vincenzo rhyolites have very high and variable 87 Sr/ 86 Sr t (0.71900-0.72507) and low 143 Nd/ 144 Nd t (0.51212–0.51222) almost reaching the extreme values of the Botro ai Marmi pluton, being therefore close representatives of crust-derived magmas (Supplemental Table 1, Fig. 2 ) (Dini et al., 2002 ; Ferrara et al., 1989 ). The Type-B San Vincenzo rhyolites have moderate and variable 87 Sr/ 86 Sr t (0.71312–0.71538) and 143 Nd/ 144 Nd t (0.51221–0.51224), shifted towards mantle end-members with respect to the Type-A rhyolite (Dini et al., 2002 ; Ferrara et al., 1989 ). The Temperino porphyry has 87 Sr/ 86 Sr t (0.71002–0.71068) and 143 Nd/ 144 Nd t (0.51221–0.51222) close to the mantle end-member represented by the latitic San Vincenzo enclaves (Dini et al., 2002 ; Poli and Peccerillo, 2016 ). This variety of igneous rocks, covering the whole geochemical range of the Tuscan Province, crop out in a restricted area, with intrusive, subvolcanic and volcanic rocks related to a single igneous plumbing system. This serendipitous geological setting was generated thanks to the quick exhumation of the very young Botro ai Marmi pluton following the eastward lateral extrusion of its carbonate overburden rheologically weakened by thermal metamorphism (Vezzoni et al., 2018 ). Distal skarn and subvolcanic porphyries were emplaced to the east of the pluton, while volcanic rocks were emplaced west of the pluton, in a crustal section not significantly affected by exhumation (Fig. 1 ). ZIRCON CRYSTALLIZATION AGES In total, 59 zircon crystals from 7 samples have been dated by CA-ID-TIMS. All the zircons show simple to oscillatory growth zoning (Fig. 3 ), typical of an igneous origin. For the Botro ai Marmi monzogranite, 13 zircon crystals were dated, 4 from each of the two samples of cordierite-biotite granite (BM5 and GBM4), and 5 from the phlogopite-titanite granite (GBM2A; Supplemental Table 2, Fig. 3 ). The two samples from pristine to slightly metasomatized cordierite-biotite granite and the sample from the metasomatized phlogopite-titanite granite all have overlapping 206 Pb/ 238 U zircon dates. This overlap demonstrates as metasomatic processes that deeply modified the petrographic/chemical features of the granite (Paoli et al., 2019a; Paoli et al., 2019b ) were not able to affect zircon composition. Overall, 206 Pb/ 238 U dates range between 5.511 ± 0.063 and 5.404 ± 0.085 Ma, with a total age range covered by zircons from the same unit (excluding the xenocrystic or xenocryst-cored zircons) ∆T h (Samperton et al., 2015 ) = 107 ± 106 ka (Fig. 3 ). The emplacement age of the granite is interpreted as linked to the date of the youngest zircon (5.404 ± 0.085 Ma), resulting identical to the 5.409 ± 0.043 Ma 40 Ar- 39 Ar age for biotite from BM5 sample (Di Vincenzo et al., 2022 ). For the mafic Temperino porphyry, 10 zircons were dated from two samples (PV319 and MGC; Fig. 3 ). Overall, 206 Pb/ 238 U dates range between 5.520 ± 0.11 and 5.068 ± 0.060 Ma, with a total spread ∆T h = 0.452 ± 0.125 Ma. The youngest zircon date (5.068 ± 0.060) is interpreted as the age of porphyry emplacement, as supported by the overlap with the biotite 40 Ar- 39 Ar age of 5.084 ± 0.027 (Fig. 3 ) (Di Vincenzo et al., 2022 ). It is possible that the oldest zircon of each sample represents an antecryst, anyway deriving from the same magmatic system. For the San Vincenzo Type-A rhyolite (sample GZT4), 25 zircon crystals have been dated. They show a total age range ∆T h = 0.564 ± 0.213 Ma, between 5.60 ± 0.21 and 5.036 ± 0.034 Ma, so that the zircon age dispersion is somewhat larger than observed for the mafic porphyry and much larger than the granite. The youngest zircon date (4.953 ± 0.020 Ma) overlaps within the error of the sanidine 40 Ar- 39 Ar age of 5.0024 ± 0.0062 Ma (Di Vincenzo et al., 2022 ) and is interpreted as the eruption age. For the Type-B rhyolite (sample SV85-1), 11 zircon crystals have been dated, showing a total range of crystallization ages ∆T h = 0.388 ± 0.008 Ma, between 4.8682 ± 0.0041 and 4.4802 ± 0.0063 Ma (Fig. 3 ). The youngest zircon gives a date 4.4802 ± 0.0063 Ma, very close to the sanidine 40 Ar- 39 Ar dates of 4.41 ± 0.04 (Feldstein et al., 1994 ), and the more precise 4.4359 ± 0.0045 Ma (Di Vincenzo et al., 2022 ), the latter interpreted as the eruption age. Crystals significantly older than the main age group are overall rare (4 of 59 dated zircons; Fig. 3 ). One has been found in Temperino porphyry PV319 (7.369 ± 0.088 Ma), two in the San Vincenzo Type-A rhyolite (6.638 ± 0.033 and 9.758 ± 0.034 Ma) and one in Type-B rhyolite (9.750 ± 0.030 Ma, Table 2SM). They could simply be interpreted as xenocrysts, yet xenocrystic, inherited zircons are proven to be very rare in San Vincenzo lavas and throughout the whole crustal magmas of the PMT. Indeed, a LA-HR-ICP-MS screening aimed to look for old xenocryst cores in the most crustal-like igneous rocks of the TMP, including San Vincenzo rhyolite, yielded a surprisingly low number of Paleozoic or older ages of 21 out of 750 data, and, as expected, no cores of Miocene to Triassic age (Paoli, 2013 ). It is therefore most likely that these few ages represent averaged values between small-volume pre-Mesozoic, inherited cores and volumetrically dominant mantle-rim young autocrystic portions (Samperton et al., 2015 ), reported as "xenocryst-cored zircons" in Fig. 3 . ORIGIN OF ZIRCON AGE DIPERSIONS The Campiglia igneous complex is a prime case study to investigate timescales in an ore deposit-related hybrid igneous plumbing system, owing to its very young age leading to very small errors on high-precision CA-ID-TIMS dates, coupled with exposures of the full range of emplacement levels. For each igneous unit, the zircon dates cover a range of ages, with two relevant common features. (1) The ages of the oldest zircons (~ 5.52 Ma) are shared by the peraluminous Botro ai Marmi pluton, the mafic Temperino porphyry, and the peraluminous San Vincenzo Type-A rhyolite: we infer this is the age of feeding and set-up of the deepest part of the plumbing system, with both a felsic, crustal magma reservoir and a mafic-intermediate, mantle-derived magma reservoir. (2) The youngest zircon dates for each unit essentially coincide with sanidine or biotite 40 Ar- 39 Ar ages for the same unit (Di Vincenzo et al., 2022 ): we interpret this age as the emplacement/eruption age. On the other hand, the Campiglia system is characterized by significantly different zircon age dispersions when different igneous episodes are compared to each other. Botro ai Marmi pluton - All the samples have zircon dates overlapping within each hand sample and across hand samples, and no antecrysts are found. At this initial stage, the plumbing system has no zircons acquired from previous magmatic pulses. The youngest zircon ages overlap the biotite 40 Ar- 39 Ar age and are interpreted as the emplacement age. Temperino mafic porphyry - The two hand samples yields different zircon crystallization time span, each one of them terminated by slightly younger biotite 40 Ar- 39 Ar age. This is interpreted as evidence for multiple extraction events. Furthermore, the oldest zircon date overlaps the oldest Botro ai Marmi pluton's dates. These latter zircons are interpreted as antecrysts deriving from the plumbing system which was established at ~ 5.5 Ma. This antecrystic origin is supported by the occurrence in the porphyry of sanidine and quartz xenocrysts from a felsic magma/mush. On the other hand, the occurrence of a hidden mantle-derived magma pool into the crust (that in late Miocene was already < 25 km thick) is also supported by (i) metasomatic input of Mg, Ba, Sr into the pluton from a coeval mafic source, (ii) mantle signature of mineralizing fluids, and (iii) extra-heat source to produce the high temperature metamorphism and metasomatism of the pluton carbonate host (Paoli et al., 2019a; Paoli et al., 2019b ). San Vincenzo Type-A rhyolite - Zircon ages show a significant dispersion of 544 ± 134 ka, covering the whole range shown by the two Temperino samples. For a similar dispersion range in a middle crust intrusion, an exhaustive discussion of the main possible interpretations (Samperton et al., 2015 ) shed light on the difficulties of choosing among possible interpretations in the case of that intrusion. On the other hand, for San Vincenzo rhyolite, three special features give tight constraints on the interpretation of the age dispersion: (i) the volcanic nature of the studied material, (ii) the availability of a precise sanidine 40 Ar- 39 Ar age coincident with the youngest zircon date and interpreted as the eruption age (Di Vincenzo et al., 2022 ), in agreement with inferences for other large-volume eruptions, where the time span of zircon crystallization terminates with the eruption event dated by sanidine 40 Ar- 39 Ar (Bachmann et al., 2007a ; Bachmann et al., 2007b ; Deering et al., 2016 ), and (iii) the dispersion of zircon dates between the eruption age (5.0 Ma) and the age of the oldest zircons of the system, inferred to represent the age of the establishment of the plumbing system (~ 5.5 Ma). Thus, these oldest zircons are envisaged as deriving from such a reservoir, fed by crustal and mantle magmas. It is to note that, in this case study, naming them cognate xenocrysts or antecrysts or autocrysts is of minor significance, owing to the crust-mantle double nature of the feeding system. San Vincenzo Type-B rhyolite - Zircon ages split into two groups: the youngest zircon of the youngest cluster has an age -almost- overlapping the sanidine 40 Ar- 39 Ar age that, as for Type-A rhyolite, is interpreted as the eruption age (Di Vincenzo et al., 2022 ); zircons from the oldest group are distinctly older, yet significantly younger than the eruption age of Type-A rhyolite. Thus, all the zircons are significantly younger than the eruption age of the Type-A rhyolite: the youngest eruption did not cannibalize any older zircon from the felsic-mafic reservoir. The zircons from Type-B rhyolite appear to have crystallized in a system with no memory of the previous plumbing system. So, what a process able to discontinue the zircon supply from the deep reservoir to the ascending magmas did happen between 5.00 and 4.45 Ma? The key is inferred to be the significant petrological difference between Type-A and Type-B rhyolites, i.e., the stark evidence for mingling-mixing between crustal and mantle magma in the pre-eruptive system in later, Type-B rhyolite which actually represent a hybrid melt. INTERPLAY BETWEEN MAGMA FEEDING, EXTRACTION AND ORE GENESIS The extended, ~ 500 ka, crystallization ages of the two rhyolite types, with no zircon age overlap between them, points out two separate igneous cycles. Both cycles were fed by felsic and mafic magmas in their earliest stages, but they nevertheless evolved in different ways. The first cycle (~ 5.5-5.0 Ma) is characterized by separate, independent emplacement of felsic magmas, mafic magma, and mineralizing fluids, with no evidence for chemical interaction between the two types of magmas. The second cycle is characterized by mingling in every emplacement episode, witnessed by the occurrence of MME in felsic dykes and MME plus mafic xenocrysts in the Type-B rhyolite. Additionally, no evidence for activity of mineralizing fluids is found in the second cycle. Thus, a history of asynchronous interplay between magma feeding, magma extraction, magma emplacement/eruption and activity of mineralizing fluids can be outlined (Fig. 4 ). The first felsic feeding event occurred at 5.52 Ma, when the oldest zircons started to crystallize. This magma batch did set up a mid-crustal reservoir, that soon gave way to the emplacement in the shallow crust of Botro ai Marmi peraluminous magma at 5.44 Ma. The 5.38 Ma development of Mg- and Fe-rich exoskarn (Di Vincenzo et al., 2022 ), proximal to the BM pluton, is interpreted as evidence for arrival in the deep reservoir of a mafic magma batch (Paoli et al., 2019a; Paoli et al., 2019b ; Vezzoni et al., 2016 ), setting up a bimodal reservoir from which mineralizing fluids are issued. The genesis of Zn-Pb-Ag ores between 5.38 and 5.1 Ma (Di Vincenzo et al., 2022 ) is related to the release of another batch of mineralizing fluids (Vezzoni et al., 2016 ). The age could be inferred to be at ~ 5.23 Ma, coincident with the second-rank peak in the abundance of zircon dates, indicating a pulse in crystallization inducing release of mineralizing fluids. The genesis of Fe-Cu ore, overprinting the previous Zn-Pb-Ag ores (reverse telescoping process) (Vezzoni et al., 2016 ), is linked to hot mafic fluids and to the minor volume of mafic Temperino Porphyry magma as well, issuing from mafic magma in the deep reservoir. This episode is inferred to coincides with the third-rank peak in zircon age distribution, around 5.24 Ma (Fig. 4 ). The San Vincenzo Type-A rhyolite then erupted at 5.00 Ma from part of the deep reservoir not affected by mass contribution of mafic melt, and nevertheless remained in a partially molten state for more than 500 ka, as indicated by the extended period of zircon crystallization. 560 ka passed before the next eruption of Type-B San Vincenzo rhyolitic hybrid magma at 4.436 Ma. The oldest zircon in this rhyolite is 4.87 Ma, and zircons older than 5 Ma are missing at all, suggesting the establishment of a new, independent reservoir. This reservoir likely fed three episodes of emplacement of felsic dikes carrying mafic microgranular enclaves, the Coquand, Ortaccio and Monticino porphyries (Vezzoni et al., 2016 ), whose 40 Ar- 39 Ar ages, even affected by some uncertainty, are overlapping with the three secondary peaks of zircon distribution of the Type-B rhyolite at ~ 4.88, ~ 4,68 and ~ 4.50 Ma, respectively. Thus, a new deep bimodal reservoir was established around 4.9 Ma and fed the MME-bearing dikes and, finally, the eruption of Type-B rhyolite. The supply of a new, independent felsic magma batch is also supported by the comparison of chemical and isotopic composition of Type-A and Type-B rhyolites: they have the same overall chemical composition, but significantly different Sr isotopic compositions (Ferrara et al., 1989 ). Assuming that isotope variabilities are originated by magma mixing, a simple Sr-isotopic modelling would require at least 20 wt% of mafic melt (San Vincenzo MME) in the hybrid system, that would displace the rhyolite to significantly lower SiO 2 content (some 5 wt%), which is not observed. The bulk of this evidence led to infer a new cycle/system, isolated from the first bimodal reservoir, also involving a mafic magma with a Nd isotopic ratio distinctly higher than the earlier mafic magma recorded by the Temperino porphyry (Fig. 2 ). This is coherent with the post-collisional geodynamic setting, where small volume of magmas are generated and rapidly extracted from a thinned crustal source (Farina et al., 2014 ) characterized by extremely high thermal gradients from underlying uplifted mantle. CONCLUSIONS In summary, for the Campiglia plumbing system, the exposures of the full range of magma emplacement levels, combined with young ages of the products and high precision CA-ID-TIMS geochronology reveal a complex distribution of zircon crystallization ages, spanning over more than 1 Ma. The full distribution of zircon ages can be understood only in the light of the dynamics of the different levels of the reservoirs integrated with the genesis of metasomatic rocks linked to the release of fluids from the plumbing system. A bimodal deep reservoir, once set-up at ~ 5.5 Ma, for the following ~ 550 ka remains in magmatic conditions (i.e., melt-present) with the help from the input of mafic, mantle-derived melt. The three events of magma emplacement/eruptions tapped the same reservoir, with common oldest zircon ages and progressively younger youngest zircons. The feeding episodes and release of mineralizing fluids show asynchrony, as revealed by the generation of skarn and/or ore deposits. Another deep reservoir is then established after the first major rhyolite eruption, to feed felsic dykes and a rhyolite eruption, all characterized by mingling processes, but not accompanied by mineralizing fluids. The two main eruption episodes both mark the end of a magmatic cycle lasting some 550 ka, with only the earliest cycle characterized by generation of ore deposits. In the Larderello geothermal area, a similar history is documented, with ore occurrences linked to the oldest igneous cycle, while no ores has been found associated with the youngest intrusions, despite the large numbers of deep wells drilled in the area. The Campiglia system thus reveals an asynchrony between transfer of magmas and mineralizing fluids, as pointed out by isotopic and relative ages of igneous rocks, metasomatic products and ore deposits. Thus, the Campiglia plutonic-subvolcanic-volcanic plumbing system represents a prime case study thanks to the quick and differential exhumation that helps understanding the connection between processes originally occurring at different crustal levels. Declarations ACKNOWLEDGMENTS This work is part of the Ph.D. project of GP at the University of Pisa and was supported by the University of Pisa research projects PRA_2018_19, PRA_2022_66, the MUR project TEOREM prot. 2017AK8C32, and by the Istituto di Geoscienze e Georisorse-CNR (EU-H2020 DESCRAMBLE Project 640573). DATA AVAILABILITY All data generated or analysed during this study are included in this published article and its supplementary information files References Bachmann, O., Charlier, B. L. A., and Lowenstern, J. B., 2007a, Zircon crystallization and recycling in the magma chamber of the rhyolitic Kos Plateau Tuff (Aegean arc): Geology, v. 35, no. 1, p. 73-76. Bachmann, O., Oberli, F., Dungan, M. 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Dini, A., Gianelli, G., Puxeddu, M., and Ruggieri, C., 2005, Origin and evolution of Pliocene-Pleistocene granites from the Larderello geothermal field (Tuscan Magmatic Province, Italy): Lithos, v. 81, p. 1-31. Dini, A., Innocenti, F., Rocchi, S., Tonarini, S., and Westerman, D. S., 2002, The magmatic evolution of the laccolith-pluton-dyke complex of Elba Island, Italy: Geological Magazine, v. 139, no. 3, p. 257-279. Farina, F., Dini, A., Davies, J. H. F. L., Ovtcharova, M., Greber, N. D., Bouvier, A.-S., Baumgartner, L., Ulianov, A., and Schaltegger, U., 2018, Zircon petrochronology reveals the timescale and mechanism of anatectic magma formation: Earth and Planetary Science Letters, v. 495, p. 213-223. Farina, F., Dini, A., Rocchi, S., and Stevens, G., 2014, Extreme mineral-scale Sr isotope heterogeneity in granites by disequilibrium melting of the crust: Earth and Planetary Science Letters, v. 399, p. 103-115. Feldstein, S. N., Halliday, A. N., Davies, G. R., and Hall, C. M., 1994, Isotope and chemical microsampling: Constraints on the history of an S-type rhyolite, San Vincenzo, Tuscany, Italy: Geochimica et Cosmochimica Acta, v. 58, no. 2, p. 943-958. Ferrara, G., Petrini, R., Serri, G., and Tonarini, S., 1989, Petrology and isotope geochemistry of San Vincenzo rhyolites (Tuscany, Italy): Bulletin of Volcanology, v. 51, p. 379-388. Large, S. J. E., Buret, Y., Wotzlaw, J. F., Karakas, O., Guillong, M., von Quadt, A., and Heinrich, C. A., 2021, Copper-mineralised porphyries sample the evolution of a large-volume silicic magma reservoir from rapid assembly to solidification: Earth and Planetary Science Letters, v. 563. Large, S. J. E., Nathwani, C. L., Wilkinson, J. J., Knott, T. R., Tapster, S. R., and Buret, Y., 2024, Tectonic and Crustal Processes Drive Multi-Million Year Arc Magma Evolution Leading up to Porphyry Copper Deposit Formation in Central Chile: Journal of Petrology, v. 65, no. 4. Large, S. J. E., Wotzlaw, J.-F., Guillong, M., von Quadt, A., and Heinrich, C. A., 2020, Resolving the timescales of magmatic and hydrothermal processes associated with porphyry deposit formation using zircon U–Pb petrochronology: Geochronology, v. 2, no. 2, p. 209-230. Leoni, L., and Tamponi, M., 1991, Thermometamorphism in the Campiglia Marittima aureole: Neues Jahrbuch Miner. Mh., v. 1991, no. 4, p. 145-157. Leuthold, J., Müntener, O., Baumgartner, L. P., Putlitz, B., Ovtcharova, M., and Schaltegger, U., 2012, Time resolved construction of a bimodal laccolith (Torres del Paine, Patagonia): Earth and Planetary Science Letters, v. 325–326, no. 0, p. 85-92. Menand, T., de Saint-Blanquat, M., and Annen, C., 2011, Emplacement of magma pulses and growth of magma bodies: Tectonophysics, v. 500, p. 1-2. Miller, J. S., Matzel, J. E. P., Miller, C. F., Burgess, S. D., and Miller, R. B., 2007, Zircon growth and recycling during the assembly of large, composite arc plutons: Journal of Volcanology and Geothermal Research, v. 167, no. 1-4, p. 282-299. Paoli, Dini, Petrelli, and Rocchi, 2019a, HFSE‐REE Transfer Mechanisms During Metasomatism of a Late Miocene Peraluminous Granite Intruding a Carbonate Host (Campiglia Marittima, Tuscany): Minerals, v. 9, no. 11. Paoli, G., 2013, Gli zirconi dei magmi crostali della Provincia Magmatica Toscana: morfologie ed età U-Pb [MSci Thesis MSci Thesis]: Università di Pisa. Paoli, G., Dini, A., and Rocchi, S., 2019b, Footprints of element mobility during metasomatism linked to a late Miocene peraluminous granite intruding a carbonate host (Campiglia Marittima, Tuscany): International Journal of Earth Sciences, v. 108, no. 5, p. 1617-1641. Payacán, I., Gutiérrez, F., Bachmann, O., and Parada, M. Á., 2023, Differentiation of an upper crustal magma reservoir via crystal-melt separation recorded in the San Gabriel pluton, central Chile: Geosphere, v. 19, no. 2, p. 348-369. Poli, G., and Peccerillo, A., 2016, The Upper Miocene magmatism of the Island of Elba (Central Italy): compositional characteristics, petrogenesis and implications for the origin of the Tuscany Magmatic Province: Mineralogy and Petrology, p. 1-25. Ridolfi, F., Braga, R., Cesare, B., Renzulli, A., Perugini, D., and Del Moro, S., 2016, Unravelling the complex interaction between mantle and crustal magmas encoded in the lavas of San Vincenzo (Tuscany, Italy). Part I: Petrography and Thermobarometry: Lithos, v. 244, p. 218-232. Samperton, K. M., Schoene, B., Cottle, J. M., Brenhin Keller, C., Crowley, J. L., and Schmitz, M. D., 2015, Magma emplacement, differentiation and cooling in the middle crust: Integrated zircon geochronological–geochemical constraints from the Bergell Intrusion, Central Alps: Chemical Geology, v. 417, p. 322-340. Schaltegger, U., Schmitt, A. K., and Horstwood, M. S. A., 2015, U-Th- Pb zircon geochronology by ID-TIMS, SIMS, and laser ablation ICP-MS: recipes, interpretations, and opportunities. Chem. Geol. 402, 89–110. doi: 10.1016/j.chemgeo.2015.02.028: Chemical Geology, v. 402, p. 89-110. Vezzoni, S., Dini, A., and Rocchi, S., 2016, Reverse telescoping in a distal skarn system (Campiglia Marittima, Italy): Ore Geology Reviews, v. 77, p. 176-193. Vezzoni, S., Rocchi, S., and Dini, A., 2018, Lateral extrusion of a thermally weakened pluton overburden (Campiglia Marittima, Tuscany): International Journal of Earth Sciences, no. 107, p. 1343-1355. Wotzlaw, J.-F., Bindeman, I. N., Watts, K. E., Schmitt, A. K., Caricchi, L., and Schaltegger, U., 2014, Linking rapid magma reservoir assembly and eruption trigger mechanisms at evolved Yellowstone-type supervolcanoes: Geology, v. 42, no. 9, p. 807-810. Wotzlaw, J.-F., Schaltegger, U., Frick, D. A., Dungan, M. A., Gerdes, A., and Günther, D., 2013, Tracking the evolution of large-volume silicic magma reservoirs from assembly to supereruption: Geology, v. 41, no. 8, p. 867-870. Additional Declarations No competing interests reported. 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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-5689469","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":398858684,"identity":"3b3ce643-c00c-4476-b01c-7059c78dfef3","order_by":0,"name":"Gabriele Paoli","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA+UlEQVRIiWNgGAWjYFACHgaGBAYLCPuBgQ0DAzMDwwEGA4JaJCDsBIM0mBZ8enhABEwLw2GYMG4t8u5nj314UCEhxyDd/PBBQsH5xO3svAcPMBT8wanF8Exe8oyEMxLGDDLHjA0SDG4n7mzmS8DrMMOGHGOGxDaJxAaJBDMJkJYNh3kM8GvpfwPU8k+ivkEi/RtQyznCWuQlQLYArWCQyAHZcoCwFgOJd8kMCcckDNtkzhQD/ZJsvOEw0C8JBsa4benPPcz4o8ZGnl+6feODD3/sZDecP3v4w4c/crhtOQBlsEnAxcCRixvIN8BYKFpGwSgYBaNgFCABAIU3UeA/3IMhAAAAAElFTkSuQmCC","orcid":"","institution":"University of Pisa, CISUP","correspondingAuthor":true,"prefix":"","firstName":"Gabriele","middleName":"","lastName":"Paoli","suffix":""},{"id":398858685,"identity":"342bf694-495b-4d9b-9cfb-46dccb5466df","order_by":1,"name":"Andrea Dini","email":"","orcid":"","institution":"Istituto di Geoscienze e Georisorse, CNR","correspondingAuthor":false,"prefix":"","firstName":"Andrea","middleName":"","lastName":"Dini","suffix":""},{"id":398858686,"identity":"cfb18895-c3a0-4fa7-a97a-1bbf5fa9e078","order_by":2,"name":"Simone Vezzoni","email":"","orcid":"","institution":"Istituto di Geoscienze e Georisorse, CNR","correspondingAuthor":false,"prefix":"","firstName":"Simone","middleName":"","lastName":"Vezzoni","suffix":""},{"id":398858687,"identity":"06fa7335-a542-4259-8b79-4d0613919ea0","order_by":3,"name":"Maria Ovtcharova","email":"","orcid":"","institution":"University of Geneva","correspondingAuthor":false,"prefix":"","firstName":"Maria","middleName":"","lastName":"Ovtcharova","suffix":""},{"id":398858688,"identity":"0a686a1d-4b88-41fd-9b0d-82d4506fed33","order_by":4,"name":"Sergio Rocchi","email":"","orcid":"","institution":"Università di Pisa","correspondingAuthor":false,"prefix":"","firstName":"Sergio","middleName":"","lastName":"Rocchi","suffix":""}],"badges":[],"createdAt":"2024-12-21 11:38:16","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-5689469/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-5689469/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s41598-025-19201-5","type":"published","date":"2025-12-05T15:57:01+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":73298579,"identity":"0c5dd9a6-fc1c-463c-b752-2a24e537e260","added_by":"auto","created_at":"2025-01-08 15:38:57","extension":"jpg","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":6052951,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Schematic geological map (Vezzoni et al., 2016) and pluton roof elevation (Vezzoni et al., 2018) with location of studied samples. (b) Schematic geological cross-section, showing the differential exhumation of the eastern block of the Campiglia system, carrying the plutonic-subvolcanic rocks at the same level of the volcanic rock.\u003c/p\u003e","description":"","filename":"Fig1.jpg","url":"https://assets-eu.researchsquare.com/files/rs-5689469/v1/5733a3413819ecbc63b22c8d.jpg"},{"id":73297521,"identity":"fdd5fb10-985c-4b70-bcbf-22ad2e175b4b","added_by":"auto","created_at":"2025-01-08 15:30:57","extension":"jpg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":442919,"visible":true,"origin":"","legend":"\u003cp\u003e\u003csup\u003e143\u003c/sup\u003eNd/\u003csup\u003e144\u003c/sup\u003eNd\u003csub\u003et\u003c/sub\u003e vs \u003csup\u003e87\u003c/sup\u003eSr/\u003csup\u003e86\u003c/sup\u003eSr\u003csub\u003et\u003c/sub\u003e showing the extreme isotopic variability recorded by the Campiglia igneous complex. Type-A and Type-B rhyolites, despite their very similar major element compositions, are characterized by isotopic ratios close to the peraluminous, crust-derived Botro ai Marmi granite and the mantle-derived Temperino porphyry/latite enclaves, respectively.\u003c/p\u003e","description":"","filename":"Fig2.jpg","url":"https://assets-eu.researchsquare.com/files/rs-5689469/v1/739c4fbb7838c1b7be685226.jpg"},{"id":73297523,"identity":"e146b88e-f40e-4d6d-a678-fd36389eac77","added_by":"auto","created_at":"2025-01-08 15:30:57","extension":"jpg","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":770460,"visible":true,"origin":"","legend":"\u003cp\u003eGeochronological framework for the Campiglia igneous complex, with zircon CA-ID-TIMS \u003csup\u003e206\u003c/sup\u003ePb/\u003csup\u003e238\u003c/sup\u003eU dates corrected for Th/U disequilibrium (Table 2SM), integrated with biotite and sanidine \u003csup\u003e40\u003c/sup\u003eAr-\u003csup\u003e39\u003c/sup\u003eAr dates (Di Vincenzo et al., 2022).\u003c/p\u003e","description":"","filename":"Fig3.jpg","url":"https://assets-eu.researchsquare.com/files/rs-5689469/v1/43819a729ed86d182e3adc77.jpg"},{"id":73297531,"identity":"9731edcb-0b02-403e-a689-73fedfe77af4","added_by":"auto","created_at":"2025-01-08 15:30:57","extension":"jpg","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":1428380,"visible":true,"origin":"","legend":"\u003cp\u003eScenario for asynchronous transfer of magmas and mineralizing fluids in the Campiglia plutonic-subvolcanic-volcanic plumbing system in relation to the geochronological framework. Continuous arrows: transfer of magma, dashed arrows: transfer of mineralizing fluids.\u003c/p\u003e","description":"","filename":"Fig4.jpg","url":"https://assets-eu.researchsquare.com/files/rs-5689469/v1/9ba6124afde41d68f89606b5.jpg"},{"id":97723762,"identity":"2c9815e4-d6e7-41c3-b86d-7c09c3297f16","added_by":"auto","created_at":"2025-12-08 16:04:32","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":9143953,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5689469/v1/ba4e2e88-8309-4af8-bd5e-d69b371e6a81.pdf"},{"id":73297524,"identity":"11c971e8-f289-4267-b31e-cfa299711c7f","added_by":"auto","created_at":"2025-01-08 15:30:57","extension":"xlsx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":10733,"visible":true,"origin":"","legend":"","description":"","filename":"SupplTable1.xlsx","url":"https://assets-eu.researchsquare.com/files/rs-5689469/v1/76155b8fbf841aeb176802c7.xlsx"},{"id":73297522,"identity":"3876fa5b-3d00-4375-9db0-2344925822f9","added_by":"auto","created_at":"2025-01-08 15:30:57","extension":"xlsx","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":27016,"visible":true,"origin":"","legend":"","description":"","filename":"SupplTable2.xlsx","url":"https://assets-eu.researchsquare.com/files/rs-5689469/v1/f34e2b6a4cb3a50c17f47e3f.xlsx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Asynchronous transfer of magmas and mineralizing fluids in a plutonic-subvolcanic-volcanic plumbing system","fulltext":[{"header":"INTRODUCTION","content":"\u003cp\u003eTimescales are key to understanding the genetic link between plutonic and volcanic realms in igneous plumbing systems. High-precision zircon geochronology by CA-ID-TIMS (chemical abrasion isotope dilution thermal ionization mass spectrometry) is pivotal in estimating timescales for magma extraction, emplacement, and fluxes (Caricchi et al., \u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e2016\u003c/span\u003e; Leuthold et al., \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e2012\u003c/span\u003e; Schaltegger et al., \u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e2015\u003c/span\u003e). Zircon geochronology is supporting the idea of prolonged periods of zircon crystallization in felsic magmas (Barboni and Schoene, \u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e2014\u003c/span\u003e; Casalini et al., \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; Wotzlaw et al., \u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e2013\u003c/span\u003e). Intrusive bodies can show cumulative time intervals of zircon crystallization significantly longer than the time required for the complete solidification of a single pulse of magma, suggesting a multistage, pulsed, growth history (Menand et al., \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e2011\u003c/span\u003e). Moreover, zircon grains found in subvolcanic and volcanic bodies can originate in and be withdrawn from partly crystallized magma mushes before or during an eruption (Caricchi et al., \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e2014\u003c/span\u003e; Miller et al., \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e2007\u003c/span\u003e), either as isolated crystals or in mobilized residual melt pockets (Cashman and Giordano, \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e2014\u003c/span\u003e), thus providing key information on otherwise inaccessible portions of igneous systems (Caricchi et al., \u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e2016\u003c/span\u003e). Finally, combining timescales of events with petrochemical and isotopic data contributes to resolve the duration of processes at different levels of the plumbing system (Deering et al., \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e2016\u003c/span\u003e) as well as the nature of magma source(s).\u003c/p\u003e \u003cp\u003eTimescale issues have been successfully addressed for rhyolite eruptions in volcanic arcs, deriving from either large-volume silicic magmas evolving as open systems assimilating older crust, or extended crystal fractionation at mid- to upper-crustal level of mantle-derived magmas (Bachmann et al., \u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e2007a\u003c/span\u003e; Payac\u0026aacute;n et al., \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e2023\u003c/span\u003e; Wotzlaw et al., \u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e2014\u003c/span\u003e; Wotzlaw et al., \u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e2013\u003c/span\u003e). Recently, timescales of such systems have also been proven as critical clues for the understanding the interplay between magmatic and hydrothermal processes in the generation of porphyry-related ore deposits in subduction systems (Large et al., \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e2021\u003c/span\u003e; Large et al., \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e2024\u003c/span\u003e; Large et al., \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e2020\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eOn the other hand, igneous plumbing systems fed by post-collisional crustal and mantle magmas and related to ore deposits are receiving comparatively little attention in terms of their timescale evolution, and even less for their relationships with magmatic-to-hydrothermal ore deposits. To contribute to fill this gap, we investigated the Miocene-Pliocene Campiglia Marittima igneous complex, Tuscany (Paoli et al., \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e2019b\u003c/span\u003e). This complex is in many respects a unique example of a plumbing system where (i) crustal and mantle magmas did interact to generate a complete range of crustal, mantle and hybrid magmas, (ii) these magmas were emplaced at plutonic, subvolcanic, and volcanic levels over a time span of c. 1 Ma, (iii) a serendipitous quick exhumation of the intrusive bodies occurred here (Vezzoni et al., \u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e2018\u003c/span\u003e), thus exposing young plutonic and subvolcanic rocks as well as to their volcanic counterpart to which apply high-precision U-Pb CA-ID-TIMS zircon dating, obtaining uncertainties smaller than the duration of processes internal to the plumbing system -also for intrusive rocks, and (iv) skarn and ore genesis occurred amidst magma emplacement/eruption events. This unveils processes internal to the plumbing system such as magma recharge-interaction in prolonged melt-present conditions, and zircon cannibalism by younger magma batches at the expense of older ones. Finally, the interleaving of igneous events with skarn/ore formation opens a window on the understanding of the link between magmatism, activity of mineralizing fluid and their timing and timescales, revealing an asynchrony between feeding processes and magma emplacement/eruption.\u003c/p\u003e"},{"header":"THE CAMPIGLIA IGNEOUS COMPLEX","content":"\u003cp\u003eThe Miocene-Quaternary Tuscan Magmatic Province is characterized by crustal peraluminous magmas, minor mantle-derived products, and volumetrically significant hybrid products (Poli and Peccerillo, \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e2016\u003c/span\u003e). Magmatic centers were activated by post-collisional extension, as the crust of the Northern Apennines fold-and-thrust belt was progressively thinned to 20–25 km and heated by asthenosphere upwelling during the eastward roll-back of the subducting Adria Plate (Dini et al., \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e2002\u003c/span\u003e). Some of the igneous complexes are characterized by a simple intrusive history, while multiple batches of crustal, mantle and hybrid magmas were emplaced in western-central Elba Island (8.4–6.9 Ma), Campiglia Marittima (5.4–4.4 Ma) and Larderello (3.8–1.6 Ma) (Dini et al., \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e2005\u003c/span\u003e; Farina et al., \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e2018\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eThe Campiglia Marittima igneous complex (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e) is made of the Botro ai Marmi granite pluton, several subvolcanic mafic and felsic porphyry dykes, and the rhyolitic volcanic complex of San Vincenzo. The intrusive sequence started with the emplacement of the Botro ai Marmi granite magma into a Jurassic limestone sequence at shallow depth (∼0.10–0.15 GPa) (Leoni and Tamponi, \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e1991\u003c/span\u003e), producing a N-S elongated thermal aureole (Vezzoni et al., \u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e2016\u003c/span\u003e). The top of the granite body crops out for as little as ∼ 0.1 km\u003csup\u003e2\u003c/sup\u003e, with a buried roof extending over ~ 18 km\u003csup\u003e2\u003c/sup\u003e (Vezzoni et al., \u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). The pluton has peraluminous monzo-syenogranite composition (SiO\u003csub\u003e2\u003c/sub\u003e = 68–72 wt%, ASI = 1.1–1.3) and is made of a light grey facies with pristine igneous features (minor) and a metasomatized white-pinkish facies (dominant). The primary paragenesis consists of quartz, K-feldspar, plagioclase, biotite, and cordierite along with accessory apatite, zircon and late-magmatic tourmaline. The metasomatized granite is characterized by replacement of oligoclase and biotite by K-feldspar and phlogopite plus titanite, respectively (Paoli et al., \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e2019b\u003c/span\u003e). Skarn occur as minor proximal masses (Paoli et al., \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e2019b\u003c/span\u003e) and large distal bodies associated with Zn-Pb(-Ag) and Cu-Fe ore deposits (Vezzoni et al., \u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e2016\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eThe Temperino mafic porphyry (Vezzoni et al., \u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e2016\u003c/span\u003e) occurs as small-volume, isolated dykelets emplaced into distal skarn bodies. The porphyry consists of phenocrysts of plagioclase, biotite, clinopyroxene, orthopyroxene and olivine, commonly replaced by actinolite, epidote, chlorite and carbonates, along with a significant xenocryst cargo of coarse-grained sanidine and quartz, all set in a fine-grained groundmass completely recrystallized to K-feldspar, quartz and chlorite. Accessory minerals are chromite, apatite, zircon, monazite, and ilmenite.\u003c/p\u003e \u003cp\u003eThe felsic porphyry dykes are found as three main lithological types (Di Vincenzo et al., \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2022\u003c/span\u003e; Vezzoni et al., \u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e2016\u003c/span\u003e). The Coquand porphyry consists of two dykes, ~ 2 km-long, and carrying dm-sized mafic enclaves. The Ortaccio porphyry consists of a ~ 8 km-long dyke crosscutting the Coquand dykes and is characterized by abundant cm-sized K-feldspar phenocrysts and scattered small mafic enclaves. The Monticino porphyry is K-feldspar-phyric.\u003c/p\u003e \u003cp\u003eThe San Vincenzo rhyolite covers ~ 10 km\u003csup\u003e2\u003c/sup\u003e as viscous lava flows/domes with a mean thickness around 100 m, for a total preserved volume of about 1 km\u003csup\u003e3\u003c/sup\u003e. Petrographic (Ridolfi et al., \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e2016\u003c/span\u003e) and geochemical-isotopic features distinguish the rhyolites into two types (Ferrara et al., \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e1989\u003c/span\u003e). Type-A have vitrophyric texture hosting phenocrysts of quartz, sanidine, plagioclase, biotite, cordierite, along with accessory apatite, monazite, zircon and ilmenite. Type-B are distinguished for the occurrence of fine-grained enclaves of latite composition, scattered ortho- and clinopyroxene xenocrysts, and lower Sr and higher Mg contents with respect to Type-A rhyolite.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe igneous units of the Campiglia complex cover the whole range of Sr-Nd isotope systematics of the Tuscan Magmatic Province (Table\u0026nbsp;1SM, Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e). Therefore, they have significantly variable petrochemical origins, ranging from purely crustal magmas to (purely) mantle-derived magmas with hybrid magmas in between.\u003c/p\u003e \u003cp\u003eThe Botro ai Marmi granite samples have the highest \u003csup\u003e87\u003c/sup\u003eSr/\u003csup\u003e86\u003c/sup\u003eSr\u003csub\u003et\u003c/sub\u003e (0.72555–0.72643) and the lowest \u003csup\u003e143\u003c/sup\u003eNd/\u003csup\u003e144\u003c/sup\u003eNd\u003csub\u003et\u003c/sub\u003e (0.51206–0.512123) of the whole Tuscan Magmatic Province, standing as typical representatives of crust-derived magmas (Supplemental Table\u0026nbsp;1, Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e). On the other hand, the latite enclaves in San Vincenzo rhyolites have the lowermost \u003csup\u003e87\u003c/sup\u003eSr/\u003csup\u003e86\u003c/sup\u003eSr\u003csub\u003et\u003c/sub\u003e (0.70790–0.70918) and the highest \u003csup\u003e143\u003c/sup\u003eNd/\u003csup\u003e144\u003c/sup\u003eNd\u003csub\u003et\u003c/sub\u003e (0.51236–0.512520) of the whole Tuscan Magmatic Province, thus representing the composition closest to a mantle end-member (Dini et al., \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e2002\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eThe Type-A San Vincenzo rhyolites have very high and variable \u003csup\u003e87\u003c/sup\u003eSr/\u003csup\u003e86\u003c/sup\u003eSr\u003csub\u003et\u003c/sub\u003e (0.71900-0.72507) and low \u003csup\u003e143\u003c/sup\u003eNd/\u003csup\u003e144\u003c/sup\u003eNd\u003csub\u003et\u003c/sub\u003e (0.51212–0.51222) almost reaching the extreme values of the Botro ai Marmi pluton, being therefore close representatives of crust-derived magmas (Supplemental Table\u0026nbsp;1, Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e) (Dini et al., \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e2002\u003c/span\u003e; Ferrara et al., \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e1989\u003c/span\u003e). The Type-B San Vincenzo rhyolites have moderate and variable \u003csup\u003e87\u003c/sup\u003eSr/\u003csup\u003e86\u003c/sup\u003eSr\u003csub\u003et\u003c/sub\u003e (0.71312–0.71538) and \u003csup\u003e143\u003c/sup\u003eNd/\u003csup\u003e144\u003c/sup\u003eNd\u003csub\u003et\u003c/sub\u003e (0.51221–0.51224), shifted towards mantle end-members with respect to the Type-A rhyolite (Dini et al., \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e2002\u003c/span\u003e; Ferrara et al., \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e1989\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eThe Temperino porphyry has \u003csup\u003e87\u003c/sup\u003eSr/\u003csup\u003e86\u003c/sup\u003eSr\u003csub\u003et\u003c/sub\u003e (0.71002–0.71068) and \u003csup\u003e143\u003c/sup\u003eNd/\u003csup\u003e144\u003c/sup\u003eNd\u003csub\u003et\u003c/sub\u003e (0.51221–0.51222) close to the mantle end-member represented by the latitic San Vincenzo enclaves (Dini et al., \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e2002\u003c/span\u003e; Poli and Peccerillo, \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e2016\u003c/span\u003e).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThis variety of igneous rocks, covering the whole geochemical range of the Tuscan Province, crop out in a restricted area, with intrusive, subvolcanic and volcanic rocks related to a single igneous plumbing system. This serendipitous geological setting was generated thanks to the quick exhumation of the very young Botro ai Marmi pluton following the eastward lateral extrusion of its carbonate overburden rheologically weakened by thermal metamorphism (Vezzoni et al., \u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). Distal skarn and subvolcanic porphyries were emplaced to the east of the pluton, while volcanic rocks were emplaced west of the pluton, in a crustal section not significantly affected by exhumation (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e).\u003c/p\u003e \u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e"},{"header":"ZIRCON CRYSTALLIZATION AGES","content":"\u003cp\u003eIn total, 59 zircon crystals from 7 samples have been dated by CA-ID-TIMS. All the zircons show simple to oscillatory growth zoning (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e), typical of an igneous origin.\u003c/p\u003e\u003cp\u003eFor the Botro ai Marmi monzogranite, 13 zircon crystals were dated, 4 from each of the two samples of cordierite-biotite granite (BM5 and GBM4), and 5 from the phlogopite-titanite granite (GBM2A; Supplemental Table\u0026nbsp;2, Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e). The two samples from pristine to slightly metasomatized cordierite-biotite granite and the sample from the metasomatized phlogopite-titanite granite all have overlapping \u003csup\u003e206\u003c/sup\u003ePb/\u003csup\u003e238\u003c/sup\u003eU zircon dates. This overlap demonstrates as metasomatic processes that deeply modified the petrographic/chemical features of the granite (Paoli et al., 2019a; Paoli et al., \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e2019b\u003c/span\u003e) were not able to affect zircon composition. Overall, \u003csup\u003e206\u003c/sup\u003ePb/\u003csup\u003e238\u003c/sup\u003eU dates range between 5.511 ± 0.063 and 5.404 ± 0.085 Ma, with a total age range covered by zircons from the same unit (excluding the xenocrystic or xenocryst-cored zircons) ∆T\u003csub\u003e\u003cem\u003eh\u003c/em\u003e\u003c/sub\u003e (Samperton et al., \u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e2015\u003c/span\u003e) = 107 ± 106 ka (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e). The emplacement age of the granite is interpreted as linked to the date of the youngest zircon (5.404 ± 0.085 Ma), resulting identical to the 5.409 ± 0.043 Ma \u003csup\u003e40\u003c/sup\u003eAr-\u003csup\u003e39\u003c/sup\u003eAr age for biotite from BM5 sample (Di Vincenzo et al., \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2022\u003c/span\u003e).\u003c/p\u003e\u003cp\u003eFor the mafic Temperino porphyry, 10 zircons were dated from two samples (PV319 and MGC; Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e). Overall, \u003csup\u003e206\u003c/sup\u003ePb/\u003csup\u003e238\u003c/sup\u003eU dates range between 5.520 ± 0.11 and 5.068 ± 0.060 Ma, with a total spread ∆T\u003csub\u003e\u003cem\u003eh\u003c/em\u003e\u003c/sub\u003e = 0.452 ± 0.125 Ma. The youngest zircon date (5.068 ± 0.060) is interpreted as the age of porphyry emplacement, as supported by the overlap with the biotite \u003csup\u003e40\u003c/sup\u003eAr-\u003csup\u003e39\u003c/sup\u003eAr age of 5.084 ± 0.027 (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e) (Di Vincenzo et al., \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). It is possible that the oldest zircon of each sample represents an antecryst, anyway deriving from the same magmatic system.\u003c/p\u003e\u003cp\u003eFor the San Vincenzo Type-A rhyolite (sample GZT4), 25 zircon crystals have been dated. They show a total age range ∆T\u003csub\u003e\u003cem\u003eh\u003c/em\u003e\u003c/sub\u003e = 0.564 ± 0.213 Ma, between 5.60 ± 0.21 and 5.036 ± 0.034 Ma, so that the zircon age dispersion is somewhat larger than observed for the mafic porphyry and much larger than the granite. The youngest zircon date (4.953 ± 0.020 Ma) overlaps within the error of the sanidine \u003csup\u003e40\u003c/sup\u003eAr-\u003csup\u003e39\u003c/sup\u003eAr age of 5.0024 ± 0.0062 Ma (Di Vincenzo et al., \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2022\u003c/span\u003e) and is interpreted as the eruption age.\u003c/p\u003e\u003cp\u003eFor the Type-B rhyolite (sample SV85-1), 11 zircon crystals have been dated, showing a total range of crystallization ages ∆T\u003csub\u003e\u003cem\u003eh\u003c/em\u003e\u003c/sub\u003e = 0.388 ± 0.008 Ma, between 4.8682 ± 0.0041 and 4.4802 ± 0.0063 Ma (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e). The youngest zircon gives a date 4.4802 ± 0.0063 Ma, very close to the sanidine \u003csup\u003e40\u003c/sup\u003eAr-\u003csup\u003e39\u003c/sup\u003eAr dates of 4.41 ± 0.04 (Feldstein et al., \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e1994\u003c/span\u003e), and the more precise 4.4359 ± 0.0045 Ma (Di Vincenzo et al., \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2022\u003c/span\u003e), the latter interpreted as the eruption age.\u003c/p\u003e\u003cp\u003eCrystals significantly older than the main age group are overall rare (4 of 59 dated zircons; Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e). One has been found in Temperino porphyry PV319 (7.369 ± 0.088 Ma), two in the San Vincenzo Type-A rhyolite (6.638 ± 0.033 and 9.758 ± 0.034 Ma) and one in Type-B rhyolite (9.750 ± 0.030 Ma, Table\u0026nbsp;2SM). They could simply be interpreted as xenocrysts, yet xenocrystic, inherited zircons are proven to be very rare in San Vincenzo lavas and throughout the whole crustal magmas of the PMT. Indeed, a LA-HR-ICP-MS screening aimed to look for old xenocryst cores in the most crustal-like igneous rocks of the TMP, including San Vincenzo rhyolite, yielded a surprisingly low number of Paleozoic or older ages of 21 out of 750 data, and, as expected, no cores of Miocene to Triassic age (Paoli, \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e2013\u003c/span\u003e). It is therefore most likely that these few ages represent averaged values between small-volume pre-Mesozoic, inherited cores and volumetrically dominant mantle-rim young autocrystic portions (Samperton et al., \u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e2015\u003c/span\u003e), reported as \"xenocryst-cored zircons\" in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e.\u003c/p\u003e"},{"header":"ORIGIN OF ZIRCON AGE DIPERSIONS","content":"\u003cp\u003eThe Campiglia igneous complex is a prime case study to investigate timescales in an ore deposit-related hybrid igneous plumbing system, owing to its very young age leading to very small errors on high-precision CA-ID-TIMS dates, coupled with exposures of the full range of emplacement levels.\u003c/p\u003e \u003cp\u003eFor each igneous unit, the zircon dates cover a range of ages, with two relevant common features. (1) The ages of the oldest zircons (~\u0026thinsp;5.52 Ma) are shared by the peraluminous Botro ai Marmi pluton, the mafic Temperino porphyry, and the peraluminous San Vincenzo Type-A rhyolite: we infer this is the age of feeding and set-up of the deepest part of the plumbing system, with both a felsic, crustal magma reservoir and a mafic-intermediate, mantle-derived magma reservoir. (2) The youngest zircon dates for each unit essentially coincide with sanidine or biotite \u003csup\u003e40\u003c/sup\u003eAr-\u003csup\u003e39\u003c/sup\u003eAr ages for the same unit (Di Vincenzo et al., \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2022\u003c/span\u003e): we interpret this age as the emplacement/eruption age.\u003c/p\u003e \u003cp\u003eOn the other hand, the Campiglia system is characterized by significantly different zircon age dispersions when different igneous episodes are compared to each other. \u003cem\u003eBotro ai Marmi pluton\u003c/em\u003e - All the samples have zircon dates overlapping within each hand sample and across hand samples, and no antecrysts are found. At this initial stage, the plumbing system has no zircons acquired from previous magmatic pulses. The youngest zircon ages overlap the biotite \u003csup\u003e40\u003c/sup\u003eAr-\u003csup\u003e39\u003c/sup\u003eAr age and are interpreted as the emplacement age. \u003cem\u003eTemperino mafic porphyry\u003c/em\u003e - The two hand samples yields different zircon crystallization time span, each one of them terminated by slightly younger biotite \u003csup\u003e40\u003c/sup\u003eAr-\u003csup\u003e39\u003c/sup\u003eAr age. This is interpreted as evidence for multiple extraction events. Furthermore, the oldest zircon date overlaps the oldest Botro ai Marmi pluton's dates. These latter zircons are interpreted as antecrysts deriving from the plumbing system which was established at ~\u0026thinsp;5.5 Ma. This antecrystic origin is supported by the occurrence in the porphyry of sanidine and quartz xenocrysts from a felsic magma/mush. On the other hand, the occurrence of a hidden mantle-derived magma pool into the crust (that in late Miocene was already\u0026thinsp;\u0026lt;\u0026thinsp;25 km thick) is also supported by (i) metasomatic input of Mg, Ba, Sr into the pluton from a coeval mafic source, (ii) mantle signature of mineralizing fluids, and (iii) extra-heat source to produce the high temperature metamorphism and metasomatism of the pluton carbonate host (Paoli et al., 2019a; Paoli et al., \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e2019b\u003c/span\u003e).\u003c/p\u003e \u003cp\u003e \u003cem\u003eSan Vincenzo Type-A rhyolite\u003c/em\u003e - Zircon ages show a significant dispersion of 544\u0026thinsp;\u0026plusmn;\u0026thinsp;134 ka, covering the whole range shown by the two Temperino samples. For a similar dispersion range in a middle crust intrusion, an exhaustive discussion of the main possible interpretations (Samperton et al., \u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e2015\u003c/span\u003e) shed light on the difficulties of choosing among possible interpretations in the case of that intrusion. On the other hand, for San Vincenzo rhyolite, three special features give tight constraints on the interpretation of the age dispersion: (i) the volcanic nature of the studied material, (ii) the availability of a precise sanidine \u003csup\u003e40\u003c/sup\u003eAr-\u003csup\u003e39\u003c/sup\u003eAr age coincident with the youngest zircon date and interpreted as the eruption age (Di Vincenzo et al., \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2022\u003c/span\u003e), in agreement with inferences for other large-volume eruptions, where the time span of zircon crystallization terminates with the eruption event dated by sanidine \u003csup\u003e40\u003c/sup\u003eAr-\u003csup\u003e39\u003c/sup\u003eAr (Bachmann et al., \u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e2007a\u003c/span\u003e; Bachmann et al., \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2007b\u003c/span\u003e; Deering et al., \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e2016\u003c/span\u003e), and (iii) the dispersion of zircon dates between the eruption age (5.0 Ma) and the age of the oldest zircons of the system, inferred to represent the age of the establishment of the plumbing system (~\u0026thinsp;5.5 Ma). Thus, these oldest zircons are envisaged as deriving from such a reservoir, fed by crustal and mantle magmas. It is to note that, in this case study, naming them cognate xenocrysts or antecrysts or autocrysts is of minor significance, owing to the crust-mantle double nature of the feeding system.\u003c/p\u003e \u003cp\u003e \u003cem\u003eSan Vincenzo Type-B rhyolite\u003c/em\u003e - Zircon ages split into two groups: the youngest zircon of the youngest cluster has an age -almost- overlapping the sanidine \u003csup\u003e40\u003c/sup\u003eAr-\u003csup\u003e39\u003c/sup\u003eAr age that, as for Type-A rhyolite, is interpreted as the eruption age (Di Vincenzo et al., \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2022\u003c/span\u003e); zircons from the oldest group are distinctly older, yet significantly younger than the eruption age of Type-A rhyolite. Thus, all the zircons are significantly younger than the eruption age of the Type-A rhyolite: the youngest eruption did not cannibalize any older zircon from the felsic-mafic reservoir. The zircons from Type-B rhyolite appear to have crystallized in a system with no memory of the previous plumbing system. So, what a process able to discontinue the zircon supply from the deep reservoir to the ascending magmas did happen between 5.00 and 4.45 Ma? The key is inferred to be the significant petrological difference between Type-A and Type-B rhyolites, i.e., the stark evidence for mingling-mixing between crustal and mantle magma in the pre-eruptive system in later, Type-B rhyolite which actually represent a hybrid melt.\u003c/p\u003e"},{"header":"INTERPLAY BETWEEN MAGMA FEEDING, EXTRACTION AND ORE GENESIS","content":"\u003cp\u003eThe extended, ~\u0026thinsp;500 ka, crystallization ages of the two rhyolite types, with no zircon age overlap between them, points out two separate igneous cycles. Both cycles were fed by felsic and mafic magmas in their earliest stages, but they nevertheless evolved in different ways. The first cycle (~\u0026thinsp;5.5-5.0 Ma) is characterized by separate, independent emplacement of felsic magmas, mafic magma, and mineralizing fluids, with no evidence for chemical interaction between the two types of magmas. The second cycle is characterized by mingling in every emplacement episode, witnessed by the occurrence of MME in felsic dykes and MME plus mafic xenocrysts in the Type-B rhyolite. Additionally, no evidence for activity of mineralizing fluids is found in the second cycle.\u003c/p\u003e \u003cp\u003eThus, a history of asynchronous interplay between magma feeding, magma extraction, magma emplacement/eruption and activity of mineralizing fluids can be outlined (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e). The first felsic feeding event occurred at 5.52 Ma, when the oldest zircons started to crystallize. This magma batch did set up a mid-crustal reservoir, that soon gave way to the emplacement in the shallow crust of Botro ai Marmi peraluminous magma at 5.44 Ma. The 5.38 Ma development of Mg- and Fe-rich exoskarn (Di Vincenzo et al., \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2022\u003c/span\u003e), proximal to the BM pluton, is interpreted as evidence for arrival in the deep reservoir of a mafic magma batch (Paoli et al., 2019a; Paoli et al., \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e2019b\u003c/span\u003e; Vezzoni et al., \u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e2016\u003c/span\u003e), setting up a bimodal reservoir from which mineralizing fluids are issued. The genesis of Zn-Pb-Ag ores between 5.38 and 5.1 Ma (Di Vincenzo et al., \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2022\u003c/span\u003e) is related to the release of another batch of mineralizing fluids (Vezzoni et al., \u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e2016\u003c/span\u003e). The age could be inferred to be at ~\u0026thinsp;5.23 Ma, coincident with the second-rank peak in the abundance of zircon dates, indicating a pulse in crystallization inducing release of mineralizing fluids. The genesis of Fe-Cu ore, overprinting the previous Zn-Pb-Ag ores (reverse telescoping process) (Vezzoni et al., \u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e2016\u003c/span\u003e), is linked to hot mafic fluids and to the minor volume of mafic Temperino Porphyry magma as well, issuing from mafic magma in the deep reservoir. This episode is inferred to coincides with the third-rank peak in zircon age distribution, around 5.24 Ma (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e). The San Vincenzo Type-A rhyolite then erupted at 5.00 Ma from part of the deep reservoir not affected by mass contribution of mafic melt, and nevertheless remained in a partially molten state for more than 500 ka, as indicated by the extended period of zircon crystallization.\u003c/p\u003e \u003cp\u003e560 ka passed before the next eruption of Type-B San Vincenzo rhyolitic hybrid magma at 4.436 Ma. The oldest zircon in this rhyolite is 4.87 Ma, and zircons older than 5 Ma are missing at all, suggesting the establishment of a new, independent reservoir. This reservoir likely fed three episodes of emplacement of felsic dikes carrying mafic microgranular enclaves, the Coquand, Ortaccio and Monticino porphyries (Vezzoni et al., \u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e2016\u003c/span\u003e), whose \u003csup\u003e40\u003c/sup\u003eAr-\u003csup\u003e39\u003c/sup\u003eAr ages, even affected by some uncertainty, are overlapping with the three secondary peaks of zircon distribution of the Type-B rhyolite at ~\u0026thinsp;4.88, ~ 4,68 and ~\u0026thinsp;4.50 Ma, respectively. Thus, a new deep bimodal reservoir was established around 4.9 Ma and fed the MME-bearing dikes and, finally, the eruption of Type-B rhyolite. The supply of a new, independent felsic magma batch is also supported by the comparison of chemical and isotopic composition of Type-A and Type-B rhyolites: they have the same overall chemical composition, but significantly different Sr isotopic compositions (Ferrara et al., \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e1989\u003c/span\u003e). Assuming that isotope variabilities are originated by magma mixing, a simple Sr-isotopic modelling would require at least 20 wt% of mafic melt (San Vincenzo MME) in the hybrid system, that would displace the rhyolite to significantly lower SiO\u003csub\u003e2\u003c/sub\u003e content (some 5 wt%), which is not observed. The bulk of this evidence led to infer a new cycle/system, isolated from the first bimodal reservoir, also involving a mafic magma with a Nd isotopic ratio distinctly higher than the earlier mafic magma recorded by the Temperino porphyry (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e). This is coherent with the post-collisional geodynamic setting, where small volume of magmas are generated and rapidly extracted from a thinned crustal source (Farina et al., \u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e2014\u003c/span\u003e) characterized by extremely high thermal gradients from underlying uplifted mantle.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e"},{"header":"CONCLUSIONS","content":"\u003cp\u003eIn summary, for the Campiglia plumbing system, the exposures of the full range of magma emplacement levels, combined with young ages of the products and high precision CA-ID-TIMS geochronology reveal a complex distribution of zircon crystallization ages, spanning over more than 1 Ma. The full distribution of zircon ages can be understood only in the light of the dynamics of the different levels of the reservoirs integrated with the genesis of metasomatic rocks linked to the release of fluids from the plumbing system.\u003c/p\u003e \u003cp\u003eA bimodal deep reservoir, once set-up at ~\u0026thinsp;5.5 Ma, for the following\u0026thinsp;~\u0026thinsp;550 ka remains in magmatic conditions (i.e., melt-present) with the help from the input of mafic, mantle-derived melt. The three events of magma emplacement/eruptions tapped the same reservoir, with common oldest zircon ages and progressively younger youngest zircons. The feeding episodes and release of mineralizing fluids show asynchrony, as revealed by the generation of skarn and/or ore deposits.\u003c/p\u003e \u003cp\u003eAnother deep reservoir is then established after the first major rhyolite eruption, to feed felsic dykes and a rhyolite eruption, all characterized by mingling processes, but not accompanied by mineralizing fluids. The two main eruption episodes both mark the end of a magmatic cycle lasting some 550 ka, with only the earliest cycle characterized by generation of ore deposits. In the Larderello geothermal area, a similar history is documented, with ore occurrences linked to the oldest igneous cycle, while no ores has been found associated with the youngest intrusions, despite the large numbers of deep wells drilled in the area.\u003c/p\u003e \u003cp\u003eThe Campiglia system thus reveals an asynchrony between transfer of magmas and mineralizing fluids, as pointed out by isotopic and relative ages of igneous rocks, metasomatic products and ore deposits. Thus, the Campiglia plutonic-subvolcanic-volcanic plumbing system represents a prime case study thanks to the quick and differential exhumation that helps understanding the connection between processes originally occurring at different crustal levels.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eACKNOWLEDGMENTS\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis work is part of the Ph.D. project of GP at the University of Pisa and was supported by the University of Pisa research projects PRA_2018_19, PRA_2022_66, the MUR project TEOREM prot. 2017AK8C32, and by the Istituto di Geoscienze e Georisorse-CNR (EU-H2020 DESCRAMBLE Project 640573).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eDATA AVAILABILITY\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAll data generated or analysed during this study are included in this published article and its supplementary information files\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eBachmann, O., Charlier, B. 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B., 2007, Zircon growth and recycling during the assembly of large, composite arc plutons: Journal of Volcanology and Geothermal Research, v. 167, no. 1-4, p. 282-299.\u003c/li\u003e\n\u003cli\u003ePaoli, Dini, Petrelli, and Rocchi, 2019a, HFSE‐REE Transfer Mechanisms During Metasomatism of a Late Miocene Peraluminous Granite Intruding a Carbonate Host (Campiglia Marittima, Tuscany): Minerals, v. 9, no. 11.\u003c/li\u003e\n\u003cli\u003ePaoli, G., 2013, Gli zirconi dei magmi crostali della Provincia Magmatica Toscana: morfologie ed et\u0026agrave; U-Pb [MSci Thesis MSci Thesis]: Universit\u0026agrave; di Pisa.\u003c/li\u003e\n\u003cli\u003ePaoli, G., Dini, A., and Rocchi, S., 2019b, Footprints of element mobility during metasomatism linked to a late Miocene peraluminous granite intruding a carbonate host (Campiglia Marittima, Tuscany): International Journal of Earth Sciences, v. 108, no. 5, p. 1617-1641.\u003c/li\u003e\n\u003cli\u003ePayac\u0026aacute;n, I., Guti\u0026eacute;rrez, F., Bachmann, O., and Parada, M. \u0026Aacute;., 2023, Differentiation of an upper crustal magma reservoir via crystal-melt separation recorded in the San Gabriel pluton, central Chile: Geosphere, v. 19, no. 2, p. 348-369.\u003c/li\u003e\n\u003cli\u003ePoli, G., and Peccerillo, A., 2016, The Upper Miocene magmatism of the Island of Elba (Central Italy): compositional characteristics, petrogenesis and implications for the origin of the Tuscany Magmatic Province: Mineralogy and Petrology, p. 1-25.\u003c/li\u003e\n\u003cli\u003eRidolfi, F., Braga, R., Cesare, B., Renzulli, A., Perugini, D., and Del Moro, S., 2016, Unravelling the complex interaction between mantle and crustal magmas encoded in the lavas of San Vincenzo (Tuscany, Italy). 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A., Gerdes, A., and G\u0026uuml;nther, D., 2013, Tracking the evolution of large-volume silicic magma reservoirs from assembly to supereruption: Geology, v. 41, no. 8, p. 867-870.\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"scientific-reports","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"scirep","sideBox":"Learn more about [Scientific Reports](http://www.nature.com/srep/)","snPcode":"","submissionUrl":"","title":"Scientific Reports","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Scientific Reports","inReviewEnabled":true,"inReviewRevisionsEnabled":true},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-5689469/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-5689469/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe geochronological-geochemical interplay between magma transfer and mineralizing fluid is studied at Campiglia igneous complex, Tuscany. Here, crustal and mantle-derived magmas were emplaced at plutonic, subvolcanic, and volcanic level (5.4 to 4.4 Ma), and were quickly exhumed, thus allowing U-Pb CA-ID-TIMS zircon dating with error of ka to tens of ka. The igneous activity is intertwined with the genesis of Cu-Pb-Zn(-Ag) ore deposits. A two-cycle scenario is reconstructed. In the first cycle, a bimodal deep reservoir remained in melt-present condition for ~\u0026thinsp;500 ka. In this time interval, a peraluminous pluton is emplaced, followed by generation of skarn with related Zn-Pb(-Ag) sulfide ore. Fe-Cu ore is then generated in association with mantle-derived mafic dykes, and a peraluminous rhyolite eruption terminates the cycle. These crust- or mantle-derived igneous units show limited evidence for interaction. Early-crystallized, antecrystic zircons were recycled within portions of melts sequentially extracted from the reservoir. In the second cycle, during the following 500 ka, an independent reservoir freshly fed by interacting crustal and mantle melts gave eventually way to eruption of a hybrid rhyolite. Timescales of the Campiglia complex reveal significant \u003cb\u003easynchrony\u003c/b\u003e between magma feeding of the plutonic-subvolcanic-volcanic plumbing system and the mineralizing activity of igneous fluids.\u003c/p\u003e","manuscriptTitle":"Asynchronous transfer of magmas and mineralizing fluids in a plutonic-subvolcanic-volcanic plumbing system","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-01-08 15:30:52","doi":"10.21203/rs.3.rs-5689469/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"editorInvitedReview","content":"","date":"2025-06-11T13:14:24+00:00","index":"hide","fulltext":""},{"type":"decision","content":"Revision requested","date":"2025-06-11T13:12:45+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-06-10T17:11:16+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"328234869649864580185504799054312669066","date":"2025-06-01T13:52:03+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"271274996918344915541709023862825609470","date":"2025-05-27T12:45:49+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-02-08T21:52:39+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"37033251085863055475522326642436321178","date":"2025-02-04T22:48:13+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-02-04T22:46:31+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-01-30T17:55:15+00:00","index":"","fulltext":""},{"type":"editorInvited","content":"","date":"2025-01-07T11:57:26+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-01-06T11:51:26+00:00","index":"","fulltext":""},{"type":"submitted","content":"Scientific Reports","date":"2024-12-21T11:33:13+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"scientific-reports","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"scirep","sideBox":"Learn more about [Scientific Reports](http://www.nature.com/srep/)","snPcode":"","submissionUrl":"","title":"Scientific Reports","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Scientific Reports","inReviewEnabled":true,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"9d74385d-4b85-4d76-b09d-73241b892afc","owner":[],"postedDate":"January 8th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2025-12-08T15:59:15+00:00","versionOfRecord":{"articleIdentity":"rs-5689469","link":"https://doi.org/10.1038/s41598-025-19201-5","journal":{"identity":"scientific-reports","isVorOnly":false,"title":"Scientific Reports"},"publishedOn":"2025-12-05 15:57:01","publishedOnDateReadable":"December 5th, 2025"},"versionCreatedAt":"2025-01-08 15:30:52","video":"","vorDoi":"10.1038/s41598-025-19201-5","vorDoiUrl":"https://doi.org/10.1038/s41598-025-19201-5","workflowStages":[]},"version":"v1","identity":"rs-5689469","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-5689469","identity":"rs-5689469","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}