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Trace element geochemistry of sphalerite and chalcopyrite in arc-hosted VMS deposits
(Elsevier, 2021-08-26)
Trace element compositions of sphalerite and chalcopyrite have been investigated for four arc-hosted Cretaceous VMS deposits (María Teresa, Perubar, and Palma in Peru, and Cerro de Maimón in the Dominican Republic) using laser ablation inductively-coupled plasma mass spectrometry. In sphalerite, Fe, Mn, Cd, Hg, Ag, Sb, Se, In, Ge, and Ga are lattice-bound, whereas Sn, Tl, Bi, and Pb occur at least partly as mineral microinclusions. Significant variations in the contents of minor and trace elements are observed in sphalerite grains from individual deposits. A strong negative correlation between Fe (Inter-Quartile Range [IQR] 44,009–18,168 ppm) and Zn indicates a dominant Fe2+ ↔ Zn2+ simple isovalent substitution. Regarding potential high-tech by-products, the contents of In (IQR 42–1.6 ppm, up to 415 ppm) and Ga (IQR 31–5.9 ppm, up to 96 ppm) in the studied sphalerite are normally much higher than those of Ge (IQR 0.85–0.16 ppm, up to 9.3 ppm). Correlation trends suggest Cu+ + In3+ ↔ 2Zn2+, Cu+ + Ga3+ ↔ 2Zn2+, and more complex substitution mechanisms of Zn involving combinations of monovalent (Cu+, Ag+), divalent (Ge2+?), trivalent (In3+, Ga3+, [Sn3+?]), and quadrivalent (Ge4+, Sn4+) cations. As for chalcopyrite, Zn, Ag, Sn, Cd, Se, In, Ga, and Ge are interpreted to be lattice-bound, whereas Mo, Au, Tl, Sb, Pb, and Bi probably occur as microinclusions. Relative to sphalerite, chalcopyrite is depleted in In (IQR 28–8.4 ppm, up to 49 ppm) and Ga (IQR 8.3–2.9 ppm, up to 24 ppm) and enriched in Ge (IQR 5.9–0.70 ppm, up to 80 ppm). Of the other trace elements, Zn (IQR 426–190 ppm) is the most highly concentrated in the studied chalcopyrite, followed by Ag (IQR 136–23 ppm), Se (IQR 64–22 ppm), Sn (IQR 53–1.3 ppm), and Cd (IQR 12–6.0 ppm). General positive correlation trends between Zn, Cd, In, Ge, and Ga in chalcopyrite suggest varied coupled substitution mechanisms of Fe and Cu with fluctuating valences due to covalent bonding. Trace-element distribution patterns in sphalerite and chalcopyrite were studied for the zone-refined Sofía-D massive sulfide body in the María Teresa deposit, which comprises a lower lower portion of dominant pyrite sheathed upward by zones of chalcopyrite (Cu zone), sphalerite (Zn zone) and galena + sphalerite ± fahlore ± barite (Pb – Zn – Ag zone). Bottom to top of the sulfide body, sphalerite records progressive depletion in In, Cu, Mn, and Se, and enrichment in Ge. This distribution pattern agrees with increasing crystallization temperatures and/or volatile magmatic influx towards the lower portion of the massive mineralization. Distribution of trace elements in chalcopyrite is rather uneven except for a sustained enrichment in Se towards the basal portion of the sulfide body. The fact that such trends are preserved in spite of extensive recrystallization during thermal metamorphism in parts of the Sofía-D massive sulfide mineralization suggests i) a closed metamorphic system and ii) that element interdiffusion was prominently local. Accordingly, we propose that sphalerite lattice-bound trace elements distribution patterns described in this article can help determine the polarity of massive sulfide bodies in VMS districts in metamorphosed and tectonized terranes.
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Distribution of indium, germanium, gallium and other minor and trace elements in polymetallic ores from a porphyry system: the Morococha district, Peru
(Elsevier, 2021-09-01)
We report indium, germanium, gallium, and other minor and trace elements contents in sphalerite, chalcopyrite, galena, and tetrahedrite-tennantite occurring in skarn and skarn-free (“Cordilleran”) polymetallic mantos and vein ore bodies in the Miocene porphyry-related Morococha District, Central Peru. Among the investigated minerals, LA-ICP-MS measurements indicate that In and Ga concentrate mostly in sphalerite (Inter-Quartile Range [IQR] 217–2.7 ppm and up to 4608 ppm In; IQR 61–2.0 ppm and up to 2137 ppm Ga) and chalcopyrite (IQR 109–32 ppm and up to 1070 ppm In; IQR 62–1.5 ppm and up to 630 ppm Ga). In coeval generations of sphalerite and chalcopyrite, the contents of In and Ga in sphalerite are at least two times higher than in chalcopyrite. Germanium content is generally low in the four analyzed minerals (IQR 1.2–0.19 ppm), although late Fe-poor sphalerite may yield much higher values (IQR 129–74 ppm). Certain trace element contents appear to correlate with (i) the evolving characteristics of the hydrothermal fluids during individual mineralization events, and (ii) the location of the studied ore bodies relative to the hydrothermal feeders. The highest In values in sphalerite are found in high-sulfidation assemblages in Cordilleran polymetallic veins and, with lower amounts, in low-sulfidation assemblages in skarn bodies. In intermediate-sulfidation assemblages in Cordilleran mineralization, In content decreases from early to late generations of sphalerite, while that of Ge increases. Spatial trace-element trends in Cordilleran veins and replacement bodies formed during the so-called “Morococha district-scale polymetallic event” include, from porphyry-distal to porphyry-proximal locations: i) In and Cu, and to a lesser extent Ga, enrichment in sphalerite; ii) Se and Hg enrichment and Sn and Ag depletion in chalcopyrite; iii) In enrichment in galena; and iv) Ag depletion in tetrahedrite-tennantite. Our dataset suggests that In is incorporated in the sphalerite crystal lattice via coupled substitutions involving Cu and subordinately also Sn and Ag. Availability of Cu in the mineralizing fluids is therefore key to In enrichment in sphalerite. Progressive dilution of metal-rich magmatic-hydrothermal fluids and Cu precipitation probably account for the progressive In depletion in distal-to-porphyry Zn-Pb-Ag and Ag-Pb Cordilleran polymetallic mineralization and in late sphalerite generations in intermediate-sulfidation assemblages.
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Trace element composition and U-Pb ages of cassiterite from the Bolivian tin belt
(Springer Science and Business Media Deutschland GmbH, 2021-11-01)
The Bolivian tin belt is a metallogenic province in the Eastern Cordillera of the Andes known for its Sn, W, Ag, and base metal deposits. Cassiterite, which is a major constituent in many magmatic-hydrothermal ore deposits from the Bolivian tin belt, can incorporate dozens of elements within its crystal lattice, making it a useful geological tracer mineral and also a potential host of critical elements. New U-Pb dating of cassiterite yields Late Triassic (Kellhuani deposit) and Late Oligocene to earliest Miocene (Viloco, Huanuni, and Llallagua deposits) ages. These ages confirm that Sn mineralization in the Bolivian tin belt occurred at least in two separate events during two major magmatic episodes apparently triggered by mantle upwelling, decompression melting, and basalt production promoting high heat flow into the overlying crust. The composition of studied hydrothermal cassiterite yields some geochemical trends that are attributed to its distance to the causative intrusion and/or level of emplacement. For example, cassiterite is generally enriched in Nb and Ta and yields higher Ti/Zr and Ti/Sc ratios in samples from xenothermal ore deposits located adjacent to intrusive complexes relative to shallow xenothermal and epithermal ore deposits. Therefore, these geochemical trends in cassiterite are useful tracers pointing to magmatic-hydrothermal centers. REE distribution in cassiterite was likely influenced by boiling processes, which resulted in tetrad-type irregularities. Cassiterite from the Bolivian tin belt is unattractive as a source for Nb (interquartile range [IQR] 4.84–0.037 ppm), Ta (IQR 0.0924–0.0126 ppm), and Ge (IQR 3.92–0.776 ppm). Some deposits, however, contain cassiterite relatively enriched in In (IQR 96.9–9.78 ppm, up to 1414 ppm) and Ga (IQR 92.1–3.03, up to 7437 ppm), that could constitute an attractive supplementary source for these elements in addition to sulfide minerals in the same deposits.
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Geology, mineralogy, and cassiterite geochronology of the Ayawilca Zn-Pb-Ag-In-Sn-Cu deposit, Pasco, Peru
(Springer Science+Business Media, 2021-09-13)
The Ayawilca deposit in Pasco, Peru, represents the most significant recent base-metal discovery in the central Andes and one of the largest undeveloped In resources globally. As of 2018, it hosts an 11.7 Mt indicated resource grading 6.9% Zn, 0.16% Pb, 15 g/t Ag, and 84 g/t In, an additional 45.0 Mt inferred resource grading 5.6% Zn, 0.23% Pb, 17 g/t Ag, and 67 g/t In, and a separate Sn-Cu-Ag inferred resource of 14.5 Mt grading 0.63% Sn, 0.21% Cu, and 18 g/t Ag. Newly obtained U–Pb dates for cassiterite by LA-ICP-MS (22.77 ± 0.41 and 23.05 ± 2.06 Ma) assign the Ayawilca deposit to the Miocene polymetallic belt of central Peru. The polymetallic mineralization occurs as up to 70-m-thick mantos hosted by carbonate rocks of the Late Triassic to Early Jurassic Pucará Group, and subordinately, as steeply dipping veins hosted by rocks of the Pucará Group and overlying Cretaceous sandstones-siltstones of the Goyllarisquizga Group. Relicts of a distal retrograde magnesian skarn and cassiterite (stage pre-A) were identified in the deepest mantos. The volumetrically most important mineralization at Ayawilca comprises a low-sulfidation assemblage (stage A) with quartz, pyrrhotite, arsenopyrite, chalcopyrite, Fe-rich sphalerite, and traces of stannite and herzenbergite. Stage A sphalerite records progressive Fe depletion, from 33 to 10 mol% FeS, which is compatible with the observed transition from low- to a subsequent intermediate-sulfidation stage (B) marked by the crystallization of abundant pyrite and marcasite. Finally, during a later intermediate-sulfidation stage (C) sphalerite (up to 11 mol% FeS), galena, native bismuth, Cu-Pb-Ag sulfosalts, siderite, Mn-Fe carbonates, kaolinite, dickite, and sericite were deposited. This paragenetic evolution shows striking similarities with that at the Cerro de Pasco Cordilleran-type polymetallic deposit, even if at Ayawilca stage C did not reach high-sulfidation conditions. The occurrence of an early retrograde skarn assemblage suggests that the manto bodies at Ayawilca formed at the transition between distal skarn and skarn-free (Cordilleran-type) carbonate-replacement mineralization. Mineral assemblages define a T-fS2 evolutionary path close to the pyrrhotite-pyrite boundary. Buffering of hydrothermal fluids by underlying Devonian carbonaceous phyllites of the Excelsior Group imposed highly reduced conditions during stage A mineralization (logfO2 < − 30 atm). The low fO2 favored efficient Sn mobility during stages pre-A and A, in contrast to other known ore deposits in the polymetallic belt of central Peru, in which the occurrence of Sn minerals is minor. Subsequent cooling, progressive sealing of vein walls, and decreasing buffering potential of the host rocks promoted the shift from low- (stage A) to intermediate-sulfidation (stages B and C) states. LA-ICP-MS analyses reveal significant In contents in Fe-rich sphalerite (up to 1.7 wt%), stannite (up to 1908 ppm), and chalcopyrite (up to 1185 ppm). The highest In content was found in stage A sphalerite that precipitated along with chalcopyrite and stannite, thus pointing to the early, low-sulfidation assemblage as prospective for this high-tech metal in similar mineral systems. Indium was likely incorporated into the sphalerite crystal lattice via Cu+ + In3+ ↔ 2 Zn2+ and (Sn, Ge)4+ + (Ga, In)3+ + (Cu + Ag)+ ↔ 4 Zn2+ coupled substitutions. Indium incorporation mechanisms into the stannite and chalcopyrite crystal lattices remain unclear.
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Combined effect of organic carbon and arsenic on the formation of sediment-hosted gold deposits: A case study of the Shahuindo epithermal deposit, Peru
(Society of Economic Geologists, Inc, 2024-01-01)
Sediment-hosted gold deposits represent a significant portion of the world’s gold resources. They are characterized by the ubiquitous presence of organic carbon (Corg; or its metamorphosed product, graphite) and the systematic occurrence of invisible gold-bearing arsenian pyrite. Yet the role played by these features on ore formation and the distribution of gold remains a long-standing debate. Here, we attempt to clarify this question via an integrated structural, mineralogical, geochemical, and modeling study of the Shahuindo deposit in northern Peru, representative of an epithermal gold deposit contained in a sedimentary basin. The Shahuindo deposit is hosted within Lower Cretaceous fluvio-deltaic carbon-bearing sandstone, siltstone, and black shale of the Marañón fold-and-thrust belt, where intrusions of Miocene age are also exposed. The emplacement of the auriferous orebodies is constrained by structural (thrust faults, transverse faults) as well as lithological (intrusion contacts, permeable layers, anticlinal hinge in sandstone) features. The defined gold reserves (59 tons; t) are located in the supergene zone in the form of native gold grains. However, a primary mineralization, underneath the oxidized zone, occurs in the form of invisible gold in arsenian pyrite and arsenopyrite. Here, four subsequent pyrite generations were identified—namely, pyI, pyII, pyIII, and pyIV. PyI has mean Au concentrations of 0.3 ppm, contains arsenic that is not detectable, and is enriched in V, Co, Ni, Zn, Ag, and Pb compared to the other pyrite generations. This trace element distribution suggests a diagenetic origin in an anoxic to euxinic sedimentary basin for pyI. Pyrite II and pyIV have comparable mean Au (1.1 and 0.7 ppm, respectively) and As (2.4 and 2.9 wt %, respectively) concentrations and precipitated under conditions evolving from lower (pyrrhotite, chalcopyrite, sphalerite) to higher (enargite, digenite, chalcocite) sulfidation, respectively. The pyIII generation is the major gold event in the primary mineralization, with pyrite reaching 110 ppm Au (mean ~7 ppm) and 5.6 wt % As (mean ~1.8 wt %), while coeval arsenopyrite attains 460 ppm Au. Pyrite III is also enriched in other trace elements such as Se, Ge, Mo, In, Ga, and Bi compared to the other pyrite generations, which is indicative of a magmatic source. Bulk analyses of the surrounding unmineralized rocks show only parts per billion levels of Au and less than 25 ppm As. These data, combined with mass balance considerations, demonstrate that the sedimentary rocks could not be the sole source of gold, as they could only contribute a minor portion of arsenic and sulfur (and iron) to the deposit. Conversely, fluids exsolved from a pluton crystallizing at depth likely provided the great part of the gold endowment. Equilibrium thermodynamics simulations, using geochemical constraints established in this study, demonstrate that interaction between Au-As-S-Fe–bearing fluids and organic carbon-bearing rocks strongly enhanced the fluid ability to transport gold by maximizing its solubility as AuI hydrosulfide complexes via a combined increase of pH and aqueous sulfide concentration. This finding challenges the traditional qualitative view of organic matter acting exclusively as a reducing agent for AuI that should promote gold deposition in its native state (Au0) rather than enhance its solubility in the fluid. Our results have significant implications for the exploration of carbonaceous sedimentary environments. Such settings may provide a very effective mechanism for focusing gold transport. Subsequent scavenging of AuI from solution in a chemically bound form is promoted by the precipitation of arsenian pyrite in permeable structural and lithologic traps, bound by more impermeable units, similar to what occurs in petroleum systems. Our integrated study underlines the important potential of sedimentary Corg-bearing rocks in the formation and distribution of gold and associated metal resources.
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Tin Mineralization in the Triassic Chacaltaya District (Cordillera Real, Bolivia) Traced by In Situ Chemical and δ18O-δ11B Compositions of Tourmaline
(Society of Economic Geologists, Inc, 2023-12-19)
We present a petrographic and geochemical study of tourmaline from the Triassic Chacaltaya Sn-polymetallic district in the Cordillera Real of Bolivia. Tourmaline is associated with greisens, breccias, and veins, which occur around the Triassic Chacaltaya peraluminous granitic stock hosted by Silurian metasedimentary rocks. Three main petrographic types of hydrothermal tourmaline have been identified: pre-ore greisen-related (Tur-1), syn-ore breccia-related (Tur-2), and syn-ore vein-related (Tur-3). The three types of tourmaline belong to the alkali group and have Fe-rich compositions mostly close to the schorl end member. Overlapping Fe/(Fe + Mg) ratios suggest broadly similar compositions of the hydrothermal fluids during the deposition of tourmaline. The most notable differences in minor and trace element contents include relative enrichment in Zn and Li in Tur-1 and relative enrichment in Ca, Sc, V, Cr, Sr, Sn, Y, Cs, Be, and Zr in Tur-3, with Tur-2 showing intermediate compositions between those of Tur-1 and Tur-3. The progressive enrichment in Sn from Tur-1 (avg = 14 ppm) through Tur-2 (avg = 311 ppm) and Tur-3 (avg = 476 ppm) indicates an increase of Sn concentrations in the hydrothermal system coinciding with cassiterite deposition in breccias and veins. The transition from high Li and Zn contents in Tur-1 to elevated Ca, Sr, V, and Cr contents in Tur-3 is interpreted as reflecting interaction between a hydrothermal fluid of magmatic origin and the metasedimentary country rocks. Strong and relatively steady positive Eu anomalies in all tourmaline types suggest dominantly reduced hydrothermal conditions. In situ δ18O and δ11B analyses of greisen-related Tur-1 reveal crystallization in isotopic equilibrium with magmatic water derived from a peraluminous S-type granite. In contrast, higher δ18O values of breccia-related Tur-2 and vein-related Tur-3 indicate crystallization in isotopic equilibrium with a fluid of metamorphic origin or a magmatic fluid that variably interacted with the metasedimentary host rocks. Geochemical modeling reproduces interactions between a fluid of magmatic origin and the host metasedimentary rocks at moderate water/rock ratios between 0.1 and 0.5. We conclude that cassiterite mineralization in the Chacaltaya district was formed primarily through interaction between B-Sn–rich magmatic fluids and the metasedimentary country rocks.
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Origin and Evolution of Gold-Bearing Fluids in a Carbon-Rich Sedimentary Basin: A Case Study of the Algamarca Epithermal Gold-Silver-Copper Deposit, Northern Peru
(Elsevier BV, 2023-12-25)
Sediment-hosted gold deposits account for the major part of economic gold in the Earth's crust. However, the origin of the gold-bearing fluid and its evolution in sedimentary basins in the presence of organic carbon and its metamorphosed products such as graphite are poorly known. In an attempt to clarify these issues, we performed an integrated mineralogical, geochemical, and fluid-inclusion study of the Algamarca epithermal Au-Ag-Cu deposit, hosted by Mesozoic sediments corresponding to an over-mature petroleum system within the Marañón fold and thrust belt (northern Peru). Results show that mineralization started with a pre-gold stage characterized by quartz veins containing gold-poor pyrite and chalcopyrite. Most gold was deposited afterwards, during the main gold stage in an “invisible” form within arsenian pyrite, followed by minor visible native gold with sulfosalts and chalcopyrite at a later stage. Fluid inclusions in quartz from the pre-gold and gold stages show features analogous to those observed in porphyry Cu-Au systems such vapor-liquid immiscibility, enrichment in K, Rb, Cu, As, and Sb, a wide range of salinity (5-35 wt % NaCl eq.), and similar elemental (atomic) ratios (Zn/Pb ∼4, 0.1<K/Na<5, Br/Cl ∼0.06), all consistent with a fluid of magmatic origin. In addition, the fluid inclusions from the pre-gold stage are highly enriched in CO2 (∼60 mol% in gas phase), CH4 (∼10 mol%) and H2S (∼30 mol%). Such high volatile contents are rather unusual for typical porphyry-epithermal systems and likely reflect reactions between the magmatic fluid and carbon-bearing sediments. This conclusion is independently supported by the temperature values of graphite metamorphic peak determined by Raman spectroscopy, which are similar to those derived by fluid-inclusion microthermometry in quartz veins. Our findings imply that strong interactions of magmatic fluid with carbonaceous matter favored gold transport through the sedimentary basin and its subsequent concentration in arsenian pyrite. Furthermore, our results point to a possible presence of porphyry-style mineralization beneath the sedimentary sequence hosting the epithermal Algamarca deposit, thereby providing new potential for exploration.
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Germanium- and Gallium-Rich Sphalerite in Mississippi Valley–Type Deposits: The San Vicente District and the Shalipayco Deposit, Peru
(Springer Science and Business Media Deutschland GmbH, 2023-06-01)
Sphalerite in Mississippi Valley–type (MVT) deposits hosts significant resources of both germanium and gallium. Here, we provide a survey on the distribution of Ge, Ga, and other minor and trace elements in sphalerite from MVT deposits in the Eastern Cordillera and sub-Andean regions of Peru, including the San Vicente deposit and the nearby Chilpes and Huacrash prospects, and the Shalipayco deposit. We present also a micro- and nano-scale textural characterization of Ge-rich sphalerite. In situ laser ablation-inductively coupled plasma-mass spectrometry analyses yielded Ge contents (inter-quartile range [IQR] = 164–36 ppm for the San Vicente district and IQR = 425–101 ppm for the Shalipayco deposit) that overlap with the range reported for sphalerite from other MVT deposits elsewhere. The highest Ge contents (IQR = 1207–375 ppm, up to 1861 ppm) were found in Fe-poor orange sphalerite deposited during a volumetrically minor second mineralization step in the San Vicente deposit located mainly in steep veins that crosscut the main first-step mineralization dominated by darker sphalerite. Reddish-brown sphalerite from Chilpes (IQR = 445–22 ppm, up to 1745 ppm) and brownish orange sphalerite from Huacrash (IQR = 650–34 ppm, up to 855 ppm) also yielded remarkably high Ge values. In Shalipayco, the highest Ge contents were analyzed in late Fe-poor yellow sphalerite (IQR = 375–267 ppm, up to 1119 ppm). The highest Ga contents were determined in reddish-brown sphalerite from the Chilpes prospect (IQR = 1156–0.26 ppm, up to 3943 ppm), although Ga contents are, in general, much lower than those of Ge in most analyzed sphalerite (IQR = 27–0.22 ppm in the San Vicente district and IQR = 2.8–0.081 ppm in the Shalipayco deposit). These figures place some of the analyzed sphalerite types among the Ge- and Ga-richest samples ever reported. Linkage of textural and compositional data points to light-colored, chiefly orange and yellow sphalerite generations crystallizing at lower temperatures and relatively late in the paragenetic sequences as those with the highest Ge contents. In contrast, the paragenetic control on Ga enrichment is unclear. Focused ion beam and high-resolution transmission electron microscopy (FIB-HRTEM) investigation combined with trace element content correlations reveal selective partitioning of Ge and Ga into sphalerite as structurally bound elements and their incorporation via substitution mostly coupled to monovalent cations triggering polytypism.
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Petrogenesis of Volcanogenic Sedimentary Lithium Ore in the Neogene Macusani Volcanic Field, Puno, Peru
(Oxford University Press, 2025-05-01)
The recently discovered Falchani volcanogenic sedimentary lithium deposit, situated within the Neogene Macusani Volcanic Field in SE Peru, represents one of the world's most significant resources of this metal. The Li ore is mainly hosted in the so-called lithium-rich tuff, a tuffaceous mudstone that is sandwiched between two Li-rich volcaniclastic units (Upper and Lower Breccia). The major and trace element composition of the Li-ore units differs from that of previously reported ash-flow tuff in the Macusani Volcanic Field. Rather, it approximates the chemistry of highly evolved peraluminous obsidian glasses, known as macusanite, and exhibits the characteristic geochemical fingerprint of peraluminous rare-metal granites and Li-Cs-Ta pegmatites. The parental magmas of the Li-ore units have been modeled as containing &lt;25% of a mantle component with the isotopic signature of potassic to ultra-potassic basaltic melts. The remaining is attributed to partial melts of Proterozoic and Paleozoic paragneiss and metapelites. High fluorine activity in the melt lowered the solidus and delayed fluid-melt immiscibility, promoting high degrees of differentiation through fractional crystallization. Pre-eruptive metasomatic processes in the upper part of the crystal mush could have increased the concentration of Li and other fluid-mobile elements. Contrary to many volcanogenic sedimentary lithium deposits worldwide, in situ post-depositional metasomatic processes associated with the formation of secondary clay and zeolite assemblages did not result in lithium enrichment, but in its partial leaching. Falchani represents a first documentation of a volcanogenic sedimentary deposit where the primary lithium enrichment to economic grades was related to pre-eruptive magmatic processes.
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Lithium mica clasts document magmatic evolution prior to eruption in the macusani volcanic field in peru
(Nature Portfolio, 2025-12-01)
Typically found in rare-metal granites and pegmatites, lithium micas are increasingly considered a resource for lithium as global demand surges. In a recently discovered major lithium resource within the Macusani Volcanic Field in Peru, lithium mica crystal clasts hosted by a tuffaceous mudstone represent an important ore constituent. The mm-scale mica clasts comprise a zinnwaldite core and a lepidolite rim. Compositionally similar to micas in global peraluminous, rare-metal-rich leucogranites and LCT pegmatites, they exhibit enrichment in incompatible, fluid-mobile lithophile elements relative to micas in other volcanogenic and intrusive units in the Macusani Volcanic Field. The compositions of the mica crystal clasts record high degrees of magmatic differentiation and exsolution of a magmatic vapor phase during their crystallization in a ligand-rich, peraluminous crystal mush. 40 Ar/ 39 Ar dating of zinnwaldite-lepidolite crystal clasts reveals cooling between 8823 ± 9 and 8717 ± 44 ka, coinciding with a regional magmatic lull in the Central Andes of southern Peru. A general slowdown in magmatic activity and a hiatus in volcanism may have contributed to extreme differentiation and pre-eruptive volatile build-up. This study provides crucial insights for lithium exploration, highlighting volcanogenic-sedimentary lithium mica deposits as a promising exploration target in peraluminous volcanic fields.
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