Abstract
The Masjeddaghi porphyry Cu-Au deposit is situated in the Alborz-Azarbaijan structural zone of northwest Iran. Chemical compositions of rock-forming (biotite, amphibole) and accessory minerals (magnetite, apatite) in the potassic to propylitic altered diorite porphyry of Masjeddaghi serve as key indicators of magmatic-hydrothermal mineralization. In situ LA-ICP-MS was conducted to analyze trace element contents of selected magnetite-bearing samples, while EMPA analyzed biotite, amphibole, and apatite compositions. The mineral compositions show a parental magma with calc-alkaline features, suggesting a source comprised of both subduction mantle-derived and crust-derived materials, and the Masjeddaghi mineralizing magmas have a relatively elevated ƒO2 and are classified as oxidized I-type magmas. The calculated temperature ranges are constrained by Al-in-amphibole geothermometry, saturation temperature of apatite, and the Ti-in-biotite geothermometer (830°C–877°C) (845°C-918°C) and (723°C–782°C), respectively, whereas the Al-in-amphibole geobarometry exhibits formation pressure (120–186 MPa; relating to depths ranging from 4 to 10 km) and H2Omelt content at time of crystallization (4.10–4.46 wt%), indicating formation of a hydrous calc-alkaline magma from a deep magmatic reservoir. The intrusion of oxidized hydrous mafic magma from a deeper magma source likely promoted wide magma mixing and prolonged fractional crystallization within the evolved dioritic magma chamber, resulting in exsolution of the ore-forming fluids and the formation of the Masjeddaghi deposit.
1 Introduction
Porphyry-related Cu (Mo-Au) deposits are magmatic-hydrothermal systems that predominantly develop in subduction settings along continental margins and island arcs (Sun et al., 2015; Rahnama et al., 2021; Shah et al., 2025). Studying chemical compositions of igneous rock-forming minerals equilibrated with magma is an effective approach to understanding ore-forming conditions ().
Biotite is a widely occurring mineral in igneous rocks used as a geothermometer and geothermobarometer in magmatic-hydrothermal systems (). Its chemical composition serves in the estimation of intrinsic thermodynamic parameters, including temperature (T), oxygen fugacity in the parent magmas (ƒO2), magmatic rock water fugacity (ƒH2O), and the contents of halogens, such as F and Cl, enabling reconstruction of granitoid petrogenesis and tectonic setting. Amphibole indicates the physicochemical conditions of the melt during crystallization. Its chemical composition can be utilized as a petrogenetic index for pressure estimation (P), temperature (T), and H2O amount, defining the melt composition in the magmatic chambers (Ridolfi and Renzulli, 2012). Apatite is a porphyry indicator mineral (). It can be used to quantify the parental magma oxidation state, determine the magma chemistry, distinguish the difference between barren and fertile host rocks, and estimate the oxygen fugacity (Zhong et al., 2021). Magnetite is the predominant oxide mineral found in the Earth’s crust and commonly appears as an accessory mineral in various ore deposits (). Depending on the various mineralizing systems, magnetite can accommodate a diverse range of trace elements in its crystal structure (). Magnetite trace element compositions can reflect the crystallization conditions across various geodynamic settings ().
The Masjeddaghi porphyry Cu-Au deposit is situated 35 km east of the Jolfa area in the East Azarbaijan Province, near the Aras River (Figure 1a,b). The exploration region covers around 8 km2. Based on drill hole data, the deposit comprises ore reserves of 272 Mt with an average grade of copper 0.31 wt% and grade of gold 0.6 ppm (). However, due to a lack of data, there is little knowledge about associated magmatic evolution and ore-forming mechanisms. To acquire a deeper comprehension of the physico-chemical parameters affecting magmatic development and ore-forming mechanisms, we have studied the chemical characteristics of rock-forming and accessory indicator minerals in the porphyry intrusion of Masjeddaghi.
FIGURE 1
In this study, element compositions of biotite, amphibole, and apatite were investigated by electron microprobe analysis (EMPA), while the trace element contents of Mn, Al, V, Si, Ti, Mg, Ni, Zn, Co., and Cr in magnetite were analyzed by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) associated with the Cu-Au mineralization in Masjeddaghi. The primary objective of this paper is to utilize mineral chemistry of biotite, amphibole, magnetite, and apatite to determine key parameters of hydrothermal mineralization and magmatic processes linked to the deposit formation.
2 The Masjeddaghi Cu-Au porphyry deposit
2.1 Geological setting of the Masjeddaghi deposit
Based on the structural-sedimentary division of Iran (
The dominant rock formations are the Cretaceous flysch-type sediment series that crop out in the southern and northeastern sections of the region (Figure 1b). These sedimentary sequences are overlain by Eocene volcanic complexes with andesitic to trachyandesitic compositions. The unit, with a relatively lighter color than diorite porphyry intrusion, is widespread in the area. The andesitic to trachyandesite rocks consist mostly of phenocryst assemblages of plagioclase and amphibole in a microlithic to glassy groundmass (Figures 2a,b). Finally, the ore-hosting diorite porphyry occurred within the Early Eocene andesitic to trachyandesitic host rock. Diorite has a porphyritic texture distinguished primarily by plagioclase, biotite, magnetite, K-feldspar, and phenocrysts of quartz (Figures 3a–f). The primary K-feldspar and biotite are altered to sericite, muscovite, opaque minerals, and secondary biotite (Figures 2c,d). The diorite porphyry is the main host of Cu-Au mineralization. Late post-ore dikes of andesitic composition intersected all these rocks.
FIGURE 2

Representative field photographs, a drill core photo, and photomicrographs of ore minerals from the Masjeddaghi Cu-Au porphyry deposit: (a,b) Phenocryst of plagioclase and amphibole in a microlithic to glassy groundmass from the andesitic to trachyandesite rocks; (c) K-feldspar and biotite altered to sericite and opaque minerals in diorite porphyry; (d) K-feldspar and biotite altered to sericite, opaque minerals, secondary biotite, and muscovite in diorite porphyry; (e) Quartz-chalcopyrite-pyrite veins in drill core from diorite porphyry; (f) Chalcopyrite and pyrite in sample M2; (g) Replacement of chalcocite by chalcopyrite in sample M1; (h) Replacement of chalcocite, covellite, and tetrahedrite by chalcopyrite in sample M4 (reflected light). Abbreviations: Amp, amphibole; Plg, plagioclase; Kfs, K-feldspar; Bt, biotite; Ser, sericite; Mus, muscovite; Py, pyrite; Cpy, chalcopyrite; Chc, chalcocite; Cov, covellite; Ttr, tetrahedrite; Opa, opaque minerals.
FIGURE 3

Representative photomicrographs, field photographs, and back-scattered electron (BSE) images of apatite and biotite from diorite porphyry of the Masjeddaghi Cu-Au porphyry deposit: (a,b) reequilibrated biotite in diorite porphyry associated with plagioclase; (c) Reequilibrated biotite and secondary biotite in diorite porphyry associated with plagioclase; (d) Reequilibrated biotite and secondary biotite associated with sericite, quartz and K–feldspar; (e) plagioclase phenocrysts replaced by hydrothermal biotite and reequilibrated magnetite in diorite porphyry; (f) plagioclase phenocrysts replaced by hydrothermal biotite and reequilibrated magnetite in diorite porphyry; (g) amphibole phenocrysts associated with plagioclase; (h) Back-scattered electron (BSE) image of zoned amphibole (core-rim textures); (i) Back-scattered electron (BSE) image of magmatic apatite (Apm) appears as inclusions in amphibole, with lesser amounts in biotite, as well as discrete crystals in the groundmass; (j) Back-scattered electron (BSE) image of hydrothermal apatite (Aph) grains partly replaced by Apm and Apm grains as inclusions within biotite; (k) Back-scattered electron (BSE) image of Magmatic-Type 1 intergrown with ilmenite, amphibole, biotite, and plagioclase; (l) Hydrothermal-Type 3 containing chalcopyrite inclusions. Abbreviations: Kfs, K-feldspar; Plg, plagioclase; Bt, biotite; R, Bt-reequilibrated biotite; S-Bt, Secondary biotite; Kfs, K-feldspar; Plg, plagioclase; Qtz, quartz; Ser, sericite; Amp, amphibole, Apm, magmatic apatite; Aph, hydrothermal apatite; MtT1, Magmatic-Type 1; MtT2, Reequilibrated-Type 2; MtT3, Hydrothermal-Type 3.
2.2 Petrography and mineral assemblages
According to petrographic observations and field investigation, the hydrothermal alteration zones in the Masjeddaghi deposit primarily consist of potassic and propylitic alteration. Cu-Au mineralization is found in sulfide-bearing veins/veinlets and as disseminations formed during the primary ore-forming phase (Figure 2e), that are linked to the potassic alteration zone located in the center of the deposit. Ore minerals consist of pyrite, chalcopyrite, chalcocite, magnetite, and covellite, with small occurrences of tetrahedrite (Figures 2f–h). Potassic alteration occurs at depths of 500–700 m and extends into the western and eastern boundaries of the seasonal Arpachaei River. The potassic alteration is composed of secondary biotite and secondary K-feldspar, with localized occurrences of magnetite, quartz, and plagioclase (Figures 3d–f). The diorite porphyry stock underwent potassic alteration. Propylitic alteration spreads horizontally and is present throughout the deposit’s margins. Sulfide minerals of this alteration include chalcopyrite and pyrite. The propylitic alteration is characterized by the occurrence of chlorite and calcite that partially replace phenocrysts (Figure 3g).
Petrographic studies of our samples have identified two distinct biotite varieties: reequilibrated and hydrothermal. The reequilibrated biotite exhibits a shreddy texture within the potassic alteration zone of the diorite porphyry (Figures 3a,b). Some appear as euhedral to subhedral phenocrysts exhibiting ragged textures and are commonly altered to secondary hydrothermal biotite with a fine-grained texture (Figures 3c,d). Figure 3c shows the best comparison between R-biotite and S-biotite. Hydrothermal biotites in diorite porphyry occur as irregular grains and fine-grained aggregates. They partially replace plagioclase phenocrysts (Figures 3e,f). Amphibole grains occur as euhedral to subhedral shapes, with a light rim and dark core (Figures 3h,i). Apatite is classified into magmatic and hydrothermal varieties. In backscattered electron (BSE) imaging, the magmatic apatite (Apm) appears as inclusions in amphibole, with lesser amounts in biotite, as well as discrete crystals in the groundmass (Figure 3i). The hydrothermal apatite (Aph) occurs as an irregular and inhomogeneous grain (Figure 3j). It seems that Aph partly replaces the magmatic apatite. The Aph crystals appear darker in color than unaltered apatites under BSE imaging (Figure 3j). Magnetites are grouped into magmatic, reequilibrated, and hydrothermal types. Magmatic-Type 1 (MtT1) forms as euhedral to subhedral grains and is relatively pristine or homogeneous (Figure 3k), intergrown with ilmenite, amphibole, biotite, and plagioclase. Reequilibrated-Type 2 (MtT2) magnetite commonly occurs in subhedral to anhedral grains associated with potassic alteration, consisting of plagioclase, hydrothermal biotite, and quartz (Figures 3e,f). Hydrothermal-Type 3 (MtT3) occurs mostly as anhedral grains and is highly fractured or pitted, containing sulfide inclusions (chalcopyrite and pyrite) (Figure 3l). The description of selected samples is summarized in Supplementary Table S1.
3 Samples and analytical methods
In this investigation, samples are selected from a collection of twenty-one polished thin sections and fifteen polished sections from various depths of the ore-bearing diorite porphyry intrusion at the Masjeddaghi deposit (Supplementary Tables).
3.1 EPMA
The key samples, including biotite, amphibole, and apatite, were selected for geochemical and mineralogical analysis. Before analysis, each sample was covered with a thin carbon coating. Masaryk University, Czech Republic, conducted electron microprobe analysis (EMPA) utilizing a Cameca SX100® electron microprobe to measure the contents of major and minor elements, along with halogens. The detection limits for major and minor elements are as follows: 0.01 wt% and 0.001 wt%, respectively. Standard operating parameters for F, Fe, Cl, and Na included a beam current of 10 nA, a beam diameter of 3 μm, defined counting times ranging from 20 to 40 s, and an accelerating voltage of 15 kV. For Ba, Ti, Ca, Cr, Si, Mg, K, Mn, and Al, analytical conditions consisted of a 15 kV accelerating voltage, a 20 nA beam current, a 3 μm beam diameter, and a total pulse integration time of up to 10 s.
3.2 LA-ICP-MS
Trace element amounts were measured in fifteen representative samples containing abundant magnetite grains using the LA-ICP-MS. Trace elements analyses (n = 54 spots) and distribution maps (n = 1) for magnetite were conducted at LabMaTer, Université du Québec à Chicoutimi (UQAC), Canada. The LA-ICP-MS technique utilized an 193-nm Excimer Resonetics Resolution M-50 laser ablation system, equipped with a double volume cell S-155 and coupled with an Agilent 7,900 × mass spectrometer. A stage movement speed of 10 μm/s, a laser frequency of 15 Hz, and a fluence of 3 J/cm2 were utilized to examine the grains of magnetite. The magnetite grain surfaces were scanned using beam diameters ranging from 11 to 55 µm. According to the grain sizes, line scans across for large grains and spot analyses were conducted for small grains. The gas blank was recorded for 30 s prior to activating the laser for at least 30 s. The ablated material was transported into the ICP-MS by an argon-helium gas mix at a rate of 0.8–1 L/min for Ar, 350 mL/min for He, and 2 mL/min of nitrogen. Internal standardization was related to 57Fe based on stoichiometric iron content of magnetite. The specified isotopes were analyzed: 28Si, 34S, 57Fe, 59Co, 60Ni, 65Cu, 66Zn, 75As, 82Se, 95Mo, 101Ru, 103Rh, 105Pd, 107Ag, 111Cd, 118Sn, 121Sb, 126Te, 185Re, 189Os, 193Ir, 195Pt, 197Au, 208Pb, and 209Bi. GSE-1 g is one of the reference materials (RM) that were taken for standardization. GSE-1 g, a natural basaltic glass fused and doped with various elements at 300–500 ppm, was provided by the U.S. Geological Survey (USGS) and was utilized for element calibration based on reference data from the GeoReM database (
4 Results
4.1 Biotite chemistry
The calculation of cations for biotite was calculated based on 22 oxygen equivalents. Component names, mole fractions, estimation of ferric and ferrous iron based on stoichiometric limitations, fluorine and chlorine intercept amounts, and the biotite geothermometer were determined using the mica recalculation scheme, and fugacity ratios were calculated using Geo-ƒO2 software (
FIGURE 4

Chemical composition of biotite, amphibole, and apatite from the Masjeddaghi porphyry deposit on categorization diagrams: (a) The Fe/(Fe + Mg) vs. AlIV diagram (
4.2 Amphibole chemistry
Calculation of amphibole structural formulae was based on 23 oxygen using WinAmptb programs (Yavuz and Döner, 2017). All analytical results are shown in Supplementary Table S3. Results show that the SiO2 contents of the diorite porphyry range from 45.70 to 47.33 wt% (6.66–6.89 apfu Si, where apfu refers to atoms per formula unit). The contents of Al2O3 are from 7.56 to 9.36 wt% (1.30–1.61 apfu Al). The TiO2 contents are between 1.19 and 1.63 wt% (0.13–0.18 apfu Ti). The amphiboles of diorite porphyry belong to calcic amphiboles with (Ca + Na)B >1.75, NaB <0.04, and CaB >1.75 (B means two M4 sites per formula unit, following the classification scheme of
4.3 Apatite chemistry
The chemical formula calculations, along with the major and trace element content of apatite, are presented in Supplementary Table S4. The apatite chemical formula was determined based on the approach outlined by (
4.4 Magnetite chemistry
The trace element concentrations in magnetite are provided in Supplementary Table S5. Concentrations of elements are shown on box and whisker plots to present an enhanced visualization of elemental distribution across different types of magnetite (Figure 5). The yellow boxplots represent a single-phase magnetite population, identified as primary igneous magnetite based on consistent textures and homogeneous backscattered electron images. While the compositional range appears broad, it reflects natural variability in magmatic conditions and is within expected limits for magnetite from similar systems. MtT1 contains the highest concentrations of Ti (2,232–40886 ppm; mean 15,562.00 ppm; S.D. 19,313.69 ppm), Cr (1814.53–226046.11 ppm; mean 105,787.32 ppm; S.D. 93,435.62 ppm), Mn (4,509–19051 ppm; mean 11,643.83 ppm; S.D. 5,428.45 ppm), Co (45.22–305.98 ppm; mean 179.69 ppm; S.D. 111.17 ppm), Zn (82.66–14509.90 ppm; mean 6,422.07 ppm; S.D. 5,986.13 ppm), and Ga (11.73–133.93 ppm; mean 77.70 ppm; S.D. 53.26 ppm) coupled with the lowest Fe (51.77–65.05 wt%; mean 60.38 wt%; S.D. 5.62 wt%). Distribution of trace elements in magmatic magnetite compositions may evolve significantly by solid-state diffusion processes, such as inter-grain geochemical exchange with ilmenite, mineral exsolution, and oxy-exsolution of ilmenite (Tian et al., 2021), which is consistent with the presence of oxy-exsolution ilmenite platelets in MtT1 (Figure 3k). MtT2 has the highest concentrations of Ni (34.76–359.16 ppm; mean 215.56 ppm; S.D. 137.99 ppm), Sn (1.50–76.00 ppm; mean 6.03 ppm; S.D. 3.17 ppm), and Fe (66.07–69.87 wt%; mean 67.50 wt%; S.D. 1.15 wt%) contents are moderate. MtT3 has the highest concentrations of Sc (0.10–54.60 ppm; mean 14.94 ppm; S.D. 15.12 ppm); V (1185.94–4,076.50 ppm; mean 2065.88 ppm; S.D. 940.14 ppm); Pb (1.14–663.88 ppm; mean 147.37 ppm; S.D. 150.49 ppm), and Fe (70.68–78.52 wt%, mean 74.54 wt%; S.D. 2.03 wt%). While certain magnetite grains exhibit elevated levels of Cu, S, Ca, and Si amounts, the unusually high values of these elements are probably attributable to the occurrence of other sulfides and silicates (e.g., chalcopyrite, pyrite) inclusions. The LA-ICP-MS elemental mapping reveals that magnetite grains contain micro-inclusions-bearing trace elements, silicates, and sulfide minerals (Figure 6). Elemental mapping was conducted to illustrate the element distributions in magnetite, offering comprehensive insights into elemental variations. Figure 6 explains the LA-ICP-MS elemental map of a representative magnetite grain (sample MS11). Elevated concentrations of Co, Cr, and Ni are concentrated more in the center. Cu, As, Mo, Sb, and Te display increasing concentrations from the center toward the rim. The Pd contents are low. The Pt, Os, Ir, Au, Re, Ag, Ru, Bi, and Re concentrations fall below the detection limits and thus do not show any distribution in this magnetite grain (Magnetite number 51).
FIGURE 5

The element contents in magnetite were illustrated by Box and whisker plots. For specific elements, the lower whisker, lower quartile, and median values coincide since the majority of measurements are at or below the detection limit. The top 75% and bottom 25% of the data are represented by the upper and lower margins of the boxes, respectively.
FIGURE 6

LA-ICP-MS elemental maps (raster) of the distribution of trace elements in magnetite (Mt) grain from the MS11 sample. Note that yellow areas represent high levels of elements, but purple areas show low concentrations.
5 Discussion
5.1 Petrogenetic implications
5.1.1 Tectono-magmatic characteristics based on biotite composition
The biotite composition is utilized to distinguish suites of alkaline anorogenic (A-type), calc-alkaline orogenic, and peraluminous (including S-type) settings in productive intrusions of porphyry systems (
FIGURE 7

Biotite chemical composition from the Masjeddaghi deposit on tectonomagmatic discrimination diagrams: (a) Ternary MgO-FeOtot-Al2O3 diagram (
5.1.2 Ti-in-biotite thermometry
Biotite is one of the most important hosts of Ti in igneous rocks. The concentration of Ti and XMg = Mg/(Mg + Fe) can be plotted on XMg vs. Ti diagram to show that the Ti concentrations decrease with an increase in Mg/(Mg + Fe) (
5.1.3 Aluminum-in-hornblende geobarometry
Numerous models were proposed based on the total Al concentration of amphibole to estimate geobarometry and geothermometry in calc-alkaline granitoid (e.g., Ridolfi and Renzulli, 2012). Ridolfi et al. (2010) provided new thermobarometric formulations for determining temperature, pressure, oxygen fugacity, and hygrometric conditions according to the phase stability and chemical balance of amphibole for calc-alkaline magmas, covering a temperature range (550°C–1120°C) and pressure (<1,200 MPa). The temperature and crystallization pressure of amphiboles in Masjeddaghi can be calculated by the subsequent Equations 1, 2 (Ridolfi et al., 2010):
The obtained temperatures are from 830 to 877°C (mean = 849°C), and also the estimated crystallization pressure of amphiboles varies between 120 and 186 MPa (mean = 144 MPa) for Masjeddaghi (Supplementary Table S3). If amphibole crystallization occurred after magma emplacement, a pressure of <200 MPa appears typical for the Masjeddaghi porphyry deposit. The diagram of T (˚C) vs. P (MPa) is presented to estimate the P-T condition of amphiboles from calc-alkaline products in subduction-related systems (Ridolfi et al., 2010). According to this diagram, selected amphiboles from Masjeddaghi are plotted mostly within the domain (1) (Figure 8a).
FIGURE 8

Amphibole compositions from the Masjeddaghi porphyry deposit plotted on: (a) Composition of calcic amphiboles on the T(°C) vs. P (MPa) diagram (Ridolfi et al., 2010); (b) H2Omelt (wt%) vs. T diagram (Ridolfi et al., 2010).
5.1.4 Crystallization conditions of apatite
In order to estimate the crystallization conditions of apatite, it is necessary to calculate the apatite saturation temperature (AST). It is assumed that the whole-rock composition represents the composition of the original melt, from which apatite crystallized, and AST can be estimated in melts with the composition of silicate (
5.1.5 Estimation of water contents
The AlVI amount in amphibole is influenced by the melt’s water abundance, therefore, AlVI can serve as an indicator of the equilibrium range of amphibole formation (Ridolfi et al., 2010). The water amount of melt relative to amphibole crystallization is estimated through the subsequent Equation 4 proposed by Ridolfi et al. (2010):where [6]Al*= ([6]Al+[4]Al/13.9 – (Si+[6]Ti)/5 – CFe2+/3 – Mg/1.7+(BCa + A[])/1.2 + ANa/2.7–1.56 K – (Fe2+/(Fe2++Mg))/1.6.
According to the diagram of H2Omelt (wt%) vs. T (Ridolfi et al., 2010), H2Omelt of the Masjeddaghi porphyry deposit ranges from 4.10 to 4.46 wt% (mean = 4.25 wt%) (Figure 8b; Supplementary Table S3). This amount of magmatic water suggests that Cu mineralization is linked to hydrous calc-alkaline magma in Masjeddaghi. The amphibole crystallization depths (km) can be estimated based on the calculated pressure, assuming standard density weights of 2.89 g/cm3 for the oceanic crust and 2.70 g/cm3 for the continental crust (Ridolfi et al., 2010). Based on the depth formula of Ridolfi et al. (2010), the amphibole formation depths are calculated within the range of 4.2–9.9 km (mean = 6.5 km) for the oceanic crust, and 3.9–9.3 km (mean = 6.08 km) for the continental crust (Supplementary Table S3). Based on amphibole crystallization data, it suggests a deep magmatic reservoir for the Masjeddaghi deposit.
5.1.6 Origin of the Masjeddaghi magnetite
Based on chemical and textural features of MtT1, MtT2, and MtT3, different origins are recognized for the three types of magnetite. MtT1 homogeneous visual textural, suggesting that it crystallized during the early phase of the cooling magma. Furthermore, the high amounts of Ti, Ni, Cr, V, Al, Mg, and Mn in the MtT1, because of high concentrations in silicate melts and/or significant distribution factors between magnetite and silicate melt at elevated temperatures (Wen et al., 2017), indicate a magmatic origin for MtT1 (Wen et al., 2017). MtT2 has lower contents for trace elements like V, Ti, and Al than the MtT1 phase, indicating MtT2 was produced by hydrothermal fluid-coupled dissolution and reprecipitation (CDRP) of the precursor magmatic magnetite. The reequilibrated magnetite in rocks is likely hydrothermal in origin due to the presence of a fluid phase. The hydrothermal alteration results in the dissolution and reprecipitation process in Magnetite MtT2. Dissolution-reprecipitation refers to the process in which the previous assemblages are substituted by more stable ones during physicochemical condition changes (
FIGURE 9

(a) Fe vs. V/Ti diagram (Wen et al., 2017); (b) Ti vs. V diagram (
5.1.7 Controlling factors in the chemical compositions of magnetite
The variation of trace elements across various types of magnetite is influenced by temperature, salinity, pressure, and oxygen fugacity (fO2), and fluid-rock interaction in porphyry deposits (Tian et al., 2021). Temperature plays a major role in controlling the trace element composition of magnetite, with a positive correlation observed between formation temperature and Ti content (Tian et al., 2021). In Masjeddaghi samples, the decreasing average Ti contents in the sequence of MtT1 (15,562 ppm)→ MtT2 (12,121 ppm)→ MtT3 (6,414 ppm), indicates a decreasing trend of Ti concentrations and magnetite formation temperature in hydrothermal magnetite. Moreover, the Ti, Al, V, and Mn element contents may also reflect the magnetite formation temperature (Tian et al., 2021). The Ti + V vs. Al + Mn diagram (Figure 9c; Tian et al., 2021) indicates that most of the magnetite formation of Masjeddaghi extends the increased-temperature range (i.e., 300°C–500°C, >500°C) and aligns with the decreasing temperature trend from MtT2 to MtT3. Vanadium, as another indicator element, can be used to detect the forming environment in magnetite. Because V exhibits high reactivity in low-temperature hydrothermal fluids (Wen et al., 2017). V3+ is more readily incorporated into the magnetite structure in a reducing environment because of its ionic radius being very similar to Fe3+, thus, V is an important indicator fluid fO2 evolution (Tian et al., 2021). At Masjeddaghi, the average V contents show a slight decreasing trend of MtT1 (2,395 ppm) → MtT2 (2,361 ppm), then increase from MtT2 through MtT3 (2,602 ppm). The small difference between MtT1 and MtT2 suggests a shared magmatic origin and fluid fO2. In contrast, V content increases in MtT3, indicating a shift to more reducing conditions during late-stage hydrothermal alteration. This trend suggests that while MtT1 and MtT2 formed from a common magmatic fluid, MtT3 reflects crystallization from a distinct hydrothermal fluid with lower fO2. Contents of Mg, Al, Si, and V elements can accumulate in hydrothermal magnetite by wide fluid-rock interactions. For the Masjeddaghi magnetite, the Mg, Al, Si, and Ti concentrations are displayed on the Ti vs. Mg + Al + Si diagram (Tian et al., 2021; Figure 9d) in order to provide a clearer insight into the effect of the extent of fluid-rock interactions. The higher Mg and lower Si content in MtT1 (Figure 9d) indicate minimal fluid-rock interaction, consistent with its magmatic origin. In contrast, MtT2 and MtT3 exhibit progressively lower Mg and higher Si contents, reflecting increasing degrees of fluid-rock interaction. This trend is illustrated by the grey arrow in Figure 9d, which represents increasing fluid-rock interaction from MtT1 to MtT3. MtT3 typically shows stronger fluid-rock interaction, whereas MtT1, formed during the magmatic phase, retains lower concentrations of fluid-mobile elements.
5.2 Metallogenic implications
5.2.1 Metallogenic implications based on magnetite chemistry
In the last decades, various research efforts have indicated that the trace elements in magnetite may serve to differentiate the origin and classification of deposits (e.g.,
FIGURE 10

Discrimination plots of Ti + V vs. Al + Mn (ppm) (
5.2.2 Oxidation conditions of parental magma
Based on investigations of porphyry deposits, oxidized magmas with elevated oxygen fugacity (ƒO2) are characteristic of most porphyry copper systems. (Sun et al., 2015). Consequently, such oxidized magmas are considered favorable for porphyry mineralization. The ternary Fe3+-Fe2+-Mg2+ diagram (Wones and Eugster, 1965) shows ƒO2 according to the compositions of biotite. Biotites in the Masjeddaghi are plotted above the Ni–NiO buffer, which implies they crystallized under conditions of high ƒO2 (Figure 11a). The biotites of the mineralized Masjeddaghi indicate ƒO2 measurements vary from 10−14.23 to 10−15.63 (Supplementary Table S2). The T (°C) vs. log ƒO2 diagram is used to represent the oxygen fugacity levels in oxidized porphyry deposits [1], biotites of the Masjeddaghi deposit fall within the Ni–NiO buffer domain (Figure 11b), and selected apatites are plotted in the I-type oxidized magma curve (Figure 10b). Thus, the Masjeddaghi intrusion is classified as an oxidized I-type magma system with high oxygen fugacity.
FIGURE 11

Compositions of biotites, and apatites from the Masjeddaghi deposit on Oxygen fugacity diagrams: (a) Ternary Fe3+-Fe2+-Mg2+ diagram in biotites (Wones and Eugster, 1965); (b) The oxygen fugacities of oxidized porphyry deposits on T(°C) vs. log ƒO2 diagram (Sun et al., 2015). Abbreviations: MH, Magnetite-Hematite buffer curve; NNO, Nickel-Nickel Oxide buffer curve; FMQ, Fayalite-Magnetite-Quartz buffer curve; IW, Iron- Wüstite.
Redox-sensitive elements like S, Ce, Mn, and Eu in apatite serve as indexes to evaluate the oxidation state of magma (
The estimated ƒO2 for the diorite porphyry varies between 10–10.3 to 10–11.1, indicating that Masjeddaghi ore-forming magmas are quite oxidized (Supplementary Table S4).
5.2.3 Halogen fugacity of fluids based on apatite chemical composition
It seems the volatile diffusions in apatite appear during the prolonged cooling of magmatic rock (Zhao et al., 2020). A model presented by
here T represents temperature (K), P is given in bar, and X(Clap), X(Fap), and X(Hap) correspond to mole fractions of hydroxylapatite, chlorapatite, and fluorapatite (
5.2.4 Comparison of hydrothermal fluid fugacity ratios in biotite with other porphyry Cu deposits
The halogen fugacity values for hydrothermal fluids associated with mineralization and alteration phenomena at the Masjeddaghi porphyry Cu-Au deposit have been contrasted with those fluids linked to other porphyry copper systems (Figures 12a,b). Various factors affect the combination of fluids related to types of porphyry deposits; the most important of them is the composition of the source and the volatile composition (especially F/Cl and F/H2O ratios of the reservoir and magma) (
FIGURE 12

Comparison of the Masjeddaghi porphyry Cu-Au deposit with other porphyry systems: (a) log(ƒH2O/ƒHCl) vs. log(ƒHF/ƒHCl) and (b) log(ƒH2O/ƒHCl) vs. log(ƒH2O/ƒHF) ratios. The fugacity ratios for the Santa Rita, Los Pelambres, Bakircay, Hanover, Bingham, Babine Lake, Casino, and Deboullie porphyry Cu deposits are from
5.2.5 Thermodynamic modeling of the evolution of volatile elements in apatite
H2O, S, Cl, and F as volatile elements in silicate melts play a key role in volcanic eruptions and the magmatic evolution (
FIGURE 13

A comparison of apatite volatile elements variations between diorite porphyry of Masjeddaghi and the intrusions of the Duolong porphyry deposit. These figures illustrate the compositional variations in apatite volatile elements during their evolution from volatile-undersaturated to volatile-saturated magma. (a) XF/XCl vs. XCl/XOH in apatite; (b) XF/XCl vs. SO3 in apatite. The blue solid curves in (a,b), derived from the Rayleigh fractionation model, depict the variation of volatile elements in apatite during fluid exsolution. Each yellow star represents calculated apatite composition corresponding to the fraction of the remaining melt (ƒ shown as %) and temperature (°C) in the Rayleigh fractionation model. Gray solid curve in (b) represents the variation of apatite SO3 contents that were estimated by the empirical equation (
5.3 Implications for the formation of the Masjeddaghi porphyry Cu-Au deposit
According to the data presented, we suggest the following model for magmatic evolution linking the formation of the Masjeddaghi porphyry Cu-Au deposit to the sequences of mineral crystallization within a dioritic magma chamber (Figure 14). Magmatic apatite grains began crystallizing from the early stage of Masjeddaghi dioritic magmas at ∼918°C (Figure 14a). Based on mineral thermometry and petrography that magmatic magnetite crystallized coeval or nearly coeval with magmatic apatite at ∼918°C in the early stages of the Masjeddaghi dioritic magma evolution (Figure 14a). Magmatic magnetite is often found intergrown with magmatic apatite (Figures 3i,k), indicating that it formed during the same magmatic pulse. It is also characterized by high Ti, Cr, Mn, and Co contents, which are compatible elements in high-temperature melts. The presence of zoned amphibole (Figure 3h) suggests that mafic magma was injected into the dioritic magma chamber, with mixing possibly taking place across several phases of amphibole crystallization at a depth of approximately ∼10 km (Figure 14b). Subsequently, magmatic biotite formed at shallower depths and lower temperatures (∼4 km and ∼782°C) as the mixed magma continued to rise; it may have intruded into the surrounding wall rocks (Figure 14b). During this ascent and magma-hydrothermal transition, partial reequilibrated magnetite occurred via fluid-coupled dissolution-reprecipitation, resulting in subhedral magnetite with reduced trace element contents. The mineral thermometer, based on the established empirical equation, confirmed the mineral crystallization sequences, where the calculated apatite saturation temperature (∼845°C-918°C) falls within the range of Al-amphibole (∼830°C-877°C) and above that of biotite temperature (∼723°C to 782°C). At a depth of 4–10 km, an oxidized and hydrous mafic magma derived from a deeper source intruded into the dioritic magma chamber (Figure 14b). The introduction of oxidized and hydrous mafic magma from the resource into the evolved dioritic magma chamber led to significant magma mixing and continuous fractional crystallization of apatite, magnetite, amphibole, and biotite, causing the formation of the Masjeddaghi deposit with ore-forming fluid exsolution (Figure 14b). Thus, the continued fractional crystallization of apatite, magnetite, amphibole, and biotite, associated with high oxygen fugacity, enhanced water amount, and metal concentrations in the mafic magma, is crucial for the formation of ore-forming porphyry in the Masjeddaghi deposit.
FIGURE 14

Conceptual model depicting the stages of mineral formation in the Masjeddaghi mature dioritic magma chamber (
6 Conclusion
According to the analysis and discussions, we derived the subsequent conclusions:
1. Biotite and amphibole compositions show a parental magma with calc-alkaline features, suggesting a source comprised of subduction-related mantle and crustal materials.
2. The Al-in-amphibole geothermometer, the apatite saturation temperature, and the Ti-in-biotite geothermometer show ranges of calculated temperatures (830°C–877°C) (845°C-918°C) and (723°C–782°C), respectively, whereas the Al-in-amphibole geobarometer exhibits pressures (120–186 MPa; equating to depths of 4–10 km), indicating the existence of a deep magmatic origin beneath the deposit. The H2Omelt contents of amphibole (4.10–4.46 wt%) display that the mineralization is associated with a hydrous calc-alkaline magma.
3. According to concentrations of trace elements and mineral associations, magnetites are classified into magmatic, reequilibrated, and hydrothermal types in the Masjeddaghi porphyry deposit. Some Masjeddaghi magnetite samples overlap between the porphyry and skarn fields in the Ti + V vs. Al + Mn (ppm) diagram, suggesting that the diagram may not be reliable for distinguishing porphyry-related deposits.
4. The estimated log ƒO2 for biotites ranges from 10–14.23 to 10–15.63 and for apatites ranges from 10–10.3 to 10–11.1, suggesting that the ore-forming magmas are consistent with characteristics of oxidized I-type magmas.
5. The Masjeddaghi porphyry system, with its negative log(ƒHF/ƒHCl) fugacity ratios, has similarities with those of the other porphyry systems, such as Bingham, Santa Rita, and Babine Lake, where negative values of log(ƒHF/ƒHCl) imply a relatively Cl-rich hydrothermal system. It seems that Cu and Au are transported by Cl-rich fluids as metal-chloride ligands to form the Masjeddaghi porphyry deposit.
6. The observed trends in the XF/XCl and XCl/XOH ratios of apatite from the Masjeddaghi deposit display a pattern of magmatic evolution characterized by volatile-undersaturated crystallization. The variation in volatile elements in apatite suggests that primary volatile exsolution likely took place at temperatures ranging from ∼880°C to 890°C.
7. The intrusion of oxidized hydrous mafic magma from a deeper magma source likely promoted wide magma mixing and prolonged fractional crystallization within the evolved dioritic magma chamber, resulting in the exsolution of ore-forming fluids and the formation of the Masjeddaghi deposit.
Statements
Data availability statement
The dataset generated for this study has been deposited in the Zenodo repository and is available at: 10.5281/zenodo.15741844.
Author contributions
ZR: Writing - original draft, Writing - review and editing, Conceptualization, Data curation, Formal Analysis, Investigation, Project administration, Methodology, Resources, Supervision, Software, Validation, Visualization. SH: Writing - review and editing, Conceptualization, Resources, Supervision, Validation. DS: Writing - review and editing, Data curation, Methodology, Validation. ZS: Writing - review and editing, Software, Data curation, Validation.
Funding
The author(s) declare that no financial support was received for the research and/or publication of this article.
Acknowledgments
The first author thanks the Islamic Azad University of Tehran, Iran, for the possibility to carry out her PhD research, where part of the unpublished results are presented here. We sincerely thank Reimar Seltmann and David R. Lentz for their valuable feedback and suggestions, which significantly enhanced the quality of earlier versions of this manuscript. We would like to express our gratitude to the Editors and Reviewers of this journal for their very useful comments and suggestions, which have greatly improved the quality of the manuscript.
Conflict of interest
Author ZR was employed by ANGLO REM CA Exploration Mining Ltd.
The remaining authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.
Generative AI statement
The author(s) declare that no Generative AI was used in the creation of this manuscript.
Publisher’s note
All claims expressed in this article are solely those of the authors and do not necessarily represent those of their affiliated organizations, or those of the publisher, the editors and the reviewers. Any product that may be evaluated in this article, or claim that may be made by its manufacturer, is not guaranteed or endorsed by the publisher.
Supplementary material
The Supplementary Material for this article can be found online at: https://www.frontiersin.org/articles/10.3389/feart.2025.1603296/full#supplementary-material
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Summary
Keywords
biotite, amphibole, apatite, magnetite, Masjeddaghi porphyry Cu-Au deposit, Iran
Citation
Rahnama Z, Hassanpour S, Savard D and Shah Z (2025) Mineral chemistry of apatite, amphibole, biotite, and magnetite from the Masjeddaghi porphyry Cu-Au deposit, NW Iran: petrogenetic and metallogenic implications. Front. Earth Sci. 13:1603296. doi: 10.3389/feart.2025.1603296
Received
31 March 2025
Accepted
12 June 2025
Published
27 June 2025
Volume
13 - 2025
Edited by
Claudia Belviso, National Research Council (CNR), Italy
Reviewed by
Tristan Childress, KeyLogic Systems, United States
Xianke Fan, Chinese Academy of Geologi-cal Sciences (CAGS), China
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*Correspondence: Zohreh Rahnama, zohrehrahnamar@gmail.com
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