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Article

Amphibole Group Minerals in the Ozren Massif Ophiolites of Bosnia and Herzegovina as Petrogenetic Indicators

by
Samir Ustalić
1,
Ondrej Nemec
1,
Stanislava Milovská
2,
Marián Putiš
1,*,
Elvir Babajić
3,
Sergii Kurylo
2 and
Peter Ružička
1
1
Department of Mineralogy, Petrology and Economic Geology, Faculty of Natural Sciences, Comenius University, Ilkovičova 6, 842 15 Bratislava, Slovakia
2
Earth Science Institute of the Slovak Academy of Sciences, Ďumbierska 1, 974 11 Banská Bystrica, Slovakia
3
Department of Mineralogy and Petrology, Faculty of Mining, Geology and Civil Engineering, University of Tuzla, Urfeta Vejzagića 2, 75 000 Tuzla, Bosnia and Herzegovina
*
Author to whom correspondence should be addressed.
Minerals 2024, 14(3), 239; https://doi.org/10.3390/min14030239
Submission received: 1 February 2024 / Revised: 24 February 2024 / Accepted: 24 February 2024 / Published: 26 February 2024
(This article belongs to the Special Issue On the Formation and Alteration of Ophiolites and Oceanic Lithospheres)
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Abstract

:
The Ozren ophiolite complex (OOC) of the Dinaridic Ophiolite Belt is one of the six ophiolite complexes in Bosnia and Herzegovina. This paper deals with the mineral chemistry of amphiboles determined by electron probe micro-analysis and micro-Raman spectroscopy. The detected amphibole generations and types in mafic, ultramafic, and metamorphic rocks suggest a polystage evolution and are therefore useful petrogenetic indicators of the investigated OOC. Most gabbroic rocks and dolerites contain primary magmatic amphibole1 (magnesio-hornblende to pargasite, occasionally hastingsite) and prismatic to needle-like aggregates of late magmatic amphibole2 (magnesio-hornblende), while plagiogranite contains ferri-winchite and ferro-ferri-winchite as primary magmatic amphibole. Post-magmatic amphiboles were detected in dolerites, troctolites, and lesser in peridotites. The Na-(Ti)-rich amphibole3 (ferri-winchite and ferro-ferri-winchite to katophorite and ferri-katophorite) with amphibole4 (grunerite) rim formed along the grain boundaries of clinopyroxene, amphibole1, and plagioclase in dolerites. A part of these amphiboles grows into amphibole1, 2. Kaersutite to ferri-kaersutite, associated with phlogopite, occur in troctolites and dunites, while Mhbl was detected in harzburgite. The ultramafic rocks (lherzolites, harzburgites, and dunites) and the gabbroic layer are crosscut by clinopyroxene–plagioclase gabbroic and clinopyroxene–plagioclase–amphibole gabbro–dolerite dykes, suggesting ‘dry’ and ‘hydrated’ percolating melts generated in inferred subridge and supra-subduction settings, respectively. The amphibole3 and 4 in gabbros and dolerites and similar amphibole types in ultramafic rocks could be related to inferred arc-type basaltic and plagiogranitic percolating melts and fluids. Low-Al amphibole5 (tremolite and actinolite) and associated chlorite, albite, and clinozoisite represent the ocean-floor alterations in mafic rocks. Amphibole6 (magnesio-hornblende to pargasite) was identified in metamorphic sole amphibolites. Micro-Raman spectroscopy provided typical Raman spectra for the studied amphiboles, highlighting distinct features such as bands related to CMg content, CFe3+ presence, TO4 ring-breathing mode, TiO6 stretching mode, presence > 0.3 apfu of CTi, and TO4 stretching indicating CFe2+ in the structure. Applied amphibole geothermobarometry revealed the formation P–T conditions of amphibole (Amp)1 (avg. 863 °C at 0.23 GPa), Amp2 (avg. 747 °C at 0.17 GPa), Amp in the mantle rocks (avg. 853 °C at 0.64 GPa), Amp5 (avg. 349 °C at 0.03 GPa), and Amp6 (avg. 694 °C at 0.46 GPa).

1. Introduction

The amphibole group of minerals represents one of the most compositionally diverse mineral groups, and this diversity is reflected in the very different rock types, tectonic environments, and wide range of P–T conditions in which they occur [1]. In general, magmatic amphiboles are very rare in ultramafic rocks, but they are mostly related to the gabbroic layers and dykes in ultramafic rocks and upper sequences of the ophiolite cross-sections (e.g., [2,3]). The presence of amphiboles and orthopyroxene with partly dissolved olivine in ultramafic rocks, may indicate a deep melt fractionation in magmatic arcs [4]. The arc magmas are commonly hydrated and crystallizing amphibole. Hornblende peridotites may indicate a reaction between a dunitic cumulate and an evolved hydrous melt around the Moho beneath the arcs [5,6]. Amphibole-rich mafic and ultramafic intrusive rocks could be a ‘hidden’ amphibole reservoir in the arc crust, and therefore amphibole plays a major role in the petrogenesis and differentiation of many arc magmas [7].
The Ozren ophiolite complex (OOC) is one of the six known ophiolite complexes in Bosnia and Herzegovina and the second largest (Figure 1; [8]). In this paper, we focused on the determination of representative amphiboles in plagiogranite (P5B), gabbro (P13B1), dolerite (P17C), troctolite (P18A), harzburgite (P21), and amphibolite (P10F), including the definition of amphibole chemistry by using electron probe micro-analysis (EPMA), as well as a description of the measured spectra and bands by using micro-Raman spectroscopy. We also determined uncommon Na–Ti amphibole phases such as ferro-ferri-katophorite reported by [9] as a new clinoamphibole from the silicocarbonatite dykes in Sierra de Maz, La Rioja, in Argentina.
The main goal is to recognize and differentiate between all the amphibole types and decipher their relationship to the petrogenesis of the investigated OOC. The obtained dataset reveals less common (Na–Ti-rich) amphibole types, which are inferred to have originated due to basaltic and/or plagiogranitic percolating melts and fluids through peridotite and gabbro layers. Such amphibole-bearing rocks might have formed under the influence of arc-type magmas. We tried to use the determined amphibole generations for a petrogenetic interpretation, documenting their relationship to magmatic, post-magmatic melt/fluid-rock interaction, and the metamorphic evolutional stages of the OOC. We estimated the formation P–T conditions of amphiboles using the chosen amphibole geothermobarometers.

2. Geological Setting

The Dinaride ophiolite belt represents one of the most remarkable stratigraphic units along the entire Balkan, which is a branch of the Alpine–Himalayan Tethyan orogenic belt. The Dinaridic segment of Neotethys was affected by widespread shortening and related subduction–obduction–accretion processes that commenced in the Middle Jurassic. The Dinaride ophiolites belong either to the Central Dinaridic Ophiolite Belt (CDOB) or to the Vardar zone (VZ, also called IDOB = Inner Dinaridic Ophiolite Belt). While areas of the VZ ophiolites are of supra-subduction origin, the dismembered CDOB ophiolites are associated with the ocean-ridge geotectonic environment. The CDOB and VZ Western Belt are collectively referred to as the Western Vardar Ophiolite Unit to distinguish them from the ophiolites of the Eastern Vardar Ophiolite Unit (or Main Vardar Belt), separated from the Western Unit by the Sava Zone (Figure 1).
The Ozren ophiolite complex (OOC) in Bosnia and Herzegovina is part of the Dinaridic Ophiolite Belt [8,10,11,12,13,14,15,16,17,18,19,20,21,22,23]. This complex shows a polystage mantle evolution and revealed an almost complete ophiolitic cross-section composed of peridotites, plagioclase peridotites, plagiogranites, troctolites, and other gabbros, gabbroic, doleritic, and fewer basaltic dykes. Pillow basalts are alternating or covered by Bajocian to Bathonian radiolarites [24,25]. Metamorphic sole amphibolites may indicate intraoceanic subduction. A sheeted dyke layer is missing in this ophiolitic complex (Figure 2a,b).

3. Materials and Methods

The fieldwork was focused on finding relatively fresh rocks that contain amphiboles suitable for further laboratory analyses (Figure 2a; see GPS of the sample location in Table 1). All principal rock types were first studied in transmitted light from the polished rock sections by a polarized light microscope. Representative samples were used for further investigation by electron probe micro-analysis (EPMA) and micro-Raman spectroscopy.
The chemical compositions of amphiboles were acquired using wavelength-dispersive (WDS) analyses on a CAMECA SX-100 electron probe microanalyzer at the State Geological Institute of Dionýz Štúr in Bratislava, and by the JEOL Super-probe JXA-8530F at the Earth Science Institute of Slovak Academy of Sciences in Banská Bystrica, Slovakia. The electron beam accelerating potential was 15 kV, with a beam current of 20 nA and a beam diameter of 3–5 µm. Measured lines, crystals, and spectrometers were Si (TAP, Kα, and wollastonite), F (LPCO, Kα, and LiF), Cl (LPET, Kα, and NaCl), Al (TAP, Kα, and Al2O3), Ca (LPET, Kα, and apatite), Fe (LLIF, Kα, and fayalite), Ti (LLIF, Kα, and TiO2), K (LPET, Kα, and orthoclase), Na (TAP, Kα, and albite), Mg (TAP, Kα, and forsterite), Mn (LLIF, Kα, and rhodonite), Cr (LLIF, Kα, and Cr), Ni (LLIF, Kα, and Ni), V (LLIF, Kα, and V), and Zn (LLIF, Kα, and willemite).
Raman spectroscopic measurements of thin sections were performed on a Labram HR800 microspectrometer (Horiba Jobin-Yvon), connected to an Olympus BX41 microscope with confocally coupled Czerny–Turner-type monochromator (focal length 800 mm) at the Earth Science Institute of the Slovak Academy of Sciences in Banská Bystrica, Slovakia. A frequency-doubled Nd-YAG laser at 532 nm was used for excitation (633 nm for verifying/excluding of luminescence effect). The Raman-scattered light was collected in 180° geometry through a 50× and 100× objective lens with numerical aperture 0.8 (100×) and dispersed by diffraction grating with 600 grooves per mm. System uses CCD detector (cooled charge-coupled device). The system resolution was 6 cm−1. The grating turret accuracy was calibrated between the zero-order line (180° reflection) and the laser line at 0 cm−1. Spectral accuracy was verified on the 734 cm−1 band of Teflon.
All determined amphiboles from this ophiolite complex are classified based on mineral calculation [28] and suitable diagrams [29,30].

Methodical Approach for the Calculation of Amphiboles

  • All amphiboles are calculated with [28] Excel Spreadsheet;
  • Calculations are based on 15 cations following one of 2 procedures: (1) Si to Ca&Li = 15 apfu for Ca amphiboles (Mhbl, Prg, and Hst) and (2) Si to Na = 15 apfu for Gru, Krs, and Wnc;
  • Fe3+ was calculated based on charge balance;
  • OH was calculated based on assumption 2 (OH, F, and Cl);
  • For Ti-rich samples, estimation of OH content was set according to OH = 2-2CTi. This estimate provides minimum OH; structure refinement provides more accurate results: [31] recommended for CTi ≥ 0.1; roughly >1.0 wt.% TiO2 by [28];
  • Mineral formula assigned based on 24 anions.
Amphibole geothermobarometry was used to constrain the P–T conditions of investigated samples. We used a combination of single-Amp geothermobarometry by [32] and Al and Ti-in-Amp geothermobarometry by [33].
Abbreviations of the rock-forming mineral names used in the text, tables, and figures are from [34] or adapted for this paper (marked by *): Ab, albite; Act, actinolite; Amp, amphibole; Bt, biotite; Chl, chlorite; Cpx, clinopyroxene; Czo, clinozoisite; Ep, epidote; Fkrs, ferri-kaersutite; Fktp, ferri-katophorite; Fwnc, ferri-winchite; Fe-Wnc*, ferro-ferri-winchite; Gru, grunerite; Hst, hastingsite; Ilm, ilmenite; Krs, kaersutite; Ktp, katophorite, Mhbl, magnesio-hornblende; Ol, olivine; Opx, orthopyroxene; Phg*, phengite; Phl, phlogopite; Pl, plagioclase; Prg, pargasite; Sdg,¸sadanagaite; Qz, quartz; Spl, spinel; Str, strontianite; Ti-Sdg*, Ti-rich sadanagaite; Tr, tremolite; Ttn, titanite; and Zo, zoisite.

4. Results

4.1. Petrographic Description of Samples

Petrographic description of samples was completed from polished rock thin sections, which were used for further analytical investigations by EPMA and micro-Raman techniques.
Gabbro (sample P10C; Figure 2 and Figure 3a) contains coarse-grained Cpx, Pl, and Amp. Prismatic to needle-like Amp aggregates occur in grain boundaries of coarse-grained Amp, Cpx, and Pl and on the rim of this Amp. A gradual transition between these two Amp types is often observable. Pyroxene and Amp margins are partly replaced by micro-needle Amp and Chl aggregates. Plagioclase is weakly altered.
Dolerite (sample P17C; Figure 2 and Figure 3b,c) shows a magmatic texture defined by porphyritic Cpx, Amp, and Pl, with an accessory opaque phase. This dolerite also contains needle-like aggregates in grain boundaries of Cpx, porphyritic Amp, and Pl, as well as on the rims of the porphyritic Amp. Transitions from Amp1 to Amp2 are visible in a microscope. Other hypidiomorphic to idiomorphic tiny individual Amp grains are observable, and all the mentioned Amp habits and Px are enclosed in very fine-grained and micro-needle-like Amp aggregates in association with Chl, Czo, and Ab.
A plagiogranite body (sample P5B; Figure 2 and Figure 3d) occurs in direct contact with peridotite (Figure 2). It is composed of Pl, Qz, Bt, needle-like Amp aggregates, and an opaque phase. Biotite is partly replaced by Chl and Ttn.
Harzburgite (sample P21; Figure 2 and Figure 3e) contains Opx1 porphyroclasts with inferred Cpx exsolution lamellae.
Troctolite (sample P18A; Figure 2) exclusively occurs within the dunite layers in peridotites. The Ol–Spl matrix is enriched in Pl and less in Cpx. The contact between Ol and Pl is accompanied by interstitial Cpx enclosing Ol and/or Spl. Olivine is serpentinized, while Pl underwent albitization and additional alterations.
The sole Pl amphibolites (sample P12A; Figure 2 and Figure 3f) contain parallel-oriented Amp porphyroblasts, which are dynamically recrystallized into fine-grained Amp aggregates. Both Amp generations are partly replaced by Chl, needle-like Amp, and Czo, while Pl is albitized.

4.2. Chemical Composition of Amphiboles

Using EPMA, a few Amp types with varying chemical compositions were identified in the rock textures (Figure 4a–h). The determined amphiboles belong to a wide range of Amp subgroups ranging from calcic and sodic–calcic to magnesium–iron–manganese subgroup and oxo-amphiboles according to the classification of [30] (Figure 5a–c) and the classification of [29] (Figure 5d). Table 2 and Table S1 display the mineral chemistry variations in the amphiboles of the OOC. Table 3 provides the genetic criteria for the Amp types. Table S1 contains recalculated amphibole analyses, which we also used in the geothermobarometry (Section 4.4).
Plagiogranite (sample P5B) contains Fe-Wnc to Fwnc as the principal Amp types (Figure 4a and Figure 5c), while the composition of Amp1 in gabbros, dolerites, and basalts corresponds to Mhbl and Prg, rarely to Hst (Figure 4b–e and Figure 5a). The TiO2 amphibole content in the gabbros, dolerites, and basalts is between 0.10 and 3.85 wt.%, while, in plagiogranites, it is commonly less, reaching up to 1.63 wt.%. The Al2O3 amphibole values are mostly lower in the gabbros, from 5.31 to 10.03 wt.%, and reach up to 14.94 wt.% in the basalts and dolerites. Very low values between 0.08 and 0.19 wt.% are found in the Amp of plagiogranite. The amphibole (Fe-Wnc to Fwnc) from plagiogranite (sample P5B) has the highest content of Na2O (3.70–5.95 wt.%). In the gabbros, dolerites, and basalts, the Na2O amphibole content is generally lower, between 0.47 and 3.33 wt.% (Table 2 and Table S1).
In the gabbros and dolerites, Amp2 is represented by prismatic to needle-like Mhbl aggregates (Figure 4b–e and Figure 5a). In the gabbros, the TiO2 amphibole content ranges from 0.07 to 3.07 wt.%, whereas, in the dolerites, it is significantly lower, ranging from 0.09 to 1.12 wt.%. The Al2O3 amphibole values in the gabbros and dolerites are very similar (4.86–11.62 wt.%). The same situation occurs with the Na2O content in these rocks (0.16–2.58 wt.%) (Table 2 and Table S1).
Dark (in BSE) Amp3, which is represented by Fe-Wnc, Fwnc, Ktp, and Fktp (Figure 4d–e and Figure 5c), was found in the core of Amp4 grains in dolerite (sample P17C). A few individual tiny grains are Sdg to Ti-Sdg (Figure 4e and Figure 5a) enclosed in Amp1. Pale Amp4 (Gru) is on the rim of the Amp3 grains (Figure 4d–e and Figure 5b). Amphibole3 has higher content of TiO2 between 1.33 and 4.13 wt.%. Amphibole4 reaches up to 1.14 wt.%. The Al2O3 content in Amp3 is 0.83–15.05 wt.% and 0.25–1.03 wt.% in Amp4. The determined Amp3 is particularly characterized by increased Na2O content compared to the Amp4 generation (2.98–4.90 wt.% in Amp3; 0.24–0.73 wt.% in Amp4) (Table 2, Table 3 and Table S1). We also determined Krs to Fkrs, or Mhbl to Prg in association with Cpx and Phl in troctolite (Figure 4f) and dunite (samples P18A and P18D, respectively) (Figure 5a,d), while an Amp in harzburgite is Mhbl (Figure 4g).
The low-Al Amp5 is represented by Tr, Act aggregates that overgrow and partly to totally replace the Amp1–4 generations, and Cpx in mafic rocks (Figure 4b,e and Figure 5a). The content of TiO2 in Amp5 ranges from 0.03 to 1.56 wt.%. The content of Al2O3 and Na2O is between 0.42 and 3.66 wt.% and 0.03–1.02 wt.%, respectively (Table 2 and Table S1).
The amphibolites (samples P10F and P12A) contain metamorphic Amp6-Mhbl to Prg, and newly formed Tr and Act (Figure 5a). The mineral chemistry of the representative amphiboles is shown in Table 2 and Table S1.

4.3. Results of Micro-Raman Spectroscopy

At the same analytical spots where we analyzed the representative amphiboles by EPMA (Figure 4a–f; Table 4), we also examined in detail the Raman spectra of these amphiboles (Figure 6a–h). All the samples have a distinct band at around 150 cm−1 (Figure 6a–h), where the most distinctly visible band is on the Krs spectra (Figure 6h). The majority of the analyzed Raman spectra (Fe-Wnc, Fktp, Ti-Sdg, and Krs; Figure 6a,d,f–h) are characterized by enhanced Raman scattering near 530 cm−1 to 570 cm−1, while this band is suppressed regarding Mhbl (Figure 6b) and Gru (Figure 6e) spectra. The strongest peak for all the amphibole spectra is at 670 cm−1 (Figure 6a–h). Ti-rich sadanagaite and Krs spectra (Figure 6f,h) reveals a peak at 750 cm−1 to 800 cm−1, while this peak is not visible on any other spectra. All the Raman spectra, except the Krs spectra, contain a Raman peak at around 1040 cm−1 (Figure 6a–h). Raman vibrations of OH- stretching were visible in all the analyzed samples at 3640–3660 cm−1.

4.4. Amphibole Geothermobarometry Results

Amphibole geothermobarometry was used to constrain the P–T condition of the genetically different Amp groups and types reviewed in Table 5 and Table S1. Among the Amp geothermobarometers, we used a combination of single-Amp geothermobarometry by [32] and Al and Ti-in-Amp geothermobarometry by [33]. Magmatic Amp1, 2 constrained the crystallization T of gabbros and dolerites during the formation of the gabbro–dolerite layer of the OOC. The group of Amp3, 4 was not suitable for any Amp geothermobarometric method because of these amphiboles’ specific chemical composition that falls outside of their calibration constraints (Figure 5; Table 2 and Table S1). Tiny inclusions of Sdg and Ti-Sdg within Amp1 (Figure 4e and Figure 5), although suitable for geothermobarometric estimates, are most likely not primary magmatic phases of dolerite (P17C) in the gabbro–dolerite layer (also see Section 5.1 and Section 5.3). On the other hand, part of the rare amphiboles (Amp percolation type in Figure 5 and Table 2 and Table S1) from ultramafic rocks, such as harzburgites, dunites, and troctolites, provided P–T conditions regarding their formation. Similarly, the Amp5 from gabbros and dolerites provided reasonable results. Also, metamorphic Amp6 from the sole amphibolites was suitable for using the chosen geothermobarometers.

4.4.1. Magmatic Amphiboles

The magmatic Amp1 from gabbros (P10C and P13B1) and dolerites (P16 and P17C) provides a crystallization T interval of 865 to 777 °C (avg. 801 °C) and P 0.17 to 0.10 GPa (avg. 0.13 GPa). The late magmatic Amp2 of these rocks shows a crystallization T between 837 and 661 °C (avg. 747 °C) at P between 0.31 and 0.08 GPa (avg. 0.17 GPa).
The magmatic Amp1 in dolerite dyke P9 in serpentinized peridotite shows T from 945 to 922 °C (avg. 931 °C) at 0.40–0.26 GPa (avg. 0.34 GPa), while basalt dyke P10D in the gabbro layer gabbro (P10A–C) indicates a P–T interval of 906–797 °C (avg. 852 °C) at 0.52–0.18 GPa (avg. 0.29 GPa). The leucogabbro dyke P13B2 in gabbro (P13B1) P–T is between 1094 and 1025 °C (avg. 1059 °C) at 0.33–0.28 GPa (avg. 0.30 GPa).

4.4.2. Amphiboles from Ultramafic Rocks and Alteration Zones

Amphibole5 from dolerite dyke P9 in serpentinized peridotite provides a T interval of 347–301 °C (avg. 324 °C) at 0.04–0.01 GPa (avg. 0.02 GPa). Amphibole5 in leucogabbro dyke P13B2 in gabbro (P13B1) provides 398 °C at 0.03 GPa.
Rare Amp in harzburgite P21 shows a P–T interval of 1000–815 °C (avg. 868 °C) at 0.60–0.30 GPa (avg. 0.39 GPa).
Rare Amp in dunite P18D and troctolite P18A in this dunite provides 908–780 °C (avg. 841 °C) at 0.79–0.42 GPa (avg. 0.61 GPa).

4.4.3. Metamorphic Amphiboles

Metamorphic Amp from amphibolite (P10F; Table S1) provides T and P of 723–664 °C (avg. 694 °C) at 0.46 GPa.

5. Discussion

5.1. Mineral Composition of Amphibole Generations and Petrogenetic Significance

Amphibole is an important constituent of the mafic, metamorphic, and occasionally ultramafic rocks of the Ozren ophiolite complex. The investigated amphiboles have a diverse mineralogical composition (Figure 5a–d; Table 2, Table 3, Table 4 and Table S1). Using the nomenclature of the amphibole supergroup by [30], we defined the members of the calcium amphiboles (Mhbl, Prg, Hst, Sdg to Ti-Sdg, and Tr; Figure 5a), monoclinic magnesium–iron–manganese amphiboles (Gru; Figure 5b), sodium–calcium amphiboles (Fe-Wnc to Fwnc Ktp to Fktp; Figure 5c), and oxo amphiboles (Krs and Fkrs; Figure 5d).
Magmatic Amp1 (Mhbl to Prg) has been identified in nearly all the gabbroic rocks and dolerites. A specific instance is the brown Amp1 in a dolerite dyke (P9), represented by Prg or Hst (Figure 5a). Additionally, Sdg or Ti-Sdg (Figure 4e and Figure 5a) tiny inclusions occur in a dolerite (P17C) Amp1. Prismatic and needle-like late magmatic Amp2 (Mhbl) is present at the rim of magmatic Amp1 in gabbros and dolerites (Figure 4b–e and Figure 5a). Amphibole2 generation formed after the crystallization of Amp1, and these transitional textures from coarse-grained Amp1 to medium-grained prismatic up to needle-like Amp2 aggregates may suggest accelerated cooling following the gabbroic melt intrusion into and onto cooler peridotite.
Amphibole3 and Amp4 are relatively rare, occurring either as individual grains or in the form of zonal grains. They have hypidiomorphic to idiomorphic habitus and grow into Amp1 and Am2 aggregates (Figure 4c–e) in a dolerite (P17C) from the gabbro–dolerite layer. Dark in BSE images Amp3 (Fwnc and Fe-Wnc to Ktp and Fktp) is in the core, whereas pale Amp4 (Gru) is on the rim of the grains in dolerite (Figure 4d,e and Figure 5b).
The generation of Na-(Ti)-rich Amp (Fwnc and Fe-Wnc) with Bt is primary magmatic in plagiogranites (P5B) but as the post-magmatic Amp3–4 in dolerites. The Amp generation of Krs to Fkrs and Phl replaces the Spl of the troctolites (Figure 4f) within the host dunite layers in peridotite. We reported troctolitization of dunite layers in peridotite by percolating basaltic melts, which crystallized Cpx and Pl in the interstitials of Ol and Spl [8]. This situation suggests that basaltic and plagiogranitic melts might have caused the formation of the Amp3 and 4 generations in the gabbro layer and similar Amp types also in the underlying, often Pl-bearing peridotites and dunites. In addition, plagiogranite (Figure 2) with a specific magmatic Amp (Wnc; Figure 5) occurs as an individual body in direct contact with peridotite, outside of the gabbro layer remnants, the latter moreover containing a different magmatic Amp1 (Mhbl or Prg). Such a situation suggests two different melt sources for the gabbro layer and plagiogranite. The Amp3, 4 types likely formed by an interaction of hydrous melt with peridotite, dunite, troctolite, and gabbro (e.g., [35]). The water-poor ‘dry’ melt percolation can be related to the Cpx-Pl gabbro dyke formation, most likely in a subridge setting, whereas the ‘hydrated’ melt percolation produced the Cpx-Pl-Amp gabbro–dolerite dykes and plagiogranites. The latter dyke group may have been influenced by the formation of arc-type melts and fluids, the source of which can be implied from the subduction-related amphibolitic sole (Figure 2a,b).
Amphibole1–4 generations and Cpx in mafic rocks are partly or totally replaced by the low-Al Amp5 generation represented by Tr and Act (Figure 5) and are broadly characteristic of the ocean floor metamorphic alterations (e.g., [36,37]).
Amphibole6 generation (Mhbl to Prg) of metamorphic origin occurs in amphibolites from the ophiolitic thrust sheet hanging walls detected in surface outcrops (P12A) or in borehole core samples (P10F; Figure 2 and Figure 5). The sheared domains contain relics of porphyroclastic Mhbl and Prg within dynamically recrystallized Mhbl and Prg aggregates and the newly formed Tr–Act–Ep–Zo–Czo–Chl–Phg–Ab aggregates. This Amp-type occurs in amphibolitized eclogites of the metamorphic sole in the neighboring Krivaja-Konjuh ophiolite massif [21].
Amphibole (Mhbl) was exceptionally found in a harzburgite sample (P21), where it occurs in parallel-oriented Cpx-Amp exsolution lamellae within the Opx porphyroclasts (Figure 4g and Figure 5). This Cpx and Amp suggest the partial breakdown of Opx into the exsolution phases (e.g., [38,39]).
The Amp-rich gabbro layer, plagiogranite intrusion, gabbro–dolerite and basaltic dykes, and Amp-poor ultramafic rocks (Pl harzburgites, dunites, and troctolites) may have been influenced by arc-type magmas, as proposed in many publications (e.g., [4,5,6,7]). Moreover, transitions from a mid-ocean ridge (MOR) to a supra-subduction zone (SSZ) or back-arc basin (BAB)-type ophiolites are characteristic in the Jurassic Neotethys of the western Vardar ophiolite belt (e.g., [40] and references therein).

5.2. Relationship of Chemical Composition and Micro-Raman Spectroscopy Data

All the studied amphiboles show typical Raman spectra of the amphibole group minerals (e.g., [41,42,43]) and have been compared against the RRUF database [44]. The samples share a distinct band at around 150 cm−1, related to MO6 mode (Figure 6a–h) [41,45], representing the presence of CMg in the structure [43]. The most distinctly visible band is on the Krs spectra (Figure 6h), where the CMg content reaches up to 3.2 apfu (Table 4). Enhancement of Raman scattering near 530 cm−1 to 570 cm−1 (Fe3+–O vibration mode) detects the presence of CFe3+. This is most prominent regarding Fe-Wnc (Figure 6a,g) and Krs samples (Figure 6h) but also visible on Fktp (Figure 6d) and Ti-Sdg (Figure 6f). On the other hand, this band is subtle on Gru (Figure 6e) and Mhbl (Figure 6b) spectra, where we have no CFe3+ present (Table 4). All the amphibole spectra (Figure 6a–g) show the strongest peak at 670 cm−1, related to the TO4 ring-breathing mode (and the presence of TAl in amphiboles [43]. Ferri-katophorite (Figure 6d) and Krs (Figure 6h) also show a small peak at 680 cm−1. This has been previously assigned as TAl–O–Si vibrations as related to TAl [46]. However, the authors in [43] assign this band to an amount of CAl. The peak is not very distinct in our samples, probably because the amount of CAl does not reach the >0.7 apfu (Table 4) described by the authors. A peak at 750 cm−1 to 800 cm−1 related to TiO6 stretching mode [46] appears on the Raman spectra of Ti-Sdg (Figure 6f) and Krs (Figure 6h), which should indicate the presence of more than 0.3 apfu of CTi (Table 4), as described by [43]. Other amphiboles from our study contain mostly negligible values of CTi (Table 4), and the peak is not visible on any other spectra. A Raman peak at around 1040 cm−1 arising from the TO4 stretching indicating CFe2+ in the structure [43] of amphiboles is clearly visible on the Raman spectra of all the samples except Krs (Figure 6a–h), with no Fe2+ in the octahedral position (Table 4).
Almost all the spectra show an OH- stretching band at 3660 cm−1 except Gru and Fe-Wnc (sample P17C; Figure 6e,g), which exhibit a non-distinct shift to 3640 cm−1. This may be due to a crystal orientation of Amp grains or caused by compositional changes at M1 and M3 sites of Amp due to a relative amount of Mg/Fe2+ [43] since both Gru and Fe-Wnc contain a higher amount of Fe2+ (>2.5 apfu; Table 4).

5.3. Amphibole Geothermobarometry Estimates

The Amp geothermobarometry constrains the variable P–T conditions of the Amp types and generations. Moreover, the compositional differences, especially significantly varying Ti and Al content, in one Amp generation influenced the estimated temperature and pressure intervals (Table 5 and Table S1).
Magmatic Amp1 to Amp2 generations provided average crystallization temperatures of 863 and 747 °C, respectively, in the gabbros and dolerites of the gabbro layer at relatively lower average pressures of 0.23–0.17 GPa, implying an oceanic lower crust level of about 5–7 km. However, single-Cpx thermobarometry [47] from gabbro–dolerite (P17C) and dolerite dyke (P9) constrained an earlier magmatic crystallization of Cpx at 1150 and 1100 °C and 0.37–0.18 GPa at the estimated depth of 13–5 km [8].
An exceptional Amp type with increased Al and Ti contents (Sdg to Ti-Sdg) was determined from a dolerite (P17C) of the gabbro–dolerite layer. This Amp provided the highest temperature (1022 °C) and pressure (0.95 GPa) of crystallization. However, these grains are rare and tiny (around 20μm) inclusions in Amp1 (Figure 4e), and their origin is not clear (brought about as xenocrysts by basaltic melts from a hydrous source at a depth of ca. 30 km to the gabbro layer?).
Amphibole3 and Amp4, such as Fwnc, Fe-Wnc, Ktp, Fktp, Gru, Krs, or Fkrs, were compositionally not suitable for the available geothermobarometers. Their special chemical composition may indicate a different melt/fluid source compared to common gabbro–dolerites, which we connect with the compositionally variable percolating melts and fluids through the peridotite and the gabbro–dolerite layers (see Section 5.1).
Amphibole (Mhbl to Prg) in ultramafic rocks (harzburgite, dunite, and troctolite) provided a temperature interval of 1000–780 °C at 0.79–0.30 GPa (Table S1). These estimates are lower than those provided for Cpx from troctolite (P18A) by single-Cpx thermobarometry [47] at 1200–1100 °C at 0.45–0.15 GPa [8]. However, the Cpx from the exsolution lamellae in Opx1 from harzburgite P21 provided temperatures of 950–850 °C at maximum 1 GPa [8], which is comparable with the temperatures of 1000–815 °C at 0.60–0.30 GPa obtained from Amp geothermobarometry from this sample (Table S1). These results suggest that the Amp in P21 harzburgite indicates cooling temperatures below 1000 °C at the estimated depths of ca. 20 to 10 km, when the exsolution lamellae of Cpx and Amp have formed within the Opx1 porphyroclasts (e.g., [38,39]). The more variable and decreasing pressures imply an extension and exhumation of the mantle section of the OOC to shallower lithospheric levels, where these rocks were crosscut by numerous gabbroic–doleritic dykes. This process also explains the hydrated percolating melts/fluids as a potential source of special Na–Ti-rich Amp3 and 4 in the gabbro layer gabbros and dolerites, but a similar type of Amp also in the underlying mantle rocks, such as troctolites (~Cpx-Pl-enriched dunites) and Pl bearing peridotites [8].
The lowest temperatures of ca. 400–300 °C and pressures 0.04–0.01 GPa were estimated from the latest Amp5 generation, which replaces the Amp1 to Amp4 in a dolerite. Such conditions are consistent with the ocean-floor-type metamorphic alterations. Other authors [36] suggested 200–300 °C at maximum 0.05 GPa for gabbro rodingitization by fluids related to serpentinization of host peridotites at the ocean floor.
The higher medium-temperature and medium-pressure conditions were constrained from the metamorphic Amp of sole amphibolites. The estimates from a borehole sample (P10F) of 723–664 °C and 0.46–0.45 GPa are slightly different from 620–600 °C and 0.85–0.6 GPa estimated from a surface outcrop of amphibolites by Ti-in-Amp thermometry and Amp–Pl thermobarometry by [8], which are related to the different exhumation depths. Eclogite and amphibolite facies conditions were estimated from the metamorphic sole of the neighboring Krivaja-Konjuh Massif by [21].

6. Conclusions

  • The complex geological setting of the Ozren ophiolite complex is also confirmed by the compositionally diverse amphiboles. Here, we determined members of the monoclinic magnesium–iron–manganese amphiboles (Gru), calcium amphiboles (Mhbl, Prg, Hst, Sdg to Ti-Sdg, and Tr), sodium–calcium amphiboles (Fe-Wnc to Fwnc Ktp to Fktp), and oxo amphiboles (Krs and Fkrs).
  • The chemical composition of the studied amphiboles provided a very good correlation with the analyzed Raman spectra.
  • Electron probe micro-analysis (EPMA), micro-Raman study, and Amp geothermobarometry constrained the genetically different Amp groups and types (Table 3) in the investigated oceanic crust and mantle rocks:
Primary magmatic Amp1 (Mhbl to Prg, rarely Hst) is present in almost all the gabbroic rocks and dolerites. Tiny inclusions of Sdg or Ti-Sdg grains in Amp1 may suggest a deeper and hotter hydrated source during the formation of the gabbro–dolerite layer.
Na-(Ti)-rich Amp (Fwnc and Fe-Wnc) occurs as the primary magmatic Amp in plagiogranites.
Late magmatic prismatic and needle-like Amp2 (Mhbl) in gabbros and dolerites followed the crystallization of coarse-grained Amp1 due to cooling of emplaced gabbroic melts in the lower oceanic crust.
Amphibole3 (Fwnc, Fe-Wnc to Ktp, and Fktp) and Amp4 (Gru) in a dolerite of the gabbro–dolerite layer are most likely linked to percolating melts/fluids accompanying the emplacement of gabbroic–doleritic dykes in peridotites, dunites, and the gabbro layer.
Similarly, Ti-rich Amp (Krs to Fkrs) associated with Phl in troctolites may indicate ‘hydrated’ melt percolation produced by Cpx-Pl-Amp gabbro–dolerite dykes and plagiogranitic intrusions in the lower oceanic crust and the underlying mantle rocks.
Low-Al Amp5 generation (Tr and Act) partly or totally replaces Amphibole1–4 and Cpx in mafic rocks, suggesting ocean-floor-type alterations.
Metamorphic Amphibole6 (Mhbl to Prg) occurs in subduction-related sole amphibolites.
4.
‘Dry’ percolating melts are most likely generated in an extensional subridge setting, while ‘hydrated’ Amp-bearing rocks may have been influenced by arc-type magmas and fluids, implying a change from the mid-ocean ridge (MOR) to a supra-subduction zone (SSZ) setting of the Ozren ophiolite complex.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/min14030239/s1, Table S1: EPMA analyses of amphiboles used for the Amp geothermobarometry and additional Amp types.

Author Contributions

Conceptualization, S.U. and M.P.; methodology, S.U., O.N. and S.M.; software, O.N., S.M. and S.K.; validation, M.P.; formal analysis, S.U., O.N., S.M. and M.P.; investigation, S.U., E.B., M.P. and P.R.; resources, M.P., E.B., P.R., S.K. and S.M.; data curation, S.U. and O.N.; writing—original draft preparation, S.U., O.N. and M.P.; writing—review and editing, M.P. and E.B.; visualization, S.U., O.N. and S.M.; supervision, M.P. and E.B.; project administration, M.P.; funding acquisition, M.P. and S.U. All authors have read and agreed to the published version of the manuscript.

Funding

Funding from the Slovak Research and Development Agency projects (APVV-19-0065 and APVV-22-0092), VEGA agency (1/0028/24), and Comenius University grant (UK/37/2022) is greatly appreciated.

Data Availability Statement

The data presented in this study are available in Supplementary Material here.

Acknowledgments

Review reports of the three referees who contributed to the original manuscript improvement are greatly acknowledged. We appreciate very much the language correction of the submitted manuscript.

Conflicts of Interest

The authors declare no conflicts of interest.

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Minerals 14 00239 g001
Figure 1. Ozren Massif (4) in Central Dinaridic Ophiolite Belt ([8]; map modified after [10,11]).
Figure 1. Ozren Massif (4) in Central Dinaridic Ophiolite Belt ([8]; map modified after [10,11]).
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Figure 2. Ozren ophiolite complex and mélange. (a) geological map compiled from the basic geological map of the former SFR Yugoslavia 1:100,000, and new data from the investigation with sample numbers (map modified after [8,25,26,27]; (b) a schematic cross-section (not to scale).
Figure 2. Ozren ophiolite complex and mélange. (a) geological map compiled from the basic geological map of the former SFR Yugoslavia 1:100,000, and new data from the investigation with sample numbers (map modified after [8,25,26,27]; (b) a schematic cross-section (not to scale).
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Figure 3. PL microscopic images of Amp: (a) Cpx-Pl-Amp-Ilm gabbro (P10C) with blue–green rim of Amp-Chl aggregates; (b,c) Cpx-Pl-Amp dolerite (P17C) with secondary aggregates of Chl, Amp, Czo, and Ab; (d) plagiogranite (P5B) texture composed of Qz, Pl/Ab, Bt, and needle-like Amp; (e) harzburgite (P21) contains Opx1 and Cpx1 porphyroclasts with exsolution lamellae accompanied by Amp; (f) sole amphibolite (P12A) texture with Amp-Pl preferred orientation. Pictures (a,c) at II P; (b,d–f) at X P.
Figure 3. PL microscopic images of Amp: (a) Cpx-Pl-Amp-Ilm gabbro (P10C) with blue–green rim of Amp-Chl aggregates; (b,c) Cpx-Pl-Amp dolerite (P17C) with secondary aggregates of Chl, Amp, Czo, and Ab; (d) plagiogranite (P5B) texture composed of Qz, Pl/Ab, Bt, and needle-like Amp; (e) harzburgite (P21) contains Opx1 and Cpx1 porphyroclasts with exsolution lamellae accompanied by Amp; (f) sole amphibolite (P12A) texture with Amp-Pl preferred orientation. Pictures (a,c) at II P; (b,d–f) at X P.
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Figure 4. Backscattered electron images of analyzed samples from gabbro layer (a–e), troctolite (f), harzburgite (g), and amphibolite (h): (a) plagiogranite (P5B) with needle-like Amp1 (Fe-Wnc) aggregates in Qz; (b) Cpx-Pl-Amp-Ilm gabbro (P13B1) with magmatic Amp1,2 (Mhbl) and newly formed aggregates of Amp5 (Tr and Act) and Chl; (c–e) Cpx-Pl-Amp-Ilm dolerite (P17C) with the primary magmatic Amp1, late magmatic Amp2, and the post-magmatic Amp3–5 types; (f) troctolite (P18A) shows partial replacement of Spl by Amp (Mhbl and Krs), Phl, Ab, and Str in Ab; (g) harzburgite (P21) Opx with Cpx and Amp-Mhbl exsolution lamellae; (h) amphibolite (P10F) with Amp (Mhbl and Prg) porphyroclasts (porphyroblasts originally) in sheared matrix of dynamically recrystallized Mhbl and Prg, partly replaced by Tr, Act, Ep, Czo, Phg, Ab, and Chl. The red circles are the places where the samples were analyzed by both EPMA and micro-Raman spectroscopy.
Figure 4. Backscattered electron images of analyzed samples from gabbro layer (a–e), troctolite (f), harzburgite (g), and amphibolite (h): (a) plagiogranite (P5B) with needle-like Amp1 (Fe-Wnc) aggregates in Qz; (b) Cpx-Pl-Amp-Ilm gabbro (P13B1) with magmatic Amp1,2 (Mhbl) and newly formed aggregates of Amp5 (Tr and Act) and Chl; (c–e) Cpx-Pl-Amp-Ilm dolerite (P17C) with the primary magmatic Amp1, late magmatic Amp2, and the post-magmatic Amp3–5 types; (f) troctolite (P18A) shows partial replacement of Spl by Amp (Mhbl and Krs), Phl, Ab, and Str in Ab; (g) harzburgite (P21) Opx with Cpx and Amp-Mhbl exsolution lamellae; (h) amphibolite (P10F) with Amp (Mhbl and Prg) porphyroclasts (porphyroblasts originally) in sheared matrix of dynamically recrystallized Mhbl and Prg, partly replaced by Tr, Act, Ep, Czo, Phg, Ab, and Chl. The red circles are the places where the samples were analyzed by both EPMA and micro-Raman spectroscopy.
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Figure 5. Amphibole chemistry in rocks from the Ozren ophiolite complex: (a–c) classification of [30]; (d) classification of [29]. Amphibole1 with thick frame in (a) is Hst. The rock types and their GPS coordinates are in Table 1.
Figure 5. Amphibole chemistry in rocks from the Ozren ophiolite complex: (a–c) classification of [30]; (d) classification of [29]. Amphibole1 with thick frame in (a) is Hst. The rock types and their GPS coordinates are in Table 1.
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Figure 6. Micro-Raman spectra of analyzed samples from gabbro layer (a–g) and troctolite (h) in dunite: (a) Raman spectra of Amp (Fe-Wnc) in plagiogranite (P5B); (b) Raman spectra of Amp2 (Mhbl) in Cpx-Pl-Amp-Ilm gabbro (P13B1); (c) Raman spectra of Amp2 (Mhbl) in Cpx-Pl-Amp-Ilm dolerite (P17C); (d) Raman spectra of Amp3 (Fktp) in Cpx-Pl-Amp-Ilm dolerite (P17C); (e) Raman spectra of Amp4 (Gru) in Cpx-Pl-Amp-Ilm dolerite (P17C); (f) Raman spectra of Ti-Sdg inclusion in Amp1 from Cpx-Pl-Amp-Ilm dolerite (P17C); (g) Raman spectra of Amp3 (Fe-Wnc) in Cpx-Pl-Amp-Ilm dolerite (P17C); (h) Raman spectra of Amp (Krs) in troctolite (P18A). The place of measurements is shown by the red circle in Figure 4a–f. Amphibole types according to Table 2, Table 3 and Table 4. All the spectra were used in their raw form, not corrected to baseline.
Figure 6. Micro-Raman spectra of analyzed samples from gabbro layer (a–g) and troctolite (h) in dunite: (a) Raman spectra of Amp (Fe-Wnc) in plagiogranite (P5B); (b) Raman spectra of Amp2 (Mhbl) in Cpx-Pl-Amp-Ilm gabbro (P13B1); (c) Raman spectra of Amp2 (Mhbl) in Cpx-Pl-Amp-Ilm dolerite (P17C); (d) Raman spectra of Amp3 (Fktp) in Cpx-Pl-Amp-Ilm dolerite (P17C); (e) Raman spectra of Amp4 (Gru) in Cpx-Pl-Amp-Ilm dolerite (P17C); (f) Raman spectra of Ti-Sdg inclusion in Amp1 from Cpx-Pl-Amp-Ilm dolerite (P17C); (g) Raman spectra of Amp3 (Fe-Wnc) in Cpx-Pl-Amp-Ilm dolerite (P17C); (h) Raman spectra of Amp (Krs) in troctolite (P18A). The place of measurements is shown by the red circle in Figure 4a–f. Amphibole types according to Table 2, Table 3 and Table 4. All the spectra were used in their raw form, not corrected to baseline.
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Table 1. GPS coordinates of investigated samples with amphiboles in Figure 2.
Table 1. GPS coordinates of investigated samples with amphiboles in Figure 2.
SamplesGPS Coordinates
P5B PlagiograniteN 44°39′1.80″, E 18°12′25.32″
P9 DoleriteN 44°39′43.82″, E 18°15′7.98″
P10A GabbroN 44°40′36.61″, E 18°17′40.59″
P10C GabbroN 44°40′36.61″, E 18°17′40.59″
P10D BasaltN 44°40′36.61″, E 18°17′40.59″
P10F AmphiboliteN 44°40′36.61″, E 18°17′40.59″
P12A AmphiboliteN 44°39′44.33″, E 18°17′25.70″
P13B1 GabbroN 44°30′40.86″, E 18°11′29.58″
P13B2 LeucogabbroN 44°30′40.86″, E 18°11′29.58″
P16 DoleriteN 44°34′15.72″, E 18°9′18.84″
P17B, C DoleriteN 44°37′8.26″, E 18°8′11.46″
P18A TroctoliteN 44°36′52.06″, E 18°7′4.42″
P18D DuniteN 44°36′52.06″, E 18°7′4.42″
P21 HarzburgiteN 44°37′42.00″, E 18°13′58.86″
Table 2. Mineral chemistry of amphiboles in the Ozren ophiolite complex from [8]. Amphibole 1 to 5 types were determined in the gabbro layer mafic rocks (gabbros and dolerites) and basalts, while Amp6 from the sole amphibolites. The other Amp types were detected in plagiogranite and ultramafic rocks (harzburgite, dunite, and troctolite).
Table 2. Mineral chemistry of amphiboles in the Ozren ophiolite complex from [8]. Amphibole 1 to 5 types were determined in the gabbro layer mafic rocks (gabbros and dolerites) and basalts, while Amp6 from the sole amphibolites. The other Amp types were detected in plagiogranite and ultramafic rocks (harzburgite, dunite, and troctolite).
Oxide (wt.%).SiO2TiO2Al2O3Cr2O3FeOMgOCaONa2O
Harzburgite—P21
Amp-P21 (following Cpx exsol. lamellae in Opx)48.08–48.860.24–0.3410.90–11.841.19–2.222.46–2.8418.51–18.9211.95–12.470.91–1.10
Dunite—P18D
Amp-P18D (from percolating melt/fluids, incl. Phl)42.23–43.963.28–4.8311.10–12.262.32–2.973.61–4.0616.40–17.4410.43–11.684.20–4.91
Troctolite—P18A
Amp-P18A (from percolating melt/fluids, incl. Phl)40.55–46.033.48–5.4711.09–16.941.39–3.391.52–2.9216.77–25.680.11–11.650.75–6.29
Gabbro—P10A-C,13B1,13B2
Amp1 (magmatic)43.04–51.110.10–3.505.31–10.030.00–0.0410.53–22.299.20–16.960.05–11.800.74–2.44
Amp2 (late magmatic)44.91–51.770.07–3.075.02–11.600.00–0.338.52–17.8610.33–17.119.67–11.660.16–2.58
Amp5 (post-magmatic alteration)51.44–55.870.11–0.321.91–3.350.00–0.168.28–19.6611.23–19.5010.53–12.970.23–0.46
Plagiogranite—P5B
Amp1 (magmatic)53.11–57.030.30–1.630.08–0.190.00–0.0315.13–25.696.59–13.574.50–6.663.70–5.95
Dolerite—P9,16,17C
Amp1 (magmatic)41.62–52.240.10–3.854.45–12.860.00–0.4310.74–17.0712.20–15.378.87–11.720.47–3.33
Amp2 (late magmatic)45.25–53.880.09–1.124.86–11.620.00–0.0711.02–17.7011.00–17.209.65–11.340.38–2.24
Amp3-P17C (from percolating melt/fluids)50.86–53.221.33–4.130.83–15.050.0017.90–27.246.08–12.444.26–9.492.98–4.90
Amp4-P17C (from percolating melt/fluids)51.67–53.680.17–1.140.25–1.030.00–0.0228.02–33.948.15–12.320.83–4.970.24–0.73
Amp5 (post-magmatic alteration)51.67–58.930.03–1.560.42–3.660.00–0.064.94–28.046.49–20.944.67–12.660.03–1.02
Basalt—P10D
Amp1-P10D (magmatic)40.18–50.460.11–2.734.84–14.940.00–0.0913.05–16.759.51–15.8311.42–12.231.00–2.71
Table 3. Review of Amp genetic types based on petrography and mineral chemistry criteria.
Table 3. Review of Amp genetic types based on petrography and mineral chemistry criteria.
Amphibole TypeGenesisCriterion 1Criterion 2Criterion 3
Amp1-Mhbl, Prg, Hst in gabbro, dolerite, basaltPrimary magmaticRock-formingCoexisting with Cpx, PlReplaced by Amp5
Amp1-Wnc in plagiogranitePrimary magmaticRock formingCoexisting with Pl, QzRare
Amp2-Mhbl in gabbro, doleriteLate magmaticFollowing Amp1 rimsChemistry like Amp1Replaced by Amp5
Amp3-Wnc, Ktp in gabbro, doleriteFrom percolating melts/fluidsGrowing into Amp1, 2Idiomorphic, hypidiomorphicRare, irregularly distributed
Amp4-Gru in gabbro, doleriteFrom percolating melts/fluidsEnclosing Amp3Outer zone on Am3Rare, irregularly distributed
Amp5-Tr, Act in gabbro, dolerite, basaltPost-magmatic alterationReplacing Amp1–4Associated with Chl, Ab, CzoCommon
Amp6-Mhbl, Prg in sole amphiboliteMetamorphicParallel-oriented aggregateAssociated with PlIn sole amphibolite
Amp-Sdg inclusion in Amp1 in doleriteXenocryst? relictTiny inclusions in Amp1Rare
Amp-Hbl, Prg, Krs in troctoliteFrom percolating melts/fluidsReaction zone with SplAssociated with Phl, Pl and CpxRare
Amp-Hbl in harzburgiteExsolution system in OpxSingle Amp or common Cpx-Amp exsolution lamellae in OpxSingle Amp type in harzburgite Rare
Table 4. Table of representative microprobe analyses of amphiboles measured by both EPMA and micro-Raman spectroscopy. Amphibole types according to Table 2, Table 3 and Table S1.
Table 4. Table of representative microprobe analyses of amphiboles measured by both EPMA and micro-Raman spectroscopy. Amphibole types according to Table 2, Table 3 and Table S1.
Type of AmpFe-WncMhblMhblFktpTi-SdgFe-WncKrsGru
Sample/anP5B/20P13B1/22P17C/1P17C/19P17C/25P17C/36P18A/6P17C/21
Spectrasp13-Amp1sp7-Amp1sp1-Amp2sp16-Amp3sp32-incl. in Amp1sp41-Amp3sp24-Ampsp18-Am4
Analysis (wt.%)
SiO253.4251.5050.0653.1639.0052.9143.2152.73
TiO20.410.170.531.554.131.385.170.17
Al2O30.085.025.551.1815.050.8313.810.25
V2O30.010.000.020.140.040.070.110.01
Cr2O30.010.000.000.000.000.002.110.02
MnO0.130.050.440.270.390.250.000.59
FeO25.6916.7917.7017.9019.9824.082.6933.94
NiO0.000.000.070.000.020.000.060.02
ZnO0.280.050.170.250.150.130.170.37
MgO6.5912.2912.1512.446.499.0816.779.71
CaO5.719.679.875.629.494.5711.580.83
Na2O4.420.161.004.902.984.690.820.09
K2O0.940.010.040.460.050.570.270.00
F0.570.030.061.130.130.490.000.80
Cl0.000.010.070.020.030.060.010.04
Initial Total98.2895.7397.7499.0297.9399.0996.7899.56
Final wt.% values
MnO0.130.050.440.270.390.250.000.59
Mn2O30.000.000.000.000.000.000.000.00
FeO23.3516.7915.1615.6117.8820.800.0033.94
Fe2O32.610.002.832.542.333.642.990.00
H2O+1.702.002.001.511.911.770.911.58
Total100.0497.7199.98100.33100.06101.0398.00100.86
Formula Assignments (apfu)
Si8.1227.6387.3397.7945.9127.8716.2398.039
Al0.0000.3620.6610.2042.0880.1291.7610.000
Ti0.0000.0000.0000.0020.0000.0000.0000.000
ΣT8.1228.0008.0008.0008.0008.0008.0008.039
Ti0.0470.0180.0590.1690.4710.1550.5620.019
Al0.0150.5160.2990.0000.6010.0160.5890.046
V0.0020.0000.0020.0170.0050.0080.0130.001
Cr0.0020.0000.0000.0000.0000.0000.2410.003
Fe3+0.2980.0000.3120.2810.2660.4070.3250.000
Ni0.0000.0000.0080.0000.0030.0030.0070.003
Zn0.0320.0050.0180.0270.0170.0140.0190.041
Mn2+0.0170.0000.0000.0000.0000.0000.0000.000
Fe2+2.9691.7441.6461.7852.1642.3830.0002.672
Mg1.4922.7172.6562.7191.4672.0133.2442.207
ΣC4.8745.0005.0004.9984.9944.9995.0004.992
Mn2+0.0000.0070.0540.0330.0500.0320.0000.076
Fe2+0.0000.3390.2130.1290.1030.2050.0001.655
Mg0.0000.0000.0000.0000.0000.0000.3660.000
Ca0.9301.5361.5510.8831.5410.7281.6340.136
Na1.0700.0450.1820.9550.3061.0350.0000.025
ΣB2.0001.9272.0002.0002.0002.0002.0001.892
Ca0.0000.0000.0000.0000.0000.0000.1570.000
Na0.2330.0000.1030.4370.5700.3160.2300.000
K0.1820.0010.0080.0860.0090.1070.0500.000
ΣA0.4150.0010.1110.5230.5790.4230.4370.000
O (non-W)22.00022.00022.00022.00022.00022.00022.00022.000
OH1.7241.9821.9541.4721.9311.7580.8731.606
F0.2760.0150.0290.5230.0610.2280.0000.384
Cl0.0000.0030.0170.0050.0070.0140.0030.010
O0.0000.0000.0000.0000.0000.0001.1240.000
ΣW2.0002.0002.0002.0001.9992.0002.0002.000
Σ T, C, B, A15.41614.92815.11115.52415.57815.42215.43814.931
Table 5. Table of P–T conditions calculated from the genetically different amphibole groups. Amphibole types according to Table 3 and Table S1.
Table 5. Table of P–T conditions calculated from the genetically different amphibole groups. Amphibole types according to Table 3 and Table S1.
Amphibole TypeMagmatic AmphiboleInclusion in Amp1Amphibole from Ultramafic Rocks and Alteration ZonesMetamorphic Amphibole
Rock TypeGabbro, DoleriteDoleriteHarzburgite, Dunite, TroctoliteDolerite, LeucogabbroMetamorphic Sole Amphibolite
Amphibole gen.Amp1Amp2Amp inclusionAmp in mantle rocksAmp5Amp6
Min/MaxMaxMinMaxMinMaxMinMaxMinMaxMinMaxMin
T (°C)1094732837661102210221000780398301664723
P (GPa)0.520.100.310.080.950.950.790.300.040.010.450.46
Avg. T (°C)8637471022853349694
Avg. P (GPa)0.230.170.950.640.030.46
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Ustalić, S.; Nemec, O.; Milovská, S.; Putiš, M.; Babajić, E.; Kurylo, S.; Ružička, P. Amphibole Group Minerals in the Ozren Massif Ophiolites of Bosnia and Herzegovina as Petrogenetic Indicators. Minerals 2024, 14, 239. https://doi.org/10.3390/min14030239

AMA Style

Ustalić S, Nemec O, Milovská S, Putiš M, Babajić E, Kurylo S, Ružička P. Amphibole Group Minerals in the Ozren Massif Ophiolites of Bosnia and Herzegovina as Petrogenetic Indicators. Minerals. 2024; 14(3):239. https://doi.org/10.3390/min14030239

Chicago/Turabian Style

Ustalić, Samir, Ondrej Nemec, Stanislava Milovská, Marián Putiš, Elvir Babajić, Sergii Kurylo, and Peter Ružička. 2024. "Amphibole Group Minerals in the Ozren Massif Ophiolites of Bosnia and Herzegovina as Petrogenetic Indicators" Minerals 14, no. 3: 239. https://doi.org/10.3390/min14030239

APA Style

Ustalić, S., Nemec, O., Milovská, S., Putiš, M., Babajić, E., Kurylo, S., & Ružička, P. (2024). Amphibole Group Minerals in the Ozren Massif Ophiolites of Bosnia and Herzegovina as Petrogenetic Indicators. Minerals, 14(3), 239. https://doi.org/10.3390/min14030239

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