Next Article in Journal
The Role of Hydrocarbons in the Genesis of Mississippi-Valley-Type (MVT) Zn–Pb Deposits: Insights from In Situ Sulfur Isotopes of Sphalerite from the Southwestern Margin of the Yangtze Block, SW China
Previous Article in Journal
Influence of Steel and Poly Vinyl Alcohol Fibers on the Development of High-Strength Geopolymer Concrete
Previous Article in Special Issue
Sulfur Isotope Characteristics in the Qian-34 Section of the Qianjiang Depression and Its Implications for the Paleoenvironment
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Minerals
Volume 14
Issue 10
10.3390/min14101008
minerals-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Mineralogy and Geochemistry of Listvenite-Hosted Ni–Fe Sulfide Paragenesis—A Case Study from Janjevo and Melenica Listvenite Occurrences (Kosovo)

by
Konrad Kluza
1,
Jaroslav Pršek
1,* and
Sławomir Mederski
2
1
Faculty of Geology, Geophysics, and Environmental Protection, AGH University of Krakow, 30 Mickiewicz Av., 30-059 Kraków, Poland
2
Luossavaara-Kiirunavaara AB (publ.), 98186 Kiruna, Sweden
*
Author to whom correspondence should be addressed.
Minerals 2024, 14(10), 1008; https://doi.org/10.3390/min14101008
Submission received: 26 August 2024 / Revised: 26 September 2024 / Accepted: 28 September 2024 / Published: 5 October 2024
(This article belongs to the Special Issue Sulfide Mineralogy and Geochemistry)
Browse Figures
Versions Notes

Abstract

:
The main goal of this paper is to determine the order of the paragenetic sequence and phase transitions of the Ni–Fe sulfide association hosted in listvenites. Listvenites are hydrothermally altered mafic and ultramafic rocks that are often associated with active tectonic settings, such as transform faults, suture zones, and regional extensional faults, usually in contact with volcanic or carbonate rocks. Listvenitization is displayed by a carbonation process when the original olivine, pyroxene, and serpentine group minerals are altered to Mg–Fe–Ca carbonates (magnesite, calcite, dolomite, and siderite), talc, quartz, and accessory Cr spinel, fuchsite, and Ni–Fe sulfides. The formed rocks are highly reactive; therefore, very often, younger hydrothermal processes are observed, overprinting the mineralogy and geochemistry of the original listvenitization products, including accessory Ni–Fe sulfide paragenesis. The studied samples of listvenites were collected from two locations in Kosovo (Vardar Zone): Janjevo and Melenica. The Ni–Fe sulfide textures and relationships with the surrounding listvenite-hosted minerals were obtained using reflected and transmitted light microscopy, while their chemical composition was determined using an electron microprobe. They form accessory mono-or polymetallic aggregates that usually do not exceed 100 μm in size disseminated in the studied listvenites. Generally, the paragenetic sequence of Ni–Fe sulfides is divided into three stages. The first pre-listvenite magmatic phase is represented by pentlandite and millerite. The second listvenite stage consists of Ni–Co bearing pyrite I (Ni content up to 11.57 wt.% [0.24 apfu], and Co content up to 6.54 wt.% [0.14 apfu]) and differentiated thiospinels (violarite + siegenite ± polydymite). The last, late listvenite stage is represented by younger gersdorffite−ullmannite and base metal mineralization: pyrite + marcasite + sphalerite + galena ± chalcopyrite ± sulfosalts. The findings obtained should help in the interpretation of many disseminated accessory Ni–Fe–Co mineralizations associated with mafic and ultramafic rocks worldwide.

1. Introduction

In recent times, listvenites, which are hydrothermally altered mafic and ultramafic rocks, have been the subject of considerable research because of their potential for subsurface CO2 sequestration by mineral carbonation [1,2,3,4,5,6] and their considerable importance in economic geology [6,7,8,9,10,11,12,13,14,15].
Listvenite is generally a quartz-carbonate rock that is formed during the interaction of peridotite with aqueous CO2-bearing fluids and can sequester more than 30 wt.% of CO2 [1,6,7]. The listvenites are composed of Mg–Fe–Ca carbonates, mainly magnesite (with variable Fe content in the magnesite-siderite solid solution), minor amounts of dolomite (±calcite), and silicate minerals such as quartz, chalcedony, and opal. [1,6,7,16,17,18,19]. Typical evidence for an ultramafic/mafic protolith is the presence of relicts of altered chromian spinels that are sensitive to hydrothermal alterations [20,21]. In addition, crystallization of Cr-bearing muscovite (fuchsite, less often mariposite) is frequently observed in close relation to chromian spinels and along the foliation if the hydrothermal fluids carry potassium [6]. Rocks associated with listvenitization and reaction with CO2-carrying fluids might show zonation associated with the replacement of peridotites/serpentinites: carbonate-bearing serpentinite (ophicarbonate) ⟹ talc-carbonate-rich rock (soapstone) ⟹, carbonate-quartz-rich rock (listvenite) [6,7,19,22,23,24].
The formation of listvenites is geotectonically mainly related to the fore-arc environment, where the presence of CO2-rich fluids is a consequence of meta-sediment devolatilization in subduction zones [6,18,25,26]. Furthermore, the carbonation process of peridotite or serpentinite rocks can be linked to other active tectonic settings, such as transform faults, suture zones, and regional extensional faults [6,17,18,26]. Stable isotope (O, C, S, Sr) investigations into listvenites by various authors [3,11,17,24,27] suggest four main sources for CO2-rich fluids: mantle-derived or magmatic fluids, metamorphic fluids from devolatilization reactions, seawater-derived fluids, and meteoric water.
Generally, listvenites form under a wide range of temperatures (ranging from 80 to 350 °C) and pressures (from 0.3 to 1.4 GPa) [2,11,18,24,27] with optimal carbonation temperatures of 150–250 °C for serpentinite [23]. Experimental studies have shown that listvenites can form under high-pressure conditions in the fore-arc mantle wedge and within a subducted slab when the concentration of CO2 is high [6,28,29].
Moreover, the products of the listvenitization process—rocks mainly composed of Mg–Fe–Ca carbonates and quartz—due to their reactivity and position proximal to major tectonic zones—easily undergo hydrothermal overprints associated with gold veins or base metal mineralization [7,8,15]. In the past, listvenites were the target of exploration of lode-gold deposits [7,8,10,11,12] but can also host Ni ± As ± Sb ± Co mineralization [7,9,13,15,30,31].
In this work, we present research on two listvenite occurrences in Kosovo, where Ni–Fe sulfide paragenesis occurs. In the Vardar Zone of the Balkans, listvenites, which are carbonate-rich rocks capable of recrystallization, are affected by younger processes related to epithermal IS mineralization associated with post-collisional magmatic events [15,32,33]. Listvenite-associated Pb–Zn–Ag deposits are reported here, and nickel mineralization occurs as an accessory in these deposits [9,15,32,33]. Accessory paragenesis of Ni–Fe sulfide associated with lisvenitization is widespread throughout the world, but since it is of no economic interest, it has been neglected by researchers. Only a few papers mention the Ni–Fe sulfide paragenesis occurring in listvenites [10,13,15,30,31,34]. In addition, especially in the Balkan region, it is very often overprinted by younger hydrothermal processes that obliterate the original textures and lead to the formation of transitional paragenesis rich in nickel sulfarsenides−sulfantimonides and base metal sulfides±sulfosalts [9,13,15]. Unlike listvenites worldwide, primary listvenites unaltered by younger epithermal fluids in the Balkans are relatively rare. These localities are associated with the Serbo-Macedonian metallogenic province, in which numerous hydrothermal Pb–Zn–Ag deposits, such as skarns, carbonate replacement, and vein-type deposits, occur and are associated with Oligocene−Miocene post-collisional magmatic events [15,35,36,37]. Janjevo occurrence is an example of carbonate-dominated (dolomite ± magnesite ± talc) listvenite with low-grade base metal mineralization and accessory Ni–Fe sulfides. In contrast, the Melenica occurrence is an example of recrystallized listvenite influenced by IS epithermal fluids, where Ni–Fe sulfide paragenesis is preserved as a relic in the primary silicified parts of the base metal ore related to listvenitization. In this work, we present a detailed mineralogical, geochemical, and textural investigation of these Ni–Fe sulfide paragenesis, its precise paragenetic position, and its relationship with younger base metal sulfide paragenesis present in studied listvenites.

2. Geological Setting

The investigated listvenite occurrences are located in Kosovo, in the hydrothermal field of the Pb–Zn–Ag Stan Terg deposit (Melenica occurrence), as well as in Kizhnica–Hajvalia–Badovc ore field (Janjevo occurrence) (Figure 1). Both localities are situated in the Vardar Zone—extending in the NW-SE direction and in the central part of the Balkan Peninsula. It borders the Dinarides mountains, the Drinsko-Ivanjicki area, and the Pelagonian area to the west, and the Serbo−Macedonian massif to the east. This zone is recognized as a suture zone between the Adriatic plate (Korabi Pelagonial continental unit) and the Eurasian plate (Serbo-Macedonian continental unit) due to the closure of the Mesozoic Vardar Ocean—a part of the Tethys Ocean [38,39]. The Vardar Zone comprises Paleozoic–Triassic metasediments, a Jurassic ophiolite complex (gabbro, ultramafic rocks like peridotites and dunites, which are often serpentinized, with minor sedimentary rocks), a Jurassic−Cretaceous complex (including flysch, carbonate rocks, volcanic, and volcanoclastic rocks), and Oligocene−Miocene volcanic and volcanoclastic rocks (such as andesites, trachytes, latites, and felsic pyroclastic rocks) [36,39,40,41,42]. In addition, because of Oligocene−Miocene volcanism, extensive alteration of older ultramafic and mafic rocks developed, which led to the formation of listvenites [15].
Both studied listvenite occurrences are part of the Trepça Mineral Belt (TMB), which belongs to the Serbian−Macedonian metallogenic province (SMMP) (Figure 1). TMB is the main metallogenic zone in Kosovo, extending over 80 km in the northern part of the country (Figure 1). The polymetallic mineralization in the Trepça Mineral Belt is of Oligocene-Miocene age and is associated with post-collisional calc-alkaline to shoshonitic magmatic events, which were accompanied by extensive hydrothermal activity [40].
The SMMP hosts significant Pb–Zn–Ag skarn and carbonate replacement deposits eq., Stan Terg [37,43,45,46] and Sasa [47]. Moreover, in the eastern part of the SMMP, the Lece−Chalkidiki metallogenic zone occurs, which hosts Tertiary Cu–Au deposits [48,49], such as porphyry deposits Skouries [50], Illovitza [51], Bučim [52,53], Vathi [54,55], and Kiseljak near the Tulare area [49,51], as well as carbonate-replacement deposits - Olympias and Piavitsa [56,57] and Plavica high-sulfidation epithermal deposits [58,59]. However, more widespread are vein-type Pb–Zn–Ag hydrothermal deposits (dominated by intermediate sulfidation IS): Crnac [9,32,33], Kizhnica–Hajvalia–Badovc ore field [15,37,60], Zletovo [61], Tulare [49], Čumavići [62], Srebrenica [63,64]. Vein-type Pb–Zn–Ag deposit/ mineral occurrences in TMB are often associated with surrounding listvenites. These altered rocks are observed, for example, in the Badovc area [13,15], Crnac [9,32,33], Selac [13,65], and Melenica, Mazhiq, and Vllahia localities [13,21].
Janjevo listvenite occurrence is located in the central part of the Kizhnica–Hajvalia–Badovc (KHB) ore field. This region was studied by [60], who described metallogenic zonation, which could be associated with an underlying concealed porphyry system (Figure 2a). Three main metal zones are observed in the KHB ore field: the Bi–Cu ± Au zone in the east, the Pb–Zn–Sb ± Ni zone in the west, while in the south, the distal Sb–As–Tl–Hg zone is observed [60] (Figure 2a). The first Bi–Cu ± Au zone exhibits occurrences of epithermal Cu–Bi veinlets in the Kizhnica andesite quarry [66], Bi–Au–Cu–Te mineralization hosted by hornfels in Kizhnica [66], and contact-metasomatic Cu–Bi–Ag ± W mineralization in Janjevo in close proximity to the studied listvenite occurrence [67,68] (Figure 2a). The most significant central Pb–Zn–Sb ± Ni zone hosts various Pb–Zn–Ag occurrences and deposits, including IS epithermal vein-type, carbonate replacement, and dissemination in hydrothermally altered ultramafic and mafic rocks—listvenites [13,15,37,69,70,71]. In addition, sediment-hosted and vein-type As–Sb–Tl–Pb ± Hg ± Au mineralization has been documented in the southern-distal Sb–As–Tl–Hg zone [72,73,74]. Listvenites of the Janjevo area occur in the SE prolongation of ultramafic rocks that host epithermal listvenite-associated Badovc Pb–Zn–Sb–Ni deposits [15]. In Janjevo, zonation depending on the distance from the tectonic zones is observed, with gabbro, serpentinized peridotites, and listvenites surrounded by a flysch series (Figure 2b).
Melenica listvenite can be found near the famous Pb–Zn–Ag Stan Terg skarn and carbonate-replacement deposits [37,43,45]. There are numerous vein-type Pb–Zn−Ag hydrothermal occurrences in the area, such as Melenica, Mazhiq, Vllahia, and Selac localities [13,21,65,75]. A considerable number of these locations are associated with listvenite occurrences [13], usually near tectonic zones, and IS epithermal fluids. In addition, some of these are associated with Ni ± As ± Sb ± Co and Bi ± Au mineral paragenesis [13,75]. Listvenites in Melenica occur along the edge of the tectonic zone at the contact of Jurassic diabase with Miocene volcanic rocks in close proximity to serpentinites (Figure 3). Mineral paragenesis shows typical IS epithermal mineralization, which leads to recrystallization of primary listvenites.

3. Investigated Materials

The subject of the study was two occurrences of listvenites with accessory Ni–Fe sulfides in Kosovo (Table 1). Despite the presence of these sulfides, the two locations are characterized by a different geological and mineralogical context.
The study area in Janjevo is not large (around 350 m profile) and is characterized by lithologically related to those zones that controlled the process in both the northern and southern parts at the contact with the flysch rocks (Figure 2b). The central parts composed of serpentinites are not significantly hydrothermally altered; only small dolomite veinlets are observed. Listvenites show mineralogical variability. In proximity to tectonic zones (JCR_1, JCR_8, and JCR_9), they are dominated by dolomite and quartz, while in proximity to serpentinites (JCR_6 and JCR_7), they show a transitional character with a higher contribution of talc and magnesite (Figure 4a). Listvenites usually have a massive texture (Figure 4b–d), while in the proximity of tectonic zones, they show foliation and the presence of small dolomite veinlets along it (Figure 4b,c). In addition, these rocks rarely show macroscopically visible ore mineralization; only tiny dispersed Fe–Ni sulfide crystals are observed. The outcrops in the creek and below the small waterfall are fresher, while the listvenite outcrops along the road show a significant contribution from weathering and the presence of numerous Fe hydroxides replacing the original Mg–Ca–Fe carbonates (JCR_6) (Figure 4e). This reveals the characteristic listvenite mesh texture on a larger scale, where irregular greenish silicified fragments of listvenites (stained by fuchsite) are surrounded by rusty weathered carbonate fragments (Figure 4e).
The presence of listvenites in Melenica is significantly more limited and is associated with a tectonic zone on the contact of diabase with volcanic rocks (Figure 3), and rarely with Miocene sediments. The tectonic zone with listvenites and gossans is visible at a length of more than a few hundred meters, and it is thick up to 20 m, but listvenites are restricted to a small area with an outcrop approximately 20 m × 50 m close to the valley, and it is surrounded by an old prospecting gallery (Figure 4f). However, in a broad area, it is possible to find outcrops of Jurassic serpentinites. Listvenites are characterized by strong alterations and an intermediate-sulfidation epithermal overprint of early listvenites. Listvenites are strongly silicified with characteristic greenish colors associated with fuchsite, while the carbonate parts, originally composed of listvenitization-associated carbonates (dolomite-magnesite), are replaced by epithermal rhodochrosite-siderite paragenesis. In addition, the epithermal overprint is manifested by IS paragenesis in the form of yellowish sphalerite (with low Fe concentrations), galena, pyrite, chalcopyrite, and baryte. Generally, epithermal mineralization in Melenica forms thin veinlets up to a few centimeters in size or disseminated sulfides in silicified rocks.

4. Methods

Samples of listvenites were studied macroscopically, and 33 thin sections (25 from Janjevo and 10 from Melenica) were prepared for mineralogical and petrological studies. Transmitted and reflected-light microscopy was used to determine textural relationships, mineral generation, and the paragenetic sequence. Studies were conducted using a Nikon 50iPol microscope with an attached Nikon DS-Ri1 camera at the Faculty of Geology Geophysics and Environmental Protection of the AGH University of Krakow (Poland).
The quantitative element composition of early listvenitization paragenesis (Ni–Fe sulfides, sulfarsenides, and sulfantimonides) was carried out on 17 thin sections (9 from Janjevo and 8 from Melenica) by JEOL Super Probe 8230 (JEOL Ltd.,Tokyo, Japan) in the Laboratory of Critical Elements at the Faculty of Geology, Geophysics, and Environmental Protection, AGH University of Krakow (Poland). The following operating conditions were used: accelerating voltage of 20 kV, beam current of 20 nA, and beam diameter of up to 5 μm. The following standards and X-ray lines (DL detection limit, in wt.%) were used for analyses of Ni–Fe sulfides, Ni–Fe–Co thiospinels, sulfarsenides and sulfantimonides: Ni (NiK α DL 0.03), Co (CoK α DL 0.03), chalcopyrite (CuKα DL 0.02), pyrite (FeKα DL 0.03, SKα DL 0.01), stibnite (SbLα DL 0.02), arsenopyrite (AsLα DL 0.14), bismuthinite (BiMα DL 0.03), Sb2Te3 (TeLα DL 0.04), Sb2Se3 (SeLα DL 0.08), and galena (PbMα DL 0.03).

5. Results

The main feature of the studied listvenites from Janjevo and Melenica is the characteristic mesh texture, which suggests the progression of the listvenitization process along the foliation in the serpentinites (Figure 5a,b). This led to the formation of mesh-like aggregates composed mainly of coarse-grained carbonates, which are sinusoidally overlain by fine crystalline carbonates and quartz ± chalcedony (Figure 5a and Figure 6a). Younger infillings form a homogeneous fine crystalline mass, which is sometimes intergrown along foliation by fuchsite, clay minerals, or chlorite. Because of their reactivity, these rocks are subject to recrystallization and intersection by younger hydrothermal veinlets and rarely breccias. In addition, chromian spinels—relics of the pre-listvenization process occur in the form of disseminated irregular aggregates (Figure 5a–c and Figure 6b–d). Interestingly, Ni–Fe sulfide paragenesis, or relics of it, are preserved in the products of early listvenitization—carbonates (dolomite ± magnesite) or silicified zones (Figure 5c and Figure 6a–d,f).
In Janjevo, Ni–Fe sulfide paragenesis forms irregular mono- or polymineral aggregates up to 100 μm in size, scattered in the listvenite matrix, and mostly in dolomites (Figure 6a–d). It consists mainly of pyrite I, pentlandite, millerite, and thiospinels (violarite and siegenite) (Figure 6c). During the late listvenitization phase, gersdorffite−ullmannite crystallization developed. Base metal mineralization in the form of pyrite II, galena, and sphalerite is very rare. Listvenites from Janjevo are composed mainly of dolomite with a smaller amount of quartz (Figure 6a–d), while magnesite and talc occur only in the vicinity of serpentinite. In general, these rocks represent the products of early listvenitization, with a minor influence of later hydrothermal processes.
An opposite example is the listvenites from Melenica, where the dominant products are IS epithermal processes that lead to the formation of rhodochrosite-siderite together with base metal sulfides (Figure 6e,f). This led to the recrystallization of the currently unobservable products of early listvenitization (probably dolomite + magnesite) into Mn–Fe carbonates. Despite this influence, mesh textures are still visible in some places in the ore (Figure 6e). In this case, Ni–Fe sulfide paragenesis was preserved mainly in strongly silicified aggregates, which were more isolated from epithermal fluids (Figure 6f). They form polymineral aggregates up to 200 μm in size, composed mainly of pyrite I, millerite, and thiospinels (violarite, siegenite, and polydymite). In addition, they are overgrown by transitional gersdorffite−ullmannite and ubiquitous base metal sulfides (pyrite II, marcasite, sphalerite, galena, and chalcopyrite) and sulfosalts (tetrahedrite-(Zn), bournonite, and robinsonite) (Figure 6f).

5.1. Janjevo Listvenite

The investigated listvenite paragenesis in Janjevo is represented by pentlandite, millerite, pyrite, Ni–Fe–Co thiospinels, and gersdorffite−ullmannite.
Pentlandite is observed only in the samples from the northern outcrop JCR_1 (Figure 2; Table 1). It forms crystals up to 100 μm, which are mostly cracked but also usually well-polished compared to the surrounding pyrite I (Figure 7a–c). It is widely distributed in samples from this location, both as tiny, scattered crystals (Figure 7a,b,e) and as an accumulation growing mainly on pyrite I (Figure 7a–f and Figure 8). In addition, because of the younger processes, pentlandite is replaced by violarite (Figure 7a,b,d,e), while residual pentlandite is often observed in its aggregates (Figure 7e). The chemical composition of pentlandite is uniform, Ni-dominant with traces of Co (up to 0.19 wt.%, 0.03 apfu). The empirical formula for pentlandite (calculated on the sum of 9 cations), based on 30 analyses, can be expressed as (Ni5.47–5.67Fe3.30–3.50Co0.01–0.03Cu0.00–0.01)Ʃ=9.00S7.97–8.23Se0.00–0.02 (Supplementary Materials).
Millerite is observed in almost every studied outcrop except for the northernmost JCR_1, while at JCR_8, only a few millerite remnants are observed (Table 1). It forms crystals of up to a few hundred micrometers in size. The largest is observed in JCR_07, where it occurs as elongated crystals or monomineral rosettes (Figure 9a,b). More often, millerite forms multimineral aggregates associated with the replacement textures of thiospinels, pyrite I, and galena (Figure 9c–h). It is often replaced by younger thiospinels (mostly siegenite), which usually create irregular replacement textures (Figure 9e); less often are regular, checkboard textures (Figure 9c,d). The chemical composition of millerite from all listvenite-types is close to stoichiometric with the formula (calculated on the sum of one cation), based on 18 analyses: (Ni0.94–0.99Fe0.00–0.04Cu0.00–0.02Co0.00–0.01)Σ1.00S0.99–1.04 (Supplementary Materials).
Pyrite is widely distributed in listvenites from Janjevo, and generally, two generations can be distinguished. The first generation, related to listvenitization, is associated with Ni–Fe sulfides and was found in all investigated outcrops. It forms replacement textures after magmatic pre-listvenitization pyrrhotite (Figure 7b). As a replacement, pyrite I forms irregular anhedral crystals or elongated crystals after pyrrhotite up to a few tenths of μm (Figure 7b). Pyrite I usually forms multimineral aggregates with pentlandite or millerite and thiospinels (sometimes with younger galena) (Figure 7a–f, Figure 8, Figure 9f–h and Figure 10). On the other hand, the second generation forms massive veins composed of anhedral to euhedral crystals up to a few centimeters in size, associated with coarse-grained dolomite veinlets (Figure 9i). Less often, it forms smaller euhedral crystals of up to tens of micrometers disseminated in a dolomite matrix. Generally, no other sulfide minerals occur in dolomite−pyrite II veinlets. Early pyrite exhibits a minor concentration of Ni (up to 11.57 wt.% [0.24 apfu], median equals 1.70 wt.% [0.03 apfu]) and Co (up to 3.20 wt.% [0.07 apfu] with median equals 1.49 wt.% [0.03 apfu]) (Figure 11). The empirical formula of early pyrite I calculated on the sum of one cation (based on 43 analyses) can be expressed as (Fe0.76–0.99Ni0.00–0.24Co0.00–0.07Cu0.00–0.01)Σ=1.00S1.95–2.05 (Supplementary Materials). On the other hand, late pyrite II shows no significant concentrations of Ni and Co (median for Ni content equals 0.03 wt.% [0.00 apfu] and for Co content equals 0.05 wt.% [0.00 apfu]) (Figure 11). The formula of pyrite II calculated on the sum of one cation (based on 32 analyses) can be expressed as (Fe0.96–1.00Ni0.00–0.03Co0.00–0.02)Σ=1.00S1.97–2.03 (Supplementary Materials).
Thiospinels are widespread and observed in most of the listvenite occurrences, except for talc-magnesite, which dominated JCR_7. Thiospinels always form replacement textures after pentlandite or millerite (Figure 7a,b,d,e, Figure 8 and Figure 9c–e) and form complex aggregates up to a few hundred micrometers in size with pyrite, pentlandite, millerite, and sometimes with gersdorffite−ullmannite members (Figure 7a,b,d,e, Figure 8, Figure 9c–h and Figure 10). At the JCR_1 location, violarite replaces pentlandite (Figure 7a,b,d,e); at the JCR_8 location, we observe the replacement of millerite by violarite, while the JCR_6 and JCR_9 locations are characterized by the presence of siegenite, which replaced millerite (Figure 9c–e). Sometimes, they are replaced by members of the gersdorffite−ullmannite solid solution (Figure 7d, Figure 8, and Figure 9h). Generally, they exhibit constant Ni content (median is equal 35.34 wt.%) and variable content of Fe (from 6.60 wt.% up to 19.59 wt.%) and Co (from 0.20 wt.% up to 14.84 wt.%). They are grouped into two populations based on 77 analyses, of which 64 are in the violarite classification field and 13 are in the siegenite classification field (Figure 12). Violarite exhibits Fe content from 14.98 wt.% (0.83 apfu) up to 19.59 wt.% (1.06 apfu) and median = 18.06 wt.% (0.98 apfu). Moreover, it shows a minor contribution of Co (up to 4.21 wt.% [0.22 apfu] and median equals 3.52 wt.% [0.18 apfu]) and rarely traces of Cu (up to 1.62 wt.% [0.08 apfu]). Its empirical formula, calculated on the sum of three cations, can be expressed as (Ni1.77–2.07Fe0.83–1.06Co0.01-0.22Cu0.00-0.08)Σ3.00S3.94–4.23 (Supplementary Materials). On the other hand, siegenite exhibits mostly constant Co content (from 10.57 wt.% [0.56 apfu] up to 14.84 wt.% [0.78 apfu], with median equals 12.09 wt.% [0.63 apfu]) and constant Ni content (between 35.07 wt.% and 36.70 wt.% with median = 35.72 wt.%). Furthermore, it is enriched with Fe (between 6.60 wt.% [0.37 apfu] and 9.26 wt.% [0.52 apfu], with median equals 8.61 wt.% [0.47 apfu]), and its empirical formula (calculated on the sum of 3 cations) is (Ni1.85–1.92Co0.56-0.78Fe0.37–0.52Cu0.00-0.01)Σ3.00S4.00–4.18 (Supplementary Materials).
Members of the gersdorffite−ullmannite series occasionally occurred in the studied listvenite samples from Janjevo. They form small, individual grains up to tenths of a micrometer disseminated in the quartz-dolomite listvenite, sometimes in association with early pyrite and violarite (Figure 7d). Moreover, they can be part of the violarite-pyrite I aggregate, where Ni–Fe sulfides are replaced by gersdorffite−ullmannite (Figure 7d,f, Figure 8, Figure 9h and Figure 10). A gersdorffite–ullmannite series was identified by 11 chemical analyses (Figure 13). The empirical chemical formula of the distinguished GUS populations divided by their As/(As + Sb) ratios can be expressed as (Ni0.89–0.94Co0.01–0.07Fe0.02–0.05)∑=1.00(As0.70–0.94Sb0.04–0.29)∑=0.91–1.03S0.97–1.03Se0.01 for gersdorffite (based on nine analyses), and (Ni0.96–0.97Fe0.03–0.04)∑=1.00(Sb0.70–0.73As0.20–0.24)∑=0.82–0.94S0.96–0.97 for ullmannite (based on two analyses) (Supplementary Materials). Gersdorffite exhibits minor concentrations of Co (in the range between 0.94 and 2.31 wt.% [0.01 and 0.07 apfu]) and Fe (from 0.56–1.44 wt.% [0.02–0.05 apfu]) (Figure 14) (Supplementary Materials). On the other hand, ullmannite exhibits low Co concentrations, while gersdorffite has low Fe concentrations (from 0.06 wt.% to 0.09 wt.% [0.00 apfu] and from 0.94 wt.% to 1.18 wt.% [0.03–0.04 apfu], respectively) (Figure 14) (Supplementary Materials). Limited As ⇔ S and Sb ⇔ S substitutions was observed; the (As + Sb)/S ratio of gersdorffite is 0.93–1.02 and in ullmannite is 0.97–0.98 (Supplementary Materials).
Base metal sulfides are rare in the listvenites studied and are represented mainly by sphalerite and galena. Sphalerite forms small separate aggregates of up to a few hundred micrometers disseminated in a dolomite matrix and as tiny veinlets at the contact of dolomite and clay minerals. Galena is more widespread than sphalerite in the studied samples. It forms small individual grains up to a few μm in a dolomite matrix, or it fills the fissures between the pyrite I and violarite aggregates in JCR_8 (Figure 9f–g).

5.2. Melenica Listvenite

The investigated listvenite paragenesis in Melenica is represented by millerite, pyrite, marcasite, Ni–Fe–Co thiospinels, and gersdorffite−ullmannite.
Millerite usually forms complex aggregates of up to hundreds of micrometers with thiospinels, gersdorffite−ullmannite, and base metal sulfides (Figure 15a–e and Figure 16). Less often, it forms elongated crystals of up to 200 μm replaced by thiospinels and gersdorffite−ullmannite (Figure 15a,b). It is close to stoichiometric with the formula (calculated on the sum of one cation), based on 34 analyses: (Ni0.94–0.99Fe0.01–0.04)Σ1.00S0.98–1.03As0.00–0.08 (Supplementary Materials).
Pyrite is the most widely distributed ore mineral in listvenite from Melenica. Generally, two generations can be distinguished, where the first, early listvenite generation (pyrite I) is associated with Ni sulfides like violarite or millerite and is rare (Figure 15c,f and Figure 16). It forms individual small crystals of up to a few tenths of micrometers scattered in the quartz matrix. Moreover, it is part of the intergrowth with Ni sulfides as the older core (Figure 15c,f and Figure 16). The second generation (pyrite II) is widespread in the studied listvenites and forms massive aggregates up to a few centimeters in size, usually intergrown with marcasite (Figure 15h). Moreover, it is commonly replaced by younger sulfides, such as chalcopyrite, galena, and sphalerite. Pyrite I exhibits a rarely minor concentration of Co (up to 6.54 wt.% [0.14 apfu], with median equals to 0.07 wt.% [0.00 apfu]) and Ni (up to 4.63 wt.% [0.09 apfu], with median equals to 0.06 wt.% [0.00 apfu]) (Figure 11). The empirical formula of early pyrite I calculated on the sum of one cation (based on 17 analyses) can be expressed as (Fe0.80–1.00Co0.00–0.14Ni0.00–0.09Cu0.00–0.01)Σ=1.00S1.88–2.08As0.00–0.01 (Supplementary Materials). In contrast, pyrite II shows no significant enrichment in Ni and Co (Figure 11). The formula for this generation of pyrite calculated on the sum of one cation (based on 44 analyses) can be expressed as (Fe0.98–1.00Ni0.00–0.01)Σ=1.00S1.92–2.01As0.00–0.04 (Supplementary Materials). Marcasite, associated with pyrite II, is close to stoichiometric with the formula (calculated on the sum of one cation), based on eight analyses: Fe0.99–1.00S1.95–1.99 (Supplementary Materials).
Thiospinels are dominant ore minerals in the listvenite stage. They usually form complex aggregates with millerite and gersdorffite−ullmannite with visible replacement textures after millerite (Figure 15a,c–f and Figure 16). Less often, they form individual anhedral crystals of up to a few micrometers in size within a rhodochrosite−siderite matrix. The chemical composition of thiospinels in Melenica is more complex than that of the thiospinels investigated in Janjevo (Figure 12). They were grouped into three populations based on 52 analyses, 44 of which fell in the violarite classification field, 5 in the siegenite classification field, and only 3 in the polydymite classification field (Figure 12). Violarite exhibits Fe content from 12.20 wt.% [0.69 apfu] up to 17.94 wt.% [0.98 apfu] and median = 14.73 wt.% [0.81 apfu], and it shows the minor contribution of Co (up to 5.34 wt.% [0.28 apfu] and median equals 1.86 wt.% [0.10 apfu]). Its empirical formula, calculated on the sum of three cations, can be expressed as (Ni1.94–2.21Fe0.69–0.98Co0.02–0.28Cu0.00–0.01)Σ3.00S3.82–4.14As0.00–0.03 (Supplementary Materials). Siegenite shows enrichment in Fe (between 9.08 wt.% [0.47 apfu] and 11.59 wt.% [0.64 apfu], with median equals 9.11 wt.% [0.52 apfu]), and its empirical formula (calculated on the sum of 3 cations) is (Ni1.42–1.68Co0.66–1.11Fe0.47–0.64Cu0.00–0.02)Σ3.00S4.05–4.15 (Supplementary Materials). Moreover, polydymite shows minor concentrations of Fe (up to 11.68 wt.% [0.69 apfu]) and Co (up to 4.70 wt.% [0.24 apfu]). Its empirical formula (calculated on the sum of three cations) is (Ni2.18–2.45Fe0.50–0.69Co0.05–0.24Cu0.00–0.02)Σ3.00S3.90–4.13As0.00–0.29 (Supplementary Materials).
Members of the gersdorffite−ullmannite series commonly occur in the studied listvenite samples from Melenica. These were extensively investigated by Mederski et al. (2021). Gersdorffite−ullmannite forms small individual crystals and aggregates associated with base metal sulfides, up to tenths of a micrometer in the quartz−carbonates matrix (Figure 15a,b,d–g). Usually, they are part of the complex intergrowths together with other Ni minerals and are replaced by base metal sulfides (Figure 15a,b,e–g and Figure 16). On the other hand, small crystals of ullmannite (a few micrometers in size) are part of veinlets connected to base metal mineralization. Gersdorffite–ullmannite was identified by 54 chemical analyses (Figure 13). The empirical chemical formula of the distinguished populations divided by their As/(As + Sb) ratios can be expressed as (Ni0.58–1.00Co0.00–0.37Fe0.00–0.10Cu0.00–0.01)∑=1.00(As0.62–1.09Sb0.00–0.35)∑=0.91–1.10S0.90–1.05 for gersdorffite (based on 47 analyses) and (Ni0.88–0.99Fe0.00–0.06Cu0.00–0.05Co0.00–0.01)∑=1.00(Sb0.53–0.90As0.07–0.42)∑=0.93–1.04S0.90–1.13 for ullmannite (based on seven analyses) (Supplementary Materials). Gersdorffite is sometimes slightly enriched in Co (in the range 0.00 [0.00 apfu]—12.76 wt.% [0.37 apfu], with median equals 0.10 wt.% [0.00 apfu]) and Fe (up to 3.25 wt.% [0.10 apfu], and median equals 0.57 wt.% [0.02 apfu]) (Figure 14) (Supplementary Materials). Moreover, ullmannite exhibits low concentrations of Co (up to 0.04 wt.% [0.01 apfu]) and Fe (up to 1.76 wt.% [0.06 apfu]) (Figure 13) (Supplementary Materials). Limited As ⇔ S and Sb ⇔ S substitution was observed; the (As + Sb)/S ratio of gersdorffite is 0.90–1.21 and in ullmannite is 0.87–1.06 (Supplementary Materials).
Base metal sulfides are widely distributed ore minerals in Melenica. They are mainly represented by sphalerite, galena, and chalcopyrite, with minor bournonite, tetrahedrite-(Zn), and Pb–Sb sulfosalts. Sphalerite is one of the main ore minerals of late-stage base−metal mineralization. It forms aggregates of up to a few millimeters in size in association with galena and chalcopyrite (Figure 15i). Moreover, it could be part of the complex intergrowths with older Ni paragenesis (Figure 15d). Galena is a common mineral in the studied samples. It forms aggregates up to a few millimeters in size, usually with sphalerite and chalcopyrite (Figure 15h,i). This is a common part of the complex sulfide aggregates replaced by Ni minerals (Figure 15a–f and Figure 16). Moreover, in some parts, they are replaced by bournonite and Pb–Sb sulfosalts (Figure 15i). Chalcopyrite is usually a part of aggregates composed of base metal sulfides (Figure 15d). Furthermore, it commonly fills fissures in the pyrite-marcasite aggregates or it replaces them (Figure 15d). In that association, there are minor Pb-Cu-Sb sulfosalts (Figure 15i): tetrahedrite-(Zn), bournonite, and Pb–Sb sulfosalts (semseyite and robinsonite).

6. Discussion

6.1. The Listvenite Paragenetic Sequence

Listvenites show great petrological variability, which reflects the conditions under which they were formed (temperature and pressure), as well as protolith and structural contexts [6]. One of the main factors determining these conditions for the formation of listvenites associated with tectonic zones is the distance from them, and thus the influence of CO2-carrying fluids. Therefore, petrological transformations are observed: peridotites/serpentinites: carbonate-bearing serpentinite (ophicarbonate) ⟹ talc-carbonate-rich rock (soapstone) ⟹ carbonate-quartz-rich rock (listvenite) ⟹ younger hydrothermal overprint [6,7,15,19,22,23,24].
Similar to rock-forming minerals, accessory ore minerals undergo phase transformations that reflect their polyphase origin. The Ni–Fe sulfides found in the studied listvenites worldwide are likely to be of magmatic origin (formed during the crystallization of peridotites), associated with serpentinization, soapstone formation, strictly defined listvenitization, younger hydrothermal activity superimposed on listvenites, and supergene activity.
The paragenesis of Ni–Fe sulfides at Janjevo and Melenica shows many similarities, especially the presence of three main stages, whose clear borders are obscured by younger hydrothermal processes. The products of the first—magmatic stage—occur only as remnants in listvenites or are recrystallized into other minerals (Figure 17). The presence of millerite ± pentlandite ± pyrrhotite is observed as disseminated in the rocks of both localities. Listvenite manifestations of older magmatic processes are also chromian spinels, which are found scattered in the studied rocks. Sulfide mineralization associated with listvenitization is represented by pyrite, as well as Ni–Fe-Co thiospinels: violarite + siegenite ± polydymite (Figure 17). This stage is accompanied by the crystallization of quartz, talc, and Mg–Fe–Ca carbonates (magnesite and dolomite), which in Melenica, except for quartz, are completely recrystallized by younger intermediate-sulfidation epithermal fluids and represented by Mn–Fe carbonates—rhodochrosite and siderite (Figure 17). Both localities exhibit the presence of gersdorffite–ullmannite, which is transitional between typical sulfide nickel listvenite mineralization and a younger base metal hydrothermal overprint. Only basic sulfides, such as pyrite + marcasite, sphalerite, galena, and chalcopyrite, in association with younger dolomite and quartz, are accessorily present in Janjevo. In contrast, in Melenica, this mineralization led to the complete recrystallization of listvenites and the formation of younger Mn–Fe carbonates, barytes, sulfides, and sulfosalts. The present mineral composition of the listvenites studied was also influenced by supergene processes. The detailed relationships between the various Ni–Fe minerals in Janjevo and Melenica are described in the following discussion.
The most complete paragenetic sequence of Ni–Co–Fe sulfides in carbonate listvenite so far in the literature is described by [30] in the example of Muranska Zdychava in Slovakia. These listvenites are composed mainly of magnesite, dolomite, and serpentine group minerals, with less calcite, quartz, talc, and Cr- and Ni-rich micas [30], and are petrologically close to the listvenitization products from Janjevo (Figure 17). In addition, the Ni–Co–Fe sulfide paragenesis from Muranska Zdychava is like the Janjevo one as well. Ferenc et al. [30] described pyrite, pentlandite, millerite, and pyrrhotite in paragenesis with thiospinels—violarite, polydymite, and siegenite, sometimes overgrown by gersdorffite and cobaltite. The interpreted primary phases are pyrrhotite, pyrite I, and pentlandite, which, in addition to pyrite in Janjevo, are also explained as magmatic remnants. Thiospinels, millerite, sulfarsenides, and pyrite II are all understood to be serpentinization products, while the main mass of Ni–Co sulfarsenides, like serpentinization—advanced listvenitization products [30].
Listvenites from the Janjevo occurrence exhibit a primary magmatic and listvenite sulfide association. Moreover, they are not strongly overprinted by younger base metal hydrothermal fluids, which are uncommon in Kosovo’s listvenite occurrences (Melenica, this study, or Badovc [15]). Nonetheless, the study of listvenites from Janjevo brings other difficulties related to the origin of the phase transition (supergene or hypogene), which are caused by surface rock sampling. Samples from outcrop JCR_6 (Figure 2, Table 1) show intensive weathering, manifested by the rusty color of carbonate fragments and the occurrence of hydroxides. This fact is of particular importance in the context of interpreting the thiospinels origin.

6.2. Phase Transitions of Ni–Co–Fe Sulfides in Individual Stages

Pentlandite and millerite are products of the first magmatic stage observed in the Janjevo listvenites. They were formed before the listvenitization and serpentinization processes during the crystallization of peridotite. A characteristic feature is the lack of their co-crystallization, as the JCR_1 outcrop shows evidence of pentlandite, while the other outcrops show the presence of millerite (Table 1). This is typical for many magmatic deposits, where pentlandite and millerite domains are observed [76]. In the JCR_1 exposure, the textures of pentlandite growth around pyrite I are observed, which exhibits an unusual crystal habit more typical of pyrrhotite than of pyrite (Figure 7b). This is explained by the younger age of pyrite I than pentlandite, which replaced primary pyrrhotite, leading to the false impression that pentlandite grew on top of pyrite I (Figure 7b). The late hydrothermal origin of pyrite I is supported by the enrichment of Ni and Co, which can be interpreted as an equilibrium state with pre-existing sulfide phases [76]. Moreover, within the gabbro unit in the studied Janjevo locality, pyrrhotite is observed in association with chalcopyrite (Figure 2). This further suggests the replacement of pyrite after pyrrhotite in the most altered listvenite rocks studied. The replacement mechanism of pyrrhotite with pyrite has been studied by many authors. Taylor et al. [77,78] investigated the formation of iron disulfides via a FeS precursor with hydrogen sulfide at temperatures between 100 °C and 160 °C. Schoonen and Barnes [79] experimentally examined the formation of pyrite (and marcasite) at temperatures up to 300 °C. They concluded that most pyrite (and marcasite) in hydrothermal ores are formed by the conversion of an FeS precursor due to the direct nucleation rate of FeS2 in slightly acidic solutions [79]. Moreover, Qian et al. [80] studied the transformation of pyrrhotite to Fe disulfides by changing the temperature up to 220 °C and vapor-saturated pressures, ΣS(-II) concentrations, pH, availability of oxygen on the reaction progress, and the resulting textures. Pyrite crystals obtained during these experiments were >10 μm in size, randomly oriented, and formed by the direct replacement of pyrrhotite and, simultaneously, by overgrowth [80]. Furthermore, Murowchick [81] reported that the pyrrhotite transformation to pyrite (±marcasite as an intermediate member) results in various textures. Typically, when pyrite directly replaces pyrrhotite, there is no orientational relationship with the original crystals [81].
Pentlandite usually forms from a magmatic sulfide melt [82,83,84]. However, an uncommon hydrothermal origin has also been reported in locations such as the Avebury deposit in Tasmania [85], GT-34 deposit in Brazil [86], and Kambalda deposit in Western Australia [87]. Hydrothermal pentlandite is mostly related to relatively high fluid temperatures—above 480 °C [86,87,88]. These environmental conditions are unrealistic for listvenites in Kosovo, where temperatures are unlikely to exceed 300 °C [13,15]. The pyrrhotite-pentlandite association occurred in sulfide-rich ores hosted by mafic and ultramafic intrusions and typically forms lamellar exsolutions of pentlandite within pyrrhotite, known as “flame” or “brush” textures [84,89,90].
A distribution of Ni minerals similar to that of Janjevo could be that of the MKD5 Ni ore body on Mount Keith in Western Australia, which is subdivided into pentlandite and millerite domains [76]. Hydrothermal alteration of the ultramafic wall rock occurred due to infiltration by H2O-CO2-rich fluids, which used faults and shears as pathways [91]. Petrological indicators suggest that the temperature during this process is below 320 °C [91]. Moreover, the talc-magnesite assemblage is observed in proximity to the faults/shears, while in the distal parts, the alteration process is represented by the lizardite-brucite assemblage with associated hydrotalcite group minerals [76,92]. The pentlandite domain is represented by a pentlandite + pyrrhotite assemblage in the dunite unit, whereas the millerite domain is S-poorer and is dominated by high-Ni pentlandite, millerite, godlevskite, and heazlewoodite without pyrrhotite evidence [76]. This may suggest that different rocks were subjected to serpentinization and listvenitization in Janjevo.
Mederski et al. [15] reported the primary pentlandite-pyrrhotite association in the epithermal listvenite-associated Badovc Pb–Zn–Sb–Ni deposit from Kosovo, but this locality is strongly overprinted by younger epithermal processes and supergene weathering. Aggregates of primary sulfides are up to 100 μm in size and are overgrown by younger sulfides [15]. Moreover, pyrrhotite in that association exhibits enrichment in Ni [15]. As in Janjevo, this paragenesis can be interpreted as magmatic relics. So far in the literature, only Cr-spinels have been described as remnants from a magmatic process [20,21,93,94]. It turns out that sulfide magmatic paragenesis can be preserved during carbonatization processes and the influence of CO2-rich fluids on mafic/ultramafic rocks.
In contrast, listvenite Ni sulfide paragenesis in the studied Melenica locality is less widespread and overprinted than in the Janjevo locality. However, some features of previous generations can be observed in the form of remnants. The basic Ni–Fe sulfide related to the listvenitization process is millerite, which forms elongated, irregular crystals, while primary pyrite I is rather minor in listvenite.
The second stage observed in both localities was the main listvenite stage (Figure 17). In addition to pyrite I, the listvenite stage is typically represented by thiospinels: violarite + siegenite ± polydymite (Figure 17). In general, thiospinels are associated with older millerite, pentlandite, or pyrite I. Overall, three types of thiospinels associations are observed: (I) violarite replacement after pentlandite (only JCR_1) (Figure 7a,b,d,e); (II) violarite association with pyrite I with any magmatic millerite/pentlandite (only JCR_8) (Figure 9f–h); and (III) siegenite replacement after millerite (JCR_6 and JCR_9) (Figure 9c–e). Moreover, the talc-magnesite rich soapstone from JCR_7 is characterized by the presence of stand-alone millerite with no thiospinels (JCR_7) (Figure 9a,b). In the literature, violarite is usually interpreted as a product of supergene alteration of massive and disseminated Ni sulfide deposits, where it replaces primary pentlandite or millerite [95,96,97]. It cannot be excluded that the formation of thiospinels at the Janjevo site may be partly due to supergene processes, since sampling was performed at the surface and did not involve fresh material from the drill hole. However, the formation of violarite in association with pentlandite or millerite could be related to hypogene processes [76]. The polymineral aggregates of violarite and pentlandite/millerite in Janjevo did not exhibit lamellar or flame textures. However, they exhibit typical replacement textures (Figure 7a,b,d,e and Figure 9f–h). On the other hand, [98] reported that hydrothermally produced violarite has textures similar to those of supergenes (fine-grained, porous, and cracked).
Another feature described in the literature regarding the origin of violarite is the enrichment of cobalt. Almost all analyses of the Janjevo violarite show enrichment in Co (Figure 12), which supports the hypogene genesis of that mineral rather than the supergene one. Misra and Fleet [97] proposed that the Co content of violarite originated from the precursor pentlandite due to a low-temperature replacement process. Moreover, [76] hypothesized that the formation of violarite-pentlandite in Mount Keith is a result of the decomposition of the Ni-rich massive sulfide solid state below 230 °C. The bulk composition of sulfides could depend on which pyrite or millerite may be present with the hypogene violarite association [76]. The high sulfidation assemblage at Black Swan indicates the coexistence of hypogene violarite and pyrite/vaesite [76]. On the other hand, the hypogene violarite-bearing assemblage reported in the literature was not observed in talc-magnesite rocks, which was suggested as not enough oxidized conditions to form the pyrite-violarite-vaesite assemblage [99,100].
The replacement of siegenite after millerite in the Janjevo occurrence typically forms two textures: a regular checkboard pattern (Figure 9c,d) or an irregular texture (Figure 9e). Siegenite is formed mainly as a secondary phase in hydrothermal deposits [101,102,103], as well as in the supergene environment in the alteration Ni–Co rich sulfide zone [104]. It is mostly associated with Co-pentlandite [101,105] and millerite [106,107,108]. The sulfide crystallization sequence of the millerite-siegenite association proposed by [108] in Morokweng impact structure in South Africa was initiated by the millerite nucleation followed by siegenite formation, which could be restricted to the range of temperatures: ~282–356 °C. The co-crystallization of siegenite and millerite results in the formation of a crystal-controlled oriented intergrowth [108].
On the other hand, millerite in Melenica is mostly replaced by violarite, which could be divided into hypogenic and supergene in this locality due to the amount of cobalt in the mineral structure [76,97].
In both the Melenica and Janjevo occurrences, minerals of the gersdorffite−ullmannite series are transitional between the listvenitization association and hydrothermal overprint assemblage (Figure 17). Mederski et al. [13] investigated gersdorffite−ullmannite minerals from listvenites in Kosovo (including studied Melenica). An antimony member of GUS—ullmannite—has been documented practically only at Melenica and Badovc, where Sb-rich base metal Pb–Zn mineralization is observed [13]. At both locations, Pb–Sb sulfosalts and Sb-dominant tetrahedrite group minerals are observed [13,15]. Gersdorffite is more widespread in the studied localities, while, in the listvenites from Badovc and Mazhiq, it occurs near massive vein orebodies [13]. Moreover, unlike some As-rich occurrences with nickel arsenides in Kosovo (e.g., Selac or Vllahia), the studied gersdorffite in Janjevo and Melenica does not show elevated As/S values associated with increased arsenic activity [13].
The only site with massive sulfarsenides in Kosovo is Mazhiq [13], which shows many similarities with the Ni–Co vein-type Dobšiná deposit in Slovakia [31,109]. Kiefer et al. [109] investigated listvenites in the Dobšiná district and identified the Ni sulfide and sulfarsenides association. The most common minerals in listvenite are pyrite and siegenite, with minor amounts of millerite + gersdorffite and accessory pentlandite + linnaeite. Kiefer et al. [109] observed some zonation depending on the distance from the ore veins, unlike in Janjevo, where zonation is observed depending on tectonic zones. The content of sulfides in listvenites from Dobšiná decreases with the distance from the massive ore veins. However, pyrite is present in all listvenite samples: in the proximal parts, it is accompanied by siegenite alone, while in the distal part by siegenite and millerite. In addition, the proportion of siegenite increases with distance from the ore veins.

7. Conclusions

To summarize, both studied localities, Janjevo and Melenica, show the polyphase evolution of Ni–Fe sulfides in listvenites. Generally, despite the overprint, the paragenetic sequence of Ni–Fe sulfides can be divided into three stages: the magmatic stage, the listvenite stage and the late listvenitization/hydrothermal overprint stage.
  • The products of the first magmatic stage are represented by millerite ± pentlandite ± pyrrhotite. They occur only as remnants (pentlandite, millerite) or are completely recrystallized (pyrrhotite to pyrite),
  • The sulfide mineralization associated with proper listvenitization is represented by Ni–Co bearing pyrite (Ni content up to 11.57 wt.% [0.24 apfu], and Co content up to 6.54 wt.% [0.14 apfu]), as well as diversified Ni–Fe–Co thiospinels: violarite + siegenite ± polydymite.
  • Thiospinels are associated with older millerite, pentlandite, or pyrite I. Three types of thiospinels associations are observed: (I) violarite replacement after pentlandite; (II) violarite association with pyrite I with any magmatic millerite/pentlandite; and (III) siegenite replacement after millerite.
  • Violarite occurs in two groups: Co-enriched violarite may be of hypogene origin, while Co-free violarite may have formed through supergene processes.
  • Talc-magnesite rich soapstone is characterized by the presence of isolated millerite with no thiospinels.
  • The listvenitization stage is accompanied by the crystallization of quartz, talc, and Mg–Fe–Ca carbonates (magnesite and dolomite).
The transitional paragenesis is represented by gersdorffite–ullmannite, followed by the base metal mineralization represented by pyrite + marcasite + sphalerite + galena ± chalcopyrite ± sulfosalts associated with dolomite ± quartz ± rhodochrosite-siderite ± baryte.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/min14101008/s1, Microprobe data of Ni–Fe sulfide paragenesis from Janjevo and Melenica occurrences.

Author Contributions

Conceptualization, S.M. and J.P.; methodology, K.K. and J.P.; formal analysis, K.K. and J.P.; investigation, K.K., J.P. and S.M.; writing—original draft preparation, K.K. and S.M.; writing—review and editing, S.M. and J.P.; visualization, K.K. and S.M.; supervision, J.P. and S.M.; funding acquisition, J.P. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the AGH University of Krakow statutory grant No. 16.16.140.315.

Data Availability Statement

Data is contained within the article or Supplementary Materials.

Acknowledgments

Jaroslav Pršek is acknowledged for the kind invitation to participate in the Special Issue ‘Sulfide Mineralogy and Geochemistry’. We would like to express our gratitude to A. Włodek and G. Kozub-Budzyń from the Laboratory of Critical Elements at AGH for their assistance during EMPA data collection. In addition, we are grateful to the AGH student group for their help in the fieldwork. We are also grateful to the anonymous reviewers, whose comments helped us to improve the manuscript.

Conflicts of Interest

The authors declare no conflicts of interest.

References

  1. Hansen, L.D.; Dipple, G.M.; Gordon, T.M.; Kellett, D.A. Carbonated Serpentinite (Listwanite) at Atlin, British Columbia: A Geological Analogue to Carbon Dioxide Sequestration. Can. Mineral. 2005, 43, 225–239. [Google Scholar] [CrossRef]
  2. Kelemen, P.B.; Matter, J.; Streit, E.E.; Rudge, J.F.; Curry, W.B.; Blusztajn, J. Rates and Mechanisms of Mineral Carbonation in Peridotite: Natural Processes and Recipes for Enhanced, in Situ CO2 Capture and Storage. Annu. Rev. Earth Planet. Sci. 2011, 39, 545–576. [Google Scholar] [CrossRef]
  3. Beinlich, A.; Plümper, O.; Hövelmann, J.; Austrheim, H.; Jamtveit, B. Massive Serpentinite Carbonation at Linnajavri, N–Norway. Terra Nova 2012, 24, 446–455. [Google Scholar] [CrossRef]
  4. Kelemen, P.; Benson, S.M.; Pilorgé, H.; Psarras, P.; Wilcox, J. An Overview of the Status and Challenges of CO2 Storage in Minerals and Geological Formations. Front. Clim. 2019, 1, 482595. [Google Scholar] [CrossRef]
  5. Beinlich, A.; Plümper, O.; Boter, E.; Müller, I.A.; Kourim, F.; Ziegler, M.; Harigane, Y.; Lafay, R.; Kelemen, P.B.; the Oman Drilling Project Science Team. Ultramafic Rock Carbonation: Constraints From Listvenite Core BT1B, Oman Drilling Project. J. Geophys. Res. Solid Earth 2020, 125, e2019JB019060. [Google Scholar] [CrossRef]
  6. Menzel, M.; Sieber, M.; Godard, M. From Peridotite to Listvenite—Perspectives on the Processes, Mechanisms and Settings of Ultramafic Mineral Carbonation to Quartz-Magnesite Rocks. Earth Sci. Rev. 2024, 255, 104828. [Google Scholar] [CrossRef]
  7. Halls, C.; Zhao, R. Listvenite and Related Rocks: Perspectives on Terminology and Mineralogy with Reference to an Occurrence at Cregganbaun, Co. Mayo, Republic of Ireland. Miner. Deposita 1995, 30, 303–313. [Google Scholar] [CrossRef]
  8. Zoheir, B.; Lehmann, B. Listvenite–Lode Association at the Barramiya Gold Mine, Eastern Desert, Egypt. Ore Geol. Rev. 2011, 39, 101–115. [Google Scholar] [CrossRef]
  9. Radosavljević, S.A.; Stojanović, J.N.; Vuković, N.S.; Radosavljević-Mihajlović, A.S.; Kašić, V.D. Low-Temperature Ni-As-Sb-S Mineralization of the Pb(Ag)-Zn Deposits within the Rogozna Ore Field, Serbo-Macedonian Metallogenic Province: Ore Mineralogy, Crystal Chemistry and Paragenetic Relationships. Ore Geol. Rev. 2015, 65, 213–227. [Google Scholar] [CrossRef]
  10. Qiu, T.; Zhu, Y. Geology and Geochemistry of Listwaenite-Related Gold Mineralization in the Sayi Gold Deposit, Xinjiang, NW China. Ore Geol. Rev. 2015, 70, 61–79. [Google Scholar] [CrossRef]
  11. Boskabadi, A.; Pitcairn, I.K.; Broman, C.; Boyce, A.; Teagle, D.A.H.; Cooper, M.J.; Azer, M.K.; Stern, R.J.; Mohamed, F.H.; Majka, J. Carbonate Alteration of Ophiolitic Rocks in the Arabian–Nubian Shield of Egypt: Sources and Compositions of the Carbonating Fluid and Implications for the Formation of Au Deposits. Int. Geol. Rev. 2017, 59, 391–419. [Google Scholar] [CrossRef]
  12. Gahlan, H.A.; Azer, M.K.; Asimow, P.D.; Al-Kahtany, K.M. Petrogenesis of Gold-Bearing Listvenites from the Carbonatized Mantle Section of the Neoproterozoic Ess Ophiolite, Western Arabian Shield, Saudi Arabia. Lithos 2020, 372–373, 105679. [Google Scholar] [CrossRef]
  13. Mederski, S.; Wojsław, M.; Pršek, J.; Majzlan, J.; Kiefer, S.; Asllani, B. A Geochemical Study of Gersdorffite from the Trepça Mineral Belt, Vardar Zone, Kosovo. J. Geosci. 2021, 66, 97–115. [Google Scholar] [CrossRef]
  14. Sarifakioglu, E. Geochemistry and Origin of Listwaenites within the Northern Branch of Neo-Tethyan Ophiolites, Turkey. J. Afr. Earth Sci. 2023, 197, 104748. [Google Scholar] [CrossRef]
  15. Mederski, S.; Pršek, J.; Dimitrova, D. Distribution of In, Sn, Ga, Ge, and Other Critical Metals in Sulfide Ores from Epithermal Listvenite-Associated Badovc Pb–Zn–Sb–Ni Deposit (Kosovo): Insights from Mineralogy and Geochemistry. Ore Geol. Rev. 2024, 164, 105824. [Google Scholar] [CrossRef]
  16. Nasir, S.; Al Sayigh, A.R.; Al Harthy, A.; Al-Khirbash, S.; Al-Jaaidi, O.; Musllam, A.; Al-Mishwat, A.; Al-Bu’saidi, S. Mineralogical and Geochemical Characterization of Listwaenite from the Semail Ophiolite, Oman. Geochemistry 2007, 67, 213–228. [Google Scholar] [CrossRef]
  17. Hinsken, T.; Bröcker, M.; Strauss, H.; Bulle, F. Geochemical, Isotopic and Geochronological Characterization of Listvenite from the Upper Unit on Tinos, Cyclades, Greece. Lithos 2017, 282–283, 281–297. [Google Scholar] [CrossRef]
  18. Ji, C.; Zhang, K.-J.; Yan, L.-L. Hydrothermal Metasomatism and Solid-Phase Transfer in Petrogenesis of Listvenite: The Meso-Tethyan Ophiolite, Central Tibet, China. Contrib. Mineral. Petrol. 2022, 178, 4. [Google Scholar] [CrossRef]
  19. Sideridis, A.; Koutsovitis, P.; Tsikouras, B.; Karkalis, C.; Hauzenberger, C.; Zaccarini, F.; Tsitsanis, P.; Lazaratou, C.V.; Skliros, V.; Panagiotaras, D.; et al. Pervasive Listwaenitization: The Role of Subducted Sediments within Mantle Wedge, W. Chalkidiki Ophiolites, N. Greece. Minerals 2022, 12, 1000. [Google Scholar] [CrossRef]
  20. Qiu, T.; Zhu, Y. Chromian Spinels in Highly Altered Ultramafic Rocks from the Sartohay Ophiolitic Mélange, Xinjiang, NW China. J. Asian Earth Sci. 2018, 159, 155–184. [Google Scholar] [CrossRef]
  21. Lizoń, K.; Tomczak, A.; Mederski, S.; Pršek, J.; Asllani, B. Geochemical Study of Accessory Chromian Spinels from Listvenites from the Trepça Mineral Belt, Vardar Zone, Kosovo. In Proceedings of the Critical Role of Minerals in the Carbon-Neutral Future 16th Biennial SGA Meeting, Rotorua, New Zealand, 28–31 March 2022; Volume 1, pp. 196–199. [Google Scholar]
  22. Frost, B.R. On the Stability of Sulfides, Oxides, and Native Metals in Serpentinite. J. Petrol. 1985, 26, 31–63. [Google Scholar] [CrossRef]
  23. Klein, F.; Garrido, C.J. Thermodynamic Constraints on Mineral Carbonation of Serpentinized Peridotite. Lithos 2011, 126, 147–160. [Google Scholar] [CrossRef]
  24. Menzel, M.D.; Garrido, C.J.; López Sánchez-Vizcaíno, V.; Marchesi, C.; Hidas, K.; Escayola, M.P.; Delgado Huertas, A. Carbonation of Mantle Peridotite by CO2-Rich Fluids: The Formation of Listvenites in the Advocate Ophiolite Complex (Newfoundland, Canada). Lithos 2018, 323, 238–261. [Google Scholar] [CrossRef]
  25. Tsikouras, B.; Karipi, S.; Grammatikopoulos, T.A.; Hatzipanagiotou, K. Listwaenite Evolution in the Ophiolite Melange of Iti Mountain (Continental Central Greece). Eur. J. Mineral. 2006, 18, 243–255. [Google Scholar] [CrossRef]
  26. Menzel, M.D.; Urai, J.L.; Ukar, E.; Decrausaz, T.; Godard, M. Progressive Veining during Peridotite Carbonation: Insights from Listvenites in Hole BT1B, Samail Ophiolite (Oman). Solid Earth 2022, 13, 1191–1218. [Google Scholar] [CrossRef]
  27. Falk, E.S.; Kelemen, P.B. Geochemistry and Petrology of Listvenite in the Samail Ophiolite, Sultanate of Oman: Complete Carbonation of Peridotite during Ophiolite Emplacement. Geochim. Cosmochim. Acta 2015, 160, 70–90. [Google Scholar] [CrossRef]
  28. Sieber, M.J.; Hermann, J.; Yaxley, G.M. An Experimental Investigation of C–O–H Fluid-Driven Carbonation of Serpentinites under Forearc Conditions. Earth Planet. Sci. Lett. 2018, 496, 178–188. [Google Scholar] [CrossRef]
  29. Sieber, M.J.; Yaxley, G.M.; Hermann, J. Investigation of Fluid-Driven Carbonation of a Hydrated, Forearc Mantle Wedge Using Serpentinite Cores in High-Pressure Experiments. J. Petrol. 2020, 61, egaa035. [Google Scholar] [CrossRef]
  30. Ferenc, Š.; Uher, P.; Spišiak, J.; Šimonová, V. Chromium- and Nickel-Rich Micas and Associated Minerals in Listvenite from the Muránska Zdychava, Slovakia: Products of Hydrothermal Metasomatic Transformation of Ultrabasic Rock. J. Geosci. 2016, 61, 239–254. [Google Scholar] [CrossRef]
  31. Kiefer, S.; Ivan, P.; Kaufmann, A.B.; Vďačný, M.; Majzlan, J. Remobilization of Ni–Co–As and Platinum-Group Elements by Carbonate Metasomatic Alteration (Listvenitization) of Metaultramafic Rocks from Dobšiná, Slovakia. Geol. Carpath. 2023, 74, 139–153. [Google Scholar] [CrossRef]
  32. Borojević Šoštarić, S.; Palinkaš, L.A.; Topa, D.; Spangenberg, J.E.; Prochaska, W. Silver–Base Metal Epithermal Vein and Listwaenite Types of Deposit Crnac, Rogozna Mts., Kosovo. Part I: Ore Mineral Geochemistry and Sulfur Isotope Study. Ore Geol. Rev. 2011, 40, 65–80. [Google Scholar] [CrossRef]
  33. Borojević Šoštarić, S.; Palinkaš, L.A.; Neubauer, F.; Hurai, V.; Cvetković, V.; Roller-Lutz, Z.; Mandić, M.; Genser, J. Silver-Base Metal Epithermal Vein and Listwanite Hosted Deposit Crnac, Rogozna Mts., Kosovo, Part II: A Link between Magmatic Rocks and Epithermal Mineralization. Ore Geol. Rev. 2013, 50, 98–117. [Google Scholar] [CrossRef]
  34. Boskabadi, A.; Pitcairn, I.K.; Leybourne, M.I.; Teagle, D.A.H.; Cooper, M.J.; Hadizadeh, H.; Nasiri Bezenjani, R.; Monazzami Bagherzadeh, R. Carbonation of Ophiolitic Ultramafic Rocks: Listvenite Formation in the Late Cretaceous Ophiolites of Eastern Iran. Lithos 2020, 352–353, 105307. [Google Scholar] [CrossRef]
  35. Janković, S. The Carpatho-Balkanides and Adjacent Area: A Sector of the Tethyan Eurasian Metallogenic Belt. Miner. Deposita 1997, 32, 426–433. [Google Scholar] [CrossRef]
  36. Borojević Šoštarić, S.; Cvetković, V.; Neubauer, F.; Palinkaš, L.A.; Bernroider, M.; Genser, J. Oligocene Shoshonitic Rocks of the Rogozna Mts. (Central Balkan Peninsula): Evidence of Petrogenetic Links to the Formation of Pb–Zn–Ag Ore Deposits. Lithos 2012, 148, 176–195. [Google Scholar] [CrossRef]
  37. Kołodziejczyk, J.; Pršek, J.; Voudouris, P.C.; Melfos, V.; Asllani, B. Sn-Bearing Minerals and Associated Sphalerite from Lead-Zinc Deposits, Kosovo: An Electron Microprobe and LA-ICP-MS Study. Minerals 2016, 6, 42. [Google Scholar] [CrossRef]
  38. Dimitrijević, M.D. Dinarides and the Vardar Zone: A Short Review of the Geology. Acta Vulcanol. 2001, 12, 1000–1008. [Google Scholar]
  39. Robertson, A.H.F.; Trivić, B.; Đerić, N.; Bucur, I.I. Tectonic Development of the Vardar Ocean and Its Margins: Evidence from the Republic of Macedonia and Greek Macedonia. Tectonophysics 2013, 595–596, 25–54. [Google Scholar] [CrossRef]
  40. Janković, S. The principal metallogenetic features of the Kopaonik District. In Proceedings of the International Symposium “Geology and Metallogeny of the Dinarides and the Vardar Zone”; Academy of Science and Art of Republika Srpska: Rotterdam, The Netherlands; Banja Luka, Bosnia and Herzegovina; 1995, Volume 1, pp. 79–101.
  41. Cvetković, V.; Prelević, D.; Downes, H.; Jovanović, M.; Vaselli, O.; Pécskay, Z. Origin and Geodynamic Significance of Tertiary Postcollisional Basaltic Magmatism in Serbia (Central Balkan Peninsula). Lithos 2004, 73, 161–186. [Google Scholar] [CrossRef]
  42. Elezaj, Z. Geodynamic Evolution of Kosovo during the Triassic and Jurassic. Yerbilimleri 2009, 30, 113–126. [Google Scholar]
  43. Strmić Palinkaš, S.; Palinkaš, L.A.; Renac, C.; Spangenberg, J.E.; Lüders, V.; Molnar, F.; Maliqi, G. Metallogenic Model of the Trepča Pb-Zn-Ag Skarn Deposit, Kosovo: Evidence from Fluid Inclusions, Rare Earth Elements, and Stable Isotope Data. Econ. Geol. 2013, 108, 135–162. [Google Scholar] [CrossRef]
  44. Hyseni, S.; Durmishaj, B.; Fetahaj, B.; Shala, F.; Berisha, A.; Large, D. Trepça Ore Belt and Stan Terg Mine—Geological Overview and Interpretation, Kosovo (SE Europe). Geologija 2010, 53, 87–92. [Google Scholar] [CrossRef]
  45. Kołodziejczyk, J.; Pršek, J.; Melfos, V.; Voudouris, P.C.; Maliqi, F.; Kozub-Budzyń, G. Bismuth Minerals from the Stan Terg Deposit (Trepça, Kosovo). Neues Jahrb. Für Mineral. Abhandlungen 2015, 192, 317–333. [Google Scholar] [CrossRef]
  46. Kołodziejczyk, J.; Pršek, J.; Asllani, B.; Maliqi, F. The Paragenesis of Silver Minerals in the Pb-Zn Stan Terg Deposit, Kosovo—An Example of Precious Metal Epithermal Mineralization. Geol. Geophys. Environ. 2016, 42, 19–29. [Google Scholar] [CrossRef]
  47. Strmić Palinkaš, S.; Peltekovski, Z.; Tasev, G.; Serafimovski, T.; Šmajgl, D.; Rajič, K.; Spangenberg, J.E.; Neufeld, K.; Palinkaš, L. The Role of Magmatic and Hydrothermal Fluids in the Formation of the Sasa Pb-Zn-Ag Skarn Deposit, Republic of Macedonia. Geosciences 2018, 8, 444. [Google Scholar] [CrossRef]
  48. Serafimovski, T. The Lece-Chalkidiki Metallogenic Zone: Geotectonic Setting and Metallogenic Features. Geologija 1999, 42, 159–163. [Google Scholar] [CrossRef]
  49. Velojić, M.; Prelević, D.; Jelenković, R. The Origin of Lead and Sulphur in Tulare Ore Field, Lece Magmatic Complex, SE Serbia. Geol. An. Balk. Poluos. 2018, 79, 19–28. [Google Scholar] [CrossRef]
  50. Kroll, T.; Müller, D.; Seifert, T.; Herzig, P.; Schneider, A. Petrology and Geochemistry of the Shoshonite-Hosted Skouries Porphyry Cu-Au Deposit, Chalkidiki, Greece. Miner. Deposita 2002, 37, 137–144. [Google Scholar] [CrossRef]
  51. Baker, T. Gold ± Copper Endowment and Deposit Diversity in the Western Tethyan Magmatic Belt, Southeast Europe: Implications for Exploration. Econ. Geol. 2019, 114, 1237–1250. [Google Scholar] [CrossRef]
  52. Serafimovski, T.; Stefanova, V.; Volkov, A.V. Dwarf Copper-Gold Porphyry Deposits of the Buchim-Damjan-Borov Dol Ore District, Republic of Macedonia (FYROM). Geol. Ore Depos. 2010, 52, 179–195. [Google Scholar] [CrossRef]
  53. Strmić Palinkaš, S.; Perković, I.; Čobić, A.; Jurković, I.; Tasev, G.; Serafimovski, T.; Spangenberg, J.E. Evolution of Ore-Forming Fluids in a Post-Collisional Porphyry Cu-Au System: A Case Study from the Bučim Deposit, Republic of North Macedonia. Ore Geol. Rev. 2022, 146, 104913. [Google Scholar] [CrossRef]
  54. Stergiou, C.L.; Melfos, V.; Voudouris, P.; Spry, P.G.; Papadopoulou, L.; Chatzipetros, A.; Giouri, K.; Mavrogonatos, C.; Filippidis, A. The Geology, Geochemistry, and Origin of the Porphyry Cu-Au-(Mo) System at Vathi, Serbo-Macedonian Massif, Greece. Appl. Sci. 2021, 11, 479. [Google Scholar] [CrossRef]
  55. Stergiou, C.L.; Melfos, V.; Voudouris, P.; Papadopoulou, L.; Spry, P.G.; Peytcheva, I.; Dimitrova, D.; Stefanova, E.; Giouri, K. Rare and Critical Metals in Pyrite, Chalcopyrite, Magnetite, and Titanite from the Vathi Porphyry Cu-Au±Mo Deposit, Northern Greece. Minerals 2021, 11, 630. [Google Scholar] [CrossRef]
  56. Siron, C.R.; Thompson, J.F.H.; Baker, T.; Friedman, R.; Tsitsanis, P.; Russell, S.; Randall, S.; Mortensen, J. Magmatic and Metallogenic Framework of Au-Cu Porphyry and Polymetallic Carbonate-Hosted Replacement Deposits of the Kassandra Mining District, Northern Greece. SEG Spec. Publ. 2016, 19, 29–55. [Google Scholar] [CrossRef]
  57. Siron, C.R.; Thompson, J.F.H.; Baker, T.; Darling, R.; Dipple, G. Origin of Au-Rich Carbonate-Hosted Replacement Deposits of the Kassandra Mining District, Northern Greece: Evidence for Late Oligocene, Structurally Controlled, and Zoned Hydrothermal Systems. Econ. Geol. 2019, 114, 1389–1414. [Google Scholar] [CrossRef]
  58. Stefanova, V.; Volkov, A.V.; Serafimovskii, T.; Sidorov, A.A. Native Gold from the Plavica Epithermal Deposit, Republic of Macedonia. Dokl. Earth Sc. 2013, 451, 818–823. [Google Scholar] [CrossRef]
  59. Melfos, V.; Voudouris, P.; Serafimovski, T.; Tasev, G. Fluid Inclusions at the Plavica Au-Ag-Cu Telescoped Porphyry–Epithermal System, Former Yugoslavian Republic of Macedonia (FYROM). Geosciences 2019, 9, 88. [Google Scholar] [CrossRef]
  60. Mederski, S. Characteristics of the Hydrothermal Base-Metal Mineralization of the Kizhnica Ore Field, Kosovo: Mineralogy, Geochemistry and Genesis. Ph.D. Thesis, AGH University of Science and Technology, Krakow, Poland, 2023. [Google Scholar]
  61. Tasev, G.; Serafimovski, T. Fluid Inclusions Study in the Quartz from the Zletovo Mine. Geol. Maced. 2012, 2, 83–90. [Google Scholar]
  62. Radosavljević, S.A.; Stojanović, J.N.; Radosavljević-Mihajlović, A.S.; Vuković, N.S. (Pb–Sb)-Bearing Sphalerite from the Čumavići Polymetallic Ore Deposit, Podrinje Metallogenic District, East Bosnia and Herzegovina. Ore Geol. Rev. 2016, 72, 253–268. [Google Scholar] [CrossRef]
  63. Radosavljević, S.A.; Dimitrijević, R.Z. Mineralogical Data and Paragenetic Association for Semseyite from Srebrenica Orefield, Bosnia and Herzegovina. Neues Jahrb. Mineral., Monatsh. 2001, 4, 145–156. [Google Scholar]
  64. Radosavljević, S.A.; Rakic, S.M.; Stojanovic, J.N.; Radosavljevic-Mihajlovic, A.S. Occurrence of Petrukite in Srebrenica Orefield, Bosnia and Herzegovina. Neues Jahrb. Für Mineral. Abhandlungen 2005, 181, 21–26. [Google Scholar] [CrossRef]
  65. Kluza, K.; Pršek, J.; Mederski, S.; Dolníček, Z.; Sejkora, J. Zinc Incorporation into Carbonate Minerals from the Selac Area, Kosovo. In Proceedings of the Mineral Resources in a Changing World 17th Biennial SGA Meeting, Zurich, Switzerland, 28 August–1 September 2023; Volume 2, pp. 377–380. [Google Scholar]
  66. Mederski, S.; Pršek, J.; Dimitrova, D.; Hyseni, B. A Combined EPMA and LA-ICP-MS Investigation on Bi-Cu-Au Mineralization from the Kizhnica Ore Field (Vardar Zone, Kosovo). Minerals 2021, 11, 1223. [Google Scholar] [CrossRef]
  67. Westner, K. Roman Mining and Metal Production near the Antique City of Ulpiana (Kosovo). Ph.D. Thesis, Goethe-Universität, Frankfurt, Germany, 2017. [Google Scholar]
  68. Mederski, S.; Pršek, J.; Kołodziejczyk, J.; Kluza, K.; Melfos, V.; Adamek, K.; Dimitrova, D. Mineralogical and Geochemical Studies of Cu-Bi-Ag±W Ores from Janjevo (Kosovo): Insights into the Bi Sulfosalt Mineralogy and the Distribution of Bismuth in Base Metal Sulfides. J. Geosci. 2023, 68, 139–162. [Google Scholar] [CrossRef]
  69. Dangić, A. Minor Element Distribution between Galena and Sphalerite as a Geothermometer—Application to Two Lead-Zinc Areas in Yugoslavia. Econ. Geol. 1985, 80, 180–183. [Google Scholar] [CrossRef]
  70. Durmishaj, B.; Hyseni, S.; Tashko, A. The Main Geochemical Association of the Sulfides of Lead-Zinc Mineralization in Trepça Mineral Belt-Hajvalia Mine, Kosovo. ARPN J. Eng. Appl. Sci 2014, 9, 1376–1380. [Google Scholar]
  71. Mederski, S.; Pršek, J.; Hincyngier, K. Pb-Zn-Sb-Ni-Au Mineralization from the Kizhnica Area, Central Kosovo: New Data on the Listwaenite Type Mineralization. In Proceedings of the Life with Ore Deposits on Earth: 15th Biennial SGA Meeting, University of Glasgow Publicity Services, Glasgow, UK, 27–30 August 2019; Volume 2, pp. 834–837. [Google Scholar]
  72. Mederski, S.; Pršek, J.; Majzlan, J.; Kiefer, S.; Dimitrova, D.; Milovský, R.; Bender Koch, C.; Kozień, D. Geochemistry and Textural Evolution of As-Tl-Sb-Hg-Rich Pyrite from a Sediment-Hosted As-Sb-Tl-Pb±Hg±Au Mineralization in Janjevo, Kosovo. Ore Geol. Rev. 2022, 151, 105221. [Google Scholar] [CrossRef]
  73. Mederski, S.; Pršek, J.; Dimitrova, D. Trace Elements in Sphalerite from the Kizhnica-Hajvalia-Badovc Ore Field, Kosovo: An Example of In-Bearing Sphalerite. In Proceedings of the Critical Role of Minerals in the Carbon-Neutral Future 16th Biennial SGA Meeting, Rotorua, New Zealand, 28–31 March 2022; Volume 1, pp. 239–242. [Google Scholar]
  74. Mederski, S.; Pršek, J.; Kluza, K.; Dimitrova, D. LA-ICP-MS Trace Element Composition of Stibnite from the Kizhnica-Hajvalia-Badovc Ore Field, Kosovo. In Proceedings of the Mineral Resources in a Changing World 17th Biennial SGA Meeting, Zurich, Switzerland, 28 August–1 September 2023; Volume 3, pp. 296–299. [Google Scholar]
  75. Węgrzynowicz, J.; Pršek, J.; Mederski, S.; Asllani, B.; Kanigowski, J. Pb-Bi(-Cu) and Pb-Sb Sulfosalts from Stan Terg Area, Kosovo. In Proceedings of the Life with Ore Deposits on Earth: 15th Biennial SGA Meeting, University of Glasgow Publicity Services, Glasgow, UK, 27–30 August 2019; Volume 1, pp. 380–383. [Google Scholar]
  76. Grguric, B.A. Hypogene Violarite of Exsolution Origin from Mount Keith, Western Australia: Field Evidence for a Stable Pentlandite–Violarite Tie Line. Mineral. Mag. 2002, 66, 313–326. [Google Scholar] [CrossRef]
  77. Taylor, P.; Rummery, T.E.; Owen, D.G. Reactions of Iron Monosulfide Solids with Aqueous Hydrogen Sulfide up to 160 °C. J. Inorg. Nucl. Chem. 1979, 41, 1683–1687. [Google Scholar] [CrossRef]
  78. Taylor, P.; Rummery, T.E.; Owen, D.G. On the Conversion of Mackinawite to Greigite. J. Inorg. Nucl. Chem. 1979, 41, 595–596. [Google Scholar] [CrossRef]
  79. Schoonen, M.A.A.; Barnes, H.L. Mechanisms of Pyrite and Marcasite Formation from Solution: III. Hydrothermal Processes. Geochim. Cosmochim. Acta 1991, 55, 3491–3504. [Google Scholar] [CrossRef]
  80. Qian, G.; Xia, F.; Brugger, J.; Skinner, W.M.; Bei, J.; Chen, G.; Pring, A. Replacement of Pyrrhotite by Pyrite and Marcasite under Hydrothermal Conditions up to 220 °C: An Experimental Study of Reaction Textures and Mechanisms. Am. Mineral. 2011, 96, 1878–1893. [Google Scholar] [CrossRef]
  81. Murowchick, J.B. Marcasite Inversion and the Petrographic Determination of Pyrite Ancestry. Econ. Geol. 1992, 87, 1141–1152. [Google Scholar] [CrossRef]
  82. Kitakaze, A.; Machida, T.; Komatsu, R. Phase Relations in the Fe–Ni–s System from 875 to 650 °C. Can. Mineral. 2016, 54, 1175–1186. [Google Scholar] [CrossRef]
  83. Mansur, E.T.; Barnes, S.-J.; Duran, C.J. Textural and Compositional Evidence for the Formation of Pentlandite via Peritectic Reaction: Implications for the Distribution of Highly Siderophile Elements. Geology 2019, 47, 351–354. [Google Scholar] [CrossRef]
  84. Barnes, S.J.; Taranovic, V.; Schoneveld, L.E.; Mansur, E.T.; Le Vaillant, M.; Dare, S.; Staude, S.; Evans, N.J.; Blanks, D. The Occurrence and Origin of Pentlandite-Chalcopyrite-Pyrrhotite Loop Textures in Magmatic Ni-Cu Sulfide Ores. Econ. Geol. 2020, 115, 1777–1798. [Google Scholar] [CrossRef]
  85. Keays, R.R.; Jowitt, S.M. The Avebury Ni Deposit, Tasmania: A Case Study of an Unconventional Nickel Deposit. Ore Geol. Rev. 2013, 52, 4–17. [Google Scholar] [CrossRef]
  86. Garcia, V.B.; Emilia Schutesky, M.; Oliveira, C.G.; Whitehouse, M.J.; Huhn, S.R.B.; Augustin, C.T. The Neoarchean GT-34 Ni Deposit, Carajás Mineral Province, Brazil: An Atypical IOCG-Related Ni Sulfide Mineralization. Ore Geol. Rev. 2020, 127, 103773. [Google Scholar] [CrossRef]
  87. Staude, S.; Scharrer, M.; Markl, G.; Simon, I.; Pfaff, K.; Monecke, T.; Blanc, P. Hydrothermal Pentlandite (Ni,Fe)9S8 from Kambalda, Western Australia: Occurrences, Formation Conditions, and Association with Orogenic Gold. Can. J. Mineral. Petrol. 2023, 61, 239–271. [Google Scholar] [CrossRef]
  88. Bath, A.B.; Walshe, J.L.; Cloutier, J.; Verrall, M.; Cleverley, J.S.; Pownceby, M.I.; Macrae, C.M.; Wilson, N.C.; Tunjic, J.; Nortje, G.S.; et al. Biotite and Apatite as Tools for Tracking Pathways of Oxidized Fluids in the Archean East Repulse Gold Deposit, Australia. Econ. Geol. 2013, 108, 667–690. [Google Scholar] [CrossRef]
  89. Durazzo, A.; Taylor, L.A. Exsolution in the Mss-Pentlandite System: Textural and Genetic Implications for Ni-Sulfide Ores. Miner. Deposita 1982, 17, 313–332. [Google Scholar] [CrossRef]
  90. Piña, R.; Gervilla, F.; Barnes, S.-J.; Ortega, L.; Lunar, R. Distribution of Platinum-Group and Chalcophile Elements in the Aguablanca Ni–Cu Sulfide Deposit (SW Spain): Evidence from a LA-ICP-MS Study. Chem. Geol. 2012, 302–303, 61–75. [Google Scholar] [CrossRef]
  91. Rödsjö, L.; Goodgame, V.R. Alteration of the Mt. Keith Nickel Sulphide Deposit. In Mineral Deposits: Processes to Processing; A. A. Balkema: Rotterdam, The Netherlands, 1999; pp. 779–782. [Google Scholar]
  92. Grguric, B.A.; Madsen, I.C.; Pring, A. Woodallite, a New Chromium Analogue of Iowaite from the Mount Keith Nickel Deposit, Western Australia. Mineral. Mag. 2001, 65, 427–435. [Google Scholar] [CrossRef]
  93. Bónová, K.; Spišiak, J.; Bóna, J.; Kováčik, M. Chromian Spinels from the Magura Unit (Western Carpathians, Eastern Slovakia)—Their Petrogenetic and Palaeogeographic Implications. Geol. Q. 2016, 6, 3–17. [Google Scholar] [CrossRef]
  94. Hajjar, Z.; Ares, G.; Fanlo, I.; Gervilla, F.; González-Jiménez, J.M. Cr-Spinel Tracks Genesis of Co-Fe Ores by Serpentinite Replacement at Bou Azzer, Morocco. J. Afr. Earth Sci. 2022, 188, 104471. [Google Scholar] [CrossRef]
  95. Nickel, E.H. Violarite—A Key Mineral in the Supergene Alteration of Nickel Sulphide Ores; Perth Conference; Australasian Institute of Mining and Metallurgy: Parkville, VIC, Australia, 1973; pp. 111–116. [Google Scholar]
  96. Nickel, E.H.; Ross, J.R.; Thornber, M.R. The Supergene Alteration of Pyrrhotite-Pentlandite Ore at Kambalda, Western Australia. Econ. Geol. 1974, 69, 93–107. [Google Scholar] [CrossRef]
  97. Misra, K.C.; Fleet, M.E. Chemical Composition and Stability of Violarite. Econ. Geol. 1974, 69, 391–403. [Google Scholar] [CrossRef]
  98. Tenailleau, C.; Pring, A.; Etschmann, B.; Brugger, J.; Grguric, B.; Putnis, A. Transformation of Pentlandite to Violarite under Mild Hydrothermal Conditions. Am. Mineral. 2006, 91, 706–709. [Google Scholar] [CrossRef]
  99. Hudson, D.R.; Groves, D.I. The Composition of Violarite Coexisting with Vaesite, Pyrite, and Millerite. Econ. Geol. 1974, 69, 1335–1340. [Google Scholar] [CrossRef]
  100. Barnes, S.J.; Hill, R.E.T. Metamorphism of Komatiite Hosted Nickel Sulfide Deposits. In Metamorphosed and Metamorphogenic Ore Deposits; Spry, P.G., Marshall, B., Vokes, F.M., Eds.; Reviews in Economic Geology, 11; Society of Economic Geologists: Boulder, CO, USA, 2000; pp. 203–216. [Google Scholar]
  101. Petruk, W.; Harris, D.C.; Stewart, J.M. Langisite, a New Mineral, and the Rare Minerals Cobalt Pentlandite, Siegenite, Parkerite and Bravoite from the Langis Mine, Cobalt-Gowganda Area, Ontario. Can. Mineral. 1969, 9, 597–616. [Google Scholar]
  102. Craig, J.R.; Carpenter, A.B. Fletcherite, Cu(Ni,Co)2S4, a New Thiospinel from the Viburnum Trend (New Lead Belt), Missouri. Econ. Geol. 1977, 72, 480–486. [Google Scholar] [CrossRef]
  103. Zakrzewski, M.A. Minerals of the Bravoite-Villamaninite Series and Cuprian Siegenite from Karniowice, Poland. Can. Mineral. 1984, 22, 499–502. [Google Scholar]
  104. Imai, N.; Mariko, T.; Shiga, Y. Siegenite from the Nippo Ore Deposit of the Kamaishi Mine, Iwate Prefecture, Japan. Mining Geol. 1973, 23, 347–354. [Google Scholar]
  105. Kovalev, S.G.; Puchkov, V.N.; Kovalev, S.S. First Findings of Siegenite (CoNi2S4) in Picritic and Picrodoleritic Complexes of the Southern Urals. Dokl. Earth Sc. 2014, 457, 796–802. [Google Scholar] [CrossRef]
  106. Von Seckendorff, V.; Drüppel, K.; Okrusch, M.; Cook, N.J.; Littmann, S. Oxide-Sulphide Relationships in Sodalite-Bearing Metasomatites of the Epembe-Swartbooisdrif Alkaline Province, North-West Namibia. Miner. Deposita 2000, 35, 430–450. [Google Scholar] [CrossRef]
  107. Hinchey, J.G.; Hattori, K.H. Magmatic Mineralization and Hydrothermal Enrichment of the High Grade Zone at the Lac Des Iles Palladium Mine, Northern Ontario, Canada. Miner. Deposita 2005, 40, 13–23. [Google Scholar] [CrossRef]
  108. Beckett-Brown, C.; Mcdonald, A.; Zhe, W. A Crystallographically Oriented Intergrowth of Siegenite (CoNi2S4) and Millerite from the Morokweng Impact Structure, South Africa: Chemistry, Texture, and Origin. Can. Mineral. 2018, 56, 705–722. [Google Scholar] [CrossRef]
  109. Kiefer, S.; Majzlan, J.; Chovan, M.; Števko, M. Mineral Compositions and Phase Relations of the Complex Sulfarsenides and Arsenides from Dobšiná (Western Carpathians, Slovakia). Ore Geol. Rev. 2017, 89, 894–908. [Google Scholar] [CrossRef]
Minerals 14 01008 g001
Figure 1. Simplified geological map of the Vardar Zone and the Trepça Mineral Belt (TMB), modified after [43,44]. Abbreviations: I = Batlava-Artana Zone; II = Belo Brdo-Stan Terg-Hajvalia Zone; III = Crnac Zone.
Figure 1. Simplified geological map of the Vardar Zone and the Trepça Mineral Belt (TMB), modified after [43,44]. Abbreviations: I = Batlava-Artana Zone; II = Belo Brdo-Stan Terg-Hajvalia Zone; III = Crnac Zone.
Minerals 14 01008 g001
Minerals 14 01008 g002
Figure 2. Simplified geological map of the Hajvalia−Kizhnica−Badovc ore field (a) and investigated Janjevo listvenite occurrence (b).
Figure 2. Simplified geological map of the Hajvalia−Kizhnica−Badovc ore field (a) and investigated Janjevo listvenite occurrence (b).
Minerals 14 01008 g002
Minerals 14 01008 g003
Figure 3. Simplified geological map of the investigated Melenica listvenite occurrence.
Figure 3. Simplified geological map of the investigated Melenica listvenite occurrence.
Minerals 14 01008 g003
Minerals 14 01008 g004
Figure 4. Field photographs of the studied listvenite localities in Janjevo (a–e) and Melenica (f): (a) Contact between serpentinite and listvenite close to JCR_6; (b) Foliated listvenite with dolomite veinlets along the foliation near the tectonic zone (JCR_1); (c) A zone of foliated listvenite surrounded by massive carbonate-type dolomite dominated listvenite (JCR_8); (d) Typical massive listvenite with greenish tint; (e) An example of weathered listvenite, where the greenish quartz-fuchsite-rich fragments are better preserved, and the surrounding carbonate-dominated elements of listvenite have been affected by weathering and the formation of Fe hydroxides (JCR_6); (f) Listvenite gossan in Melenica.
Figure 4. Field photographs of the studied listvenite localities in Janjevo (a–e) and Melenica (f): (a) Contact between serpentinite and listvenite close to JCR_6; (b) Foliated listvenite with dolomite veinlets along the foliation near the tectonic zone (JCR_1); (c) A zone of foliated listvenite surrounded by massive carbonate-type dolomite dominated listvenite (JCR_8); (d) Typical massive listvenite with greenish tint; (e) An example of weathered listvenite, where the greenish quartz-fuchsite-rich fragments are better preserved, and the surrounding carbonate-dominated elements of listvenite have been affected by weathering and the formation of Fe hydroxides (JCR_6); (f) Listvenite gossan in Melenica.
Minerals 14 01008 g004
Minerals 14 01008 g005
Figure 5. Examples of typical listvenite textures from Janjevo (a,b) and Melenica (c,d) observed in thin sections: (a) Dolomite−quartz mesh texture in listvenite accompanied by disseminated relics of chromian spinels; (b) Dolomite−quartz mesh texture in listvenite with a younger dolomite−quartz veinlet intersecting it; (c) Completely recrystallized listvenite to rock composed of rhodochrosite-siderite and some quartz accompanied by disseminated sulfides and chromian spinels; (d) Irregular patchy listvenite with older silica-rich zones, younger carbonate-rich zones, elongated carbonate veinlets, and disseminated sulfides. Abbreviations: Dol = dolomite; Qtz = quartz; Rds = rhodochrosite; Sd = siderite.
Figure 5. Examples of typical listvenite textures from Janjevo (a,b) and Melenica (c,d) observed in thin sections: (a) Dolomite−quartz mesh texture in listvenite accompanied by disseminated relics of chromian spinels; (b) Dolomite−quartz mesh texture in listvenite with a younger dolomite−quartz veinlet intersecting it; (c) Completely recrystallized listvenite to rock composed of rhodochrosite-siderite and some quartz accompanied by disseminated sulfides and chromian spinels; (d) Irregular patchy listvenite with older silica-rich zones, younger carbonate-rich zones, elongated carbonate veinlets, and disseminated sulfides. Abbreviations: Dol = dolomite; Qtz = quartz; Rds = rhodochrosite; Sd = siderite.
Minerals 14 01008 g005
Minerals 14 01008 g006
Figure 6. Reflected-light photomicrographs (a–d,f) and transmitted light photomicrograph (e) of listvenite textures from Janjevo (a–d) and Melenica (e,f): (a) Mesh texture of dolomite aggregates and quartz with Fe–Ni sulfides mostly at their contacts; (b) Disseminated chromian spinels and Ni–Fe sulfides in dolomite−quartz matrix; (c) Chromian spinel and pentlandite around pyrite I in a quartz−dolomite matrix; (d) Chromian spinel, sphalerite, and Fe–Ni sulfides in dolomite−dominated listvenite; (e) Epithermal rhodochrosite-siderite surrounded by quartz; (f) Fe–Ni sulfide polymineral aggregate in quartz surrounded by epithermal baryte with galena-sphalerite aggregates. Abbreviations: Brt = baryte; Cr spl = chromian spinel; Dol = dolomite; Gn = galena; Qz = quartz; Pn = pentlandite; Py = pyrite; Rds = rhodochrosite; Sd = siderite; Sp = sphalerite.
Figure 6. Reflected-light photomicrographs (a–d,f) and transmitted light photomicrograph (e) of listvenite textures from Janjevo (a–d) and Melenica (e,f): (a) Mesh texture of dolomite aggregates and quartz with Fe–Ni sulfides mostly at their contacts; (b) Disseminated chromian spinels and Ni–Fe sulfides in dolomite−quartz matrix; (c) Chromian spinel and pentlandite around pyrite I in a quartz−dolomite matrix; (d) Chromian spinel, sphalerite, and Fe–Ni sulfides in dolomite−dominated listvenite; (e) Epithermal rhodochrosite-siderite surrounded by quartz; (f) Fe–Ni sulfide polymineral aggregate in quartz surrounded by epithermal baryte with galena-sphalerite aggregates. Abbreviations: Brt = baryte; Cr spl = chromian spinel; Dol = dolomite; Gn = galena; Qz = quartz; Pn = pentlandite; Py = pyrite; Rds = rhodochrosite; Sd = siderite; Sp = sphalerite.
Minerals 14 01008 g006
Minerals 14 01008 g007
Figure 7. Reflected-light photomicrograph (a) and back-scattered electron images (BSE) (b–f) of listvenitization paragenesis from the Janjevo occurrence: (a) Multimineral aggregate of pyrite I and pentlandite, which is replaced by thiospinels and gersdorffite; (b) Pyrite I replacement after pyrrhotite overgrown by pentlandite crystals; (c) Pyrite I overgrown by pentlandite crystals; (d) Pentlandite crystals replaced by violarite and pyrite I; (e) Pentlandite remnants within violarite and pyrite I; (f) Pentlandite and pyrite I aggregate surrounded by younger gersdorffite crystals. Abbreviations: Dol = dolomite; Gdf = gersdorffite; Pn = pentlandite; Py = pyrite; Vio = violarite.
Figure 7. Reflected-light photomicrograph (a) and back-scattered electron images (BSE) (b–f) of listvenitization paragenesis from the Janjevo occurrence: (a) Multimineral aggregate of pyrite I and pentlandite, which is replaced by thiospinels and gersdorffite; (b) Pyrite I replacement after pyrrhotite overgrown by pentlandite crystals; (c) Pyrite I overgrown by pentlandite crystals; (d) Pentlandite crystals replaced by violarite and pyrite I; (e) Pentlandite remnants within violarite and pyrite I; (f) Pentlandite and pyrite I aggregate surrounded by younger gersdorffite crystals. Abbreviations: Dol = dolomite; Gdf = gersdorffite; Pn = pentlandite; Py = pyrite; Vio = violarite.
Minerals 14 01008 g007
Minerals 14 01008 g008
Figure 8. EPMA maps of the distribution of Fe, Ni, Co, S, As and BSE–image of multimineral pyrite I-pentlandite−violarite−gersdorffite aggregate from Janjevo listvenite. Abbreviations: Gdf = gersdorffite; Pn = pentlandite; Py = pyrite; Vio = violarite.
Figure 8. EPMA maps of the distribution of Fe, Ni, Co, S, As and BSE–image of multimineral pyrite I-pentlandite−violarite−gersdorffite aggregate from Janjevo listvenite. Abbreviations: Gdf = gersdorffite; Pn = pentlandite; Py = pyrite; Vio = violarite.
Minerals 14 01008 g008
Minerals 14 01008 g009
Figure 9. Reflected-light photomicrograph (c,f,g,i) and back-scattered electron images (BSE) (a,b,d,e,h,i) of listvenite paragenesis from Janjevo occurrence: (a) Monomineral millerite aggregate; (b) Monomineral millerite aggregate; (c) Millerite with regular, checkboard replacement by siegenite; (d) Millerite with regular, checkboard replacement by siegenite; (e) Millerite aggregate replaced by siegenite; (f) Violarite and pyrite crystals associated with galena; (g) Violarite associated with pyrite I crystals and galena infillings around aggregates; (h) Pyrite I—violarite aggregate with younger gersdorffite and ullmannite crystals; (i) Pyrite II aggregate crosscutted by dolomite II veinlet. Abbreviations: Dol = dolomite; Gdf = gersdorffite; Gn = galena; Mlr = millerite; Py = pyrite; Seg = siegenite; Ull = ullmannite Vio = violarite.
Figure 9. Reflected-light photomicrograph (c,f,g,i) and back-scattered electron images (BSE) (a,b,d,e,h,i) of listvenite paragenesis from Janjevo occurrence: (a) Monomineral millerite aggregate; (b) Monomineral millerite aggregate; (c) Millerite with regular, checkboard replacement by siegenite; (d) Millerite with regular, checkboard replacement by siegenite; (e) Millerite aggregate replaced by siegenite; (f) Violarite and pyrite crystals associated with galena; (g) Violarite associated with pyrite I crystals and galena infillings around aggregates; (h) Pyrite I—violarite aggregate with younger gersdorffite and ullmannite crystals; (i) Pyrite II aggregate crosscutted by dolomite II veinlet. Abbreviations: Dol = dolomite; Gdf = gersdorffite; Gn = galena; Mlr = millerite; Py = pyrite; Seg = siegenite; Ull = ullmannite Vio = violarite.
Minerals 14 01008 g009
Minerals 14 01008 g010
Figure 10. EPMA maps of the distribution of Ni, Co, Fe, S, As and BSE–image of polymineral pyrite I-violarite−gersdorffite−ullmannite aggregate from Janjevo listvenite. Abbreviations: Dol = dolomite; Gdf = gersdorffite; Py = pyrite; Qz = quartz; Vio = violarite.
Figure 10. EPMA maps of the distribution of Ni, Co, Fe, S, As and BSE–image of polymineral pyrite I-violarite−gersdorffite−ullmannite aggregate from Janjevo listvenite. Abbreviations: Dol = dolomite; Gdf = gersdorffite; Py = pyrite; Qz = quartz; Vio = violarite.
Minerals 14 01008 g010
Minerals 14 01008 g011
Figure 11. Ni vs. Co binary plot of n different generations of pyrite from Janjevo, Melenica, and Badovc [15] with marked detection limits for EPMA.
Figure 11. Ni vs. Co binary plot of n different generations of pyrite from Janjevo, Melenica, and Badovc [15] with marked detection limits for EPMA.
Minerals 14 01008 g011
Minerals 14 01008 g012
Figure 12. Composition of thiospinels from the Janjevo and Melenica compared to thiospinels from Badovc—Kosovo [15].
Figure 12. Composition of thiospinels from the Janjevo and Melenica compared to thiospinels from Badovc—Kosovo [15].
Minerals 14 01008 g012
Minerals 14 01008 g013
Figure 13. Sb vs. As binary plot of gersdorffite−ullmannite series from Janjevo and Melenica localities.
Figure 13. Sb vs. As binary plot of gersdorffite−ullmannite series from Janjevo and Melenica localities.
Minerals 14 01008 g013
Minerals 14 01008 g014
Figure 14. Ternary Ni–Co–Fe diagram of gersdorffite−ullmannite series from Janjevo and Melenica listvenite localities.
Figure 14. Ternary Ni–Co–Fe diagram of gersdorffite−ullmannite series from Janjevo and Melenica listvenite localities.
Minerals 14 01008 g014
Minerals 14 01008 g015
Figure 15. Back-scattered electron images (BSE) (d,h) and reflected-light photomicrograph (a–c,e–g,i) of listvenitization paragenesis from Melenica occurrence: (a) Millerite crystal replaced by violarite and overgrown by gersdorffite, ullmannite, and galena; (b) Millerite replaced by galena and overgrown by gersdorffite; (c) Millerite, violarite, and pyrite aggregate replaced by galena; (d) Polymineral aggregate of millerite, violarite, gersdorffite−ullmannite, galena, sphalerite, and chalcopyrite; (e) Millerite replaced by violarite, gersdorffite and galena in quartz matrix; (f) Polymineral aggregate of millerite, violarite, gersdorffite, ullmannite, galena, sphalerite in rhodochrosite−siderite and quartz matrix; (g) Gersdorffite crystals replaced by galena in quartz matrix, rhodochrosite−siderite; (h) Marcasite aggregates in rhodochrosite−siderite crosscutted by quartz−galena veinlet; (i) Galena associated with sphalerite and Pb–Sb sulfosalts. Abbreviations: Dol = dolomite; Gdf = gersdorffite; Gn = galena; Mlr = millerite; Mrc = Marcasite; Qz = quartz; Py = pyrite; Rds = rhodochrosite; Sd = siderite; Sp = sphalerite; Ull = ullmannite; Vio = violarite.
Figure 15. Back-scattered electron images (BSE) (d,h) and reflected-light photomicrograph (a–c,e–g,i) of listvenitization paragenesis from Melenica occurrence: (a) Millerite crystal replaced by violarite and overgrown by gersdorffite, ullmannite, and galena; (b) Millerite replaced by galena and overgrown by gersdorffite; (c) Millerite, violarite, and pyrite aggregate replaced by galena; (d) Polymineral aggregate of millerite, violarite, gersdorffite−ullmannite, galena, sphalerite, and chalcopyrite; (e) Millerite replaced by violarite, gersdorffite and galena in quartz matrix; (f) Polymineral aggregate of millerite, violarite, gersdorffite, ullmannite, galena, sphalerite in rhodochrosite−siderite and quartz matrix; (g) Gersdorffite crystals replaced by galena in quartz matrix, rhodochrosite−siderite; (h) Marcasite aggregates in rhodochrosite−siderite crosscutted by quartz−galena veinlet; (i) Galena associated with sphalerite and Pb–Sb sulfosalts. Abbreviations: Dol = dolomite; Gdf = gersdorffite; Gn = galena; Mlr = millerite; Mrc = Marcasite; Qz = quartz; Py = pyrite; Rds = rhodochrosite; Sd = siderite; Sp = sphalerite; Ull = ullmannite; Vio = violarite.
Minerals 14 01008 g015
Minerals 14 01008 g016
Figure 16. EPMA maps of the distribution of Fe, Ni, Co, S, As and BSE–image of multimineral pyrite I-millerite-violarite-gersdorffite-galena aggregate from Melenica listvenite. Abbreviations: Gdf = gersdorffite; Gn = galena; Mlr = millerite; Py = pyrite; Vio = violarite.
Figure 16. EPMA maps of the distribution of Fe, Ni, Co, S, As and BSE–image of multimineral pyrite I-millerite-violarite-gersdorffite-galena aggregate from Melenica listvenite. Abbreviations: Gdf = gersdorffite; Gn = galena; Mlr = millerite; Py = pyrite; Vio = violarite.
Minerals 14 01008 g016
Minerals 14 01008 g017
Figure 17. Paragenetic sequence of listvenite occurrences in Janjevo and Melenica. * = Intermediate-sulfidation epithermal mineralization; ** = GUS—Gersdorffite−ullmannite series; ? = minerals not observed in studied samples—replaced by younger minerals.
Figure 17. Paragenetic sequence of listvenite occurrences in Janjevo and Melenica. * = Intermediate-sulfidation epithermal mineralization; ** = GUS—Gersdorffite−ullmannite series; ? = minerals not observed in studied samples—replaced by younger minerals.
Minerals 14 01008 g017
Table 1. Description of the studied localities and samples from Janjevo and Melenica.
Table 1. Description of the studied localities and samples from Janjevo and Melenica.
LocalityOutcrop CodeNumber of Samples (Sample Names)Brief Locality/Sample DescriptionMineral
Composition *		Accessory
Minerals **
JanjevoJCR_16 (JCR_1A,
SV128, SV150A-D)		A small outcrop of 0.5 m thick listvenite at the contact of serpentinite with the flysch. Both foliated and massive listvenites are present.Dol, Qz, Ms, Cr SplPy, Pn, Vio,
Gdf, Sp, Gn
JCR_64 (JCR_6A,
SV133A-C)		Strongly weathered listvenite outcrop at contact with serpentinite along the road. Visible greenish mesh silica-fuchsite rich aggregates, while the surrounding carbonates are replaced by abundant Fe hydroxides.Dol, Qz, Mgs, MsCr Spl, Cal, Py, Mlr,
Seg, FeOOH
JCR_71 (JCR_7A)The outcrop of massive greenish listvenites below the waterfall. Products of initial/transitional listvenitization (talc and magnesite) are not visible macroscopically.Mgs, Dol, Tlc, QzCr Spl, Py, Mlr
JCR_82 (JCR_8A-B)An outcrop of listvenite with both foliated (dolomite veinlets) and massive textures.Dol, Qz, Lz, MntCr Spl, Cal, Py, Vio, Ulm, Sph, Gn
JCR_912 (JCR_Ni1-12)Big outcrop at the contact of listvenite and flysh series with a significant contribution of disseminated and veinlets of pyrite visible macroscopically.Dol, Qz, PyCr Spl, Mlr, Seg, Ccp
MelenicaM110 (M1_1-8,
N1_5, M3_1)		Outcrop of strongly silicified listvenite with veinlets and disseminated base metal sulfides.Qz, Rds, SdCr Spl, Py, Mrc, Gn,
Sp, Ccp, Vio, Seg, Mlr, Gdf, Ulm, Pld, Brt, Bnn, Ttr-Zn, Pb–Sb ss
Abbreviations: Bnn = bournonite; Brt = baryte; Cal = calcite; Ccp = chalcopyrite; Cr Spl = chromian spinel; Dol = dolomite; FeOOH = Fe hydroxides; Gdf = gersdorffite; Gn = galena; Lz = lizardite; Mgs = magnesite; Mlr = millerite; Mnt = montmorillonite; Ms = muscovite; Qtz = quartz; Pb–Sb ss = Pb–Sb sulfosalts; Pn = pentlandite; Py = pyrite; Rds = rhodochrosite; Seg = siegenite; Sd = siderite; Sp = sphalerite; Tlc = talc; Ttr-Zn = tetrahedrite-(Zn); Ulm = ullmannite; Vio = violarite; * = based on XRD and EPMA; ** = based on EPMA.
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

Share and Cite

MDPI and ACS Style

Kluza, K.; Pršek, J.; Mederski, S. Mineralogy and Geochemistry of Listvenite-Hosted Ni–Fe Sulfide Paragenesis—A Case Study from Janjevo and Melenica Listvenite Occurrences (Kosovo). Minerals 2024, 14, 1008. https://doi.org/10.3390/min14101008

AMA Style

Kluza K, Pršek J, Mederski S. Mineralogy and Geochemistry of Listvenite-Hosted Ni–Fe Sulfide Paragenesis—A Case Study from Janjevo and Melenica Listvenite Occurrences (Kosovo). Minerals. 2024; 14(10):1008. https://doi.org/10.3390/min14101008

Chicago/Turabian Style

Kluza, Konrad, Jaroslav Pršek, and Sławomir Mederski. 2024. "Mineralogy and Geochemistry of Listvenite-Hosted Ni–Fe Sulfide Paragenesis—A Case Study from Janjevo and Melenica Listvenite Occurrences (Kosovo)" Minerals 14, no. 10: 1008. https://doi.org/10.3390/min14101008

APA Style

Kluza, K., Pršek, J., & Mederski, S. (2024). Mineralogy and Geochemistry of Listvenite-Hosted Ni–Fe Sulfide Paragenesis—A Case Study from Janjevo and Melenica Listvenite Occurrences (Kosovo). Minerals, 14(10), 1008. https://doi.org/10.3390/min14101008

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop pFad - Phonifier reborn

Pfad - The Proxy pFad of © 2024 Garber Painting. All rights reserved.

Note: This service is not intended for secure transactions such as banking, social media, email, or purchasing. Use at your own risk. We assume no liability whatsoever for broken pages.


Alternative Proxies:

Alternative Proxy

pFad Proxy

pFad v3 Proxy

pFad v4 Proxy