The Vathi porphyry Cu-Au±Mo deposit is located in the Kilkis ore district, northern Greece. Hydrothermally altered and mineralized samples of latite and quartz monzonite are enriched with numerous rare and critical metals. The present study focuses on the bulk geochemistry and the mineral chemistry of pyrite, chalcopyrite, magnetite, and titanite. Pyrite and chalcopyrite are the most abundant ore minerals at Vathi and are related to potassic, propylitic, and sericitic hydrothermal alterations (A- and D-veins), as well as to the late-stage epithermal overprint (E-veins). Magnetite and titanite are found mainly in M-type veins and as disseminations in the potassic-calcic alteration of quartz monzonite. Disseminated magnetite is also present in the potassic alteration in latite, which is overprinted by sericitic alteration. Scanning electron microscopy and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analyses of pyrite and chalcopyrite reveal the presence of pyrrhotite, galena, and Bi-telluride inclusions in pyrite and enrichments of Ag, Co, Sb, Se, and Ti. Chalcopyrite hosts bornite, sphalerite, galena, and Bi-sulfosalt inclusions and is enriched with Ag, In, and Ti. Inclusions of wittichenite, tetradymite, and cuprobismutite reflect enrichments of Te and Bi in the mineralizing fluids. Native gold is related to A- and D-type veins and is found as nano-inclusions in pyrite. Titanite inclusions characterize magnetite, whereas titanite is a major host of Ce, Gd, La, Nd, Sm, Th, and W.

The colloform pyrite variety incorporates many trace elements that are released in the environment during rapid oxidation. Colloform pyrite from the Chiprovtsi silver–lead deposit in Bulgaria and its oxidation efflorescent products were studied using X-ray diffractometry, scanning electron microscopy, electron microprobe analysis, and laser ablation inductively coupled plasma mass spectrometry. Pyrite is enriched with (in ppm): Co (0.1–964), Ni (1.8–3858), Cu (2.9–3188), Zn (3.1–77), Ag (1.2–1771), As (8179–52,787), Se (2.7–21.7), Sb (48–17792), Hg (4–2854), Tl (1.7–2336), Pb (13–7072), and Au (0.07–2.77). Gypsum, anhydrite, szomolnokite, halotrichite, römerite, copiapite, aluminocopiapite, magnesiocopiapite, coquimbite, aluminocoquimbite, voltaite, and ammoniomagnesiovoltaite were identified in the efflorescent sulfate assemblage. Sulfate minerals contain not only inherited elements from pyrite (Cr, Fe, Co, Ni, Cu, Zn, Ag, In, As, Sb, Hg, Tl, and Pb), but also newly introduced elements (Na, Mg, Al, Si, P, K, Ca, Sc, Ti, V, Mn, Ga, Rb, Sr, Y, Zr, Sn, Cs, Ba, REE, U, and Th). Voltaite group minerals, copiapite, magnesiocopiapite, and römerite incorporate most of the trace elements, especially the most hazardous As, Sb, Hg, and Tl. Colloform pyrite occurrence in the Chiprovtsi deposit is limited. Its association with marbles would further restrict the oxidation and release of hazardous elements into the environment.

The Gerakario Cu-Au porphyry deposit in the Kilkis ore district, northern Greece, contains epithermal quartz-stibnite veins on the eastern side of the deposit, which crosscut a two-mica gneiss. Metallic mineralization in these veins consists of stibnite + berthierite + native antimony + pyrite + arsenopyrite, and minor marcasite, pyrrhotite, chalcopyrite, löllingite, and native gold. Bulk geochemical analyses of the ore reveal an enrichment in critical and rare metals, including Ag, Au, Bi, Ce, Co, Ga, La, and Sb. Analysis of stibnite with LA-ICP-MS showed an enrichment in base metals (As, Cu, Pb), as well as weak to moderate contents of critical and rare metals (Ag, Bi, Ce, La, Re, Sm, Th, Ti, Tl). A statistical analysis of the trace elements show a positive correlation for the elemental pairs Ce-La, Ce-Sb, and La-Sb, and a negative correlation for the pair Bi-Sb. Fluid inclusions in the A-type veins of the porphyry-style mineralization show the presence of fluid boiling, resulting in a highly saline aqueous fluid phase (35.7 to 45.6 wt.% NaCl equiv.) and a moderately saline gas phase (14 to 22 wt.% NaCl equiv.) in the system H₂O-NaCl-KCl at temperatures varying between 380° and 460 °C and pressures from 100 to 580 bar. Mixing of the moderate saline fluid with meteoric water produced less saline fluids (8 to 10 wt.% NaCl equiv.), which are associated with the epithermal quartz-stibnite vein mineralization. This process took place under hydrostatic pressures ranging from 65 to 116 bar at a depth between 600 and 1000 m, and at temperatures mainly from 280° to 320 °C.

This paper describes a newly discovered Bi-Cu±Au mineralization co-occurring with Pb-Zn-Ag hydrothermal mineralization within the Kizhnica-Hajvalia-Badovc ore field, central Kosovo, Vardar Zone. The mineralogy of two styles of Bi-Cu±Au mineralization was described using EPMA in combination with reflected and transmitted light microscopy. Hydrothermal Cu-Bi veinlets in the Kizhnica andesite quarry consist of Bi sulfosalts (bismuthinite, cosalite, aikinite, and krupkaite), pyrite, hematite, chalcopyrite, galena, sphalerite, and tetrahedrite group minerals. Disseminated Bi-Au-Cu-Te mineralization from the contact type of mineralization (hornfels) consists of Bi sulfosalts (cannizzarite, bismuthinite, galenobismutite, cosalite), associated with sulfarsenides (arsenopyrite, gersdorffite, and cobaltite), base metal sulfides (chalcopyrite, pyrite, sphalerite, pyrrhotite, and galena), native gold, native bismuth, and tetradymite. LA-ICP-MS analyses of sphalerite, chalcopyrite, and tetrahedrite indicate increased content of In and Sn in the Kizhnica Bi-Cu-Au mineralizing system, while LA-ICP-MS analyses in pyrites show the presence of many elements, e.g., Au, As, Co, Sb, Tl, Hg, Pb, Bi related to the structure of pyrite or controlled by nano-inclusions. The results suggest a connection between Bi-Cu±Au mineralization and the proximity to intrusive rocks, which may be helpful for Au exploration in Kosovo.