In weakly metamorphosed massive sulfide deposits of the Urals (Dergamysh, Yubileynoe, Yaman-Kasy, Molodezhnoe, Valentorskoe, Aleksandrinskoe, Saf’yanovskoe), banded sulfides (ore diagenites) are recognized as the products of seafloor supergene alteration (halmyrolysis) of fine-clastic sulfide sediments and further diagenesis leading to the formation of authigenic mineralization. The ore diagenites are subdivided into pyrrhotite-, chalcopyrite-, bornite-, sphalerite-, barite- and hematite-rich types. The relative contents of sphalerite-, bornite- and barite-rich facies increases in the progression from ultramafic (=Atlantic) to bimodal mafic (=Uralian) and bimodal felsic (=Baymak and Rudny Altay) types of massive sulfide deposits. The ore diagenites have lost primary features within the ore clasts and dominantly exhibit replacement and neo-formed nodular microtextures. The evolution of the mineralogy is dependent on the original primary composition, sizes and proportions of the hydrothermal ore clasts mixed with lithic serpentinite and hyaloclastic volcanic fragments together with carbonaceous and calcareous fragments. Each type of ore diagenite is characterized by specific rare mineral assemblages: Cu–Co–Ni sulfides are common in pyrrhotite-rich diagenites; tellurides and selenides in chalcopyrite-rich diagenites; minerals of the germanite group and Cu–Ag and Cu–Sn sulfides in bornite-rich diagenites; abundant galena and sulfosalts in barite- and sphalerite-rich diagenites and diverse tellurides characterize hematite-rich diagenites. Native gold in variable amounts is typical of all types of diagenites.

For the first time, extremely high Se and In contents were determined for the pinches of massive sulfide orebodies that are composed of small-clastic layered sulfide sediments transformed during submarine supergenesis. Se (clausthalite and naumannite) and In (roquesite) minerals were found. Hydrothermal chalcopyrite, a significant amount of which is present in the clasts of paleohydrothermal black smoker chimneys, was the source of Se. Most of the amount of In was contributed during dissolution of clasts of hydrothermal sphalerite, which is unstable in the submarine oxidation zone in the presence of oxidized pyrite.

The pyrite nodules from ore diagenites of the Urals massive sulfide deposits associated with various background sedimentary rocks are studied using optical and electron microscopy and LA-ICP-MS analysis. The nodules are found in sulfide–black shale, sulfide–carbonate–hyaloclastite, and sulfide–serpentinite diagenites of the Saf’yanovskoe, Talgan, and Dergamysh deposits, respectively. The nodules consist of the core made up of early diagenetic fine-crystalline (grained) pyrite and the rim (±intermediate zone) composed of late diagenetic coarse-crystalline pyrite. The nodules are replaced by authigenic sphalerite, chalcopyrite, galena, and fahlores (Saf’yanovskoe), sphalerite, chalcopyrite and galena (Talgan), and pyrrhotite and chalcopyrite (Dergamysh). They exhibit specific accessory mineral assemblages with dominant galena and fahlores, various tellurides and Co–Ni sulfoarsenides in sulfide-black shale, sulfide–hyaloclastite–carbonate, and sulfide-serpentinite diagenites, respectively. The core of nodules is enriched in trace elements in contrast to the rim. The nodules from sulfide–black shale diagenites are enriched in most trace elements due to their effective sorption by associated organic-rich sediments. The nodules from sulfide–carbonate–hyaloclastite diagenites are rich in elements sourced from seawater, hyaloclastites and copper–zinc ore clasts. The nodules from sulfide–serpentinite diagenites are rich in Co and Ni, which are typical trace elements of ultramafic rocks and primary ores from the deposit.

Halmyrolysis, as one of the global processes of alteration of seafloor hydrothermal sediments, needs to be recognized in terms of mineral and trace element evolution to elaborate new criteria for metallogenic and geoecological forecasts with respect to ocean exploration. The purpose of this paper is to explain trace elements’ behavior during the halmyrolysis of sulfide deposits. This task is resolved using an LA-ICP-MS analysis of iron oxyhydroxides (IOHs) on examples of oxidized pyrrhotite-rich diffusers of the ultramafic-hosted Pobeda-1 hydrothermal field (Mid-Atlantic Ridge). The IOHs formed after the sulfides were enriched in seawater-derived trace elements (Na, K, Mg, Ca, Sr, P, U, Mo, V, REE, Cr). Six trace element assemblages (TEAs) are statistically recognized for the IOHs. TEA-I (Cu, In, Sn, Bi, Se, Te) is inherited from chalcopyrite, isocubanine and bornite microinclusions. TEA-II is typical of Zn sulfides (Zn, Cd, Sb, Tl, Ag) interacted with seawater (Mg, U, Mo, Ni, Na, K) and hydrothermal fluid (Eu). TEA-III (Ca, Sr, Cu, Si, Se, P, As) reflects the inclusions of aragonite, opal, atacamite and possibly native selenium, while P and As occur as absorbed oxyanion groups on IOHs or Ca–Fe hydroxyphosphates. TEA-IV (Al, Ga, Ge, Tl, W, Ti ± Mn, Co, Ba) indicates the presence of minor clays, Co-rich Mn oxyhydroxides and barite. TEA-V with Pb and V is closely related to TEA-VI with REEs except for Eu. The halmyrolysis of sulfides includes two stages: (i) oxidation of S(II) of primary sulfides and the formation of supergene sulfides, which scavenge the redox-sensitive elements (e.g., U, Mo, Ni, Eu), and (ii) oxidation of Fe (II) to Fe (III) and absorption of most elements of TEAs III, IV, V and VI by IOHs.