Inclusions of the mineral-forming media in quartz of the Vysokogorskoe deposit are studied in detail. The compositions of the melts correspond to peraluminous potassium granites of normal alkalinity, depleted in rare alkalis, F, and Cl. The water content in the melts reached 7–9 wt %; CO2 and CH4 were also important in mineralizing fluids. Quartz crystallized at 620–650°C. Assemblages of four types have been identified as primary fluid inclusions: (1) inclusions of carbonate or sulfate aqueous solutions coexisting with melt inclusions, (2) low-density vapor-dominated primarily magmatic inclusions, (3) presumably postmagmatic low-salinity aqueous and vapor-dominated inclusions, and (4) multiphase fluid inclusions associated with vapor-dominated ones also formed at the postmagmatic stage. Daughter pyrosmalite–(Fe) and hibbingite, which was found for the first time in inclusions from quartz of the Vysokogorskoe deposit, made it possible to characterize the solutions as high-salinity chloride Na/K and Fe2+. Presumably, those solutions may have been the most efficient in Sn transport during the formation of fluid–explosive breccias and vein mineralization of the Vysokogorskoe deposit. The magma chamber itself most likely served as a heat source and, to a large extent, a source of aqueous fluid for the hydrothermal system of the deposit.

Inclusions of the mineral-forming media in quartz of the Vysokogorskoe deposit are studied in detail. The compositions of the melts correspond to peraluminous potassium granites of normal alkalinity, depleted in rare alkalis, F, and Cl. The water content in the melts reached 7–9 wt

An Erratum to this paper has been published: https://doi.org/10.1134/S1028334X22330017

Rare minerals represented by oxides, fluorides, F-carbonates and REE arsenates in association with monazite-Ce, monazite-Th, xenotime-Y and zonal REE fluorite were identified in the rare-metal ores of the Sn–W deposits of Lesser Khingan, Amur region. Rare lanthanide minerals are described, including fluocerite, bastnaesite, and gasparite-Ce, which was found for the first time in Russia in the Sn–W greisens, and chernovite-Y, the second find in the greisens of the Russian Far East. The influence of arsenic fluids at the late hydrothermal stage caused the replacement of xenotime-Y and monazite-Ce by diverse REE minerals with different lanthanide proportions. It is found that these minerals differ in chemical composition from the same minerals described in other deposits elsewhere. Due to the variable valence state of arsenic and the complete isomorphism between rare earths, arsenates can be used as indicators of redox conditions of their deposition.

In the Sn–W greisen deposits of the Karadub ore field, rare arsenates of REEs chernovite-(Y) and gasparite-(Ce), associated with topaz, fluorite, fluocerite, and bastnaesite, have been identified. They replace early xenotime-(Y) and monazite-(Ce). Chernovite-(Y) and gasparite-(Ce) from Sn–W greisens differ in their chemical composition from the same minerals previously described elsewhere. Chernovite-(Y) differs in the minimum content of Y with only 0.47 to 0.26 atoms in the formula (a.p.f.) and a relatively high content of light REEs of 0.111–0.254 (a.p.f.). Gasparite-(Ce) has a high Nd content of 0.28 (a.p.f.). REE arsenates were formed by substituting xenotime (Y), monazite (Ce), and REE-bearing fluorite under strongly oxidizing conditions.

Geochemical, isotope-geochemical, geochronolochical and thermobarometric study showed that the Badzhal, Mayo-Chan and Kavalerovo zones from Sikhote-Alin-Northern Sakhalin orogenic belt comprise: (1) oldest and geochemically and isotopically distinctive alkali mafic rocks, whose formation was related to mantle (asthenospheric) diapir. The possible regional distribution of the diapir is likely marked by subalkaline rocks (monzonites) having mantle Sr (0,7050) and Nd (0,5125) isotopic compositions at the Central (Tigrinoe deposit) and Southern (Kavalerovo district) Sikhote-Alin; (2) Tin-bearing ore-magmatic systems of the studied zones at the “ore region” level have similar intricate multi-root structure of generation area. 3) Magmatic evolution accompanying by increasing ore-bearing potential results in the final appearance of Li-F granites in the Badzhal Complex, and tourmaline granites in the Silinka Complex of the Myao-chan zone (Gonevchuk, 2002). The elevated F and Cl contents and high water content as parameters responsible for ore potential of melt were confirmed by thermobarometric data (Bortnikov et al, 2019). Some associations of fluid and melt inclusions indicate that magma crystallization was accompanied by degassing with exsolution of water-rich fluids, which is required to form ore bodies in OMS. These data confirm significant role of mantle in the formation of the Myao-Chan and Badzhal zones, as well as early cassiterite—stannite—sulfide stage of the Arsen’evskoe deposit of the Kavalerovo district. Numerical simulation of granitoids of the studied zones performed using logical-information method by I.A. Chizhova (2010) confirms crustal-mantle nature of magmatic complexes formed under transform continental margin and subduction settings. These systems are characterized by different geochemical features, in particular, different proportions of high-field strength (Sc, Y, Zr, Hf, Pb, U, Th, Nb), REE, and siderophile (Co, Ni, Cr, V, Cu) elements. Obtained results in combination with previous data indicate that the Badzhal, Myao-Chain, and Kavalerovo zones were formed through several episodes of the growth and reworking of the Sikhote Alin’ Mesozoic continental crust, which were triggered by underplating. Granitoids and genetically related tin—base metal deposits were formed at final stage. The revealed difference in Sr-Nd composition of the granitoids could be caused by both initial geochemical crustal heterogeneity and the different degree of crustal contamination. Geochemical and isotopic characteristics of the studied granitoids show that they were mainly derived through melting of juvenile metamafic crust, with subordinate contribution of metasedimentary rocks. The ore-bearing magmatic complexes were formed during a change of transform margin setting by accretion of Early Cretaceous terranes of the Sikhote Alin—North Sakhalin orogenic belt. Observed petrogeochemical diversirty of the granitoids from different zones could be caused by variations of sedimentary material, as well as by contamination of magmas by upper crustal material during emplacement, different contribution of mantle source, and diverse mechanisms of mantle-crustal interaction (Khanchuk et al, 2019). Obtained petrochemical, geochemical, and isotopic-geochemical data on the granitoids from the studied zones provide better understanding of diversity of tin-bearing magmatism and conditions of magma generation and evolution in transform margin setting at the continent-ocean boundary.

Tourmaline from the Solnechnoe hydrothermal granitoid-related tin deposit in the Khabarovsk Krai, Russian Far East has been studied with electron microprobe, infrared and Mossbauer spectroscopy. Tourmaline formed in three distinct stages with different types of chemical substitution. Tourmaline from the first unmineralised stage is classified as dravite or schorl, which could be enriched locally in Ca, the X-site vacancy and F. This tourmaline is characterised by the Fe <-> Mg and X vacancy + Al <-> Na + Fe substitutions. The second, molybdenum-stage tourmaline, is schorl-dravite and fluor-schorl-fluor-dravite enriched in Ca, and a few compositions belong to the calcic group. The predominant substitution is Ca + Mg <-> Na + Al. The third, tin-stage tourmaline, is classified as schorl-dravite with some tourmalines being fluor-schorl, oxy-schorl, foitite and magnesio-foitite. The tin-stage tourmaline is characterised by the substitutions Fe2+ <-> Mg, Al-tot + O2- <-> Fe2+ + OH-, and Fe3+ <-> Al-tot. An increase of the Fe3+/Fe-tot value from 3-9% in the molybdenum stage to 12-16% in the tin-stage tourmalines indicates an increase in oxidation potential, which possibly contributed to cassiterite deposition. Comparison of tourmalines from greisen, porphyry and intrusion-related tin deposits worldwide shows they differ in primary chemical substitutions so can be characterised by this mechanism. The Fe3+/Fe-tot value in tourmaline also appears to be one of the indications for the tin deposit type. The Fe3+/Fe-tot value increases from <10% in greisen tourmaline through 15% in tourmaline from intrusion-related deposits to 20% in tourmaline from porphyry deposits.

With a view to reveal special characteristics of the transition stage from granite crystallization to rare-metal ore deposition it is studied Badzhal tin-bearing magmatic-fluid system of eponymously-named volcano-plutonic zone of the Middle Priamyrie. For that end the detail research of melt, fluid-melt and fluid inclusions and oxygen isotopes from minerals of granitoids from Verkne-Urmi massif from Badzhal volcano-plutonic zone and also minerals of Sn-W deposits Pravo-Urmi and Blizhnee have been carried out. The formation of greisens and hydrothermal veins were caused by the development of the integrated system associating with establishing of Verkne-Urmi granite massif which is one of a dome fold of Badzhal cryptobatholith. For the first time for tin deposits it has been followed up the transition from the magmatic phase of granite crystallization to the hydrothermal ore formation stage and the evolution of magmatic fluid from its separation from magmatic melt to Sn-W ore deposition. The direct evidence of tin-bearing fluid separation under melt crystallization is combined fluid-melt inclusions. Glass composition in inclusions shows that granites and granite-porphyry were crystallizing from acid and from limited to high-aluminous melts, that is value ASI changes from 0.95 to 1.33 and a content of alkalies varies from 6.02 up to 9.02 mass.%. Cl and F concentrations in glasses are according 0.03–0.14 and 0.14–0.44 mass.% and turned out to be higher of same in the total composition of rocks (0.02 and 0.05–0.13 mass.% in accordance). These differences indicate that Cl and F could be separated from granite melt under its crystallization and degasation. H2O content made from total deficiency electron microprobe analysis is 8–11 mass.%. This evaluation was made inclusive of a probable effect of “Na loss” (Nielsen, Sigurdson, 1981) under aqueous glass crystallization. Considering a high error of a such estimation (Devine et al., 1995), it should take to obtained values as a very approximate evaluation and consider that examined melts contained about 9,5–10,0 mass.% of H2O. The results of melt inclusion examination show that at any rate a part of melt forming magmatic rocks of Badzhal Ore Magmatic System are crystallizing at about T = 650 °C. These melts were acid, limited fluoride and meta- and high aluminous. The reason of low temperatures of its crystallization are likely a high pressure of aqua and also a increased content of F. Most likely that examined inclusions characterize the final stage of establishing of the massif, herewith at the system crystals, residual liquor and magmatic fluid phase coexist. The fluid from which greisens of Pravo-Urmi deposit formed is similar in properties to the supercritical fluid absorbing by magmatic minerals. The salinity of this fluid varying from ~9 to 12 mass.% equiv. NaCl, maximal T = 550 °C (with consideration for the temperature correction of T gom on a pressure ~1 кbar) are similar to such of magmatic fluid, which permit to connect its origin with pluton cooling. The formation of greisens and quartz-topaz veins of Pravo-Urmi deposit is related to fall of temperature of magmatic fluid from 550–450 up to 480–380 °C. The evolution of fluid deposited quartz-cassiterite veins of Blizhnee deposit, which based upon oxygen isotope composition (d18ОН2О ≈ 8.5‰) also separated from magma, was going at more subsurface conditions under much lesser pressure. That led to the gas separation of a fluid with salinity ~13 mass.% equa. NaCl under T = 420–340 °C on thin low salinity vapour and brine with concentration 33.5–37.4 mass.% equiv. NaCl. The research of oxygen isotope system testifies that oxygen isotope composition of ore-forming fluid controlled by equilibrium with granites at wide interval tempera­tures (from ~700 °С up to the beginning of greisen crystallization). Correspondence of measured and calculation data of the offered model indicates that the considerable volume of external fluid with other isotope characteristics which did not reach the isotope equilibrium with Verkhne-Urmi massif did not come into the magmatic isotope system. The discovered differences of physico-chemical conditions for two studied deposits are not “critical” and support an idea about their formation as the single magmatic-fluid system.

The colloform tin ores from the deposit Verkhnee at the Primorye have been studied with the aid of X- ray spectroscopic microanalysis and the scanning electron microscopy with the energy dispersive analyzer LINK-ISIS that allowed revealing the primary and the secondary zoning of a colloform cassiterite and to determine the phase composition of these formations. The primary zoning of the mineral forms at the early stage of the deposition of stannates from colloidal solutions and is characterized by the alternation of hydrostannates of various composition. The secondary zoning is superimposed zonality, and it forms at the process of the stannate crystallization. The metacolloidal varieties of concentric-zonal aggregates are produced by hydrostannates of Ca, Fe, Cu, In, of variable compositions, soluble in acids, in which the admixtures of As, Al, Si, Cd, Co, Sb, Zn, Ag are marked. Sn content according to the energy dispersive analysis is 42—54%. Infrared adsorption spectroscopy allowed finding out in hydrostannates the presence of the hydroxyl water at the area of the valence vibrations Sn-OH. In the colloform cassiterite a new phase Pb5 As2 O8 with various correlation of Pb and As in size 30—50 mk has been found.

The colloform tin ores from the deposit Verkhnee at the Primorye have been studied with the aid of X- ray spectroscopic microanalysis and the scanning electron microscopy with the energy dispersive analyzer LINK-ISIS that allowed revealing the primary and the secondary zoning of a colloform cassiterite and to determine the phase composition of these formations. The primary zoning of the mineral forms at the early stage of the deposition of stannates from colloidal solutions and is characterized by the alternation of hydrostannates of various composition. The secondary zoning is superimposed zonality, and it forms at the process of the stannate crystallization. The metacolloidal varieties of concentric-zonal aggregates are produced by hydrostannates of Ca, Fe, Cu, In, of variable compositions, soluble in acids, in which the admixtures of As, Al, Si, Cd, Co, Sb, Zn, Ag are marked. Sn content according to the energy dispersive analysis is 42—54%. Infrared adsorption spectroscopy allowed finding out in hydrostannates the presence of the hydroxyl water at the area of the valence vibrations Sn-OH. In the colloform cassiterite a new phase Pb 5 As 2 O 8 with various correlation of Pb and As in size 30—50 mk has been found.

С целью выяснения особенностей переходной стадии от кристаллизации гранитов к отложению редкометальных руд изучена Баджальская оловоносная магматогенно-флюидная система одноименной вулкано-плутонической зоны среднего Приамурья. Для этого проведено детальное исследование расплавных, флюидно-расплавных и флюидных включений и изотопного состава кислорода минералов гранитоидов Верхнеурмийского массива Баджальской вулкано-плутонической зоны и минералов Sn-W руд месторождений Правоурмийское и Ближнее. Образование грейзенов и гидротермальных жил Правоурмийского и Ближнего месторождений происходило в результате развития единой магматогенно-флюидной системы, связанной со становлением Верхнеурмийского массива гранитов – одного из куполов Баджальского криптобатолита. Впервые для оловорудных месторождений прослежены переход от магматической фазы кристаллизации гранитов к гидротермальной стадии рудообразования и эволюция магматогенного флюида от его отделения от магматического расплава к отложению Sn-W руд. Прямым доказательством отделения оловоносного флюида при кристаллизации магмы служат комбинированные флюидно-расплавные включения. Состав стекол в них указывает на то, что граниты и гранит-порфиры массива кристаллизовались из кислых от умеренно- до высокоглиноземистых расплавов, значения ASI в которых изменяются от 0.95 до 1.33, а содержание щелочей варьирует от 6.02 до 9.02 мас.%. Концентрации Cl и F в стеклах составили соответственно 0.03–0.14 и 0.14–0.44 мас.% и оказались выше таковых в валовом составе пород (0.02 и 0.05–0.13 мас.% соответственно). Эти различия указывают, что хлор и фтор могли быть удалены из гранитного расплава при его кристаллизации и дегазации. Содержание H 2 O, определенное по недостатку суммы микрозондовых анализов, составило 8–11 мас.%. Это определение было сделано с учетом возможного эффекта “потери натрия” (Nielsen, Sigurdson, 1981) при анализе водосодержащих стекол. Учитывая высокую погрешность такого определения (Devine et al. , 1995), к полученным величинам следует относиться как к очень приблизительной оценке и считать, что изученные расплавы содержали около 9.5–10.0 мас.% воды. Результаты исследования расплавных включений показывают, что по крайней мере часть расплава, формировавшего магматические породы Баджальской РМС, кристаллизовалась при температурах около 650 °С. Эти расплавы по составу были кислыми, умеренно фтористыми и мета- и высокоглиноземистыми. Причиной низких температур их кристаллизации, по-видимому, являются высокое давление воды, а также повышенное содержание фтора. Наиболее вероятно, что изученные включения характеризуют заключительную стадию становления массива, на которой в системе ­сосуществуют кристаллы, остаточный расплав и магматогенная флюидная фаза. Флюид, из которого образовались грейзены Правоурмийского месторождения, очень близок по своим свойствам к надкритическому флюиду, захваченному магматическими минералами. Его соленость, изменяющаяся от ~9 до 12 мас.% эквивалентных NaCl, а максимальные температуры 550 °С (с учетом коррекции температур их гомогенизации на давление ~1 кбар) близки к таковым магматогенного флюида, что позволяет связать его происхождение с остыванием гранитного плутона. Образование грейзенов и кварц-касситерит-топазовых жил Правоурмийского месторождения связано с понижением температуры магматогенного флюида от 550–450 до 480–380 °С. Эволюция флюида, отложившего кварц-касситеритовые жилы Ближнего месторождения, который судя по изотопному составу кислорода (d 18 О Н2О ≈ 8.5‰) также отделился от магмы, протекала в более приповерхностных условиях при значительно меньших давлениях. Это привело к тому, что флюид с соленостью ~13 мас.% эквивалентных NaCl при температурах 420–340 °С претерпел фазовую сепарацию на малоплотный низкосоленый пар и рассол с концентрацией 33.5–37.4 мас.% эквивалентных NaCl. Изучение изотопной системы кислорода свидетельствует, что изотопный состав кислорода рудообразующего флюида контролировался равновесием с гранитами в широком интервале температуры (от ~700 °С до начала кристаллизации грейзенов). Соответствие измеренных и расчетных данных предложенной модели указывает на то, что в магматогенно-флюидную систему не поступило значительных объемов внешнего флюида с иными изотопными характеристиками, который не достиг изотопного равновесия с Верхнеурмийскими гранитами. Выявленные различия физико-химических условий двух изученных месторождений не являются “критическими” и подтверждают мнение о формировании их в составе единой магматогенно-флюидной системы.

Ванадиевый травяно-зеленый дравит обнаружен в маломощных (до 10 см) кварцевых жилах, пересекающих черные кремнистые сланцы позднего протерозоя, обогащенные ураном и ванадием (до 50 ppm). Содержание V2O3 в – до 5.34% при низком содержании железа и повышенном магния. По всей вероятности, ванадий занимает в структуре минерала в основном Z-позицию. Получены спектры диффузного отражения в диапазоне 350–2500 нм и люминесценции при возбуждении УФ-излучением N-лазера. Появление ванадия в качестве хромофора и люминофора в метаморфических породах интерпретируется как индикатор древних океанических структур на континентах. В статье 11 рисунков, 2 таблицы, 21 литературная ссылка.

Detailed geological observations and analytical studies make it possible to distinguish two groups of fluid-explosion breccias (FEB) in the Vysokogorskoe tin deposit of the Kavalerovo ore district. These breccias are assumed to be related to different stages of geological (geodynamic) evolution and played different roles in ore formation. The earlier breccias (79–69 Ma), which were altered by boron metasomatism and subsequent main tin mineralization, were most probably formed at the Cretaceous subduction stage. The later breccias (55–51 Ma) are syngenetic to the dacite (rhyolite) porphyry dikes of the Paleocene–Eocene transform stage. They were formed after precipitation of the majority of the cassiterite, but prior to the latest quartz–fluorite–carbonate stage of ore formation. According to the Sillitoe classification, the explosion breccias of the Vysokogorskoe deposit correspond to a magmatic–hydrothermal genetic type. They are characterized by multiple brecciation and intersection by small bodies of porphyritic rhyolites.

The distribution of REEs and some minor elements in tourmalines of different associations and deposits of the Russian Far East is studied by the methods of ICP-MS, ICP-MS with laser ablation and scanning electron microscopy. The duality of REE speciation in tourmaline is established: in high-temperature varieties, most REEs (mainly HREEs) are incorporated in rare minerals (monazite, xenotime, zircon, and F–Ce–Y carbonate), whereas hydrothermal ores are characterized by isomorphic incorporation of LREEs in the mineral structure, as well as by a fine admixture of zircon at the expense of detrital clasts in flyschoid rocks with the zones of tourmalinization.

The paper considers for the first time the morphology, composition, and conditions of formation of the greisens of the Solnechnoe deposit (Komsomol’sk ore district), a typical cassiterite–silicate assemblage. The greisens are localized in the root parts of the deposit and represent a system of veins and veinlets formed in the contraction fractures of the metasomatically altered roof of the monzogranite intrusion (age of 94–92 Ma). The cassiterite–chlorite–carbonate–muscovite–quartz composition of the greisens with admixture of topaz, fluorite, and apatite reflects the composition of the monzogranites. The greisens are close in age (85.3 Ma on muscovite) to the granitic aplites (80–85 Ma on the whole-rock and biotite) of the final phase of the intrusive magmatism. The fluid regime of their formation differs from that of the economic ores in higher temperature, pressure, and salinity. One distinguishing feature of the greisens is elevated contents of LREE, U, and Th, which are incorporated in the REE fluorcarbonates, thorite, and uranothorite crystallizing together with cassiterite.