HYDROTHERMAL AND ORE-BEARING APATITES
Аннотация и ключевые слова
Аннотация (русский):
An extensive review describes the unique properties of apatite, which, due to the peculiarities of its structure, allows for diverse isomorphic substitutions both in its cationic part (Mn, Sr, Ba, REE, U, etc.) and in the anionic part (CO 2, SO3, SiO 2, OH, F, Cl, etc.). Since these substitutions occur under well-defined conditions in both endogenous thermal and exogenous low-temperature processes, the composition of apatite turns out to be an indicator of these processes. At the same time, the conditions of formation of most igneous and metamorphic rocks can be judged by the composition of accessory apatite, and the genesis of phosphorus ores, both endogenous (Khibiny, Kiruna type, etc.) and exogenous (phosphorites), is judged by the composition of ore-forming apatite. The review is based on the recent "Irish" review 2020, covering 147 literary sources and compiled by 4 co-authors from Dublin and one from Stockholm [130]. Since the compilers of the "Irish" review practically did not use literature in Russian, it became necessary to seriously supplement it with the data given in the domestic literature, as well with a number of foreign works that are not covered by the "Irish" review. The resulting text should make it much easier for the geologist reader to use apatite in practice as a remarkable mineral-an indicator of various geological processes

Ключевые слова:
apatite, carbonate-apatite (francolite), halogens, sulfate, trace elements, REE, manganese, strontium, neodymium, uranium
Текст

In 2012, Ukrainian authors [18] assessed the feasibility of using REE in apatites of endogenous deposits of the Ukrainian Shield as an indicator mineral of ore formation conditions. Apatite from arrays of gabbro-syenite and alkaline-ultramafic formations of the Ukrainian Shield, as well as from P-Fe-Ti deposits within anorthosite-rapakivi granite plutons, apatite-bearing metagabbroids and calcifyres were analyzed. It is shown that apatite from deposits of different formation affiliation differs significantly in the concentration of impurity elements and the form of chondrite-normalized REE spectra. According to the authors [18], the values of Sr, REE, Y concentration, values (La/Yb)N and Eu/Eu* in apatite obtained by them can be used to diagnose the formation affiliation of apatite-bearing rocks, the type of their mineralization and conditions of mineral formation. The interpretation of the processes of magmatic-hydrothermal ore formation is particularly controversial, as can be seen from the works of Ural geologists who studied the morphology and composition of accessory apatite in the granitoids of the Urals with quartz-vein gold mineralization [69]. The genetic concept proposed by them is striking in its complexity: according to the features of apatite, the authors try to judge the facies of the depth of granitoids, the P-T conditions of their crystallization, the compositions of magmas and their fluid regime! In particular, they studied in detail gabbro-tonalite-granodiorite-granite massifs (GTGG) of gold-metallogenic profile, as part of the granitoids of the plutonic group, which are suprasubduction formations of the active continental margin. The formation of such massifs began with water-based mantle magmatism, the products of which (gabbroids) in the conditions of the lower crust (at pressures of 6–8 kbar) were then subjected to partial melting (water anatexis) giving rise to the earliest members of the magmatic series – gabbro-tonalite-granodiorites, which are mantle by substrate, and anatectic by the mechanism of formation. And then the crustal anatexis of the rocks of these early series followed – with the formation of later adamellite-granite rocks, with which the golden and gold-sheelite mineralization is associated in the Urals (Berezovseoe, Kochkarskoye, etc. deposits). During the evolution of this very long (60–80 million years) crustal water anatexis, there was a multiple redistribution of gold from melts and crystallizing rocks into a weakly chlorine-bearing ore-forming fluid enriched with sulfur and carbon dioxide. Therefore, in pre-ore apatites, the chlorine content is 0.1–0.2%, and in apatites from ores, the fluorine content increases greatly with a decrease in chlorine to zero values. The second important sign of apatites from ores and ore-bearing metasomatites –berezites) is a sharp increase in in their sulphate sulfur content to 1% by weight. 5.1. Platinum-metal deposits In 2018, the outstanding Moscow mineralogist Ernst Spiridonov, in collaboration with A. A. Serova, presented a detailed picture of the formation of Norilsk sulfide ores with PGE – based on the study of the composition of accessory apatites of three generations [60]. The authors assumed that apatite concentrates F and Cl, which play an important role in the formation of pneumatolite minerals of platinum group elements. Apatite I, whose composition evolved from hydroxychlorapatite to chlorapatite, is common among the sulfide bodies of massive Norilsk ores and in the fringes of fluid action over sulfide droplets in interspersed ores. Apatite I is associated with Ti biotite, titanomagnetite, ilmenite with baddeleyite lamellae, anhydrite, low-titanium kersutite, chlorine-containing hastingsite and edenite, jerfisherite and bartonite, EPG and gold minerals. Apatite I contains up to 2.3 wt.% lanthanides, mainly Ce, La, Nd. Apatite I increases and replaces it with apatite II, the composition of which has evolved from hydroxychlorofluorapatite to fluorapatite. Apatite II also composes numerous isolated crystals in the mass of sulfides. The lanthanide content in apatite II is up to 0.9 wt.%. Pneumatolite chlorapatite and fluorapatite contain ~0.5% SiO2. The composition of apatite testifies to the discrete evolution of fluids released during the crystallization of Norilsk sulfide melts: at the first stage from water-chloride to chloride, in the second stage from water-chloride-fluoride to substantially fluoride. Lanthanides released during the replacement of chlorapatite I with fluorapatite II were probably part of the pneumatolite zonal orthite-(Ce). In the areas of late metamorphism in the prenite-pumpellite facies among metamorphosed sulfide ores, apatite I and apatite II are partially or completely replaced by apatite III, whose composition varies from hydroxychlorapatite to hydroxyapatite, and which is poor in fluorine and lanthanides. Lanthanides released during the substitution of apatite I and II with metamorphogenic hydroxyapatite III are probably fixed in metamorphogenic nonzonal orthite-(Ce). In 2015, Voronezh geologists, using the chlorine content in excessory apatites from the section of the stratified Kivakka intrusion in north Karelia, proposed a new criterion for searching for zones of platinum-metal mineralization, to which they gave the name "Kivakka Reef type" [3]. They claim that the identification of the stratigraphic level with the maximum chlorine content, as well as the most significant range of changes in the chloricity of apatite, may correspond to the level of development of the Kivakka Reef mineralization zones containing Cu-Ni and EPG, especially Pd and Pt. The proportion of sulfide mineralization in rocks, distributed very heterogeneously, varies from the first% to 10%; on average, within the exposed part of the vertical section, about 3-5 vol.%. Sulfide minerals are represented by an association of pyrrhotite, chalcopyrite, pentlandite, with local development of bornite, secondary and rare pyrite, sphalerite, galenite, AuAg alloy, secondary violarite and chalcosine. EPG minerals are represented by members of the merenskite-moncheite (PdTe2–PtTe2), kotulskite (PdTe) and sperrilite (PtAs2) series. The ore zone is characterized not only by the maximum concentrations of Cl in apatite (> 6 wt.%), but also by the most significant range of detected variations. Along the section of this intrusion, significant variations in the composition of the rock-forming plagioclase and accessory apatite are also observed. 5.2. Kiruna type deposits As noted in the article by Buryat geologists [51], not so many apatite-magnetite deposits are known in nature. Some of them belong to the apatite-containing titanomagnetite type associated with gabbroids (for example, Volkovskoye in the Urals). The other part, described under the name nelsonites, contains increased amounts of silicate minerals and is a product of differentiation of alkaline rocks. The third group represents the Kiruna type. In addition to Sweden (Kirunavara, Luosavara, Grangesberg, etc.), such deposits have been established in China (Meishan), Iran (Bafc, Esford), South America (El Laco) and Chile. For the ore regions of Russia, this type of deposits was previously considered not characteristic. Only later the Markakul and Kholzun manifestations of Altai were attributed to this type. Apatite-magnetite deposits of the Kiruna type are usually large objects in terms of reserves. The specific features of such deposits, in addition to the presence of apatite in the ores, are increased concentrations of REE, sharp contacts with host rocks and insignificant scale of near-ore changes. So, Kiruna-type ore deposits are characterized by a sulfide-poor mineral association of low-titanium magnetite, fluorapatite and actinolite, and varies from giants with hundreds of millions of tons of high-grade ore to small vein and veined manifestations. Both tend to riftogenic structures – either marginal (back-arc) or intracontinental (anorogenic). Facially, the deposits are confined either to deposits of shallow-sea basins or to subaerial ones and are accompanied by manifestations of volcanic-plutonic activity and the strongest fluid influences expressed in albitization. The genesis of these deposits is fiercely debated, and the proposed mechanisms vary from magmatic (liquation) to exhalative-synsedimentation and to epigenetic hydrothermal. However, in recent years, the concept has prevailed that Kiruna-type deposits are the final member of an extensive group of Fe-oxide-Cu-Au deposits designated as IOCG. This idea is supported by the similarity of tectonic settings, the abundance of early magnetite, the presence in massive magnetite ores of small amounts of late pyrite and chalcopyrite ± Au ± REE and some common secondary and vein minerals, especially actinolite and apatite. It was proved that evaporites participated in the formation of ores – they served as a source of chlorine and sodium, which caused typical albitization for ores, and a high degree of oxidation of ores due to large-scale circulation of basin brines, enhanced by intrusive magmatism. Apatite-magnetite ores of the Kiruna type are described in the Ningwu volcanic basin in eastern China – in the Meishan deposit [137]. Here, massive and brecciated ores are isolated in the main ore body located at the contact between gabbro-diorite porphyry and biotite-pyroxene andesites, as well as subeconomic stockwork and scattered ores. There are 4 stages of mineralization, the features of which can be judged by the composition of apatite. At the first stage (in massive magnetite ore) apatite associates with magnetite, andradite and quartz, and at the second (in scattered magnetite ore) – with magnetite and siderite. Accessory apatites in modified gabbro-diorite porphyry have a mixed OH-Cl-F anionic composition, whereas apatites from ores are much more polarized – up to the terminal members, F- and OH-varieties. Low Mn contents in apatites are characteristic - usually less than 0.17%, which indicates a high oxidative potential of the hydrothermal fluid. This is consistent with the universally observed negative Eu anomaly in ore apatites enriched with light REE – and the absence of such in igneous apatites. As usual, such an anomaly of europium in ore apatite is explained by the extraction of Eu2+ by earlier magmatic plagioclase. In general, all the features of ore apatite confirm the genetic relationship of mineralization with altered gabbro-diorite porphyries. In an older Chinese article with the same first author [136], almost the same ideas are presented, but as it was popular in those years, the main emphasis in the genetic interpretation of Kiruna-type ores is on the mechanism of liquid immiscibility. Figures were given here: early igneous apatites contain 3031–12080 ppm REE, whereas late hydrothermal ones contain only 1958 ppm REE. This means that the late ore-bearing fluids were depleted of REE compared to magmas. As noted in the article of the Iranian-German collective [132], the Bafq ore province is located in Central Iran, where magnetite-apatite deposits of the Kiruna type with iron ore reserves (million tons) are located within the Cambrian volcanic-plutonic arc: Choghart (216), Chador-Malu (400), Se-Chahun (140) and Esfordi (17). In the latter, apatite reserves amount to 17 million tons (with 14% P2O5 and 17.2% Fe), and the REE content in certain areas of the deposit enriched with apatite reaches 2% by weight. Apatite here is low-calcium fluorapatite with a small admixture of hydroxyl and REE. The relic mineral has undergone a strong change with the removal of Na, Cl and REE. The extracted REE were mobilized and became part of the secondary monazite (by which the age of mineralization was determined), and also in a small proportion into allanite and xenotime, which either form independent crystals or are present as inclusions in apatite. The time has passed when Kiruna-type ores were unknown in Russia, and in 2017, and according to a number of signs, ores of the North Gurvunursky metrogenition (Western Transbaikalia) were also attributed to this type. According to the description of Buryat geologists [51]. pink apatite (color from finely sprayed hematite, up to 0.5-1 wt. % FeO), composes idiomorphic grains and prismatic crystals in ores, less often their segregation. The size of the crystals is usually 0.5-1 cm along the long axis. The mineral is distributed unevenly, usually in the amount of 1-3%, sometimes up to 10% of the ore volume. Part of the grains of apatite is crushed and cemented with fine-grained magnetite. The mineral belongs to fluorapatite (2.7-4.2 wt. %F), sulfur and chlorine are not characteristic of it. In apatite, there is an emulsion impregnation, and in some cases, larger monazite secretions and less often xenotima. The composition of impurities in the mineral contains strontium, yttrium (500–900 ppm), thorium, uranium, and the REE content reaches 1–1.5 wt. %, with a predominance of LREE. Within the areas with the release of emulsion inclusions of monazite, apatite is sharply depleted of REE, often less than 0.1 wt. %. In the "spectrum" of REE, the europium minimum is clearly expressed. The value of Eu/Eu* varies between 0.2–0.4, the REE differentiation index (La/Yb)N is low and ranges from 1.75–3.63 (average 2.58). Sometimes small grains of apatite are found in hydrothermal veins. This apatite-2 is devoid of impurity elements, including REE. Altai geologists [14], who studied Kiruna-type deposits in the western part of the Central Asian folded belt on the territory of Russia, Kazakhstan and North China, noted that at the early stage of ore formation, there was a noticeable selection and enrichment of the entire REE group in the earliest generations due to the sharp depletion of REE fluids, which were significantly consumed during the crystallization of rare earth minerals proper (orthite, monazite, xenotim, cerium epidote) [14, p. 77]: "This is clearly visible in the early and late generation of apatite. In the second generation of apatite, the concentrations of all REE are noticeably lower. In parallel, there is a decrease in the ratio of light to medium and light to heavy rare earths. The Eu/Eu* ratio in the second generation of apatite also decreases by almost an order of magnitude compared to the first". 5.3. Gold deposits In order to clarify the genetic relationship of the Berezovsky gold deposit with the granites of the Shartash massif, Ural geologists in 2011 studied the composition of the volatile phase (F, Cl, S) of apatite from the granites of the Shartash massif, from the dikes of the granite porphyry of both the massif itself and the Berezovsky gold deposit, as well as from the berezites formed by these dikes – in polished sections according to the samples of S. V. Pribilkin [33]. On the graph constructed by the authors in coordinates P2O5, % (from 40.5 to 43%) by abscissa and SO3,% (from 0 to 1.20%) by ordinate, the field of inverse correlation in apatites from granite porphyry and berezite dikes (where SO3% is greater than 0.40%) is quite clearly distinguished, and in the lower part of the graph (where SO3% is less than 0.40%) there is an uncorrelated field for apatites from granite of the Shartash massif. The authors concluded [33, p. 135]: "The data obtained indicate an increase in the sulfur content in apatites, in the process of formation of the Shartash massif – from granites of the main phase to vein series completing its formation, reaching the highest values in apatites of dykes of blue-ore granite porphyries of the Berezovsky formation and in apatites of berezites according to them <...>." Thus, in apatites from medium-grained granites of the Shartash massif, the SO3 content is 0.15–0.26%, in blue-ore granite porphyries 0.26–1.08% and in metasomatites (berezites) according to them – 0.44-1.05%. Unfortunately, the Bengge polymetal gold deposit in syenites in the South of China is known to us only from the meager English abstract of the Chinese article of 2019 [139]. As can be judged by the extremely general, non-specific data of this abstract, the content of impurity elements in apatites can be used for genetic purposes. In particular, as the intensity of gold mineralization in apatites increases, the contents of Mn and Ga decrease and the contents of Cl and SO3 increase. The data on regular variations in the composition of accessory apatite in rocks and ores of the giant Precambrian Olympic Dam deposit in South Australia, where Fe-Si-Au ores form a hydrothermal halo around the Roxby Downs granite reef massif (RDG), about 1.6 billion years old, are very indicative [110]. Based on the data on the composition of zonal apatite, the authors evaluate the indicator possibilities of the morphology and composition of REE in apatite for judging the evolution of the ore-forming fluid - from early to late hydrothermal stages. Zonal magmatic apatite usually has REE-poor cores and REE-enriched grain edges. The nuclei are enriched with light REE (LREE) normalized by chondrite, with a strong negative Eu anomaly. In hydrothermal ores, igneous apatite-1 disappears, replaced by hematite and sericite, and a newly formed apatite-2 is formed, in which the "spectrum" of REE normalized by chondrite has a convex shape due to the relative accumulation of medium REE (MREE), with a weak negative anomaly of Eu. The grains of such apatite-2 contain abundant inclusions of florencite and sericite. In the high-grade bornite ores of the apatite deposit, an even higher concentration of MREE with a positive Eu anomaly is demonstrated. The latter is explained by alkaline fluid conditions. The U and Th contents in apatite generally repeat the REE distribution – they are highest in igneous apatite of granitoids and consistently decrease in hydrothermal apatites. 5.4. Other deposits In 2018, Yekaterinburg geologists examined the distribution of mineralizing elements F, Cl, S in coexisting apatites, hornblende and biotites of diorites and granodiorites composing the main part of the East Verkhotursky massif, and in diorites of dikes cutting them [37]. It was shown that the S and Cl ratios in these apatites are closest to the compositions of apatites of suprasubduction diorite-granodiorite-porphyry complexes accompanied by gold-copper-porphyry and copper-molybdenum-porphyry mineralization. The authors cautiously suggested that the reduced content of sulphate sulfur in apatites from diorite dikes dissecting intrusive rocks may indicate a decrease in the oxidative potential at the final stage of the formation of the East Verkhotursky massif, which eventually led to the imposition of mineralization in the form of native copper. A new diagnostic triangle "F-Cl-S in apatites" has been proposed, which which may be useful for a preliminary assessment of the ore prospects of magmatic complexes of different composition. Yekaterinburg geologists [13] studied apatites from rocks containing (Mo)-Cu-porphyry deposits of the Urals. The average S content in apatite crystals from minimally modified dioritoids is 0.05-0.08 wt. %. Apatite from sericitized-propylitized granitoids of quartz-diorite composition of the two largest (Mo)-Cu-porphyry deposits of the Urals (Gumeshevsky and Mikheevsky) is also not rich in sulfur - usually 0.01–.03 wt. %. Thus, the amount of S in apatite of quartz-diorite magmatites does not depend on the scale of deposits, the nature of metasomatic changes in granitoids and the content of pyrite with a small amount of it (up to 1–3 wt. %). Slightly increased S contents are observed in all apatite crystals from everywhere propylitized and epidotized rocks of the extensive Sapov subvolcanic structure. Apatite from dolerites and diorite porphyrites that break through them, as well as highly pyritized dolerites (up to 15 wt. % pyrite), contains (0.05–0.08) ±0.01 wt. % S. The maximum concentration of S in apatite (0.10–0.20 wt. %) is observed only in rocks (Cu)-Mo of the Talitsky deposit and the Verkhneuralsky ore occurrence. The highest concentration of S is observed in apatite from metasomatites formed during acid leaching. For example, in apatite from the apodiorite sericite-quartz metasomatite of the Vostochno-Artemovsky ore occurrence, the S content often reaches 0.04-0.07, and in individual crystals – 0.11–0.25 wt. %. The average S content in newly formed apatite crystals in pyrite-bearing metasomatites of the Gumeshevskoe deposit is usually 0.07-0.14 wt. %, and in two crystals – 0.24-0.53 wt. %. The authors conclude that the activity of S in the ore-forming fluid tended to increase with the acidic fluid alkalinization. In the Streltsov uranium ore field of the Southern Transbaikalia [48], the Talan manifestation of phosphates is known, which belong to the complex of Precambrian metamorophytes developed in the Southern Baikal region, on the Aldan, in China, the DPRK, Tanzania and other regions of the world. Phosphates are represented here by francolite and fluorapatite. Francolite is metamorphosed Middle-Riphean phosphorites, and fluoro-apatite is igneous, from the Middle-Riphean moderately alkaline peridotite-gabbro-gabbrodiorite complex, an example of which is the large Seligdar deposit in Yakutia [81, p. 38, 39].

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