Abstract (English):
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

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

Relatively recently, a completely new use of accessory apatite has appeared – the so-called track method, adopted not by mineralogists or geochemists, but primarily by tectonists! This method allows us to reconstruct the details of the geological history of sedimentary strata of entire regions - episodes of their immersion and uplift, up to "exhumation" (that is, reaching the daytime surface), as well as reliably reconstruct the stages of thermal metamorphism of strata (or intrusions) – their heating and cooling. Since all this was completely unthinkable earlier, during reconstructions of the history of geological development, the new method gained enormous popularity in geology and, accordingly, generated an avalanche of literature numbering many hundreds of names Below we will give a brief summary of the theoretical foundations of the track method, based on the doctoral dissertation of A.V. Solovyov, defended at the GIN RAS in 2005 [61], and we will give just a few randomly selected examples of its application – in different regions. A complete review of the existing (almost immense) literature is out of the question. 8.1. Theoretical foundations of the track method According to the presentation in the abstract of A. V. Solovyov [61], in the early 1960s, American researchers developed a new method for determining the age of minerals based on calculating the density of tracks of fragments of spontaneous fission of uranium nuclei accumulating in the mineral during geological history <...>. In the English literature, the method was called fission-track dating. It has been shown that counting tracks in minerals can be carried out using optical microscope, as their size can be increased by chemical etching in a certain reagent <...>. Translated into Russian language method is called "Dating in the tracks of fission fragments of uranium" <...>. For brevity, A. V. Solovyov proposes to use the term fission-track Dating Nuclear fission is one of the processes of decay of heavy radioactive nuclides. During fission, an unstable nucleus splits into two daughter fragments of approximately the same size. In this case, several neutrons are released, a significant amount of kinetic energy of two fragments of the nucleus, which scatter in the opposite direction at high speed and carry a high positive charge. When passing through a solid, a fast charged particle leaves a disturbance at the atomic level, oriented along the trajectory of its movement. These disturbances are called nuclear tracks (or tracks of charged particles), and the material in which the tracks are recorded is a detector. The spontaneous fission tracks observed in natural materials were mainly formed due to the fission of 238U. The other two isotopes of uranium and thorium have too low a content and/or a much longer half-life to produce a number of tracks comparable to the number of decay tracks of 238U. Tracks that have not been etched with a chemical reagent are usually called hidden, and their observation is possible only with an electron microscope at a magnification of 50000x<...>. For visual examination of tracks using an optical microscope, techniques for increasing the size of tracks or visualization have been developed. The most popular and widely used technique of chemical etching based on that hidden tracks are primarily dissolve chemically aggressive reagent <...>. In chemical pickling, the mineral is immersed in acid, which dissolves first and foremost places of defects and increases the size of the tracks (Fig. 2). For dating using optical microscope (magnification 1250х and above). Track dating is based on the classical equation describing the decay rate of a radionuclide <...>.. The calculation of the track age is based on the measured number of spontaneous fission tracks and the number of atoms in a certain volume of matter. Determining the number of atoms is also based on counting tracks. To do this, the sample is irradiated in a nuclear reactor by a stream of thermal neutrons, resulting in induced fission of uranium atoms. The development of isotope geochronology methods has led to the emergence of the concepts of true age, apparent age and closure temperature of the isotope system <...>. The true age of a rock (mineral) corresponds to the time interval between its formation and the present time. The apparent age is the age of a rock (mineral) obtained by some isotopic method and different from the true age. Fig. 2. Apatite crystal with 238U spontaneous fission tracks enlarged by chemical etching. Taken from the Internet: http://www.uib.no/en/project/tectonics/57161/thermochronology (University of Bergen) The closing temperature (or blocking temperature) of an isotope system is the temperature at which the rate of loss of an isotope due to diffusion becomes insignificant compared to the rate of its accumulation <...>. The apparent age value measured during dating is the time interval from the moment when the mineral under study last cooled below the closing temperature of the isotope system, provided that from that moment the isotope system remained closed. Various geological factors, such as temperature, time, pressure, hydrothermal action, ionizing radiation, can destroy tracks of spontaneous fission of uranium in crystals. The main one is the temperature. The effect of temperature on the annealing of tracks depending on the exposure time is described by Arrhenius lines. The longer the sample is kept, the lower the temperature at which the tracks are annealed. The disappearance of tracks does not happen instantly, the annealing of tracks is a gradient process. The temperature range in which the tracks are annealed is called the partial annealing zone (PAZ). It is defined for zircons, sphenes and apatites. The thermal stability of the tracks increases in the following order: apatite  zircon  sphene <...>. The annealing properties of apatite are affected by its chemical composition. For example, tracks in chlorine-containing apatite are more stable than in fluorine-containing <...>. During annealing, not only the density of tracks decreases, but their length also decreases. The study of track lengths in apatite is very important for the correct interpretation of data. Track age, in physical terms– is the period of time during which the accumulation of tracks in the crystal occurred. It is necessary to keep in mind a clear distinction between the "physical measurement" and the "geological interpretation" of track ages. Interpretation of track ages is not always trivial and requires careful analysis of both the obtained material and consideration of various geological factors. Track dating is used to solve a wide range of problems in geology. As a traditional method of tephrochronology, track dating is used to determine the age of volcanic glasses <...>. The method is also actively used for dating impactites <...> and kimberlites <...>. Dating of terrigenous deposits, correlation of sections, reconstruction of provenances. Current research using fission-track analysis, aimed at determining the age of the cuts deprived of fauna, the reconstruction of the source rocks of terrigenous material, the study of exhumation of orogenic belts and the establishment of the thermal history of sedimentary basins <...>. Fission-track dating is applicable to studying the dynamics of tectonic processes (accretion, collision, exhumation) by quantifying the time and the speed of their development <...>. Fission-track age reflects the time of cooling of the mineral below a certain threshold or temperature closure. In this sense, track ages correspond to the formation time for rapidly cooled volcanic rocks (age of eruption) or reflect the cooling time of rocks slowly rising from the depths (age of exhumation). Detritus thermochronology is a technique that allows us to estimate the ages of rock cooling in provenances based on the study of track ages of detritus minerals from sedimentary sections. The main advantage of detritus thermochronology is that it allows you to trace in time the relationship between tectonic processes and sedimentation. Tracks in apatite are stable only in near-surface conditions (at temperatures below 60 °C), which limits the use of apatite in detritus thermochronology. Study of exhumation rates of complexes of feeding provinces . One of the modern directions of track analysis is the dating of apatite and zircon from sections in order to study the exhumation of rocks in sources of terrigenous material <...>. This direction aims to study the temporal relationship between relief formation, erosion, climate and sedimentation. Each feeding province (block, complex) supplies clastic grains with certain track ages to the adjacent basin, which depend on the thermal history of this province. Study of the thermal history of sedimentary basins. The stability of tracks in minerals depends on temperature and time, which led to the use of track analysis for the reconstruction of the thermal history of sedimentary basins. A large number of studies are devoted to the study of apatite, since the temperature range of the partial annealing zone of tracks in apatite is very close to the temperatures at which liquid hydrocarbons are generated. The formation of oil and gas in sedimentary basins is known to occur under certain temperature conditions. In particular, the formation of liquid hydrocarbons proceeds most intensively in the range from 60 ° to 130 ° C, and gaseous hydrocarbons – in the range of 130 °–220 ° C at a heating rate of 1–10 ° C /million years <...>. The formation of methane from coal during coalification occurs in the temperature range of 80–230 °С, and the most intense generation of coal methane is characteristic of the range 150–230. Track analysis, unlike other methods (for example, vitrinite reflectivity analysis), makes it possible to trace the change in paleotemperature over time. Study of the rates of uplift of orogenic systems. This is one of the important and complex problems of modern geotectonics. The formation and evolution of the relief depends on many factors, this system is the result of an integral interaction of endogenous (tectonic forces, magmatism) and exogenous (climate, erosion, sedimentation) factors. Since the track analysis provides quantitative information about the cooling processes, it can be used to estimate the rates of uplift, erosion and tectonic denudation. Reconstruction of the structural evolution of complexes. Track dating is actively used to study the evolution of structural inhomogeneities of the earth's crust, for example, regional thrusts, discharges. A lot of complex studies based on structural analysis and track dating have been carried out to decipher the history of the evolution of metamorphic cores of the Cordillera type <...>. These studies make it possible to establish a link between deformation and denudation, to restore the time and speed of discharge movements. Study of the tectonic evolution of accretion prisms. The formation of accretion prisms is a process leading to the buildup of the continental crust; the study of these structures is one of the fundamental problems of modern geodynamics. Using the examples of the accretion prisms of Shimanto (Japan) and Cascadia (North America), it is shown that the track dating of zircon and apatite can be successfully used to study the age of accreted sediments, the accretion time and the rates of removal of complexes to to the surface. In addition to the above, we note that counting the number of tracks under a microscope is a tedious and very time-consuming procedure. Therefore, with the development of computer technology, the idea of automating this procedure arose, for which the University of Melbourne developed the Autoscan technique, hoping to save the geologist from unproductive mechanical work [100]. Unfortunately, this technique leads to big errors, because the machine does not know how to filter tracks of different genesis, so it requires mandatory correction of counting - manually, by the usual optical method. 8.2. Some examples Out of many hundreds of works using track thermochronometry, we have arbitrarily selected only a few typical examples showing the solution of various geological problems. In 2012, V. A. Soloviev and J. Garner demonstrated the effectiveness of the track method for sedimentary and volcanic-plutonic complexes of the North. Kamchatka [62]. Track dating of apatite from autochthonous, allochthonous and neoautochthonous rocks of the Lesnovsky thrust allowed us to conclude that in the process of collision of the Achaivayam-Valaginsky arc with the northeastern margin of Eurasia on the North. In Kamchatka, a thin allochthonous plate was pushed over the autochthonous deposits, which sank to the depths of the first kilometers (less than 4 km). After the collision was completed, neoautochthonous volcanic-plutonic complexes of the Kinkil belt were formed, so that apatite in the upper parts of the autochthon was exposed to thermal effects 45–40 million years ago. Then the ultra-slow post-collision exhumation began, in the period from 40 to 13 million years ago at a rate of 10–15 m/million years. In 2013, Novosibirsk geologists, together with foreign colleagues, evaluated the history of the Mesocainozoic peneplain of the Eastern Sayan by the track method and received unexpected conclusions [2]. Unexpected because they are directly related to the genesis of weathering crusts – and hence related minerals. The largest relic of the leveling surface of this area is the Okinskoe plateau, separated from the xp. Kropotkin Okino-Zhombolok fault. The formation of peneplene in the area of the Okinsky plateau falls, according to track analysis, on the Late Jurassic-Early Cretaceous. This age is much younger than the age of the alignment surfaces preserved in the Tien Shan, Gobi and Mongolian Altai (early Jurassic), but older than the peneplain on the Chulyshman plateau in Altai (Late Cretaceous), which indicates the asynchrony of the formation of the ancient peneplain of Central Asia. A similar story of exhumation of samples from the Okinsky Plateau and from the XP. Kropotkina testifies that these morphotectonic structures from the Jurassic to the end of the Miocene developed as a single block undergoing continuous slow denudation at an average rate of 0.0175 mm/year. In the late Miocene, active tectonic processes led to the destruction of the leveling surface and the elevation of its individual sections to different hypsometric levels. At the same time, an approximate estimate of the velocity of vertical movements along the Okino-Zhombolok fault for the Pliocene-Quaternary period was 0.046-0.080 mm/year, which is several times higher than the denudation rate in this area. The Okin plateau at the Pliocene-Quaternary stage did not undergo significant morphological changes due to its intermediate position between the summit and the base surface of the East. Sayan and partial reservation by basalt lavas. O. M. Rosen and A.V. Solovyov successfully applied the track method for dating apatites from the cores of deep wells that opened the foundation of the Siberian platform at a depth of 2–3 km [53]. Although accessory apatites were formed in the early Precambrian, they showed Mesozoic age values due to the cooling of the host rocks below 100 °C. Thermal events of Mesozoic age in the crystalline basement of the Siberian Platform have not yet been known. It is most likely that the annealing of the tracks occurred as a result of intensive heating of the sedimentary cover during the introduction of platobasalts. In 2015, the international team [134] obtained the first data on decay tracks in apatites of the Khibiny massif aged 368±6 million years (according to U-Pb dating), taken in wells from a depth of 520 and 950 m. Cooling took place in three stages: 290-250 million years – rapid cooling from 110° to 70°-50°; 250–50 million years –stable stage and 50–0 million years - slow cooling to modern temperatures. The geothermal gradient over the last 250 million years was 20 °C/km, during which the massif was exhumed from a depth of 5–6 km. In 2012, Pakistani geologists published in Russian (!) the results of an assessment using the track method of the time and level of introduction of the Silai Patti carbonatite complex in the North of Pakistan [68]. In the alkaline magmatic province of the Peshawar Valley of Northern Pakistan, this complex is represented by the second largest body of carbonatites. Carbonatites occur in the form of a formation intrusion 12 km long and 2–20 m thick, embedded mainly along the fault separating the meta-sediments and granitogneisses, but locally they also occur in metamorphosed sedimentary rocks. The age dating of carbonatites = 29.40 ± 1.47 million years was obtained by the track method. Comparison with other radiometric dating indicates the introduction of the Sillai Patti carbonatite complex into the upper horizons of the crust and its subsequent exceptionally rapid cooling to near-surface temperatures (<60 °C), necessary for the complete preservation of fission tracks in apatite. Comparison with the world data of denudation rates caused by uplift clearly indicates the presence in the region of a post-collision stretching situation south of the main mantle fault in the Oligocene time. This conclusion strongly rejects the idea of the predecessors about the formation of carbonatite complexes in the Lo Shilman and Sillai Patti areas along the upwelling in the Oligocene time. A large Chinese team (8 co-authors) in 2012 proved that based on the materials of track chronometry, two successive stages of cooling of Cretaceous porphyry-like iron ores of China can be distinguished [112]. Apatites were studied at four deposits formed about 130 million years ago: Dongshan, the familiar Meishan (Ninu Basin), Nihe and Lohe (Luzong Basin). Apatites of these deposits have ages, respectively, 106.3±5.4; 94.2±4.0; 81.3±4.0 and 79.1±3.3 million years, decreasing with increasing depth of burial and approaching the age of mineralization, depending on the size of the uplift and the degree of post-ore denudation. The simulation of the thermal history reflects two stages of cooling with a change of rapid cooling associated with the loss of a heat source, slow cooling due to an uplift. Judging by the temperature of the cooling rate change, it appeared at a depth of 1.7–1.8 km. It is shown that since 110 million years, the rate of uplift and denudation in the Ninu Basin has been significantly higher than those in the Luzong Basin. This led to less burial or exposure on the surface of the deposits of the Ninu basin. Although with great delay, but in 2018 there was work with the use of a new (though not track) method of thermometry for apatite and in our Institute of Geology. This was a study by Yu. V. Denisova, who studied the thermal history of the Nikolaishor granite massif in the Circumpolar Urals, which had been studied by our petrographers for a long time and repeatedly [16]. To do this, she applied the so-called Watson saturation thermometry (with a clarifying Bea coefficient) for apatite. As a result, it was concluded that the crystallization of the rocks of the Nikolaishor massif occurred in a temperature range including two episodes (633.5–699.1 ° C and 751.2–77.4 °C). Yu. V. Denisova concluded that Watson saturation thermometry with the addition of Bea for apatite provides the same accurate information about the evolution of the temperature regime during the formation of granites as the evolutionary-crystallomorphological analysis of Pyupin and Turko for zircons (which was previously done by her). The application of the track method to the Cenozoic strata of the North of Turkey made it possible in 2012 to draw non-obvious tectonic conclusions [90]. According to the tracks of apatite decay in Zap. 3 episodes of Cenozoic exhumation were identified in the Pontides, which correlate with the main supra-regional tectonic episodes. 1. The exhumation of the Paleocene-Early Eocene reflects the closure of the Izmir-Ankara Ocean. 2. The exhumation of the Late Eocene–the beginning of the Oligocene is a consequence of the resumption of tectonic activity along the Izmir–Ankara suture. 3. Exhumation of the Late Oligocene-Early Miocene records the manifestation of stretching of the north. parts of the Aegean region. Samples collected to C and Y from the tectonic contact between the forming Zap. The Pontides of the Istanbul and Sakari terranes record the same episodes of cooling, indicating that these terranes were amalgamated in the pre-Cenozoic time Since the erosion of the High Himalayas ensures the flow of enormous volumes of sedimentary material to the shelf of the Indian Ocean, the reconstruction of the tectonic history of the Himalayas, made by the team in 2012, is important for recreating the details of Cenozoic sedimentation [129]. This paper presents the results of dating along the tracks of the decay of apatites and zircons from the rocks of the upper parts of the slopes of Mount Everest and along a number of valleys that are the catchments of Mount Everest and the Makalu massif, forming vertical intersections of a series of High Himalayas in the East. Nepal with a length of almost 8000 m. The age of apatites varies in the rocks of the Himalayan series from 0.9±0.3 to 3.1±0.3 million years, systematically increasing from bottom to top along the section. The apatites of the Everest and Ordovician limestone series are much older and reach an age of 30.5±5.1 million years. The ages of zircons in the rocks of the Himalayan series range from 3.8 ± 0.4 to 16.3 ±0.8 million years. The rates of brittle exhumation calculated on the basis of these data indicate that the rocks of the Himalayan series were exhumed from about 9 million years ago at speeds of 1.0–0.4 mm/year, and in the Pliocene the rate increased to 1.7 ± 0.3 mm/year. These values do not differ significantly from the estimate of the plastic exhumation rate (1.8 mm/year) established for metamorphic minerals that experienced decompression between 18.7 and 15.6 million years ago, but are noticeably lower than the rates determined on the basis of thermomechanical models. Higher exhumation rates are associated with increased erosion during glaciation of the High Himalayas in the Late Pliocene-Pleistocene. In 2005, a thorough review of the application of the track method for the purposes of oil and gas geology was published [94]. The authors emphasized that exhumation, removal of overburden rocks as a result of the uplift of tectonic blocks from the maximum depth of burial, occur both regionally and locally in marine sedimentary basins and have important consequences for assessing the prospects of oil and gas basins. The issues to be solved by an oil geologist in these basins include: the time of thermal heating and cooling of blocks of oil-bearing rocks, lithogenetic restrictions imposed by the maximum depth of reservoir rocks, physical and mechanical characteristics of tire rocks during and after exhumation, the structural evolution of traps and the history of the placement of hydrocarbons in them. Central to solving these problems is the ability of a geologist to identify exhumation events, assess their scale and determine their timing. GENERAL CONCLUSION In the course of the presentation, some particular conclusions have already been made in this review; here we will try to bring them together and, if necessary, supplement them. 1. The widest distribution of accessory apatite in igneous rocks is explained by the properties of phosphorus – its extremely limited ability to enter into the composition of rock-forming minerals. In rocks with poor P2O5 contents (such are some granites and rhyolites), there is no apatite. Therefore, accessory apatite is both a concentrator and a carrier of rock phosphorus. 2. As a rock-forming mineral, apatite is present only in some cumulative and rare types of igneous rocks – some pegmatites, nelsonites and carbonatites, as well as in hypergenic phosphorites (the world's largest source of phosphorus for fertilizers). 3. Structurally, apatite Ca5(PO4)3(F,Cl,OH) is unique, because in its cationic and anionic parts, extremely diverse isomorphic substitutions are possible – both homo- and heterocharged. Since these substitutions were defined in a variety of characteristics of the environment of formation of Apatite – Apatite makes it remarkable genetic "marker": the composition of Apatite could judge the TR-conditions in the magma oxygen fugacity in them, their alumina content, the sulfur content, the content of water, Halogens, sulphur, etc. 4. In the cationic parts of Ca2+ can replace Na+, K+, Ag+, Sr2+, Mn2+, Mg2+ Zn2+, Cd2+, Ba2+ , Sr2+, REE3+, Y3+, Sc3+, U4+ and Th4+. Of these, Mn, Sr, REE and U are of the greatest importance for the use of apatite as an indicator of geological processes. In addition, apatites are also a real raw material source of REE and U. 5. In the anionic part, phosphate, halogens and hydroxyl can be replaced by СО32–, SO42–, Cr2O42– , AsO43– , VO43–, BO33– , JO33– , CO3F3– , CO3OH3–, SiO44–. Of these, carbonate and sulfate are the most important. 6. Isomorphic substitutions of Ca are further complicated depending on the position of Ca in the structure, since Ca enters both the phosphate skeleton of the structure (Ca1 atoms) and the channels of the structure (Ca2 atoms). The Ca1 atoms are in 9-coordination, forming a regular trigonal prism of the CaO9 composition, while the Ca2 atoms are in 7-coordination, forming an irregular polyhedron of the CaO6A composition, where A are oxygen-substituting anions, that is, halogens, CO32–, etc. 7. The impetus ("trigger") for the compilation of our review was the recent (2020) generalizing publication on the composition of apatite, covering 147 works: Gary O'Sullivan, David Chew, Gavin Kenny, Isadora Henrichs, Dónal Mulligan. The trace element composition of apatite and its application to detrital provenance studies // Earth-Science Reviews, 2020, vol. 201. 103044. Since 4 of the authors of this review are from Dublin, and only Gavin Kenny is from Stockholm, for simplicity it is called by us the "Irish review". The authors of the Irish review for the first time covered all known applications of the composition of accessory apatite to indicate the conditions in which host (or associated) rocks or ores were formed. As a result of thorough consideration of various diagnostic graphs, the authors especially recommend the logarithmic "biplot" LREE - Sr/Y, in which the important diagnostic value of the Sr/Y value was justified by E. A. Belousova. The authors focused on detrital accessory apatite of igneous and metamorphic rocks (falling into terrigenous sedimentary rocks) and much less on apatite of phosphorites, which they call "autigenic". As in the West in general, Russian-language works remained out of the sphere of attention of the authors of the Irish review. The only exception concerns the works of our outstanding geologist E. A. Belousova, but only because these works are English-language. 8. The formation of bioapatite, which largely consists of the bones and teeth of vertebrates (including humans) is a complex, stage-by-stage process. Under natural conditions, biogenic hydroxyapatite Ca10(PO4)6(OH)2 is not formed immediately, but is preceded by biophosphate-1 – or octacalcium phosphate Сa8(HPO4)2(PO4)4.5H2O, or brushite CaHPO4.2H2O, and with particularly strong supersaturation of the saline solution – amorphous Ca-phosphate CaxHy(PO)z.nHO (n = 3–4.5). Thus, hydroxyapatite turns out to be biophosphate-2, it is formed only by the substrate of biophosphate-1, most often – octacalcium phosphate. 9. In 2014, it was possible to prove experimentally that in urolithiasis (nephrolithiasis), the formation of calcium oxalate monohydrate of vevellite CaC2O4·H2O, which has long been known to urologists, is closely related to the earlier formation of hydroxyapatite. Model experiments have clarified why vevellitis in the renal tissue, as a rule, grows on the so-called Randall plaques - areas with disperced hydroxyapatite. 10. Both Russian and foreign petrologists have reliably proved that the ratio of halogens in apatite is an excellent indicator of the fluid regime in petro- and ore genesis. Two trends of magmatic differentiation of basaltoid magmas are known: (1) tholeiitic – the evolution of the melt towards the accumulation of iron – with the formation of ferruginous gabbroids, with which titanium-magnetite ores are associated, and (2) calcareous-alkaline – the evolution of the melt towards an increase in its silicic acid and alkalinity, which is associated with scarn-magnetite mineralization. These trends are well documented by the content of chlorine and fluorine in apatites. Comparison of the ferruginous index of melts f (f = Fe/(Fe + Mg), at.%) with the content of halogens in accessory apatites showed that chlorine in apatites exhibits pronounced ferrophilicity, and fluorine - magnesiophilicity. 11. Ural geologists who have studied fell near Chelyabinsk chondrites "Chelyabinsk", "Ural" and "Lake", confirmed that the characteristic phosphate chondrites is merrilite Ca9Na[Fe,Mg][PO4]7 – anhydrous end member in a series of 14 solid solutions merrilite – whitlockite. 12. Apatity may contain sulfur from the substitution of the anion phosphate anion sulfate. The content of S in apatite is directly dependent on the former content of S in the melt. Experimentally, it was possible to show that the introduction into the rhyolite melt under oxidizing conditions up to 0.5 wt. %S dramatically increased the solubility of apatite in the melt. As proved by Ural geologists, high-sulfur apatites (up to 0.65 wt. %S) are good indicators of the prospects of gabbrodolerites for Cu-Ni mineralization. 13. Francolite Ca10–a–bNaaMgb[PO4]6–x(CO3)x–y–z(CO3F)y(SO4)zF2, a low-temperature fluorocarbonatapatite (often referred to simply as carbonatapatite), is the main mineral of hypergenic phosphoric ores - phosphorites. As proved by Russian geochemists from Moscow State University – V. S. Savenko and his daughter A.V. Savenko, francolite is formed in the diagenesis of sea silts – as the sediment is buried and removed from the section "bottom water/sediment". In this process, the carbonate alkalinity of the pore waters increases, as a result of which the initially formed calcium phosphate precipitate begins to dissolve and return the phosphate group PO43– to the pore waters (and then to the above-bottom water – "phosphorus respiration of the sediment"), which is replaced by the carbonate group CO32– in the sediment. However, some carbonatapatites have a primary biogenic nature, being formed, in particular, in dental tissue, where CO32-radicals can replace both OH– and PO43–in the lattice of biogenic hydroxyapate An important discovery of recent years is the discovery of huge resources of francolite not in marine sedimentary rocks, but in the weathering crust of carbonatites of our unique rare-metal Tomtor deposit, which has no world analogue in its size and composition 14. The value of the cerium anomaly CeA = CeN/Ce*, where Ce* = 1/3 (1.44LaN + 0.66 NdN) in apatites is an important diagnostic tool. Since in the modern aerated ocean (most likely also in the oceans of the Phanerozoic) the value of CeA <1 (which is commonly called "negative"), then apatites formed in equilibrium with seawater should also have a "negative" value of the cerium anomaly. Accordingly, any increase in the value of CeA indicates the formation of apatite either in deep suboxic waters (where the Ce content is greatly reduced), or in anoxic waters, where Ce (III) is not oxidized at all, so that the value of CeA in such apatites is close to unity. 15. The value of the Europium anomaly EuА = EuN/Eu*, where Eu* = ½ (SmN + GdN) in most low-temperature apatites is close to 1 - as in seawater. However, in some igneous apatites, the value of Eu/Eu*<1 was noted, which indicates the occurrence of the reduced Eu2+ in an earlier plagioclase. Despite the theoretical impossibility of restoring Eu in hypergenesis, Eu/Eu* <1 values were occasionally observed in sedimentary apatites of hydrogen sulfide ("euxine") facies; thus, the value of EuА can serve as an indicator of such facies. 16. The often observed close association of fluorapatite with monazite reflects the history of polymetamorphism. Usually monazite is formed before fluorapatite, taking the REE resource from the medium. However, when the temperature decreases, monazite becomes unstable, reacting with the host silicates and dumping the REE contained in it. This leads to an increase in the primary monazite-1 of remarkable "crowns" consisting of fluorapatite and allanite, in which, with a new episode of a decrease in the temperature of metamorphism, growths of newly formed monazite-2 appear. 17. Along with REE, strontium and manganese are very informative elements of the cationic part of apatites. The Sr/Mn ratio was proposed in one of the works by E. A. Belousova and colleagues, and then successfully used on the Sr/Mn (ordinate) – LREE (abscissa) biplot designed by the authors of the Irish review, where LREE contained 7 lanthanides from La to Gd. Note that only two fields contoured by the authors need an abscissa axis: the minimum LREE contents for the LM field (low-grade metamorphites and metasomatites) and the maximum for the ALK field (alkaline magmatites). For the remaining 4 fields, the LREE parameter "does not work", and they are quite satisfactorily (with overlaps not exceeding 15% of the area) recognized by a single Belousova's parameter Sr/Mn. 18. The actinides uranium and thorium in the cationic part of apatites can also be used for diagnostic purposes. Uranium has two different states: U6+ compounds are highly soluble in oxygen conditions, and U4+ oxide is insoluble in oxygen-free waters. At the same time, the solubility of Th is not affected by redox changes, which leads to an increase in the Th/U ratio in anoxic hydrophations. If the degree of oceanic anoxia becomes significant (as, for example, it was assumed for the early Triassic), then the uranium reservoir in seawater will be depleted, which will lead to an increase in the Th/U ratio in apatite. 19. In addition to using uranium as a geochemical indicator (for the diagnosis of sedimentation hydrofacies), apatites are a real raw material source of uranium. From phosphate ores, which have reserves in dozens of countries around the world, it is possible to extract from 9 to 22 million tons of uranium. This would ensure the supply of uranium for nuclear power for 440 years. 20. The isotopic ratio 87Sr/86Sr, which has found the widest application for dating carbonate sedimentary rocks, has become actively used for phosphate strontium - for dating apatites. In the pelagial of the ocean, fossilized remains of fish (ichthyolites) preserve the isotopic composition of strontium of ocean waters at the time of fish life, therefore, the isotopic composition of strontium of ichthyolites can be used to determine their age. 21. The isotopic ratios δ18O in the oxygen of apatites and δ13С were as widely used as the value δ87Sr –- to assess the climate of the sedimentation epoch. Phosphate of bones and teeth of terrestrial animals, phosphate of ichthyolites have been studied, but the isotopic analysis of oxygen and carbon of conodonts should be recognized as the most promising. It is this method that has become the most widespread in recent years. 22. Isotopic analysis of neodymium using the value Nd – "epsilon neodymium" has found enormous application. i.e., the isotope ratio R = 143Nd/144Nd normalized by chondrite: Nd = (RS/ RCHUR – 1), in ten thousandths. Here RS is the 143Nd/144Nd in the sample, and RCHUR is the value of это 143Nd/144Nd в образце, а RCHUR – значение 143Nd in CHUR – (chondritic uniform reservoir), which is assumed to be 0.512638. Since apatites concentrate REE in their cationic part (including neodymium), it is apatite that seems to be the most convenient object for using the value Nd for diagnostic purposes – namely, for the diagnosis of the petrofund from which detritus apatite was deposited. The fact is that the mantle (and its young magmatic derivatives) has a ratio of 143Nd/144Nd higher than the Earth as a whole – and, accordingly, positive values of Nd. On the contrary, ancient crustal rocks have 143Nd/144Nd lower than in the Earth as a whole, and accordingly, negative values of Nd, the more negative the older the rocks. These data make it possible to determine the petrofund with great reliability by the value of Nd in apatite. 23. Another remarkable property of the value of Nd in apatite (in particular, in the phosphate of conodonts) allows it to be used for the reconstruction of paleogeography details, since, as shown for the modern ocean, the value of Nd in seawater is a remarkable tracer of ocean circulation. 24. Apatites from igneous rocks of ultrabasic and basic composition, with which deposits of Ti-Fe-V ores are genetically related, have the highest values of the Sr/Y index at low LREE contents. The most chlorinated apatites were identified by Russian geologists in stratified mafic-ultamafite intrusions with zones of low-sulfide EPG-containing mineralization. As the process of magmatic differentiation of basaltoid magmas from gabbro to diorites and quartz diorites develops, the content of Cl in apatites decreases, and fluorine increases. With further differentiation up to tonalites, the chlorinity of apatites continues to decrease, and the fluorinity increases. 25. Apatites from kimberlites contain silicon, which is explained by the conjugate substitution of the PO43– ion with CO32− and SiO44– ions, reflecting a higher CO2 content in the initial melts, as well as the accumulation of Si in kimberlite magma due to the predominant crystallization of carbonates compared to mica/monticellite. 26. Apatites from granites on the logarithmic graph LREE – Sr/Y form two separate fields: IM and S. The IM field (median, intermediate values on both axes) includes apatites from granodiorites and "mafic" I-granites with low index values ASI = Al/(Ca+Na+K). Fluorapatites from anatectic granites of the S-type, as well as from "felsic" granites of the I-type, with a high value of the ASI index, fall into the S field. With some average LREE abscissa contents, they are clearly distinguished by the minimum values for the Sr/Y ordinate. 27. Detection by cathodoluminescence of a clear zonality in apatites from granite Shap in the North. In England, it was a real gift for petrologists who previously did not have a suitable way to judge the evolution of granite magmas. Cathodoluminescent images of zonal apatite combined with the analysis of trace elements by the LA-ICP-MS method provide powerful tools for decoding the crystallization of granites. Prolonged crystallization of apatite, which has not undergone secondary changes, allows us to recreate a complete picture of the evolution of the grant magmatic system. 28. Apatites from alkaline rocks are known to have strong concentrations of REE. Therefore, on the logarithmic graph LREE – Sr/Y, they form the rightmost field of ALK with the maximum digits on the abscissa LREE, but with wide (non-diagnostic) variations on the ordinate Sr/Y. 29. Apatites from carbonatites on the same LREE – Sr/Y graph fall into the "ultramafic" UM field together with pyroxenites, lherzolites and "mafic" I-granites with a low ASI index. This field is characterized by the highest values for the Sr/Y ordinate and moderately high values for the LREE abscissa. 30. The geological evolution of carbonatites and associated mineralization is extremely complex - multi-stage, Based on the composition of apatites, apparently, Siberian geologists made a decisive contribution to understanding the evolution of carbonatites and their successor metasomatites and hydrothermalites in 2017. 31. Apatite of granite pegmatites is distinguished by its exceptional originality, especially in the pegmatites of anatectic granites of the S-type. The fact is that in the initial high–alumina melts that arose from metapelites, apatite is highly soluble - better than in low-alumina melts, due to Ca deficiency, which goes into plagioclase. That is why there are so many non-calcium phosphates in residual (pegmatite) melts. The presence of unusual phosphates (Li, Fe, Fe-Mn and Mn), for example, high-manganese fluorapatite and beusite CaMn2[PO4]2, named after our famous geochemist and mineralogist A. A. Beus, can be considered characteristic of granite pegmatites. With the subsequent hydrothermal change of pegmatites, apatite disappears altogether, and the predominant Fe-Mn-phosphates are replaced by such calcium-free minerals as rare alumophosphates montebrasite LiAlPO4(OH) and childrenite Fe2+AlPO4(OH)2•H2O. 32. Metamorphite apatite has characteristic differences from igneous apatite. Among the characteristic minerals of metamorphites can be called goyazite SrAl3(PO4)(PO3OH)(OH)6 – aluminum and strontium phosphate from the crandallite group, as well as the appearance of a low-temperature florencite association (Ce,La,Nd)Al3(PO4)2(OH)6 and crandallite CaAl3(PO4)2(OH)5.H2O – the extreme aluminum members of the group of aluminum-sulfate-phosphates from the supergroup of alunite. 33. An increase in the temperature of metamorphism up to anatexis reduces the REE content in primary magmatic apatites and lowers Sr/Y - due to a simultaneous increase in Y concentrations and a decrease in Sr concentrations. On the logarithmic graph LREE – Sr/Y, the compositions of apatites form two disjoint fields. The LM field (a wide, non-diagnostic range of values for the Sr/Y ordinate and the minimum LREE contents for the abscissa) are low- and medium-graded metamorphites, which are characterized by dissolution and redeposition of apatite – with a corresponding loss of REE. The HM field (low Sr/Y values and moderate LREE contents) are apatites from high-grade metamorphites and metasomatites; apatite compositions from anatectic metamorphite leukosomes also fall here. 34. Hydrothermal apatites (including apatites from various ores) are characterized by high variability of composition. In particular, fluorapatites from Ural quartz-vein Au ores associated with granitoids are distinguished by the presence of a noticeable SO3 content – up to 1% by weight. %. In Norilsk sulfide ores with PGE mineralization, Moscow geochemists isolated up to 3 generations of apatite, the composition of which indicates the discrete evolution of fluids accompanying ore formation: from water-chloride to chloride, then from water-chloride-fluoride to significantly fluoride. Lanthanides released during the replacement of chlorapatite-I with fluorapatite-II were probably part of the pneumatolite zonal orthite-(Ce). Fluorapatite from iron ore deposits of the "Kiruna type" is low–calcium, with a small admixture of hydroxyl and REE. This apatite is a relict that has undergone a strong change with the removal of Na, Cl and REE. The removed REES were included in the composition of secondary monazite, and partly also in allanite and xenotime, forming either independent crystals or inclusions in apatite. For apatite from Fe-Cu-Au ores of the giant Olmpik Dam deposit in South. Australia is characterized by the accumulation of MREE – which is expressed by the bell-shaped shape of the curve in the "spectrum" of REE normalized by chondrite. 35. Bioapatites are represented by both modern teeth and bones (including human ones) and ancient ones - buried in sediments and sedimentary rocks. These groups vary greatly in composition. Modern bioapatites are represented by poorly crystallized hydroxyapatites, which become noticeably carbonate in diseases (caries, coxoarthrosis). They are, as a rule, very poor in impurity elements (Mn, Sr, REE, U). Ancient bioapatites (vertebrate bones, ichthyolites, and especially conodonts) are much richer in fluorine and impurity cations due to diagenesis than modern ones. For example, the REE content in conodonts can reach or even exceed 1000 ppm. 36. The compositions of hypergenic apatites in phosphorites most often correspond to fluorocarbonatapatite – francolite. Such commonly used indicators of apatites as Sr/Y, La/Yb, REE, the ratio of LRSE, MRSE, HRSE, the magnitude of Ce- and Eu anomalies, the ratio of REE with the isotopic composition of carbonates associated with phosphorites and organic matter – vary greatly. Nevertheless, according to the composition of hypergenic apatites, geologists persistently try to recognize the conditions of sedimentation (in particular, topo- and hydrophation) and lithogenesis (especially diagenesis). According to Ural geologist A.V. Maslov, in relation to phosphorites, these attempts are not effective enough due to multifactorial effects on the composition of apatites. Among the factors are: – the composition of seawater of different epochs, which did not remain constant; – the speed and redox conditions of sedimentation; – the content and composition of organic matter and carbonates associated with phosphorites; – diagenetic changes, among which poorly understood microbial processes played an important or even decisive role; complications of sedimentation by exposure to endogenous hydrotherms. In general, we can conclude that the diagnostic application of the composition of hypergenic apatites is still in the process of development – it is necessary to find such indicators that could be trusted without special reservations. 37. As for the theory and practice of using apatite for thermochronology – by the track method, these materials are included in this review only "for completeness", since these materials have nothing to do with the composition of apatites (of course, except for data on the contents in apatites 238U). However, they complement the characteristic of apatite, which has no analogue – in terms of the variety of use as a unique indicator mineral.

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