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

As for the rock-forming apatites of phosphorites, in the Irish review [130] they are quite rightly called "autigenic" in order to distinguish them from accessory detritus apatites of "silicoclastic" (that is, clastic) sedimentary rocks. Voronezh geologists tried to reconstruct the conditions of phosphorite formation based on the distribution of lanthanides in phosphorites [77]. In particular, they used the indicators La/Yb, La/Sm and Ce/Sm to diagnose topofations. It is believed that these indicators increase in coastal facies, while the indicators Yb/Sm, Y/Sm decrease. In pelagic facies, the behavior of these indicators is the opposite. Thus, modern ocean phosphorites of the Mataiva Atoll have high values of Yb/Sm, Y/Sm compared to other phosphorites, as well as a low index of Ce/Y. It is believed [77, pp. 1105-1106] that this "reflects the nature of lanthanide fractionation in sedimentation environments significantly remote from land." In 2016, Ural geologist A.V. Maslov published a review of 49 papers with data on the geochemistry of REE in Neoproterozoic-Cambrian phosphorites [44]. It is characteristic that only 2 of them are Russian-speaking, including A.V. Ilyin's book [27] on ancient (Ediacaran) phosphorites. The purpose of the review was an attempt to use the data provided in it for the purposes of paleogeography. Maslov listed some more or less reliably established empirical patterns: 1) similarity of the REE "spectra" normalized for clay shale to the distribution of lanthanides in seawater with negative Ce anomaly and enrichment with heavy REE (HREE); 2) "shale" distribution of REE, characteristic of Miocene phosphate aggregates and younger formations off the coasts of South Africa and South America; 3) pronounced negative Ce anomalies and depletion of REE of almost all Pre-Mesozoic phosphorites; 4) phosphate crusts and The contractions associated with nodules and crusts of Fe-Mn may contain a positive Ce anomaly. Nevertheless, it can be seen from this review that such commonly used indicators as REE, LREE (sum of light REE), HREE (sum of heavy REE), MREE (sum of medium REE), ratios of LREE, MREE, HREE – relative accumulation or depletion (depletion) of them in phosphorites, the magnitude of Ce- and Eu anomalies, the ratio of REE with the isotopic composition of carbonates associated with phosphorites and organic matter – strongly vary. The noted variations are due to several factors, among which are: - the composition of seawater of different epochs, which did not remain constant; - sedimentation rate; redox-sedimentation environment; - the content and composition of the organic matter associated with phosphorites; - content and composition of carbonates associated with phosphorites; - diagenetic changes, among which poorly understood microbial processes played an important or even decisive role; - complication of sedimentation by exposure to endogenous hydrotherms. And although A.V. Maslov himself evaded certain conclusions of his review, in our opinion, the materials generalized by him make the use of apatite REE for diagnostic purposes a very dubious procedure, since it is not possible to separately assess the extent of the influence of individual factors. This assessment is not helped by the normalization of the REE content for the "shale", nor by the search for mutual correlations of indicators, for example, indicators of the isotopic composition of oxygen with the ratios of individual REE. In general, A.V. Maslov came to approximately the same conclusions in 2017, having considered the distribution of REE in Pre-Ordovician phosphorites from different regions of the world [43]. Based on the analysis of a significant data bank, he showed that at present there are no universal parameters, guided by which it is possible to judge sedimentation and diagenetic conditions of phosphorite formation with any confidence, first of all, about redox conditions. Any reconstruction of this plan requires a thorough analysis of both geological facts and extensive and diverse geochemical information. Approximately the same results were presented by A. V. Maslov in a 2016 article, but with a more optimistic assessment of the use of REE as a "paleomarine" indicator [44]. After G. N. Baturin discovered the process of modern phosphorite formation in carbonaceous diatom silts on the shelf of Namibia (southwest Africa) [5; 4], it was possible to think that the situation described by him is unique and has no analogues. Therefore, the Miocene nodules described by him in 2012 from the bottom of the Sea of Japan [6] proved to be an important confirmation of the reality of the open mechanism, but with characteristic differences. The lithological and geochemical study of Miocene nodular phosphorites from four underwater uplifts of the Sea of Japan - Northern Yamato, Southern Yamato, East Korean and Krystofovich was performed using scanning electron microscopy, chemical and modern plasma (ISP-MS) analysis. The obtained data on the microstructures of phosphorites and the distribution of 57 macro- and microelements in them revealed their significant similarity with the late Quaternary granular phosphorites of the Namibian shelf and with phosphorites in general, which is evidence of their genetic similarity. But unlike the phosphorites of the Namibian shelf, traces of the influence of volcanogenic-hydrothermal activity have been found in the phosphorites of the Sea of Japan, as evidenced by examples of positive cerium anomaly in some samples and positive europium anomaly in others, as well as a slightly increased gallium content in phosphorite from the Chentsov volcano (22 g/t Ga versus 2–6 ppm in other phosphorites). Unlike many others, the phosphate of the zhelvak phosphorites of the Middle-Riphean Strelnogorsk formation of Eastern Siberia contains so little CO2 (<1%) that it is certified not as francolite, but as fluorapatite, which proves that phosphorites pass the stage of deep catagenesis [26]. The authors explain the sharp negative anomalies in La and Yb by the same reason. Nevertheless, an abnormally high content of the amount of REE was recorded, reaching a record figure of 2978 ppm in one sample. The "spectrum" of REE normalized by the average shale has a bell-shaped shape, meaning the accumulation of average REE. In the technological sample (weighing about 400 kg) of Fe-Mn crusts from the underwater Magellanic Mountains (NW of the Pacific Ocean), the share of the cementing phosphate fraction accounts for about 10%. The rest is made up of Mn and Fe oxides (21 and 19%, respectively) and silica (23.5%). As a thorough study of the phosphate fraction showed, the facets of apatite crystals were often covered with a thin cerianite rash (CeTh)O2 and less often – parisite (Ce, La)2Ca [CO3]3F2, with the size of the discharge in hundredths of a micron. It turned out [8, p. 924] that "a significant part of the REE, primarily cerium, are part of cerianite, and not molecules of the apatite mineral." Thus, important differences between the phosphates of these crusts and shallow shelf phosphorites were discovered [8, p. 924]: "it is noteworthy that phosphates and carbonates of REE are formed in shelf phosphorites <...>, and in phosphorites of seamounts – mainly REE oxide (cerianite), i.e. the dependence of the nature of rare-earth mineralization on the facies situation is traced. It can also be assumed that the initial stage of REE accumulation is associated with their sorption from seawater by collomorphic phosphate, which, as they crystallized and self-purified, displaced them beyond their crystal lattice, where they formed autigenic minerals."

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