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

As indicated in the Irish review [130], the admixture elements of igneous apatite have been successfully used as a petrogenetic tool. Very commonly used «biplots» – binary graphs where characteristic relationships are laid down along the axes, for example: - La/Lu, - La/Sm, - the sum of all REE (ΣREE), - the ratio "light REE /heavy REE" (LREE/TREE), where light REE includes elements from lanthanum to praseodymium, and heavy REE - from terbium to lutetium, - the ratio "light REE /medium REE" (LREE/MREE), where the average REE includes elements from neodymium to gadolinium, - Th/U, - Sr /Y and a number of others, in particular, the Sr/Y – LREE biplot is promoted, on which 6 fields are allocated with mutual overlaps not exceeding 15% of the field area. 2.1. REE, their "spectra" and characteristic relations Rare earth elements (REE in English literature) are the most important impurity elements in the cationic part of apatite. They are usually divided into groups of light (LREE, La–Nd or sometimes wider, La–Gd), medium (MREE, Pm–Ho) and heavy (HREE, Er-Lu). In the Russian literature, according to D. A. Mineev [45], a slightly different division of lanthanides into groups is accepted, used, for example, in V. V. Gordienko's article on granite pegmatites [12]. REE are divided into cerium – Ce (from La to Nd) and yttrium Y (Eu–Lu). Moreover, yttrium REE are divided into two subgroups – Y1 and Y2. It is obvious that those REE, which in the West are called "average" (MREE), in terms of Mineev are REE of the group Y1, and "heavy" – Y2 . Graphs ("spectra") have received the widest application, where the REE symbols are located along the abscissa in order of increasing their atomic number (from La = 57 to Lu = 71), and according to the ordinate – their contents in apatite, normalized most often by chondrite, and less often by "shale", that is, by the average composition of post-Archean clay shale (PAAS), calculated at the time by S. Taylor and S. McLennan [64]. Another normalization was proposed by D Piper [121] according to the composition of the "middle shale" (AS) N. America, Europe and the USSR. Normalization is usually represented by the lower index N, for example, LaN or SmN. The REE contents used for normalization are shown in Table 1. Table 1 Average REE contents (ppm) in chondrites and two average "shales" used for normalization REE La Ce Pr Nd Sm Eu Gd Chondrites 0.3 0.5 0.1 0.6 0.2 0.08 0.4 AS 41 83 10.1 38 7.5 1.61 6.35 PAAS 38 80 8.9 32 5.6 1.1 4.7 REE Tb Dy Ho Er Tm Yb Lu Chondrites 0.05 0.35 0.07 0.2 0.04 0.2 0.035 AS 1.23 5.5 1.34 3.75 0.63 3.53 0.61 PAAS 0.77 4.4 1.0 2.9 0.4 2.8 0.43 With a strong predominance of light REN over medium and heavy, the broken curve connecting the points of the contents of individual lanthanides is strongly "upturned" on the left; with comparable contents of LREN with SRZEN + TRZEN, the curve is "flat", approaching the horizontal, and with increased contents of SRZEN, the curve in its middle part is convex - "bell-shaped". Therefore, the shape of the "spectra" (along with numerical indicators La/Lu, La/Yb or La/Sm) serves as an important element in describing the distribution of REE in apatites – and, accordingly, one of the criteria for the genetic diagnosis of apatites and their host rocks. For example, the analysis of bioapatites of the Upper Frasnian and Lower Famenian conodonts of the Southern Urals performed by the ISP-MS method with laser ablation [30], after normalization of REE contents by PAAS, showed a bell-shaped "spectrum" shape, meaning the accumulation of average REE. The reason for the difference of the "spectrum" from the typical one for phosphates formed in equilibrium with seawater is considered to be "lithogenic effect – diagenetic enrichment of REE by bioapatite from the host sediments. Widely used indicators, called Cerium and Europium anomalies, denoted as CeA = Ce/Ce* and EuA = Eu/Eu*, require separate consideration. Cerium anomaly CeA = Ce/Ce* The cerium anomaly is calculated as the ratio of analytically determined chondrite-normalized cerium (CeN) to the calculated value of Ce*, which is a "weighted" sum of normalized lanthanum and neodymium contents (i.e., as it were, the "theoretical" cerium content): CeA = CeN/Ce*, where Ce* = 1/3 (1.44LaN + 0.66 NdN). Thus, CeA = 3CeN/(1.44LaN + 0.66 NdN) The coefficients 1.44 and 0.66 correspond to the ratio of lanthanum, cerium and neodymium in the composite (combined sample) North American shale NASC (La = 31 ppm, Ce = 67, Nd = 34). Although there can be no negative values here, in the literature, the values of CeA > 1 are usually called "positive", and the values of CeA < 1 are "negative". It is more correct, of course, to call them excessive and deficient. However, there are works in the literature <...> in which the value of the Ce anomaly is calculated differently, according to the formula CeA = log [3CeN / (2LaN + NdN)]. In this form, it can really be both negative and positive (without quotes). As is known [80, pp. 277–288], cerium is the only element from the lanthanide group that, at Eh values characteristic of aerated waters, is able to oxidize from the form of Ce3+ to the form of Ce4+. In this form, it is easily hydrolyzed, captured by Fe-Mn hydroxides and removed from the water. In this process, the curve of the normalized REE distribution there is a characteristic minimum of the cerium – oxygen indicator facies characteristic of modern well-aerated ocean <...>. In 1983, by comparing the precision of the definitions of REE in surface and deep (2500 m) waters of the Atlantic and Pacific was reliably proven that with the depth of content of LREE (Ce, La, Nd, Sm) decreases, and the heavy (Eu, Gd, Dy, Er, Yb) – increasing. At the same time, among the LREE, the decrease in Ce is most sharply manifested, for example, in the North Atlantic, it decreases from 120x10-7 to 24x10-7 ppm. This global oceanic phenomenon is due to the absorption of LREE from seawater on a suspension of Fe-Mn hydroxides generated by the discharge of underwater hydrotherms. Even at a distance of up to 1400 km from the axis of the East Pacific Uplift, 90% of all manganese is in water in the form of suspended particles with a dimension of <0.4 microns <...>. As can be seen from these data, the Ce content can vary fivefold, therefore, the value of the Ce anomaly is a sensitive indicator of the fine redox zonality of the water column <...>. In oxygen-depleted (suboxide) water the Ce/Ce* index is ~0.6–0.9, and in oxygen-free water it can reach a value of 1.0. Thus, the value of the cerium anomaly in minerals formed in former seawater is an important "paleomarine" indicator of redox conditions, i.e. conditions that existed in ancient seas, and allows us to judge the depth of apatite formation. Europium anomaly EuA = Eu/Eu*. The europium anomaly is calculated as the ratio of analytically determined chondrite-normalized europium (EuN) to the calculated value of Eu*, which is a half-sum of the normalized contents of the neighbors of europium – samarium and gadolinium (i.e., as if the "theoretical" content of europium): EuA = EuN/Eu*, where Eu* = ½ (SmN + GdN) Thus, EuA = 2EuN/(SmN + GdN) Although there can be no negative values here, in the literature, the values of EuA >1 are usually called "positive", and the values of EuA <1 are "negative". It is more correct, of course, to call them excessive and deficient. Like cerium, trivalent europium – Eu(III) can also change its valence, but not oxidize, but recover to Eu(II). However, the current redox conditions of the ocean are such that even in an anoxic environment, the Eh values of seawater are not low enough to reduce europium. Therefore, both in seawater and in autigenic minerals in equilibrium with it, the value of Eu/Eu* is close to 1. Nevertheless, there are rare cases when significantly reduced values of the Eu/Eu* index were observed in autigenic minerals, proving that the reduce of europium still took place. Such cases were noted in autigenic apatites formed not just in anoxic, but in hydrogen sulfide ("euxine") environments of diagenesis. An additional sign of such situations is not only the absence of a negative Ce anomaly, but sometimes even a positive value of the Ce/Ce* value. However, more often such cases are explained not by diagenesis, but by the penetration of reduced underwater hydrotherms into the marine sediment. As for detritus apatites from igneous rocks, the value of Eu/Eu*<1 was observed much more often for them, since in the reducing conditions of hot magmatic melts, europium is reduced and the resulting Eu2+ is absorbed by the rock-forming plagioclase (where it replaces Ca2+), which leads to a sharp depletion of the accessory apatite formed later by europium. Thus, the "negative" value of the europium anomaly in apatite indicates either detrital magmatic apatite formed in magmas with low oxygen fugacity, or (much less often) – newly formed low-temperature autigenic apatite formed in euxine (hydrogen sulfide) medium of diagenesis. From the literature on REE in apatites, not covered by the Irish review [130], several works, both domestic and foreign, deserve attention. In 2013, a major Novosibirsk geochemist, German Kolonin, performed (in collaboration with G. P. Shironosova) thermodynamic modeling of the association of apatite with monazite, which is important for petrogenesis. The authors wrote [78, p. 455]: "A close association of apatite with monazite has been noted, while either monazite inclusions are observed in fluorapatite, or fluorapatite crowns sometimes with xenotime and allanite are the result of monazite substitution <...>." Their calculations, in accordance with the data of their predecessors, showed that dark apatites with monazite inclusions are formed at 300-400 ° C. In 2007, R. Kolonin and co-authors [32] studied a heterogeneous collection of monazites (including our Timan ones, from the collection of I. V. Shvetsova). Comparing the composition of monazites with the known thermodynamic data on the solubility of monazite and xenotime, he came to the conclusion that monazites crystallized from acidic fluids (in which the REE content can be two orders of magnitude higher than in alkaline ones) and especially from low-temperature ones can be highly enriched with yttrium and heavy lanthanides [32]. Thus, the accumulation of yttrium and heavy REE in monazite may indicate its low-temperature nature and the acidic nature of the hydrothermal fluid. As shown by the Moscow region mineralogists who conducted experiments in "crustal" conditions, i.e. at P = 0.5 GPA, and T = 1200 oC, for the elements REE, Y, Th (as well as Cu and W), the coefficient of distribution D between apatite Apt and carbonate melt Lcarb exceeds one [11]: "Therefore, compared to the carbonate melt, Apt is a more efficient concentrator for the elements." At the same time, a remarkable difference was found in the behavior of light and heavy REE – namely, the different dependence of their D on the atomic number (i.e., on the atomic weight): for light REE (from La to Eu), the D numbers increase with growth, and for heavy REE they decrease! 2.2. Strontium and manganese As shown in the Irish review [130], the "Sr – Mn" biplot in detrital magmatic apatite is useful for determining both the degree of fractionation of the parent magma and for assessing the oxygen fugacity in the former melt. Usually, the Sr/Mn ratio of magmatic apatite makes it possible to distinguish three situations: (1) the value of Sr/Mn is very low; such is apatite from highly fractionated melts due to the increased content of manganese (up to 1 wt.% or even more); (2) the value of Sr/Mn is close to unity (1:1); such is apatite from igneous granitoids of type I, where the contents of both Sr and Mn are tens or several hundred ppm; (3) the value of Sr/Mn is very high; such is apatite from mafic melts, in which the Sr contents reach several thousand ppm (i.e. 0.n%!), which was shown in particular in one of the works of E. A. Belousova and colleagues [85], while detrital apatite from ultrabasic rocks can be easily distinguished from apatite basites, since the former is much richer in strontium and extremely depleted in relation to severe REE. Of the works not covered by the Irish review, one can note the recent acutely critical article by Jeffrey Bromley [86], "Do concentrations of Mn, Eu and Ce in apatite reliably record oxygen fugacity in magmas?" He came to the conclusion that Eu and Ce are not suitable for this, but the content of apatite manganese can be used with caution as a redox-sensitive indicator. The correlation of the manganese distribution coefficients between apatite and the host rock as a function of the silicicity of the rock (and the parent magma, respectively), for which the ASI alumina indices and polymerization indices were calculated, allows us to propose a model in which the Mn content in apatite largely depends on the structure of the melt. In more developed magmatic systems, a decrease in the availability of non-conjoining oxides in silicate melts transforms Mn from an incompatible element into an increasingly compatible element in apatite. 2.3. Uranium and thorium In the article of the Chinese team [127], the Th/U ratio in the bioapatite of conodonts was used together with the value of CeA to assess redox conditions in ancient seas on the territory of Southern China. As is known, uranium has two different states: under oxygen conditions, U6+ is stable and highly soluble, but it turns into insoluble U4+ in oxygen-free waters, while the solubility of Th is not affected by redox changes. This leads to an increase in the Th/U ratio in anoxic facies. If the degree of oceanic anoxia becomes significant, as it was assumed for the early Triassic, then the uranium reservoir in the ocean will be depleted, which will lead to an increase in the Th/U ratio. From other works, where the uranium content in apatite is given, the unique deposit of metalliferous (uranium-rare earth) bone detritus Melovoye, located within the Southern Mangyshlak (Kazakhstan), is of particular interest [7]. Here, native minerals of uranium and rare earths were recorded as part of bone bioapatite: uraninite UO2, coffinite USO4, ningioite (U, Ca, Ce)2[PO4]2(1–2)H2O, otenite Ca2[UO2][PO4]2(8–12)H2O and cherchite YPO4(2H2O). The deposit, formed in the Oligocene–early Miocene, was a series of bed-like deposits consisting of bone detritus of fish (ichthyolites) and marine animals with abundant inclusions of iron sulfides and admixture of terrigenous material. The phenomenon of accumulation of a colossal mass of biogenic phosphate material enriched with rare metals at the bottom of a reservoir is of interest from the point of view of the evolution of biogeological systems. The accumulation of uranium and REE in this and similar deposits occurred in several stages due to a series of reducing and oxidizing episodes during the formation of ore layers. The circulation of thermal metalliferous solutions coming from deep horizons of the sedimentary strata could also have a certain effect on the ore process. It should be noted that according to the estimates of foreign experts [79], the extraction of uranium from phosphate fertilizers is not only economically justified, but also environmentally important, since it cleanses them from undesirable impurities. It is noted that, depending on the origin of phosphate minerals, the concentration of uranium can vary from 150 mg/kg (francolite in sedimentary rocks) to 220 mg/kg in ores of volcanic origin. 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 make it possible to ensure the supply of uranium for nuclear power for 440 years at the price of uranium obtained from traditional sources. Technologically, the extraction of uranium from mineral raw materials during the production of phosphate fertilizers is not very difficult. In a number of countries, including the USA and Germany, uranium was obtained from phosphate ores in significant quantities as long as it was economically feasible. For all countries with reserves of phosphate minerals, it is important to understand that the use of uranium extracted from ore in the production of phosphorus fertilizers will make it possible to use cleaner fertilizers, and therefore will help prevent contamination of the soil, natural reservoirs and the atmosphere. 2.4. Other elements-impurities in apatites In 2013, Russian geochemists discovered that native gold particles of 5-30 microns in size, with a probity of 875-990 are visible on the surface of biogenic apatite from the reference sections of the Lower Paleozoic of Sweden, the southern coast of the Gulf of Finland and the Ladoga region. [65]. Data are presented that indicate the redistribution of Au in the thickness of the Lower Paleozoic sediments of Baltoscandia, followed by sorption on biogenic apatite under the influence of a slightly acidic fluid with a temperature below 80 °C. The 87Sr/86Sr value of such a fluid was significantly lower than the values characteristic of the Early Paleozoic oceanic reservoir, which, taking into account the absence of sedimentary carbonates with low 87Sr/86Sr values in the Phanerozoic section in the northwest of the East European Platform, may indicate the juvenile nature of the fluid. The American team analyzed 171 apatite phenocrystals from 4 consecutive layers of K-bentonites from outcrops in the north of the Mississippi Valley in the Caradoc Decor formation [99]. Each grain was analyzed at several points from 3 to 6 times for REE and other impurity elements. The contents of magnesium and manganese were the most variable. According to them, a diagnostic graph was constructed in the coordinates Mg (0.01–0.18 %) – Mn (0.0–0.08 %). In this graph, the of dots of each bentonite formation (in the amount from 29 to 47) differed well. Thus, it was proved that the composition of apatites can be used for stratigraphic correlation of bentonites.

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