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

The components of apatite with the general simplified formula Ca5[PO4]3 (OH, F, Cl) may have isotopic variations carrying important genetic information. In particular, isotopic ratios were studied: – rock-forming Ca; – rock-forming O; – a small element Sr, isomorphically substituting Ca; – rare lanthanide Nd, isomorphically substituting Ca. But if only a few papers have been devoted to the isotopy of Ca in apatites, then dozens of studies have already been devoted to the isotopy of phosphate O and Sr, and recently work on the isotopy of Nd has also increased dramatically. 3.1. Calcium It is known that with the "classical" mechanism of growth from a solution of Ca-containing crystals, the solid phase is enriched with a light isotope of calcium – 43Ca. If crystallization occurs according to a "non-classical mechanism", in particular, when whole clusters are captured on the active growth surface, then it can be expected that no significant fractionation of Ca isotopes will occur. This idea was tested in experiments carried out in 2018 by Catherine Schilling and colleagues [124], using the most modern, extremely fine methods - with mineralogical characterization and nanoscale visualization of growth features to determine the high-speed fractionation of Ca isotopes during the seed growth of hydroxyapatite (HAP) with the participation of a precursor – octacalcium phosphate (OCP). It turned out, in particular, that the growth rates are greatly weakened with an increase in pH, because the binding of OH ions of Ca2+ prevents the precipitation of phosphate. Nanoscale images of the surface topography showed direct deposition of primary particles on the surface of micron HAP crystals after steady growth, visually proving the dominance of the non-classical hydroxyapate growth pathway. At the same time, as expected, the difference in the isotopic composition of Ca between the initial solution and the precipitated phases of phosphates turned out to be insignificant – within the limits of the analysis error. 3.2. Strontium As is known, the method of strontium isotope chemostratigraphy is based on the fact that the 87Sr/86Sr ratio is currently homogeneous in the World Ocean, which has been the case throughout the entire existence of the oceans. The fact is that the residence time of Sr in the ocean exceeds the time of complete mixing of all the sea waters of the Earth, which leads to the homogenization of the isotopic composition of strontium in seawater In the geological history of the Earth, the isotopic composition of strontium in seawater has changed. The 87Sr/86Sr ratio in seawater is controlled by mixing the following sources: 1) continental runoff resulting from the weathering of the earth's crust by surface and river waters; 2) hydrothermal flow arising from the interaction of seawater with volcanic rocks in the area of mid-Oceanic ridges (MOR); 3) the flow resulting from the dissolution and recrystallization of marine carbonate sediments. Strontium chemostratigraphy of pelagic sediments is based on the determination the age of sediment by the ratio of strontium isotopes (87Sr/86Sr) in biogenic foraminifera carbonate or bone detritus apatite. 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. As an example of the successful application of the strontium method, we can name the precision work of Russian geochemists dedicated to determining the age of only two ichthyolites, 34.7×30.3×6.2 mm and 40.2×26.5×9.5 mm in size, sealed in the Cape Basin in the southern part of the Atlantic Ocean [59]. The age of the tooth enamel of sample 2188/5 was 6.6±0.3 million years, and sample 2188/4 was 5.2±0.2 million years. Thus, the use of a complex (mechanical and chemical) technique for cleaning tooth enamel from the nuclear part of the Fe-Mn nodules of the Cape Basin from Fe and Mn oxyhydroxides made it possible to reliably determine the isotopic composition of Sr in biogenic apatite. Some materials on the isotopy of phosphate strontium were contained in our 2011 book (all references made there are replaced here with angle brackets <...>. In particular, it was reported [80, pp. 99, 439] that a molar of a terrestrial mammal (Gomphotera) was found in the pebbles of Miocene sandstone south of Stockholm. Isotopic analysis of the elements of the phosphate substance of enamel (C, O, Sr, Nd) was compared with that of the host rocks and with analyses of other bone residues of the same age in Sweden and the Center. Europe. The value 87Sr/86Sr (0.71592) is typical for ancient rocks and is significantly higher than in the teeth of phosphate residues from the Center. Europe (from 0.70650 to 0.71063, according to 17 analyses). The value 87Sr/86Sr (0.71592) is typical for ancient rocks and is significantly higher than in the teeth of phosphate residues from the Center. Europe (from 0.70650 to 0.71063, according to 17 analyses). The general conclusion is as follows: in the Miocene in Scandinavia there were terrigenous deposits with mammalian fauna that were eroded during the Pleistocene glaciation). In particular, it was reported [SK-2011, pp. 99, 439] that a molar of a terrestrial mammal (Gomphother) was found in the pebbles of Miocene sandstone south of Stockholm. Isotopic analysis of the elements of the phosphate substance of enamel (C, O, Sr, Nd) was compared with that of the host rocks and with analyses of other bone residues of the same age in Sweden and the Center. Europe. The value 87Sr/86Sr (0.71592) is typical for ancient rocks and is significantly higher than in the teeth of phosphate residues from the Center. Europe (from 0.70650 to 0.71063, according to 17 analyses). Since modern autigenic francolites show exactly the same 87Sr/86Sr ratio as in seawater (0.70916), it is logical to assume that ancient phosphorites also inherit the isotopic ratio of the age-appropriate seawater. At the same time, it turns out that during metasomatic phosphatization of limestones, primary carbonate strontium is completely exchanged for strontium of seawater. This means that the 87Sr/86Sr value in phosphorites, compared with the "standard geochronological curve" constructed from carbonate rocks, can date phosphorites. So, phosphates desert Sechura in Peru showed the age 11.8 ± 0.5 million years, offshore Namibia – 1.15 ± 0.25 million years, at an underwater ridge Chatham – 4.90 ± 0.35 million years, which is consistent with other (independent) age <...>. There are examples of using isotope of strontium and for high-temperature magmatic and hydrothermal apatite. Thus, Murmansk geologists [40] determined the isotopic composition of strontium hydrothermal apatites and francolites formed in the post-carbonatite stage of development of the Kovdorsky foscorite-carbonatite complex. The values of 87Sr/86Sr obtained by them were 0.7036-0.7059, whereas the known average value for carbonatites is 0.7043. Values below the "middle carbonatite" (characteristic of the calcite stage of the Kovdorsky complex) are treated as mantle, and those above (characteristic of the later dolomite stage of the Kovdorsky complex) are treated as typical of the crust. 3.3. Oxygen As you know, the Cenozoic was a period of gradual transition from greenhouse conditions to glacier conditions, and this process was not smooth, but was interrupted by sharp cold spells. Two such breaks occurred at the boundary of the Eocene and Oligocene and in the Middle Miocene. Both were found to be associated with the growth of the East Antarctic ice sheet. Cenozoic climate changes were intensively studied mainly from the archives of deep-sea sediments using the value δ18O. Most of these determinations were made using the δ18O data in benthic foraminifera carbonate. However, these values of δ18O reflect only the temperature of the ocean bottom waters, as well as the salinity and volume of ice. The oscillation amplitudes do not always correctly reflect the change in air temperature on the surface of the continent. Therefore, the method of climatic reconstructions by the value δ18O of bones and teeth of herbivorous mammals was proposed and successfully used, because it reflects the composition of drinking water of these animals, which, in turn, was closely related to the air temperature on the continent. The obvious disadvantage of this method is the comparative rarity of finding the remains of large mammals, moreover, concentrated in a relatively short period of time. In this sense, the technique of paleoclimatic reconstructions according to δ18O of rodent teeth has obvious advantages. An example is the work on Southern. Germany with an abundance of such localities, which made it possible to give a paleoclimatic reconstruction covering the period from the Late Eocene to the Miocene [106]. The authors managed to show that the air temperature in the South. Germany in the period from the late Eocene to the beginning of the Late Miocene ranged from 12 °C to 25 °C, and at the Eocene/Oligocene boundary, the average decrease in air temperature was either ~2 °C (taking into account classical biostratigraphy) or ~6 °C (taking into account the revised biostratigraphy). Changes in the humidity of the climate on the territory of Chad (Central Africa) were tried to clarify with the help of oxygen isotopy in the apatite of tooth enamel of freshwater fish, during the Upper Miocene – in Messinian, covering the period between 7,246 ± 0.005 million and 5,332 ± 0.005 million years ago [117]. It turned out that the most open habitat of fish, with a lower content of δ18O in Hydroconus teeth, existed in four Chadian vertebrate localities – Toros-Menalla, Kossom-Bugudi, Kolle and Koro-Toro, dated respectively 7.04±0.18 Ma, 5.26±0.23 Ma, 3.96±0.48 Ma and 3.58±0.27 Ma. The value of δ18O increases by ∼2 in two locations corresponding to the age of the Messinian; there is also a slight increase by ∼0.6 in three Pliocene locations. These results reflect a change in the precipitation regime in the Center. Africa during the Late Neogene. Oxygen isotopy in the bioapatites of ichthyolites and conodonts in the lower carboniferous layers on the Northern Ireland made it possible to confirm the data on permocarbon glaciation [83]. Compared with normal seawater, the values of δ18O phosphate oxygen were shifted by +2.4%. This was the result of an increase in the volume of ice during a cooling of 4.5°C on the surface of the equatorial sea between the beginning of the Asbian and the middle of the Brigantine time of the late Vise. It is shown that the δ18O apatite of conodonts and ichthyolites reflect the stabilization of the climate of the "ice house" during the Brant-Serpukhov time. The Visean cooling revealed on the basis of δ18O is consistent with global glacioeustatic data. Positive excursions of isotopic characteristics were recorded in the phosphate of conodonts of Mississippian age: 18O to +2 and up to +1.5 - for late Tourne and Serpukhov, and in carbon 13Ccarb, respectively, to +6.5 and up to +5 [89]. This ratio may mean that the Serpukhov cold snap occurred before the accumulation of carbonaceous precipitation (i.e., the latter was not the cause of the cold snap?). In general, these isotopic data indicate that the first big cold snap began already in the tour (even with possible glaciation?), the first known glaciation manifested itself in the Vise, and the second – in Serpukhov Oxygen data are interpreted as direct indications of cooling and an increase in the volume of ice. Carbon data (both Sorg and Scarb) can be associated with the burial of Sorg in black shales, which lowers the CO2 content in the atmosphere and, as a result, causes cooling. As is known, in Pennsylvania–early Permian there was a high-latitude glaciation in Antarctica and the adjacent continents of Gondwana. The beginning of glaciation dates back to the Serpukhov-Bashkir century, and the first maximum glaciation reached in the Moscow century. In the Gzhel century, the area of glaciation decreased, but increased again in the early Permian, reaching a second maximum in the Assel-Sakmar time. The study of the Pennsylvania sediments showed frequent cyclical expansion and contraction of the Gondwanan cover glaciers, which generated corresponding fluctuations in sea level. In 2006, German authors [108] studied the oxygen isotopy in the bioapatite of Midcontinent conodonts to assess glacio-eustatic sea level fluctuations in Pennsylvania (Middle-Late Carboniferous). It is known that in the Pennsylvanian time, the ocean covered most of the Midcontinent. The northern and central part of the Midcontinent basin was relatively shallower, and the basin deepened to the south. This pool was open to the Pantalassa Ocean to the Z and NW. The Pennsylvania deposits of the Midcontinent are represented by a cyclic alternation of thin layers of transgressive limestones, offshore gray to black phosphate shales and thicker layers of regressive limestones. These cycles are underlain and overlapped by coastal or terrestrial shales with paleosols and coals. Glacioeustatic fluctuations in sea level are considered as the main cause that generated cycles. 18Ophosph were obtained in comparison with the Vienna Standard of Mean value for seawater (VSMOW): The following average values of 18Ophosph were obtained: black shales = 20.1 ± 0.5%, gray shales = 20.5 ± 0.5%, regressive limestones = 21.0 ± 0.3%, transgressive limestones = 21.1 ± 0.6‰, The maximum difference of values 18Ophosph for individual data between shales and limestones is 1.7%. This difference compares well with the difference obtained for Pleistocene equatorial intraglacial and interglacial shallow-water foraminifera, which confirms the reliability of the figures obtained from conodont phosphate. However, since the Pennsylvanian glacial maxima are represented by terrestrial facies that are not documented by conodonts, glacio-eustatic sea level fluctuations in Pennsylvania were probably greater than 120 m, reached in the Pleistocene. Some materials on the isotopy of phosphate oxygen were given in our 2011 book (all references made there are replaced here with angle brackets <...>. In particular, there was shown, that with 18Ophosph of fossil bone remains it is possible to judge the climate in which mammals lived 18Ophosph of hydroxylapatite of their bones and teeth, in particular tooth enamel (in which fluorapatite is also present) is very informative. And since the value of 18OH2O depends on the climate, it is indicated there [80, p. 165] that important climatic information can be obtained by the value of 18Ophosph of biogenic phosphates, since the oxygen-isotopic composition of the water that terrestrial mammals drink (and herbivores, in addition, receive as part of the green mass they eat) directly affects the value of <...> 18Ophosph, significantly less than the first [80, p. 166]. The reason for these differences is the determining influence of the mountain barrier on the humidity of the climate. Despite seasonal complications, the Sierra Nevada ridge with an average height of 2800 m clearly divides the humid climate area to the west, at a distance of about 300-350 km to the Pacific coast – from the arid climate area to the east of the ridge. This is because the winds that carry masses of moist air from the Pacific Ocean to the east, reaching the barrier of the Sierra Nevada, lose up to 90% of moisture in the form of precipitation. Direct measurements of the isotopic composition of precipitation showed that to the west of the Sierra Nevada, the values of OH2O (SMOW) are – (3–10), on the ridge itself they drop sharply by 6–7 % and further east at a distance of 400–1100 km from the coast they remain at the level of –(12–16) % <...> OH2O (SMOW)) in precipitation (in the form of rain or snow. This phenomenon has received the beautiful name of the isotopic "rain shadow" The higher the barrier, the stronger its isotopic "rain shadow". On average, for our planet, the gradient of decreasing magnitude is is –0.28 % for every 100 m of increase in the height of the mountain barrier. Analysis of the isotopic composition of phosphate oxygen from the famous location of Neogene mammals in southern Germany [80, p. 221] allowed us to make amazing reconstructions: to determine what water (lake or rain) lake turtles, small and large terrestrial mammals drank – Table 2 Table 2 Isotopic composition of phosphate oxygen of paleontological remains of Lake Steinheim and its probable interpretation Compiled according to T. Tuetken et al., 2006. <...> Objects Number of analyses 18Ophosph = 18OН2О, ‰ SMOW Interpretation The bones of the shell of freshwater turtles 6 +2.0 ± 0.4 Such was the isotopic composition of oxygen in the lake water Tooth enamel of small mammals 7 +2.7 ± 2.3 Such water was drunk by small mammals; therefore, they drank lake water Tooth enamel of large mammals 31 –5.9 ± 1.7 Such water was drunk by large mammals; therefore, they did not drink lake water, but rain water Measurements of the value of In the carbonate substance of phosphate-bearing carbonaceous diatoms on the shelf of Namibia [80, p. 329], the value of 18Ophosph (Holocene-Pleistocene nodules, bones of fish and marine mammals) give temperatures in the range from 10.9 to 14.8 oC, which is also quite plausible for upwelling zones with their cool waters 18Ocars (SMOW) is 30.4 %, which fully corresponds to the temperature of surface waters equal to 18.8 <...>. A comparison of the values of 18Ophosph in two types of Upper Cretaceous and Paleocene/Eocene phosphate fossils of Tunisia – in shark teeth and in coprolites – showed that, on average, the phosphate oxygen of the former is about 0.4 % lighter than the latter: 19.2–20.5 % vs. 20.4–21.2 % [80, pp. 377-378]. This small but significant shift reflects the temperature difference of the bathymetric facies in which the phosphate was located: coprolites were formed mainly in the higher warm layers of the water column, whereas shark teeth were buried mainly in the pelagial, where the phosphate reached isotopic equilibrium with colder waters <...>. Autigenic phosphate mineralization in carbonaceous silts of Peruvian upwelling shows values of 18Ophosph in the range of 20.2-24.8 % [80, p. 453]. At the same time, phosphates formed from an "impersonal" phosphorus resource near the water boundary/sediment, have values of 18Ophosph equilibrium with seawater, whereas phosphates in deeper sediment horizons, genetically related to the Porg that entered the pore waters from the organic matte are more or less disequilibrium in terms of values of <...>. However, in ocean sediments to the north of Africa, disequilibrium is established, on the contrary, in the surface layers. Although there is no unambiguous interpretation of the discovered phenomenon, among the possible factors is the sedimentation rate, when bacterial phosphate consumption does not keep pace with its release from the buried organic matter <...>. If this version is true, then the isotopic composition of phosphate oxygen could serve as an indirect characteristic of the subtle features of diagenesis. In the siliceous-phosphate black shales of the Chatkalo-Naryn structural zone of the North the Tien Shan, the oxygen isotopic composition of carbon-siliceous-phosphate nodules was found to be facilitated, in which the average value of 18O is +15.6 %, whereas in the host silicites this value is significantly higher than +(26-27) %. It is believed that the oxygen relief of autigenic phosphate and flint is directly related to the intensity of diagenesis, since the value 18O positively correlates with the phosphate content in the studied nodules/ Finally, the data [80, p. 334] on the development of the so-called phosphate paleothermometer are very interesting. When phosphate is deposited in equilibrium with seawater, isotopic exchange is possible according to the scheme: H218O + 1/4 [P16O4]3- (water)  H216O + 1/4 [P18O4]2– (phosphate). After a series of not entirely successful experiments, A. Longinelli was still able to establish a linear relationship between temperature and the value of the isotopic densification 18O: ТоС = –80.0 – 4.8 (18Ophosph – A). Thus, if syngenetic carbonates and phosphates are present in the rock (or, better, if phosphate forms an impurity in the carbonate), then the use of two independent thermometers seems to allow an absolute estimate of the paleotemperature. At the same time, the isotopic shift in the formation of phosphate is greater than in the formation of carbonate and averages 12%. This situation, apparently, only favors an increase in the accuracy of paleothermometry. Unfortunately, as R. Bowen points out <...>, isotopic measurement of phosphate oxygen is a very difficult task, since natural phosphates contain impurities of non-phosphate oxygen in the form of OH and CO3. Nevertheless, R. Bowen (who was only aware of the preliminary results of A. Longinelli's work) optimistically assessed the possibilities of the phosphate thermometer <...> 3.4. Carbon Using the isotopy of phosphate carbon of conodonts, it was possible to confirm the global nature of the Late Ordovician cooling [98]. The samples of marine phosphates represented the section interval of the late Ordovician corresponding to ~10 million years before the Hirnant glaciation. The authors found out whether the climatic fluctuations of the orbital scale controlled the growth and melting of continental glaciers, which led to glacial-eustatic changes in sea level and the development of widespread marine sedimentary cycles. The values of δ18O of conodont apatite from 14 cycles of the Late Ordovician (Catian) vary from ~17 to 21. Isotopic indices are minimal in deep-sea facies and maximal in shallow-water facies, which confirms the hypothesis that glacioeustasy was the dominant factor in controlling the depth of the sea. The measured intracycle changes in δ18O (0.7–2.5%) were controlled by changes in ice volume (sea level changes <60 m), sea surface temperature (<5 °C) and potentially a local increase in seawater evaporation during drier and/or windier glacial stages. These isotopic interpretations confirm recent interpretations of the dynamic and long transition of the Ordovician greenhouse (greenhouse) to the glacier (ice house). Permafrost conditions in the northeastern regions of Siberia allowed the remains of large mammals that lived in these territories in earlier Cenozoic epochs to be preserved here. Horse mummies are quite rare among them, but bone remains are ubiquitous. In 2013, a predominantly Russian team of authors [17] performed complex isotopic studies of five mummies and several bones of Late Pleistocene horses found in the north of Yakutia. The obtained results suggest that the carbon isotopic composition of carbonate hydroxyapatite of Yakut horse bones can be used as a paleoclimatic indicator. It was established in which climatic conditions the horses lived (warm or cold, wet or dry), the remains of which were investigated. According to preliminary data, the habitat conditions of Late Pleistocene horses of Yakutia and Zap. Europe was close. The authors cite the graph "Evolution of the carbon isotope composition of hydroxyl-apatite carbonate of the bones of large herbivores of Northern Yakutia in the late Pleistocene", where the values of δ13Ccarb in the range from –11 to –16 % are plotted on the abscissa, and three "marine climatic stages" are plotted on the ordinate, up to 12 (?) thousand years ago (1), up to 25 thousand years (2) and up to 50 thousand years (3). Note that no trend is visible on the graph. The authors themselves interpret the graph as follows [17, p. 98]: "A possible conclusion is the instability of the Late Pleistocene climate of Northern Yakutia, which was expressed in sharp short-term (500–2000 years) irregular episodes of relatively mild climate, having the rank of interstadials in intensity". 3.5. Neodymium Recently, the rare-earth element neodymium has become extremely popular, according to the ratio of isotopes of which the value of "epsilon neodymium" – Nd is calculated. The neodymium isotope 143Nd is formed as a result of alpha decay of 147Sm, with parameters = 6.54x10-12, T1/2 = 10.06x1011 years. The isotopic composition of neodymium is usually depicted Nd – the 143Nd/144Nd (R) isotope ratio 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 143Nd/144Nd in CHUR – "chondritic uniform reservoir”, which is assumed to be 0.512638. Since the continental crust has a smaller Sm/Nd ratio than the mantle, the mantle (and its young magmatic derivatives) has a 143Nd/144Nd ratio higher than the Earth as a whole – and, accordingly, negative values of Nd On the contrary, ancient crustal rocks have 143Nd/144Nd lower than in the Earth as a whole, and positive values of Nd – the more negative the older the rocks As G. Faure writes in his remarkable book [66, p. 223]: "The model assumes that the terrestrial Nd evolved in a homogeneous reservoir, the Sm/Nd ratio in which is equal to this ratio in chondrite meteorites. The current value of 143Nd/144Nd in this reservoir is 0.512638 relative to 146Nd/144Nd =0.7219. The current ratio (147Sm/144Nd) in CHUR is 0.1967. This information allows us to calculate the ratio 146Nd/144Nd in CHUR at any other time t in the past <...>". It should be noted that at present, the literature on the use of the value "epsilon neodymium" for the diagnosis of the petrofund of marine sediments has become so extensive that it can be considered practically unlimited. Without fear of seeming immodest, it can be noted that one of the good reviews can be found in our book-2011 [80, p. 100–102] (we omit references to the literature used here and replace them with angle brackets). In this case, the value Nd is often used in conjunction with the value ISr = 87Sr/86Sr. In the stratigraphic sequence, examples of such use relate to Precambrian sediments <...>; Paleozoic, in particular, Cambro-Ordovician and Upper Ordovician carbonates and phosphates <...>; Mesozoic, including for the Upper Cretaceous anoxic event OAE-2 <...>; Cenozoic, including for young sediments of the Labrador Sea <...>, the Indian Ocean <...>, the flysch strata of Kamchatka and the South of the Koryak Ridge <...>, for alluvial sediments of the Indo-Gangetic plain <...>, young sediments of the Central Basin of the Indian Ocean <...>. In the aspect of this review (apatite as a geological indicator), we note that there are data in this book [80] directly related to our topic – on the use of Nd in the apatite of conodonts. In particular, it is noted that the comparison of two remote sections of Upper Ordovician carbonates – in Saskatchewan and Iowa – showed synchronous fluctuations in the value of Nd: the alternation of two characteristic maxima and minima in seawater <...>. These fluctuations, thus acquiring important stratigraphic significance, are explained by the changing contributions of two provenance with significantly different isotopic characteristics: (a) low-lying Precambrian basement, in the rocks of which value of Nd ranges from –22 to –15, and (b) young the high-altitude Taconian orogen with Nd in the range from –6 to –9. The expansion of the transgression of the epicontinental Ordovician sea (and, accordingly, in carbonates) increased; regression led to the opposite result The Upper Cretaceous and Cenozoic strata of the Kamchatka flysch and the south of the Koryak Ridge had at least two petrofunds. One of them was juvenile – suprasubduction volcanic complexes, to a lesser extent basalts of MOR or back-arc basins. This petrofund is characterized by low 87Sr/86Sr ratios and high values of Nd(T) <...> Another source was apparently represented by complexes of ancient continental crust. This petrofund is characterized by the accumulation of radiogenic 87Sr and negative values of Nd <...>. Good results were obtained when using the value Nd in combination with the value Hf <...>. So, isotope diagram in the coordinates Hf (in the range from –35 to +25) – Nd (in the range from –25 to +15) – good differs some genotypes of marine sediments – Fe-Mn nodules, clayey silts and sands <...>. In addition to its value as a great indicator of petrofond of rocks and sediments, the value of Nd is an excellent tracer of ocean circulation. This property discovered in the study of the modern ocean, has been successfully used for paleogeographic reconstruction of the Iapetus ocean in the territory of the Eastern United States and to the Upper Devonian sediments of Morocco and Poland <...>. Like other REES, neodymium accumulates in phosphates. Therefore, the study of such biogenic phosphates as conodonts or ichthyolites allows us to judge the isotopic composition of seawater of the corresponding epochs, which makes it possible to make completely non-trivial paleogeographic reconstructions. For example, the study of isotopic geochemistry of conodonts and their host limestones in precisely dated (~454 million years) the interval of sections of the Upper Ordovician on the territory of the East. Laurentia (from Iowa to Pennsylvania) showed that the values of Nd and (to a lesser extent) 13Ccarb showed strong variations depending on the reconstructed paleogeography of the epicontinental "Mojave Sea", which represented the northwestern (shelf) part of the ancient Iapetus Ocean. On the territory of the Midcontinent – in the western part of the sea fed by the terrigenous material of the ancient Canadian shield, the value of Sm/Nd in conodonts is low, on average 0.19 ± 0.01; the values of Nd are strongly negative,–15 ± 2.6 (from –12 to –19); the values of 13Сcarb are also negative, on average –0.6 ± 1.3. It is obvious that the composition of seawater in this part of the sea was affected by the ancient acidic petrofund and the flow of isotope-light carbon from the river runoff. In the southeastern facies zone and in the extreme east of the sea – in the Taconian Foreland, isotopic characteristics 13Ccarb are positive, on average +2.2 ± 0.2%. This was clearly affected by the influence of the basite petrofund eroded in the young Taconian orogen at the boundary of the shelf sea with the Iapetus Ocean <...>. These results are important for the correct interpretation of isotopic data. The fact is that, as you know, the vast majority of the stratosphere is composed of shallow-sea strata – the former sediments of epicontinental seas. Consequently, the detected isotopic variations (primarily Nd) sensitively reflecting the individual characteristics of inhomogenized water masses of ancient seas (= facies zones!), should not be uncritically transferred to the global level of the World Ocean. And indeed, in this case, the values of Nd of the water of the Iapetus open ocean ranged from –5 to –0.6 (!), i.e. they were strikingly different from the values for the facies zone of the Midcontinent <...>. Another example of the effective application of the value Nd is the analysis of conodonts from the Upper Devonian sections in Morocco and Poland, representing both the shelf of Gondwana and Euramerica, and deeper sediments of the Variscian Ocean that separated these continents. It turned out that the shelf sediments were characterized by low values of Nd Nd from –7 to –12, while the ocean sediments showed less negative values of Nd, from –7 to –1. This means that the waters of the shelf could not freely mix with the surface waters of the open ocean, which is possible only under conditions of predominance of low sea level. And only in the sediments of the semihovae conodont zone (zone No. 11), the transgression turned out to be powerful enough for the surface waters of the ocean to penetrate the shelf: in this interval of all sections, the values of Nd fall into the "ocean" interval from –6 to –2. At the same time, it turns out that according to the values of Nd the ancient Variscian Ocean is more similar to the modern Pacific Ocean than to the Atlantic and Indies that emerged later in its place In the ichthyolites from the Upper Cretaceous black shales on the Demerara underwater ridge (opposite the coast of Suriname, the extreme west of the equatorial Atlantic), two opposite anomalies of magnitude Nd (T) are recorded: <...> 1) very low background values for ocean sediments from –14 to –16.5; 2) an unusually sharp and powerful positive excursion Nd, up to 8! It corresponds to the very beginning of the Cenomanian-Turonian OAE-2, covers a column interval of about 1.6 m (which corresponds to only 120–160 thousand years) and completely coincides with the positive excursion of 13Corg (shift by +8 %). If the first can be explained (with reservations) by the local influence of a terrigenous source – a close Guianan shield composed of ancient metamorphites and granites with a magnitude of Nd (T) up to –30, then the second is more difficult to explain. The most plausible idea is the powerful influence of mantle basalt volcanism - the "trigger" of OAE-2. Thus, the basalts of the Great Caribbean Volcanic Province have values of Nd (T) equal to +10. It has already been noted above that the values of Nd should be inversely correlated with the values of ISr = 87Sr/86Sr. Indeed, in the works of recent years, both indicators are used together. These are, in particular, examples of a very successful decoding of the petrofund of alluvial sediments of the Indo-Gangetic Plain <...>, the Tibetan Plateau <...> and young pelagic sediments of the Central Basin of the Indian Ocean <...>. Among the more recent works (not included in the review of the book-2011), we will name the study of apatite shells of neogene phosphate brachiopods (Lingulidae and Discinidae) from the South. parts of the North Sea, Center. Parathetis and the Atlantic coast of Europe – as a paofacial indicator [109]. Here the value of εNd is used in conjunction with the value of ε18O of phosphate oxygen. The shells of the genus Glottidia of the North Sea showed a low value of εNd and a high value of ε18OPO4 during the Mio-Pliocene, which indicates the cold temperature of the brachypod habitat, where the local seawater corresponded to the water of the Atlantic Ocean. On the contrary, brachypods of the genera Lingulidae and Discinidae of Parathetis in the Middle Miocene inhabited warm subtropical sea waters with a possible influence of the Indian Ocean (via the Mediterranean), which is confirmed by their average value of εNd –8.3. Combined geochemical data support thermal and marine separation of Parathetis from the North Sea without direct connection or significant exchange or significant water exchange. The temperature in Parathetis was very similar to that derived from the data of the Middle Miocene brachiopods West. France, but the value of the sea water's εNd here is identical to the same age in the Atlantic Ocean. Late Miocene lingulids from the South. Portugal has a high value of ε18OPO4, similar to specimens studied from the North Sea. This reflects either the deep-sea habitat of the lingulids, or the situation after the onset of global cooling, which ended with an increase in the value of ε18OPO4 of seawater. As another example of using the value of epsilon neodymium (not specified in the book-2011), we can name an article where the calcium isotopy in apatites was considered together with the data on the εNd (T) – to clarify the conditions of global phosphogenesis at the turn of the Cretaceous and Eocene [128]. It was shown that the values of εNd (T) and δ44Ca, as well as the accumulation rates of P and Ca, experienced clear changes. In particular, the sharp increase in the εNd (T) after the Cenomanian period is explained by the increased penetration of Pacific waters enriched with radiogenic neodymium, which was caused by global sea level rise at the end of the Cretaceous period, the emergence of a link between the North and South Atlantic, global post-Santonian cooling and the gradual expansion of the Caribbean threshold, all this combined significantly enhanced the Tethys circular current (TCC). This also reflects the weakening of the continental Nd signal due to a decrease in open landmasses caused by increased flooding of continental shelves. High values of δ44Ca at that time also indicate a decrease in Ca2+ fluxes during weathering and the expansion of carbonate deposits on the shelves, which enriches seawater with isotopically heavy Ca2+. The study of bioapatite of Devonian ichthyolites in the Escuminac formation of Quebec (Canada) can serve as an example of using the value of epsilon neodymium in close connection with the 87Sr/86Sr index [115]. The values of 87Sr/86Sr in biopatite range from 0.70804 to 0.70845, which overlaps the values for sea water of the Frasnian time. Although a small part of the values fall within the "Frasnian sea water interval", most of them are shifted towards more radiogenic continental (freshwater) values. This trend seems to be due to the postmortem exchange between fossils and a fluid isotopically different from seawater. All bioapatites are enriched with REE and for values normalized by shale, they show depletion of HREE and some enrichment by MREE. The values of the εNd (T) for rocks in the range from –4.8 to –6.4 are consistent with the post-Taconic Appalachian provenance. By contrast, for bioapatites, the values of εNd (T) are more radiogenic: from –2.6 to –4.6. This difference between rocks and fossils means the presence of of a secondary, diagenetic Nd reservoir. It is assumed that part of this reservoir was seawater. The neodymium similarity between the Escuminacian fossils and the Upper Devonian conodonts of Poland indicates a close connection between the Devonian Rheic Ocean and the Escuminac Formation basin.

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