Main empirical regularities of the phosphorus geochemistry in the hypergenesis

Research subject. The study investigates the distribution of phosphorus (as percentages of P₂O₅ and P) and 4 phosphorus modules introduced by the authors - phosphorus-titanium FTM (P₂O₅/TiO₂), phosphorus-calcium FCM (P₂O₅/CaO), phos-phorus-iron FIM (P2O5/Fe₂O₃) and phosphorus-general-iron FGiM (P₂O₅/(Fe2O₃ + FeO)) - in the main types of sedimentary rocks, such as psammites, pelites, carbonates, silicites, in volcanic-sedimentary rocks (tuffoids), as well as in soils, sediments and such specific rocks as nodules and weathering crusts. Methods. On the basis of a large data bank (several tens of thousands of silicate analyses), new clarks of phosphorus were calculated. Clark estimates were based on average median contents for all the above-mentioned rock groups. For the first time, lithochemistry methods were successfully applied to characterize the composition of phosphorites. Correlation analysis was used to identify forms of phosphorus in rocks. Only the most reliable linear correlation coefficients of phosphorus and phosphorus modules with rock-forming components were considered significant - with a significance level no greater than 0.01 and 0.05.

Results and conclusions. In some cases, new estimates of clarks differed markedly from the estimates of our predecessors. For a number of objects, clarks were determined for the first time. Interpretation of the revealed relationships allowed us to identify the following main correlations and corresponding forms of phosphorus in sedimentary rocks and their analogues (soils and sediments): positive correlation with CaO - phosphorus in the form of accessory apatite or francolite dominated; positive correlation with Fe₂O₃ - phosphorus sorbed on iron hydroxides dominates; positive correlation with MgO - phosphorus dominated in the composition of smectite or chlorite, initially sorbed on the clay substance of precipitation; positive correlation with TiO₂ - phosphate sorbed on leucoxene, dominates. Thus, in addition to the previously known calcium and iron hydroxide, a titanium geochemical barrier for phosphorus was first identified.

1. Algeo T.J., Ingall E. (2007) Sedimentary Corg:P ratios, pale-ocean ventilation, and Phanerozoic atmospheric pO2. Pa- laeogeogr., Palaeoclimatol., Palaeoecol., 256(3-4), 130155.

2. Altshuler Z.S. (1977) Weathering of phosphate deposits: aspects of geochemistry and environment. Phosphorus in the Environment. Moscow, Mir Publ., 47-16. (In Russian)

3. Baturin G.N. (1978) Phosphorites on the Ocean Floor. Moscow, Nauka Publ., 232 p. (In Russian)

4. Baturin G.N. (2004) Phosphates accumulation in the Ocean. Moscow, Nauka Publ., 464 p. (In Russian)

5. Baturin G.N. (2009) Bioproductites and volcanism. Dokl. AN, 426(5), 653-657. (In Russian)

6. Berg G. (1933) Geochemistry of Mineral Deposits. M.; L., Gornogeol. oil. publishing house, 352 p. (In Russian)

7. Bliskovskii V.Z. (1967) Phosphorite-bearing weathering crust at the Bolshye Dzhebarty Deposit (Vostochnyi Sa-yan). Litol. Polezn. Iskop., 1, 23-42. (In Russian)

8. Bliskovskii V.Z. (1968) Geochemistry and peculiarity of the trace elements concentration in phosphorites. Cand. geol. and min. sci. diss. Lyubertsy, 252 p. (In Russian)

9. Bliskovskii V.Z. (1983) Material composition and enrichment of phosphorite ores. Moscow, Nedra Publ., 200 p. (In Russian)

10. Bliskovskii V.Z., Mineev D.A. (1986) Stones of Fertility. Moscow, Nedra Publ., 213 p. (In Russian)

11. Bok I.I. (1955) Agronomic Ores. Alma-Ata, AN Kazakh. SSR, 177 p. (In Russian)

12. Brodskaya N.G. (1974) Role of volcanism in the formation of phosphorites. Tr. GIN AN SSSR, 258. Moscow, Nauka Publ., 198 p. (In Russian)

13. Chambers J.M., Cleveland W.S., Kleiner B., Tukey P.A. (1983) Comparing Data Distributions. Graphical Me-thods for Data Analysis, 62. Belmont, California, Wadsworth International Group.

14. Dudkin O.V. (1980a) Behavior of phosphorus in post-magmatic processes. Geology of Apatite Deposits: Methods of Forecasting and Prospecting. Moscow, Nedra Publ., 18-20. (In Russian)

15. Dudkin O.V. (1980б) Geochemistry of phosphorus in magmatic processes. Geology of Apatite Deposits: Methods of Forecasting and Prospecting. Moscow, Nedra Publ., 14-18. (In Russian)

16. Eganov E.A. (1983) The Structure of the Phosphorite-bearing Deposits. Novosibirsk, Nauka Publ., 135 p. (In Russian)

17. Eganov E.A. (1988) Phosphorite formation and stromatolites. Novosibirsk, Nauka Publ., 89 p. (In Russian)

18. Felitsyn S.B. (2004) Volcanism, weathering and variation of the cycle of phosphorus in the Vendian of the East European platform. Litol. Polezn. Iskop., 4, 375-386. (In Russian)

19. Fersman A.E. (1959) Phosphorus (P-15). Geochemistry. V. 4. (Selected works. Vol. V). Moscow, AN SSSR, 100-112. (In Russian)

20. Froelich P.N., Arthur M.A., Burnett W.C. et al. (1988) Early diagenesis of organic matter in Peru continental margin sediments: phosphate precipitation. Marine Geol., 80(3/4), 309-343.

21. Frolov V.T. (1984) Genetic typing of marine sediments. Moscow, Nedra Publ., 222 p. (In Russian)

22. Gulbrandsen R.A. (1966) Chemical composition of phosphorites of the Phosphoria Formation. Geochim. Cosmo- chim. Acta, 30, 769-778.

23. Harder Н. (1978) Synthesis of iron layer silicate minerals under natural conditions. Clay and Clay Minerals, 96(1), 65-72.

24. Hess P.P. (1977) Phosphorus in lake sediments. Phosphorus in the Environment. Moscow, Mir Publ., 625-637. (In Russian)

25. Il'in A.V. (1983) Phosphorites of the Low Himalayas - another ancient phosphorite-bearing province. Dokl. AN SSSR, 286(1), 154-158. (In Russian)

26. Il'in A.V. (2008) Ancient (Ediacaran) phosphorites. Tr. GIN RAN, 587. Moscow, GEOS Publ., 160 p. (In Russian)

27. Ivanov V.V. (1994) Ecological Geochemistry of Elements. Main r-Elements. Phosphorus-15. Book 2. Moscow, Nedra Publ., 197-214. (In Russian)

28. Kazakov A.V. (1939) Phosphorite Facies. The Origin of Phosphorites. Tr. NIUIF, 145. Moscow, NIUIF Publ., 3-108. (In Russian)

29. Kazanskii Yu.P. (1969) Weathering and Its Role in Sedimentation. Tr. IGG SO AN SSSR, 73. Moscow, Nauka Publ., 127 p. (In Russian)

30. Kholodov V.N., Paul' R.K. (1995) The Black Sea - geochemical model of phosphate accumulation. Litol. Polezn. Iskop., 6, 563-581. (In Russian)

31. Kotova O.B., Ponaryadov A.V. (2020) Phosphate sorption on leucoxene. Vestn. Geonauk, 1(301), 19-23. DOI: 10.19110/geov.2020.1.3. (In Russian)

32. Makarov M.I. (2009) Phosphorus of Soil Organic Matter. Moscow, GEOS Publ., 397 p. (In Russian)

33. Maslennikov V.V. (1999) Sedimentogenesis, Galmirolysis and Ecology of Pyrite-bearing Paleohydrothermal Fields (on the Example of the Southern Urals). Miass, Geotur Publ., 348 p. (In Russian)

34. Murray J., Renard A.F. (1891) Report of Science Result of the Voyage of HMS Challenger during in the years 1872 to 1876. London, Edinburg, Dublin, 688 p.

35. Pustovalov L.V. (1933) Geochemical facies and their significance in general and applied geology. Problemy Sovetskoi Geologii, 1(1), 57-80. (In Russian)

36. Ronov A.B., Korzina G.A. (1960) Phosphorus in sedimentary rocks. Geokhimiya, 8, 667-687. (In Russian)

37. Savenko V.S., Savenko A.V. (2005) Physical and Chemical Analysis of Modern Ocean Phosphorite Formation. Moscow, GEOS Publ., 142 p. (In Russian)

38. Sheldon R.P. (1982) Deposition of apatite at the water-sediment boundary - non-conformist process. Geology of phosphorite deposits and problems of phosphorite formation. Novosibirsk, Nauka Publ., 15-25. (In Russian)

39. Silaev V.I. (1996) Mineralogy of Phosphate-bearing Weathering Crusts of the Polar Urals. St.Petersburg, Nauka Publ., 136 p. (In Russian)

40. Smirnov A.I. (1972) Material composition and conditions for the formation of the main types of phosphorites. Tr. GIGKhS, 14. Moscow, Nedra Publ., 196 p. (In Russian).

41. Smirnov H.G., Votyakov S.L., Sadykova N.O., Kiseleva D.V., Shchapova Yu.V. (2009) Physical and chemical characteristics of mammalian fossil bone remains and the problem of estimating their relative age. Pt 1. Thermal and mass spectrometric element analysis. Ekaterinburg, Goshchitskii Publ., 118 p. (In Russian)

42. Sokolov A.S. (1996) Evolution of uranium-bearing phos-phorites. Geokhimiya, 11, 1117-1119. (In Russian)

43. Strakhov N.M. (1971) Development of lithogenetical ideas in Russia and USSR. Critical Review. Tr. GIN AN SSSR, 228. Mocsow, Nauka Publ., 622 p. (In Russian)

44. Tsykin R.A., Udina I.I. (1975) Manganese and phosphorus in bauxite-bearing deposits of the Angara-Yenisei pro-vince. Questions of mineralogy, petrography and geo-chemistry of the Krasnoyarsk territory. VMO of the Akad Nauk SSSR Krasnoyarsk Department. Materials 3. Krasnoyarsk, Knizhn. izdvo, Publ., 144-151. (In Russian)

45. Yanshin A.L., Il'in A.V., Eganov E.A. (1984) Main problems of ancient phosphates accumulation. 27 Intern. Geol. Congress. Non-metallic mineral resources. Sect. C. 15. Reports. V. 15. Moscow, Nauka Publ., 95-103. (In Russian)

46. Yanshin A.L., Zharkov M.A. (1986) Phosphorus and Potassium in Nature. Novosibirsk, Nauka Publ., 190 p. (In Russian)

47. Yudovich Ya.E. (1980) Experience of the genetic classification of nodules and concretion rocks: In order of discus-sion. Litol. Polezn. Iskop., 4, 110-123. (In Russian)

48. Yudovich Ya.E. (1981) Regional Geochemistry of Sedimentary Strata. L.: Nauka Publ., 276 p. (In Russian)

49. Yudovich Ya.E. (2009) Once again about anoxia and phosphogenesis. Vestnik In-ta geologii Komi NTs UrO RAN, 2(170), 22-23. (In Russian)

50. Yudovich Ya.E. (2018a) 11 genotypes of phosphogenesis in stratisphere. Ural. Geol. Zhurn., 3(123), 18-39. (In Russian)

51. Yudovich Ya.E., Belyaev A.A., Ketris M.P. (1998) Geo-chemistry and ore genesis of black shales of the Pai- Khoy. St.Petersburg, Nauka Publ., 366 p. (In Russian)

52. Yudovich Ya.E., Ketris M.P. (1988) Geochemistry of Black Shales. Leningrad, Nauka Publ., 272 p. (In Russian)

53. Yudovich Ya.E., Ketris M.P. (1994) Trace Elements in Black Shales. Ekaterinburg, UIF Nauka Publ., 304 p. (In Russian)

54. Yudovich Ya.E., Ketris M.P. (2000) Fundamentals of Litho-chemistry. St.Petersburg, Nauka Publ., 479 p. (In Russian)

55. Yudovich Ya.E., Ketris M.P. (2005) Toxic Trace Elements in Fossil Coals. Ekaterinburg, UrO RAN, 656 p. (In Russian)

56. Yudovich Ya.E., Ketris M.P. (2006) Valuable Trace Elements in Coal. Ekaterinburg, UrO RAN, 538 p. (In Russian)

57. Yudovich Ya.E., Ketris M.P. (2008) Mineral Indicators of Lithogenesis. Syktyvkar, Geoprint Publ., 564 p. (In Russian)

58. Yudovich Ya.E., Ketris M.P. (2010) Geochemical and Mineralogical Indicators of Volcanogenic Products in Sedimentary Strata. Ekaterinburg, UrO RAN, 412 p. (In Russian)

59. Yudovich Ya.E., Ketris M.P. (2011) Geochemical Indicators of Lithogenesis (Lithological Geochemistry). Syktyvkar, Geoprint Publ., 740 p. (In Russian)

60. Yudovich Ya.E., Ketris M.P. (2014) Geochemistry of Man-ganese. Syktyvkar, IG Komi NTs UrO RAN, 540 p. (In Russian)

61. Yudovich Ya.E., Ketris M.P. (2016) How to designate a Carbonate-Bearing rock? (From the practice experience). Vestn. In-ta geol. Komi NTs UrO RAN, 3(255), 33-36. DOI: 10.19110/2221-1381-2016-3-33-36 (In Russian)

62. Yudovich Ya.E., Ketris M.P., Nikulova N.Yu., Soin V.N. (2006) Sochi balls. Vestn. In-ta geologii Komi NTs UrO RAN, 3(135), 7-14. (In Russian)

63. Yudovich Ya.E., Ketris M.P., Rybina N.V. (2018a) Geo-chemistry of Titanium. Syktyvkar, IG Komi NTs UrO RAN, 436 p. (In Russian)

64. Yudovich Ya.E., Ketris M.P., Rybina N.V. (2018б) Phosphorites and glauconite: the cause of paragenesis. Vestn. In-ta geologii Komi NTS UrO RAN, 11(287), 43-47. DOI: 10.19110/2221-1381-2018-11-43-47 (In Russian)

65. Yudovich Ya.E., Ketris M.P., Rybina N.V. (2019a) Lithochemistry of Phosphorites. Ural. Geol. Zhurn., 3, 1-86. (In Russian)

66. Yudovich Ya.E., Ketris M.P., Rybina N.V. (2019b) Five Ge-netic Correlations of Phosphogenesis in the Sedimentary Shell. Ural. Geol. Zhurn., 1, 1-60. (In Russian)

67. Yudovich Ya.E., Ketris M.P., Rybina N.V. (2020) Phosphorus in carbonate rocks. Vestn. Geonauk, 3(303), 14-20. DOI: 10.19110/geov.2020.3.2 (In Russian)

68. Yudovich Ya.E., Ketris M.P., Tereshko V.V., Rybina N.V. (2016) Essays on Lithochemistry of the Timan-Urals Region. Syktyvkar, IG Komi NTs UrO RAN, 236 p. (In Russian)

69. Zanin Yu.N. (1975) Material Composition of Phosphatebearing Weathering Crusts and Associated Phosphorite Deposits. Novosibirsk, Nauka Publ., 210 p. (In Russian)

70. Zanin Yu.N., Ternovoi V.I. (1980) Geochemistry of phosphorus in the zone of weathering. Geology of Apatite Deposits: Methods of Their Forecasting and Search. Moscow, Nedra Publ., 24-26. (In Russian)