Formation of Biogeochemical Anomalies in the Baksan River Basin

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ation of Biogeochemical Anomalies in the Baksan River Basin V. V. Ermakova, *, S. F. Tyutikova, A. P. Degtyareva, V. N. Danilovaa, U. A. Gulyaevaa, and D. N. Dogadkina aVernadsky

Institute of Geochemistry and Analytical Chemistry, ul. Kosygina 19, Moscow, 119991 Russia *e-mail: [email protected] Received April 1, 2020; revised April 8, 2020; accepted April 8, 2020

Abstract—The higher accumulation of Mo, W, Cu and Re by soils and organisms in the Baksan River basin owing to the anthropogenic contamination by the former Tyrnyauz W–Mo industrial complex and migration of the metals with natural waters are discovered during biogeochemical studies of W–Mo mining landscapes of the North Caucasus and background territories. The man-made transformed soils of the Baksan River valley and natural waters are enriched in moderately mobile compounds of Mo and other metals. The competitive relationships are found not only between Mo and Cu, but also between Mo and W while assessing the biogenic migration of metals. An increased content of Mo and W is found in the hair coat, blood and milk of farm animals, which is accompanied by changes in the activity of some enzymes. Keywords: biogeochemical anomaly, tungsten, blood, copper, molybdenum, migration, xanthine dehydrogenase/oxidase, milk, soil, plants, Baksan River, rhenium, Tyrnyauz DOI: 10.1134/S0016702920100067

INTRODUCTION Molybdenum is an essential trace element of practically all life forms. It operates as a cofactor of some enzymes that catalyze important chemical transformations in the biogeochemical cycles of nitrogen, carbon, and sulfur (Anke et al., 2010; Ermakov et al., 2018). Biological significance of molybdenum has been long known. In 1930, Bortels published first works on the role of molybdenum in the catalytic processes of biological nitrogen fixation by microorganisms Azotobacter chroococcum and Clostridium pasteurianum. In 1940s, Vinogradova reported data on the molybdenum content in plants of the Leguminosae family (Vinogradova, 1943). Subsequent extensive Russian and foreign studies of molybdenum role in feeding plants provided insight into physiological function of molybdenum (Anke et al., 2010). Some microorganism cultures extracted from Mo-rich soils are used in biotechnology for obtaining biologically active trace-element-bearing feed additives (Ermakov et al., 2012; Gradova et al., 2013). Molybdenum is ascribed to essential trace elements, playing an especially important role in the nitrogen metabolism of plants, animals, and human. It was proved that molybdenum is necessary and peculiar for some redox enzyme systems, which are involved in the reduction of nitrates, biological nitrogen fixation in plants and microorganisms, as well as in purine metabolism in animal organism. The molybdenum-bearing enzymes are subdivided into two main classes: nitrogenases and molybdopterin enzymes,

whose synthesis in organisms is genetically regulated (Boll et al., 2005; Brondino et al., 2006; Rish, 2003). The complex competitive interaction of molybdenum with copper an