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Structural features and distribution of framboidal pyrite were studied during lithological, mineralogical and geochemical studies of sediments in the South Caspian Basin. The lithological and geochemical parameters affecting the intensity of the formation of authigenic pyrite in sediments of the South Caspian Basin under conditions of hydrogen sulfide contamination were determined. According to X-ray diffraction (XRD), the content of pyrite in pelitic ooze reaches 4%. Microscopic studies have shown that pyrite formation occurs intensively in sediments with a high content of biogenic mineral components, such as opal diatom frustules and calcite plates of coccolithophores. Scanning electron microscopy (SEM) has demonstrated the presence of spherical pyrite framboids, as well as individual pyrite crystallites and their disordered clusters of various shapes. The diameter of the framboids varies from 3 to 10 microns. Pyrite crystallites have subspherical, complicated polyhedral, prismatic, octahedral, pentagonal dodekahedron shapes. The crystallite sizes range from 0.5 to 3 microns. Based on geochemical data, there is no direct correlation between the intensity of pyrite formation and the high content of such components as Fe and C org in bottom sediments. We assume that the formation of authigenic framboid pyrite in surface sediments (including the fluffy layer) is most likely due to the presence of hydrogen sulfide contamination in the near bottom water of the South Caspian Basin. Framboidal pyrite in the deeper layers (up to a depth of 35 cm) is the result of diagenetic processes that occur in accordance with the classical scheme of vertical zonality of diagenetic transformations in sediments.

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This paper presents the results of complex lithological, mineralogical, and geochemical studies of bottom sediments of deep-water basins of the Caspian Sea (Derbent and South Caspian Basins) in areas contaminated by hydrogen sulfide. In the course of complex studies, numerous manifestations of authigenic mineral formation associated with the stage of early diagenesis have been established. Authigenic minerals belonging to the groups of sulfates (gypsum, barite), chlorides (halite), carbonates (calcite, low Mg-calcite; kutnohorite), and sulfides (framboidal pyrite), as well as their forms and composition, have been identified by a complex of analytical methods (X-ray diffractometry (XRD), scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy (EDS); atomic absorption spectroscopy (AAS); coulometric titration (CT)); the nature of their distribution in bottom sediments has been assessed. Carbonates and sulfates are predominant authigenic minerals in the deep-water basins of the Caspian Sea. As a part of the study, differences have been established in the composition and distribution of associations of authigenic minerals in the bottom sediments in the deep-water basins. These are mineral associations characteristic of the uppermost part of the sediments (interval 0–3 cm) and underlying sediments. In the Derbent Basin, in sediments of the interval 3–46 cm, an authigenic association is formed from gypsum, calcite, magnesian calcite, siderite, and framboidal pyrite. An association of such authigenic minerals as gypsum and calcite is formed in sediments of the 0–3 cm interval. In the South Caspian Basin, in sediments of the interval 3–35 cm, an association of such authigenic minerals as gypsum, halite, calcite, magnesian calcite, and framboidal pyrite is formed. The association of such authigenic minerals as gypsum, halite, calcite, magnesian calcite, kutnohorite, and framboidal pyrite is characteristic of sediments of the 0–3 cm interval. We consider the aridity of the climate in the South Caspian region to be the main factor that determines the appearance of such differences in the uppermost layer of sediments of the basins. Judging by the change in the composition of authigenic associations, the aridity of the South Caspian increased sharply by the time of the accumulation of the upper layer of sediments (interval 0–3 cm). Taking into account lithological, mineralogical and geochemical data, the features of the processes of authigenic mineral formation in the deep-water basins of the Caspian Sea under conditions of hydrogen sulfide contamination have been determined. Analysis of the results obtained and published data on the conditions of sedimentation in the Caspian Sea showed that hydrogen sulfide contamination recorded in the bottom layer of the water column of the deep-water basins of the Caspian Sea may affect the formation of authigenic sulfides (framboidal pyrite), sulfates (gypsum), and carbonates (calcite and kutnohorite) associated with the activity of sulfate-reducing bacteria in reducing conditions.