Authigenic Minerals of the Derbent and South Caspian Basins (Caspian Sea): Features of Forms, Distribution and Genesis under Conditions of Hydrogen Sulfide Contamination

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.

Seascape ecological view as a new insight of benthic foraminiferal community

<p>Foraminifers secrete various chemicals for chamber walls. They are calcium carbonates such as calcite, aragonite, Mg-calcite, organic compounds for agglutinated chambers and/or organic cemented test walls.  Foraminiferal test walls basically form according to genetic information.  However, same test group is tended to gather at specific microenvironments.  For instance, turf shaped algal microhabitat such as coralline algae at rocky shore is composed of both frond and thallus parts as microhabitat.  Frond part is open space where fresh seawater moves inbetween one frond and the other.  <em>Elphidium crispum</em>, <em>Pararotalia nipponica</em> and <em>Patellina corrugate</em> and other calcareous foraminifers dwell at frond surface.  In contrast, thallus part is muddy and high concentration of organic matters.  The thallus part shows less oxygenated than frondal part as the space is close.  Microbial cascades are developed at thallus part.  Minor elements such as Mg or Sr are relatively high in sediment.  Soft-shelled forms such as <em>Allogromia</em>, gromiid, agglutinated forms and miliolids groups with high magnesian calcite tests flourish at the thallus part.</p><p>Microhabitat segregation and microenvironmental differences may cause similar biomineralization of benthic foraminiferal tests.  I would like to stress that micro-seascape should be important to characterize benthic foraminiferal assemblages.</p>

Mineralogical, chemical and stable C and O isotope characteristics of surficial carbonate structures from the Mediterranean offshore Israel indicate microbial and thermogenic methane origin

The Eastern Mediterranean continental slope offshore Israel became a focus of exploration for, and production of, natural gas in recent years. The 2010–2011 Nautilus ROV expedition performed detailed video recordings and sampling in two areas offshore Israel: the Palmachim disturbance, southwest of Tel Aviv, and an area offshore Acre, north of Haifa. An analytical programme regarding the carbonate structures was carried out, examining the overall mineralogy, stable C and O isotopes, and Ca, Mg, and Mn concentrations. This provided information on their composition and as a result, an indication of the carbon sources and temperature of formation. The major authigenic minerals identified comprised magnesian calcite, dolomite, aragonite, and kutnohorite. The detrital minerals included quartz, clays, feldspars, and rare augite and enstatite, likely transported from the Nile estuary. The carbon isotope composition of aliquots taken from nineteen samples from these areas have an overall δ13C range from −62.0 to −0.1‰PDB, indicating a range of microbial/biogenic and thermogenic methane contributions. The range of δ18O from 2.7 to 7.0‰PDB reflects the range of temperatures of formation. The δ18O characteristics differ among areas. In general, high values; δ18O >5‰PDB are recorded from area N2 of the Palmachim disturbance, indicating low temperature of formation. Low values of δ18O (<5‰PDB) were measured from areas W2 and W3 of the Palmachim disturbance, together with samples from area N2 of the Palmachim disturbance, and samples from areas A1 and A2 offshore Acre indicate high temperature origin. Samples from an inactive chimney from area N2 range from pure dolomite to pure magnesian calcite. This trend is linked to δ13C increase from −39.9 to −0.1‰(PDB), and δ18O decrease from 6.2 to 4.7‰(PDB). These values indicate a decrease in the methane-derived carbon contribution and an increase in temperature. Kutnohorite, Ca(Mn2+, Mg, Fe 2+)(CO3)2 is a major component in samples from Acre, and less so in the Palmachim disturbance. An exploratory investigation of the relationship between Mn/Ca, δ18O and δ13C revealed that samples having Mn/Ca < 0.1(wt./wt.) have δ13C<−50‰PDB indicating a microbial methane source, while samples with Mn/Ca > 0.1 have δ13C between −35 and −22‰PDB suggesting a thermogenic origin. These results suggest that the mineralogical, isotopic δ13, δ18O, and chemical (Mn/Ca indicative of kutnohorite) characteristics of surficial carbonate structures can indicate and distinguish between deep and shallow methane sources in the Eastern Mediterranean.