The respective environments in two ancient rivers were studied using geochemical methods with paleogeographic reconstructions of fossil material represented by shells of freshwater bivalve mollusks. The studied outcrops are located in the basins of the Dniester and Prut rivers. Materials were collected from two Pliocene (Brînza, Giurgiuleşti) outcrops and the ages of the second group of localities (Sucleia, Slobozia Mare, Gura Bîcului) are from Middle to Late Pleistocene. The determination of the taxonomic position was carried out using standard malacological methods. Geochemical data were used for the environmental reconstruction and included stable isotope ratio and trace element compositions in subfossil freshwater bivalve shell (Bivalvia: Unionoida). Key indicators of paleoenvironments show changes in water temperature. Changes in the taxonomic composition of bivalve mollusk assemblages also occurred. In the present study, increasing the water temperature caused a change of stenobiont species of bivalve mollusks to eurybiont species. Eutrophication of watercourses, caused by anthropogenic pollution and climate change in the direction of warming, has led to the replacement of pearl mussels of the family Margaritiferidae by more eurybiont species of the family Unionidae in the benthic communities of European oligotrophic rivers. These processes are similar to those deduced for the Neogene-Quaternary watercourses of the Prut and Dniester basins, but they proceed at a much faster pace. They are processes of eutrophication of watercourses – the main factor leading to the catastrophically rapid modern reduction of the ranges of pearl mussel.
The article provides information on the outcrops of the Neogene-Quaternary riverine sediments of the North-Western Black Sea coastal area. A description of five outcrops of fluvial deposits located on the territory of the modern basins of the Dniester and Prut rivers is given. Based on the granulometric composition of the sediments and the presence in them of the fossil shells of freshwater bivalve mollusks (Bivalvia: Unionoida), an assumption has been made about the characteristics of the ancient river ecosystems of the Dniester and Prut on different Pliocene and Pleistocene time sections. A review of the data in the body of literature on the geological age of the studied outcrops was undertaken. The localities considered provide information on the sedimentation conditions in this region from the Pliocene to the Late Pleistocene. Previously, various approaches were used for dating such rocks and for determining the stratigraphic position of fossil material found in them. The article considers the method of amino acids racemization as one of the approaches. Racemization allows to obtain new data on the stratigraphy of Neogene-Quaternary riverine sediments and to solve the problem of their dating. The sampling principles of carbonate material for the analysis of amino acids from the mollusk shells and features of sample preparation are described. Five amino acids were used: aspartic acid (Asp), glutamic acid (Glu), leucine (Leu), phenylalanine (Phe) and isoleucine (Ile). The D/L ratios were analyzed (amino acid racemization (or AAR) is the interconversion of amino acids from one chiral form (the L – (laevo) amino acids which are the building blocks of proteins) to a mixture of L- and D- (dextro) forms. The extent of racemization is measured by the ratio of D/L isomers (it increases as a function of time and temperature and can be used for geochronology) from the same group of fossils (genera), which were preserved under similar environmental conditions, inorganic geochemistry and thermal histories. Based on the obtained values, it can be concluded that the analysis of the racemization of amino acids is useful for determining the geological age of fossil shells of freshwater bivalve mollusks, but there are limitations regarding age. In the shells of the Pliocene sites, the values of some amino acids are close to one, indicating that the racemization took place. D/L values in shells from Pleistocene localities allowed the determination of their stratigraphic position.
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