A compositional approach to the reconstruction of geochemical processes involved in the evolution of Holocene marine flooded coastal karst basins (Mljet Island, Croatia)

Geochemical patterns in the environment are always the result of certain processes. Therefore, it is essential to decipher a process to properly evaluate the environmental role and potential of chemical elements/compounds. This allows the distinction between natural and anthropogenic influence on elemental concentrations. However, if the compositional nature of geochemical data is neglected, erroneous or misleading conclusions regarding the processes involved are probable. In this study the reconstruction of depositional environments and processes through the Holocene in two sediment cores obtained from submerged sinkholes located on the island of Mljet, Croatia, was performed by taking into account the compositional nature of geochemical, mineralogical and grainsize data. Problems involving compositional data are always multivariate; for example, the concentration of a single element does not carry any interpretative information, as only the ratios between elements do. This has led to the discovery of a large number of geochemical proxies based on elemental ratios, which describe certain environmental conditions and processes involved. Nevertheless, some proxies have been found to be restricted to only some specific environments, thus preventing them from being used in general; therefore, some kind of relation between different proxies is necessary to obtain final conclusions. However, when using simple elemental ratios, those correlations cannot be obtained due to the nature of compositional data. With a sequential binary partition of a compositional vector, orthonormal log ratio (olr) coordinates (proxies) can be constructed. When based on expert knowledge, those proxies fully acknowledge the geochemical properties of the chosen elements with one major difference - that the correlation between newly obtained variables is mathematically well grounded. As a result, the final conclusion is more accurate. In this research, geochemical proxies obtained as a representation in olr coordinates of the elements that are enriched compared to the local soil were used to perform principal component analyses. It helped to unravel the evolution of sedimentary environments. Mineralogical (XRD and heavy mineral data) and grain size analyses supported the conclusions obtained based solely on geochemical data. Furthermore, data analysis suggests that the proxies for redox conditions described in the literature should be used with caution, as their use is somewhat limited