Geochemistry of recent aragonite-rich sediments in Mediterranean karstic marine lakes: Trace elements as pollution and palaeoredox proxies and indicators of authigenic mineral formation.

This study investigates the geochemical characteristics of recent shallow-water aragonite-rich sediments from the karstic marine lakes located in the pristine environment on the island of Mljet (Adriatic Sea). Different trace elements were used as authigenic mineral formation, palaeoredox and pollution indicators. The distribution and the historical record of trace elements deposition mostly depended on the sedimentological processes associated with the formation of aragonite, early diagenetic processes governed by the prevailing physico-chemical conditions and on the recent anthropogenic activity. This study demonstrated that Sr could be used as a proxy indicating authigenic formation of aragonite in a marine carbonate sedimentological environment. Distribution of the redox sensitive elements Mo, Tl, U and Cd was used to identify changes in redox conditions in the investigated lake system and to determine the geochemical cycle of these elements through environmental changes over the last 100 years. The significant enrichment of these elements and the presence of early formed nanostructured authigenic framboidal pyrite in laminated deeper parts of sediment in Malo Jezero, indicate sporadic events of oxygen-depleted euxinic conditions in the recent past. Concentrations of trace elements were in the range characteristic for non-contaminated marine carbonates. However, the increase in the concentrations of Zn, Cu, Pb, Sn, Bi in the upper-most sediment strata of Veliko Jezero indicates a low level of trace element pollution, resulting from anthropogenic inputs over the last 40 years. The presence of butyltin compounds (BuTs) in the surface sediment of Veliko Jezero additionally indicates the anthropogenic influence in the recent past.

Organotin persistence in contaminated marine sediments and porewaters: In situ degradation study using species-specific stable isotopic tracers.

This paper provides a comprehensive study of the persistence of butyltins and phenyltins in contaminated marine sediments and presents the first data on their degradation potentials in porewaters. The study's aim was to explain the different degradation efficiencies of organotin compounds (OTC) in contaminated sediments. The transformation processes of OTC in sediments and porewaters were investigated in a field experiment using species-specific, isotopically enriched organotin tracers. Sediment characteristics (organic carbon content and grain size) were determined to elucidate their influence on the degradation processes. The results of this study strongly suggest that a limiting step in OTC degradation in marine sediments is their desorption into porewaters because their degradation in porewaters occurs notably fast with half-lives of 9.2 days for tributyltin (TBT) in oxic porewaters and 2.9±0.1 and 9.1±0.9 days for dibutyltin (DBT) in oxic and anoxic porewaters, respectively. By controlling the desorption process, organic matter influences the TBT degradation efficiency and consequently defines its persistence in contaminated sediments, which thus increases in sediments rich in organic matter.

Organotin compounds in seawater and Mytilus galloprovincialis mussels along the Croatian Adriatic Coast.

In this work, data on the level of organotin compounds (OTCs) in seawater and mussels collected along the entire Croatian Adriatic Coast are presented. The samples were collected in 2009 and 2010 at 48 locations representing different levels of maritime activities, including marinas, ports and reference sites. Butyltins (BuTs) were found in all analyzed samples, representing >97% of OTCs, and ranged from 0.46 to 27.98 ng Sn L(-1) in seawater and from <6 to 1675 ng Sn g(-1) in mussels. The results indicate a recent input of TBT, with the highest concentrations of BuTs found in the marinas. It appears that the Adriatic coast is still polluted with TBT despite the fact that TBT-containing antifouling paints have been banned in Croatia since 2008. It is questionable how much TBT pollution decreased since 2005, when a high incidence of imposex was established in the same area.