Size-dependent distribution of metal(loid)s in recent marine sediments of the Adriatic sea.

This paper investigates occurrence of metal(loid)s, and size-dependent changes in their concentration in recent marine sediments from coastal and open-sea environments in the eastern Adriatic. Size fractionation of sediments was performed after removal of organic matter (OM), and the individual fractions, comprising particles below 8 µm, 4 µm, 2 µm, 1 µm and 0.45 µm, were analysed using HR ICP-MS. The concentrations of most elements increased with decreasing particle size, as a result of accumulation of clay minerals and Fe and Mn (oxyhydr)oxides. A decrease in concentrations was observed for Ba, Sr, Ti and U, due to lowering of the carbonate content and presence in the coarse-grained and heavy mineral fraction. The highest element concentrations were determined in the fraction comprising particles below 1 µm. Occasionally, depending on the sedimentological environment and/or the element in question, the peak concentrations occurred in the <2 µm or <0.45 µm fraction. The lowest size-dependent enrichment was observed for elements associated with aluminosilicates (Al, Be, Cs, Co, Fe, K, Li, Rb). A different size-dependent behaviour of the elements was observed between deep-sea areas and shallow environments under greater coastal influence, mainly due to differences in sediment sorting, and between the northern and central vs. southern Adriatic due to the different catchment geologies. The Fe and Mn (oxyhydr)oxides, abundant in the deep-sea sediments, played an important role in the geochemical cycle of As, Cd, Co, Mo, Sb and V.

Origin and history of trace elements accumulation in recent Mediterranean sediments under heavy human impact. A case study of the Boka Kotorska Bay (Southeast Adriatic Sea).

The history of metal pollution in the semi-enclosed and human-influenced marine system of the Boka Kotorska Bay (Southern Adriatic) was studied considering geological composition of the surrounding catchment, the sedimentation rate and the mineralogical and early diagenetic processes in the recent sediments. The determination of background concentrations of metals, undertaken for the first time in this environment, proved to be particularly important for Ni and Cr, which are naturally enriched in the sediments of the southern Adriatic. The results showed widespread moderate contamination with Pb and Sn since the 1970s, while the upper layers of sediments near shipyards, marinas and urban areas were more contaminated with Sn, Cu, Pb, Zn, Cd, As, Sb and Mo. The transport of material through the narrow straits separating different parts of Boka Kotorska Bay resulted in a different geochemical composition of the smaller bays and a limited distribution of contaminated sediments from local sources.

Distribution and Origin of Major, Trace and Rare Earth Elements in Wild Edible Mushrooms: Urban vs. Forest Areas.

This paper investigates the composition of major, trace, and rare earth elements in 15 different species of wild edible mushrooms and the possible effect of urban pollution on elemental uptake. The collected mushrooms include different species from the green areas of the city, exposed to urban pollution, and from the forests, with limited anthropogenic influence. Through a comprehensive approach that included the analysis of 46 elements, an attempt was made to expand knowledge about element uptake by mushroom fruiting bodies. The results showed a wide variability in the composition of mushrooms, suggesting a number of factors influencing their element uptake capacity. The data obtained do not indicate significant exposure to anthropogenic influences, regardless of sampling location. While major elements' levels appear to be influenced more by species-specific affinities, this is not true for trace elements, whose levels presumably reflect the geochemical characteristics of the sampling site. However, the risk assessment showed that consumption of excessive amounts of the mushrooms studied, both from urban areas and from forests, may have adverse health effects.

Anthropogenic influence on the environmental health along Montenegro coast based on the bacterial and chemical characterization.

Coastal marine sediments are particularly exposed to human activities. The function of a coastal ecosystem is largely affected by eutrophication, wastewater discharges, chemical pollution, port activities, industry and tourism. Bacterial classification can be used as a measure in assessing the harmful effects on the ecosystem. This study provided insight into the environmental health of the coastal region of Montenegro analyzing the possible impact of PAHs and PCBs upon the bacterial community diversity and function as well as nutrients. Two stations at the shipyards were defined as very high PAH polluted together with PCB concentration exceeding threshold values. The bacterial community at the OTU level clustered together all stations except the most polluted site (SBL), the main tourist destination in Montenegro (BDV) and the estuary site (ADB) forming the independent clusters. Bacterial community based on the OTU level was driven by PAHs, TOC and silt content. The lowest richness and diversity were indicated at the site with the highest concentration of PAHs and PCBs with the highest abundance of Alphaproteobacteria followed by Gammaproteobacteria. OTUs affiliated to phyla BRC1, Dadabacteria and Spirochaetes were present with a total abundance higher than 1% only at the most polluted site indicating their persistence and possible potential for degradation of aromatic compounds. To compare functional capabilities potentially related to biodegradation of aromatic compounds and active transport systems, PICRUSt was used to predict metagenomes of the sediments. From our data, we identified specific bacterial community and predicted metabolic pathways that give us a picture of the environmental health along the coast of Montenegro, which provides us a new insight into human-induced pollution impacts on the coastal ecosystem.

Simultaneous analysis of butyltins and total tin in sediments as a tool for the assessment of tributyltin behaviour, long-term persistence and historical contamination in the coastal environment.

This study presents a new approach for the investigation of tributyltin (TBT) behaviour and fate in the marine environment. The approach is based on a simultaneous analysis of butyltins (BuTs) and total Sn in sediments, thus enabling an assessment of long-term persistence and historical input of TBT. The study also presents first evaluation of the extent to which the TBT-antifouling paints contribute to the contamination of coastal environments with inorganic Sn; it was demonstrated that the inorganic Sn in the investigated areas primarily originates from TBT degradation. The study was conducted by analyzing BuTs and total Sn in sediments from 34 locations along the Croatian Adriatic coast. The results revealed that 85% of the locations were contaminated with both BuTs and inorganic Sn. The share of Æ©BuTs/total Sn was low (<10%) even in sediments with low TBT degradation efficiency (TBT/Æ©BuTs >40%), demonstrating that only small portion of TBT introduced into the water column reached the sediment before being degraded. This means that recent TBT input into the marine environment may be at least 10 times higher than the amount estimated if only BuTs levels in sediments are considered. It was also demonstrated that TBT concentration in sediments with TOC <1% is not a good indicator of the overall pollution level, even if TBT/TOC approach is used in pollution assessment. Finally, in situ investigation showed that resuspension of contaminated sediments leads to significant release of MBT and DBT into the water column, whereas TBT mainly remains in sediment.

Size-related mineralogical and surface physicochemical properties of the mineral particles from the recent sediments of the Eastern Adriatic Sea.

The mineral composition and surface physico-chemical properties, i.e., specific surface area (SSA), cation exchange capacity (CEC), and surface charge of recent sediments and their submicron mineral fractions from different sedimentological environments of the Eastern Adriatic were investigated. The influence of organic matter on these properties was also investigated. It was shown that illite and mixed-layered clay minerals (MLCM) were ubiquitous and showed no size-related preferences while the occurrence of smectites, chlorites, and kaolinites varied. The smectites content increased and the chlorites decreased slightly with decreasing particle size. The sediments from the carbonate-rich environment contained no smectites or chlorites and had the highest kaolinite content. For the first time, in the recent sediments of the Adriatic Sea the poorly- and the well-crystallised kaolinite (Kl and KlD) were distinguished. While Kl predominates in the submicron-sized fraction, KlD occurred only in micron-sized fractions. Authigenic aragonite of submicron-sized was determined in a distinct environment of the semi-enclosed marine lake. The differences in mineral composition and particle size of sediments and their separated fractions were reflected in a wide range of the SSA and CEC values obtained. The highest values of SSA and CEC were determined in the phyllosilicates-rich submicron-sized fractions range, 109 m2g-1 and 87.4 cmol+kg-1, respectively. The submicron-sized fraction from aragonite-rich marine lake showed the lowest values of SSA (56.4 m2g-1) and CEC (38.8 cmol+kg-1), which are still unexpectedly high for carbonate-rich environments. The removal of organic matter resulted in a significant increase in SSA and CEC, up to 150% and 76%, respectively.

Multi-element composition of soil, mosses and mushrooms and assessment of natural and artificial radioactivity of a pristine temperate rainforest system (Slavonia, Croatia).

This study investigates multi-element composition of soil, mosses and mushrooms from a pristine temperate rainforest (Prasnik, Croatia). Additionally, the activity levels of natural (238U, 235U and 232Th decay chains, 40K and 7Be) and anthropogenic (137Cs and 134Cs) radionuclides in the investigated soil samples, obtained by gamma spectrometry, provide baseline of environmental radioactivity levels in this area. The aim of investigation was to explore the uptake of metal(loid)s by bioindicator species (mosses, mushrooms) growing in a pristine environment characterized by naturally elevated concentration of metals. The calculated enrichment and bioaccumulation factors, correlations between different groups of elements and similar multi-element patterns in mosses, mushrooms and soil samples revealed the prevailing influence of the local substrate geochemistry on element concentrations in mosses and mushrooms. The results suggest atmospheric deposition of Bi, Cd and Pb, while radionuclide activities point to atmospheric fall-out (including global contamination by radiocaesium) and influence of the pedological substrate. The confined area of investigation, with limited variations in soil characteristics and geological composition, allowed clearer insight into the origin of metal(loid)s in mosses and mushrooms. On the other hand, using bioindicator species with different element uptake mechanisms enabled distinction between different sources of elements.

Influence of soil characteristics on rare earth fingerprints in mosses and mushrooms: Example of a pristine temperate rainforest (Slavonia, Croatia).

The present study aims to investigate levels and distribution of rare earth elements (REE) in soils, mosses and mushrooms of a pristine temperate rainforest, a non-polluted natural system, in order to characterise their environmental availability and mobility. The multielement analysis of digested soil, moss and mushroom samples was performed by High Resolution Inductively Coupled Plasma Mass Spectrometry. The distribution of rare earths in mosses and mushrooms was found primarily affected by local pedological setting. Mosses displayed a consistent lithological signature with an almost insignificant REE fractionation compared to soils. Mushrooms showed differences in REE concentrations in certain parts of the fruiting body with regard to their main physiological function and indicated a significant impact of soil organic content on the overall REEs uptake. Results of our work highlight the importance of substrate characteristics on the initial levels of REEs in mosses and mushrooms. Moreover, this study provides baseline data on the rare earth element levels in mosses and mushrooms growing in a pristine forest area characterised by naturally elevated REE levels in the soil.

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.