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 ƩBuTs/total Sn was low (<10%) even in sediments with low TBT degradation efficiency (TBT/ƩBuTs >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.
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•Simultaneous analyses of BuTs and total Sn enable assessment of overall TBT behaviour.•Simultaneous analyses of BuTs and total Sn enable assessment of initial TBT input.•Sn contamination of coastal environment principally originates from TBT-antifoulings.•Less than 10% of the initial TBT input reaches sediment before being degraded.•Contrary to MBT and DBT, TBT remains attached in the sediments during resuspension.
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.
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•Micron and submicron-sized fractions of recent Adriatic sediments were investigated.•Mineralogical and surface properties of mineral particles are size related.•Phyllosilicate-rich submicron-sized sediment fraction showed highest SSA and CEC.•The removal of organic matter resulted in a significant increase in SSA and CEC.•Prevalence of submicron-sized authigenic aragonite induced low SSA and CEC.
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.
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•Total PAHs, TOC and silt are potential drivers of the bacterial community on the OTU level.•The high concentration of PAHs and PCBs influenced the lowest richness and diversity.•High differences in the functional capabilities of bacterial communities were recorded.
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.
•Rare earths in soils, mosses and mushrooms of a pristine temperate rainforest.•The REE in mosses and mushrooms primarily affected by soil characteristics.•Mosses display soil signature with an insignificant REE fractionation.•Mushrooms indicate an impact of soil organic content on the REEs uptake.
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.
This study investigates multi-element composition of soil, mosses and mushrooms from a pristine temperate rainforest (Prašnik, 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.
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•Multi-element composition of soil, mosses and mushrooms from a pristine forest.•Soil radioactivity levels (238U, 235U, 232Th, 40K, 7Be,137Cs, 134Cs) determined.•Element levels in mosses and mushrooms influenced by substrate geochemistry.•Indications of atmospheric deposition of Bi, Cd and Pb.
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.
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•The history of metal pollution in Boka Kotorska Bay was determined in sediment cores.•Verified local metal backgrounds are required to assess the extent and history of pollution.•Metals have different vertical profiles depending on the pollution source.•Shipyards are the main sources of metal pollution of coastal sediments.•Mineral and geochemical composition of sediments varies due to geological setting.
Exposure of soil constituents to elevated temperatures during wildfire can significantly affect their properties and consequently, increase the mobility of the bound contaminants. To estimate the ...potential of wildfires to influence metal remobilization from the burned soil due to the changes in cation exchange capacity (CEC) after organic matter combustion and mineral alteration and degradation, changes in soil properties after exposure to different temperatures was investigated. This was accomplished through analysis of geochemical, mineralogical and surface physicochemical properties of a soil sample exposed to different temperatures in a laboratory. Heating the soil sample at 200 °C, 500 °C and 850 °C resulted in an increase in pH (from 5.9 to 12.3), decrease in cation exchange capacity (from 47.2 to 7.3 cmol
kg
) and changes in the specific surface area (observed only at 500 °C), that are associated with structural modifications of clay minerals and ferromagnetic minerals. Extraction analysis showed the increase in the concentration of almost all analysed elements (Al, Cd, Co, Cr, Fe, Mn and Zn) in soil eluates. The observed increase, following high– temperature heating (500 °C and 850 °C), was as much as 15 times higher (e.g., Al), compared to the native soil sample (25 °C). This strongly indicates that wildfire can act as a trigger for remobilization of heavy metals.
Purpose
The geochemistry of pore waters from sediments deposited in the semi-enclosed bay of the Zrmanja River estuary, encompassing two small interconnected basins, the Novigrad Sea and the Karin ...Sea, was investigated. The conducted research aimed to identify diagenetic processes occurring in surficial bottom sediments and to assess the impact of these reactions on trace element concentrations in the overlying water.
Materials and methods
Sediment pore waters were extracted from sediment cores in a nitrogen atmosphere. Multielemental analysis of prepared samples was performed by high-resolution inductively coupled plasma mass spectrometry (HR-ICP-MS). All samples were analysed for the total concentration of 15 elements (As, Ba, Co, Cr, Fe, Li, Mn, Mo, Ni, Rb, Sb, Sr, Ti, U and V).
Results and discussion
Results indicate enrichment of sediment pore waters in the majority of measured elements relative to the estuary water. Degradation of organic matter and dissolution of Mn-Fe-oxyhydroxides under suboxic and anoxic conditions were identified as principal sources of dissolved cations in the studied pore waters. While sediments from the Novigrad Sea act as a permanent geochemical sink, the estimated fluxes for the Karin Sea sediments indicate transfer of certain elements from the sediment back to the water column, amounting to ~ 0.3 μg m
−2
day
−1
for Co, Ti and U; ~ 0.7 μg m
−2
day
−1
for As; between 1 and 5 μg m
−2
day
−1
for Mo, Ni and Ba; and ~ 70 μg m
−2
day
−1
for Fe and Mn.
Conclusions
In the Zrmanja River estuary, the observed differences in the sediment pore water geochemistry and the role of the sediments in terms of mass exchange at the sediment-water interface could not be solely attributed to the sediment particle characteristics, but are considered to be a combined effect of organic matter input and local hydrogeological setting.
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.
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•Sr was used as a proxy indicating authigenic formation of aragonite in marine sediments.•Distribution of Mo, Tl, U and Cd indicate changes in redox conditions in core sediments.•Mo, Tl, U and Cd are associated early formed nanostructured authigenic framboidal pyrite.•Concentration of Zn, Cu, Pb, Sn and Bi in core sediments indicates a low level of pollution.
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