Relationships between radionuclides, metals, and sediment properties in sediment of a bay exposed to anthropogenic pressure and mixed sediment sources (Kastela Bay, Adriatic Sea, Croatia).

Natural and anthropogenic radionuclides, metals, organic matter, sediment grain size, mineral composition, and sediment sources were studied in marine sediment of Kastela Bay up to a depth of 0.5 m. Deposition of man-modified material into the sea was evidenced in sediment mineral composition. Presence of pyrite and hematite in this sediment may pose an environmental concern. Metals, radionuclides, and organic matter were grouped in three groups: (i) variables under no anthropogenic influence and preferentially associated with carbonates (Ca, Sr); (ii) variables under no or weak anthropogenic influence and preferentially associated with aluminosilicates (Al, K, Ti, V, Cr, Mn, Fe, Co, Ni, Ga, Rb, Y, 40K, 232Th); (iii) variables under notable anthropogenic influence and/or natural processes of separation (Cu, Zn, Pb, As, 226Ra, 238U, 137Cs, organic matter). Predominant influencing parameters change with sediment depth for some variables. Anthropogenic influence was the most emphasised for Cu, Zn, and Pb, followed by 137Cs.

Atmospheric depositional fluxes of 210Pb in bulk precipitation at the Adriatic coast, Croatia.

The atmospheric bulk depositional fluxes of 210Pb were measured at a station on the Adriatic coast, Croatia over 4 years period from March 2017 to December 2020. The monthly depositional fluxes followed oceanic deposition patterns with a lower flux between 0.0735 and 16.9 Bq m-2 month-1. The volume-weighted activities were 0.000514 and 1.35 Bq L-1 and decreased with increasing precipitation. A clear seasonal trend was observed with higher depositional flux in autumn and minimum value in the winter season. The average annual bulk depositional flux and volume-weighted activities of 210Pb were 73.8 Bq m-2 y-1 and 0.119 Bq L-1 respectively. The precipitation normalized enrichment factor (α) indicates higher depositional fluxes of 210Pb during summer and spring than desired value according to the amount of precipitation. We found that the 210Pb depositional fluxes in the coastal stations are lower due to 210Pb-depleted oceanic air masses and increase with the amount of precipitation.

A preliminary study of the cultivable microbiota on the plastic litter collected by commercial fishing trawlers in the south-eastern Adriatic Sea, with emphasis on Vibrio isolates and their antibiotic resistance.

Mediterranean Sea is the sixth largest area of marine litter accumulation in the world, and plastic pollution is a growing problem in its Adriatic sub-basin. The aim of the present study was to evaluate the cultivable microbiota associated with plastic litter collected by commercial fishing trawlers in the south-eastern Adriatic Sea in comparison with microbiota in seawater and sediment. Plastic litter in the sea contains an autochthonous microbiota that is different from that of the surrounding seawater and sediment. Vibrio abundance was higher on plastic litter than in surrounding seawater and sediment. All isolated Vibrio showing resistance to ampicillin and vancomycin, while resistance to other antibiotics depended on the isolated species. Overall, this study provides for the first time information on the cultivable microbiota associated with plastic litter collected by commercial fishing trawlers and provides a data base for further studies.

Correlation of metals and degraded marine (micro)plastic litter in geologically similar coastal areas with different anthropogenic characteristics.

The association and statistical correlation of anthropogenically important trace metals (TM) Cd, Cu, Pb, Zn and degraded marine microplastic (MP) extracted from the bulk debris samples at two locations from two marine systems, estuarine and coastal, in the Croatian Adriatic coastal area were assessed. The abundance of MP particles at both sites were primarily defined by local wave climate, with the open coastal site containing 9-fold more microplastic particles (>4 mm) as compared to the semi-closed estuarine, or twice as much considering bulk plastics. Generally, the higher abundance of adsorbed metal on MP were observed in the more anthropogenically influenced estuary than in the open coastal site and followed the order: polystyrene > polypropylene > low density polyethylene. The amounts of adsorbed zinc were the highest on all types of plastics at both sites, while the affinity of polystyrene for metals followed: Zn > Pb ≈ Cu > Cd.

Microeukaryotic and Prokaryotic Diversity of Anchialine Caves from Eastern Adriatic Sea Islands.

Anchialine ecosystems in the eastern Adriatic Sea are diverse both morphologically and biologically. In this study, for the first time, we explored the microeukaryotic and prokaryotic community of anchialine caves in the Mediterranean region using high-throughput sequencing. Four anchialine caves located on nearby islands with a well-pronounced salinity gradient were sampled at the surface freshwater area, halocline area, and seawater area. Sequencing revealed a surprisingly wide diversity of the microeukaryotic and prokaryotic community with the relative abundance of major phyla differing within the salinity gradient and between the caves. Interestingly, microeukaryotic and prokaryotic communities clustered into four groups based on location, pointing out that sampled anchialine caves have different microbial community patterns and high microbial endemism. Our results indicate that even with the halocline acting as a selecting barrier, the salinity is not the only community structuring factor. Despite the short geographical distance, the isolation of anchialine caves facilitated high microbial community adaptation and endemism. Our study suggests that anchialine caves represent reservoirs of new biodiversity, maintaining unique and complex microbial diversity influenced by biotic interactions and abiotic environmental conditions.

Uranium isotopes as a possible tracer of terrestrial authigenic carbonate.

The concentration and isotopic composition of uranium (δ238U, 234U/238U activity ratio) in combination with traditional isotopes (δ18O, δ13C) were examined as potential tracers of authigenic carbonate formation in a karst aquifer. The U concentration and 234U/238U activity ratios in the tufa-precipitating sections of two connected karst rivers (Krka and Zrmanja, Croatia) decreased downstream in water and in precipitated carbonate due to active self-purification processes, i.e. adsorption of isotopically lighter U(VI) on mineral particles, sedimentation and co-precipitation with carbonate. The isotopic composition of carbonate in tufa mostly resembled the 234U/238U activity ratio and the δ238U values of dissolved U in water but was also affected by the presence of detrital carbonate flushed into the river from soil and weathered bedrock. This interpretation was supported by the δ18O and δ13C values of tufa, which were shifted out of equilibrium with river water and dissolved in organic carbon and in their isotopic signature, which showed the presence of lithic carbonate. Large fluctuations of the δ238U values of water, leachable U (eluted in acetic acid buffered with Na-acetate) and residual U fraction could not be fully explained by available data due to the overlapping U isotopic signatures of leachable (mainly carbonate) and residual fractions of soil, bedrock and tufa. Therefore, a long-term, systematic, seasonal and event-based observation of the isotopic composition of dissolved and suspended particulate U in water is necessary. Nevertheless, the U isotopes were found to have the potential to be used as identifiers of authigenic carbonate and the storage of CO2 in terrestrial river sediments, to improve knowledge on fluxes within local and global biogeochemical carbon cycle.

Evaluation of diffusive gradients in thin films (DGT) technique for speciation of trace metals in estuarine waters - A multimethodological approach.

Understanding the potential bioavailability of trace metals (TM) in marine systems is of prime importance to implement adapted regulations and efficiently protect our coastal and estuarine waters. In this study Diffusive Gradients in Thin films (DGT) technique with two different pore size was used to evaluate the potentially bioavailable fractions (DGT-labile) of Cd, Co, Cu, Ni, Pb and Zn at various depths of a highly stratified estuary (the Krka River estuary, Croatia) both in winter and summer. DGT-labile concentrations were compared to (1) total dissolved concentrations, (2) concentrations of labile species measured by anodic stripping voltammetry (ASV-labile) for Cu and (3) concentrations derived by chemical speciation modelling. High correlation between dissolved and DGT-labile concentrations was found for all metals, except for Zn where contamination problems prevented reliable conclusions. Percentages of DGT-labile fractions over total dissolved concentrations were (AVG ±â€¯SD): 92 ±â€¯3%, 64 ±â€¯2%, 23 ±â€¯5%, 61 ±â€¯3% and 57 ±â€¯6% for Cd, Pb, Cu, Ni and Co, respectively. No significant difference was found between trace metal concentrations measured with an open pore and restricted pore devices, implying the predominance of kinetically labile metal complexes smaller than 1 nm. For Cu, ASV-labile and DGT labile concentrations were highly correlated (0.97) with ASV-labile concentration being around 35% lower than that of the DGT-labile. Modelling of chemical speciation reliably predicted dynamic (free, inorganic and part of organic complexes) concentration of Cd, whereas dynamic concentrations of Cu and Pb were underestimated by 32% and 65%, respectively. In view of the relative simplicity of DGT devices, they are well suited for the monitoring effort of coastal waters, informing on potentially bioavailable concentrations of TM and thereby, helping to achieve good environmental status of coastal waters, as stipulated within the EU Water Framework Directive.

Anthropogenic mercury contamination in sediments of Krka River estuary (Croatia).

Coastal and estuarine sediments play an important role in the biogeochemical cycle of mercury (Hg) in the aquatic environment. When contaminated, sediments can act as a potential source of Hg and may pose a long-term risk to aquatic biota. The aim of this research was to assess spatial and historical distribution of Hg in the sediments of the Krka River estuary, an environment that so far has been regarded as relatively unpolluted. To achieve this goal, 40 surface sediment samples and 7 sediment cores were collected along the entire estuary. Hg concentrations in the surface and deep sediments of the Krka River estuary were found in a broad range 0.042-57.8 mg kg-1, demonstrating significant spatial and temporal differences in Hg input to the estuarine sediments. Two distinct areas were distinguished; upper estuary where the Hg content was comparable to other unpolluted Adriatic sediments, and the lower estuary where sediment profiles reflected the history of anthropogenic Hg input associated with the city of Sibenik. The vertical Hg profile from the most affected area of the estuary, combined with 210Pb and 137Cs dating, demonstrated that a significant increase of Hg input started in late 1940s/early 1950s, mainly related to shipyard activities. This study provided more insight on the Hg concentration in the Krka River estuary, demonstrating that the high values obtained, although localized, were comparable to the ones found in some of the most contaminated sites in the Mediterranean.

Assessing trace metal contamination and organic matter in the brackish lakes as the major source of potable water.

On small and medium karstic coastal islands in the Adriatic Sea, brackish lakes are often the only source of freshwater. Therefore, it is important to adequately evaluate the biogeochemical processes occurring in these complex water systems, as well as to determine the origin of contaminants present. In this study, the distribution and origin of trace metals (Tl, Hg, Cd, Pb, Cu, Zn, Ni, Co) and organic matter in the water column, sediment, and surrounding soil of the brackish lakes on Mljet Island, South Adriatic Sea, Croatia, were evaluated. Thallium and mercury concentrations in the lake water were up to two orders of magnitude higher compared to ranges found in the adjacent coastal sea water. Elevated thallium concentrations were of anthropogenic origin resulting from previous use of rodenticide, while elevated mercury content was naturally enhanced. Levels for the other metals were characteristic of uncontaminated water systems. Speciation modelling showed that dissolved trace metals such as Cu, Pb, and Zn were mostly associated with organic matter, while Tl, Co, and Ni were present predominantly as free ions and inorganic complexes. The presence of organic matter (OM) clearly influenced the speciation and distribution of some trace metals. OM was characterised by the determination of the complexing capacity for Cu ions (CuCC), surface active substances, and catalytically active compounds. Reduced sulphur species (glutathione and other thiols) representing significant Cu-binding ligands were determined and discussed as well.

Heavy metal contents in water, sediment and fish in a karst aquatic ecosystem of the Plitvice Lakes National Park (Croatia).

An evaluation of the quality status of the pristine karst, tufa depositing aquatic environment of the Plitvice Lakes National Park based on the analysis of heavy (ecotoxic) metals was examined for the first time. Analyses of trace metals in water, sediment and fish (Salmo trutta, Oncorhynchus mykiss, Squalius cephalus) samples were conducted either by stripping voltammetry (Zn, Cd, Pb and Cu) or cold vapour atomic absorption spectrometry (Hg). The concentration of dissolved trace metals in water was very low revealing a pristine aquatic environment (averages were, in ng/L: 258 (Zn), 10.9 (Cd), 11.7 (Pb), 115 (Cu) and 1.22 (Hg)). Slightly enhanced concentrations of Cd (up to 50 ng/L) and Zn (up to 900 ng/L) were found in two main water springs and are considered as of natural origin. Observed downstream decrease in concentration of Cd, Zn and Cu in both water and sediments is a consequence of the self-purification process governed by the formation and settling of authigenic calcite. Anthropogenic pressure was spotted only in the Kozjak Lake: Hg concentrations in sediments were found to be up to four times higher than the baseline value, while at two locations, Pb concentrations exceeded even a probable effect concentration. The increase of Hg and Pb was not reflected on their levels in the fish tissues; however, significant correlations were found between Cd level in fish tissues (liver and muscle) and in the water/sediment compartments, while only partial correlations were estimated for Zn and Cu. A high discrepancy between values of potentially bioavailable metal fraction estimated by different modelling programs/models raised the question about the usefulness of these data as a parameter in understanding/relating the metal uptake and their levels in aquatic organism. The aquatic environment of the Plitvice Lakes National Park is characterized, in general, as a clean ecosystem.

C and O stable isotopic signatures of fast-growing dripstones on alkaline substrates: reflection of growth mechanism, carbonate sources and environmental conditions.

Secondary carbonate precipitates (dripstones) formed on concrete surfaces in four different environments--Mediterranean and continental open-space and indoor environments (inside a building and in a karstic cave)--were studied. The fabric of dripstones depends upon water supply, pH of mother solution and carbonate-resulting precipitation rate. Very low δ(13)C (average-28.2‰) and δ(18)O (average-18.4‰) values showed a strong positive correlation, typical for carbonate precipitated by rapid dissolution of CO(2) in a highly alkaline solution and consequent disequilibrium precipitation of CaCO(3). The main source of carbon is atmospheric or biogenic CO(2) in the poorly ventilated karstic cave, which is reflected in even lower δ(13)C values. Statistical analysis of δ(13)C and δ(18)O values of the four groups of samples showed that the governing factor of isotope fractionation is not the temperature, but rather the precipitation rate.

A recent history of metal accumulation in the sediments of Rijeka harbor, Adriatic Sea, Croatia.

We studied metal pollution in the sediments of Rijeka harbor, including anthropogenic influence during recent decades and at the present time. Sediment profiles were collected at ten sampling points. The concentrations of 63 elements in bulk sediment were obtained using ICP-MS, and the concentrations of selected elements were evaluated by statistical factor analyses. We also calculated metal-enrichment factors and geoaccumulation indices and constructed spatial-distribution maps. Mercury (Hg) was the heaviest pollutant, with concentrations exceeding 4 mg/kg. Silver (Ag) was the second most important pollutant, with constantly increasing values. The average concentrations of the most toxic elements were comparable to those found in sediments of other ports throughout the world, and their toxicity ranged from threshold values [chromium (Cr), arsenic (As)] and midrange-effect values [cadmium (Cd), lead (Pb), copper (Cu), zinc (Zn), nickel (Ni)] to extreme-effect values (Hg). Metal pollution has decreased during recent decades, except for Ag and barium (Ba).

Origin and transport of (238)U and (226)Ra in riverine, estuarine and marine sediments of the Krka River, Croatia.

Spatial distribution of (238)U and (226)Ra activities in sediment columns along the Krka River and estuary, were studied using gamma spectrometry. Markedly different (238)U and (226)Ra activities between riverine, estuarine and marine sediments were observed. Distribution of these radionuclides, as well as their anthropogenic and natural origin, was evaluated by activity measurements, taking into account sedimentation rates estimated by (137)Cs distribution in sediment columns. Naturally present (238)U and (226)Ra activities were highest in riverine and lowest in marine sediments. (238)U and (226)Ra activities in historic riverine sediments revealed anthropogenic influence from town of Knin, which diminished for 15-20% in 1990s due to warfare that caused stop of industrial, agricultural and transport activities. Drainage of the flysch material naturally elevates (238)U and (226)Ra activities in the vicinity of its inflow in the upper part of estuary. (238)U and (226)Ra from the phosphate ore discharge in the port of Sibenik did not spread further in estuary, which was also confirmed by (238)U and (226)Ra activities detected in Mytilus sp. mussels' tissue.

Spatial distribution of trace metals in the Krka River, Croatia: an example of the self-purification.

The spatial distribution of dissolved and total trace metals (Zn, Cd, Pb and Cu) in the Krka River (partly located in the Krka National Park) has been studied using a "clean" sampling, handling and analysis technique. Differential pulse anodic stripping voltammetry (DPASV) with a hanging mercury drop electrode (HMDE) has been used for trace metal analysis. The Krka River has been divided into the upper and lower flow region with respect to the metals concentration and main physico-chemical parameters. A significant increase in trace metal concentration as the result of the untreated waste water discharge downstream of Knin Town has been registered in the upper flow region. Due to a specific characteristic of the Krka, the so-called self-purification process, a decrease in the elevated trace metals concentration from the water column takes place at numerous small lakes formed by tufa barriers (at the end of the upper flow region). The clean groundwater input at the beginning of the lower flow region additionally contributes to the observed decrease in trace metals concentration in the Krka, maintaining them at a very low level in the remaining region of fresh-water flow. The determined median total concentrations were zinc 120-7400 ng l(-1), cadmium 3-8 ng l(-1), lead 11-250 ng l(-1) and copper 110-440 ng l(-1). Karst rivers, such as the Krka River, with extremely low natural concentrations of trace metals are highly sensitive to the anthropogenic influence. Therefore, such aquatic systems require implementation of strict protection regimes in the entire catchments area.

Mercury in aquatic sediments and soils from Croatia.

Mercury is one of the most toxic and hazardous pollutant which occurs in the environment in different chemical forms, of which methylmercury is the most dangerous. Recently it was recognised that long-term anthropogenic inputs of mercury into environment resulted in the global mercury pollution and it was concluded that action should be taken to quantify the pollution sources and reduce human-generated releases of mercury. This paper presents new data on mercury levels in aquatic sediments from about 15 Croatian rivers, lakes and estuaries. It also brings data on mercury concentrations in soils from eight different regions of Croatia. Distribution of mercury species is discussed in more details for the Sava River, the Krka estuary and the Kastela Bay on the eastern Adriatic coast. Results show that sediments and soils from Croatia are generally not contaminated by mercury, except for some rivers and coastal locations under direct anthropogenic influence.

Uranium in sediments, mussels (Mytilus sp.) and seawater of the Krka river estuary.

The response of an aquatic environment to the decrease of phosphate discharges from a technologically improved transhipment terminal, situated at the Croatian Adriatic coast in the port of Sibenik, has been assessed based on uranium activity and concentration in sediment, seawater and mussels Mytilus sp. The highest 238U activities (485+/-16Bqkg(-1) dry weight) were found in the sediment sample collected from the sampling site closest to the terminal. The maximum concentrations in the sediment samples are above the natural ranges and clearly indicate the harbour activities' influence. The 238U/226Ra activity ratios in sediment samples demonstrate the decreasing trend of phosphate ore input. Mussel samples showed levels of 238U activities in the range from 12.1+/-2.9 to 19.4+/-7.2 Bqkg(-1) dry weight, thus being slightly higher than in normally consumed mussels. Only the seawater, taken just above the bottom sediment at the sampling site closest to the terminal, shows a slightly higher uranium concentration (3.1+/-0.2 microgL(-1)) when compared to the samples taken in upper seawater layers (2.1+/-0.2 microgL(-1)) but is in the range of the concentration level of uranium in natural seawater. Since the transhipment terminal in the port of Sibenik was modernised in 1988, discharge of phosphate ore into the seawater was drastically reduced and, consequently, uranium concentration levels in seawater have decreased. However, enhanced uranium activity levels are still found in deeper sediment layer samples and in mussel.