Krka River Estuary Research Articles

Vanadium redox speciation in the acid-extractable phase of Krka River estuary surface sediment

This study investigated the redox speciation and mobility of V in the acid-extractable fraction of surface sediments from the Krka River estuary using an optimized IC-UV/Vis analytical method. The separation of V(IV) and V(V) redox species was done using anion-exchange based chromatographic method, while pseudo-total V concentrations were measured using HR ICP-MS analytical instrumentation. Extracted V concentrations from the sediment fraction (pH = 5, HCl) and determined pseudo-total V concentrations were used to calculate the Enrichment Factor (EF) and Risk Assessment Code (RAC), indicating potential anthropogenic influence and environmental risk. A simple PHREEQC model was developed to asses V speciation in the oxic bottom seawater layer simulating possible remobilization of the leached sediment phase. The results of the study show that minor fraction of V is present in the acid-extractable phase across the surface sediment of Krka River estuary. Higher V mobility is mostly observed at locations rich with clay minerals, terrigenous input, and carbonates. Anthropogenic influence was linked to higher enrichment but lower mobility, suggesting binding to less mobile sediment phases (reducible, organic and residual fractions). The predominance of reduced V(IV) species in the acid-extractable sediment fraction indicates a potentially low V toxicity risk in the sediments of Krka River estuary, even in cases of high potential remobilization of V. However, the model predicted complete oxidation of V(IV) to V(V) upon remobilization into the oxic bottom water layer. This highlights the complexity of V behavior in natural estuarine systems, where the toxicity risks of possible V remobilization still remain unclear. Results of this study demonstrate the need for the strengthening efforts in speciation of V in the mobile sediment phase to obtain a cohesive outlook on its potential toxicity and biogeochemical cycling.

Adsorption of trace metals onto different plastics during long-term exposure in an estuarine environment: Influence of time, stratified water column, and specific surface area

The pervasive increase of plastics in marine systems and subsequent trace metals (TM) adsorption represents a critical environmental challenge. This long-term study is first to investigate how duration of exposure and stratified water column impact TM adsorption on various plastics in an estuary. We exposed polypropylene (PP), polyethylene (PE), poly(ethylene terephthalate) (PET), and fluorinated ethylene propylene (FEP) to estuarine conditions, categorizing them into three distinct groups to capture diverse human activities: pre-production pellets (Pellets), single-use plastics (SUP) and laboratory plastics (Lab). Plastic and water samples were analyzed before deployment and 1, 4, 7 and 16 months after deployment at three depths in the stratified Krka River estuary (Croatia). We measured TM concentrations, pH and salinity in the water column, and adsorbed TM amounts on plastics. Additionally, we examined plastic sample surfaces by Raman spectroscopy and scanning electron microscopy. TM speciation was modeled from water column data to better explain adsorption processes. Statistical analysis indicates that Zn, Cd, Pb, Ni, and Co adsorption depends on both duration of exposure and stratified water column, while Cu is influenced solely by duration of exposure to estuarine environment. Adsorbed TM amounts varied significantly among the plastic groups (Pellets, SUP and Lab), but not among different polymer types (PP, PE, PET and FEP). A noteworthy observation was the difference in the results of statistical analysis when investigating TM amounts expressed by plastic sample mass and by plastic sample surface area. Results expressed by plastic sample mass showed a difference between SUP group versus Pellets and Lab groups, while results expressed by plastic sample surface area distinguished Pellets group compared to other two groups. Therefore, we suggest presenting TM adsorption results in similar studies both by plastic sample mass and by plastic sample surface area. This approach will improve the understanding of TM adsorption on plastics, and enable more effective comparisons among the scientific literature dealing with plastics of different specific surface areas.

Mytilus galloprovincialis shell growth – Insights from shell geochemistry

Despite the wide geographic distribution of mussels and their importance in fisheries and aquaculture, understanding of temporal and spatial variations of their growth is still limited. This can be, at least partly, attributed to the lack of distinct growth lines in their shells. Our study uses geochemical properties of shells, particularly oxygen (δ18Oshell) and carbon (δ13Cshell) stable isotope values, to reconstruct mussel growth. Mytilus galloprovincialis specimens were collected from two of the most important bivalve aquaculture sites in the eastern Adriatic - Krka River estuary and Mali Ston Bay. The first site has variable environmental conditions, influenced mainly by the Krka River, resulting in a strong temperature and salinity gradient along the estuary. In contrast, Mali Ston Bay is a relatively shallow enclosed bay with more stable conditions. Samples for δ18Oshell and δ13Cshell analysis were acquired by manual microdrilling cross-sectioned shells from three similar sized shells from each site. In addition, analysis of elemental profiles (Mg/Ca, Sr/Ca, and Ba/Ca) in shells from the Krka River estuary was conducted using laser ablation ICPMS. Temperature and salinity values were obtained for each site through research and monitoring projects and used to calculate predicted δ18Oshell values. By aligning the measured δ18Oshell data along the predicted δ18Oshell curve, it was possible to reconstruct the timing and rate of seasonal shell growth. Results show that M. galloprovincialis shell deposition slows down and/or ceases during high temperature and low salinity periods. Specimens from the Krka River estuary had faster shell growth rates and were characterised by higher δ13Cshell values. Mg/Ca profiles of M. galloprovincialis specimens from the Krka River estuary, confirm growth periodicity data obtained by δ18O analysis. Ba/Ca peaks were also discussed by comparison with δ13C time-series and environmental data. Results have potential applications in fisheries studies as well as in palaeoecology and palaeoceanography research.

Stable isotopic composition of tissues and shells in the Mediterranean mussel, Mytilus galloprovincialis, in estuarine and aquaculture settings

The Mediterranean mussel, Mytilus galloprovincialis Lamarck, 1819 is a widely distributed commercially important bivalve species, and is one of two cultivated bivalve species in the Adriatic Sea, with the Krka River estuary being a key aquaculture location. Understating the feeding ecology of M. galloprovincialis could help aquaculture be more efficient. The aim of this study is to use stable isotopes to advance our understanding of M. galloprovincialis feeding ecology, as well as explore the potential of their shell as proxies for environmental change. We analyzed stable isotope composition (hereafter, δ13C and δ15N), of M. galloprovincialis soft tissue, as well as the δ15N signature of its shell, over one year at multiple sites in the Krka River estuary. Mussels showed differences in the isotopic niche depending on the site, indicating that feeding varies according to geographic location, likely due to specific conditions in the Krka River estuary and differences in food availability. During our entire survey period, marine organic carbon was the dominant source in the mussels cultivated in the Krka estuary. However, in the period from late summer to late autumn, the contribution of freshwater carbon sources increased for both sites situated in the middle estuary. The distinct feeding patterns observed at each sampling site could be attributed to a combination of factors such as local hydrographic conditions, food availability, and the presence of other competing species. Overall, the stable isotope results present valuable information on the feeding ecology of Mytilus galloprovincialis, highlighting the complex interactions between environmental factors and feeding habits. The results of our study contribute to the isotope data archive for M. galloprovincialis. Furthermore, this work shows the potential of M. galloprovincialis shell δ15N values as an indicator for nitrogen loading in aquaculture settings and coastal marine environments.

Early Diagenetic Processes in the Sediments of the Krka River Estuary

To study the processes that govern the post-depositional mobility of metals in the estuarine sediment, five sediment cores were sampled in the Krka River estuary (Croatia). The obtained concentration ranges in the pore water were 0.057–49.7 μM for Fe, 0.310–100 μM for Mn, 0.068–26.8 nM for Co, 0.126–153 nM for Cu, 11.5–2793 nM for Zn, 0.222–31.3 nM for Pb, 4.09–59.4 nM for U, 38.8–2228 nM for Mo, and 0.065–2.29 nM for As. The vertical distribution of metals in the dissolved and solid fraction of the sediment, coupled with other diagenetic tracers (e.g., dissolved sulphide), demonstrate the importance of early diagenetic reactions, in particular Fe and Mn oxyhydroxide and sulphate reduction, for the cycling of metals in the sediment. The redox zonation in the sediment was compressed, and the suboxic zone occurs immediately below the sediment–water interface. The estimated benthic fluxes in the estuary were 5220 kg y−1 for Fe, 27,100 kg y−1 for Mn, 6.00 kg y−1 for Co, 20.5 kg y−1 for Cu, 5.16 kg y−1 for Pb, 111 kg y−1 for Mo, and 87.3 kg y−1 for As. The riverine input was more important than the benthic flux, except in the case of Mn and Fe.

Spatial Distribution, Ecological Risk Assessment, and Source Identification of Metals in Sediments of the Krka River Estuary (Croatia)

To evaluate the level of contamination and predict the potential toxicity risk, selected metal concentrations (Cd, Pb, Cr, Mn, Co, Ni, Cu, Zn, and As) were determined in 40 surface sediment samples from the stratified karstic Krka River estuary (Croatia). In addition, diffusive gradients in thin films (DGT) probes were deployed in situ to understand the mobilization mechanisms and bioavailability of metals in the sediment. The results show significant spatial differences between the upper and lower estuary, with the latter being more affected by anthropogenic pollution. The pollution assessment using the enrichment factor (EF), the geoaccumulation index (Igeo), and the pollution load index (PLI) showed a strong enrichment of metals in the lower part of the estuary, especially of Mn, Cu, Zn, Pb, and As. The statistical analysis (PCA) revealed the former ferromanganese factory and the port as major sources of pollution in the area. Nickel, Co, and Cr, although slightly elevated, may be attributed to the natural origin. The metal mobility in the estuarine sediment was primarily governed by early diagenetic processes (aerobic organic matter mineralization, Fe and Mn oxyhydroxide reduction), which caused the release of metals from the sediment into the pore water and subsequently into the overlying water column.

Prostorna i sezonska raspodjela partikularnog fosfora u obalnim vodama i otvorenom moru srednjeg Jadrana

The seasonal and spatial distributions of particulate phosphorus (PP) in the water column of the coastal area and open sea of the middle Adriatic Sea area were investigated for the first time. The relationship between PP and two other important forms of phosphorus (dissolved inorganic phosphorus (DIP), and organic phosphorus (P-ORG)), and the relationship between PP and other nutrients (nitrogen and silicon salts) and oceanographic parameters (temperature, salinity, oxygen saturation, chlorophyll a) from the water column were also examined. PP concentrations ranged from 0.007 μmol dm-3 in the open sea near Palagruža archipelago to 0.589 μmol dm-3 in the Krka River estuary. In the coastal area, PP concentrations were highest in autumn and lowest in winter. The vertical distribution of PP concentrations in the water column of the coastal area were highest in the surface layer during most of the year due to input of PP by freshwater inflows. In the open sea area, there were no significant seasonal or vertical differences in the distribution of PP concentrations in thewater column. Seasonal analysis of the total phosphorus pool (PP, DIP and P-ORG) in the water column indicated that PP and P-ORG concentrations were higher in the coastal area compared to the open sea, while DIP concentrations were comparable.The results further demonstrate that PP can be an important fraction of the total phosphorus pool. A significant positive correlation was found between PP and chlorophyll a, indicating that PP was mainly of biological origin, and with nutrient salts of nitrogen and silicon, while a negative correlation was found with salinity.

Integrated Reconstruction of Late Quaternary Geomorphology and Sediment Dynamics of Prokljan Lake and Krka River Estuary, Croatia

The upper part of the Krka River estuary and Prokljan Lake are a specific example of a well-stratified estuarine environment in a submerged river canyon. Here, we reconstructed the geomorphological evolution of the area and classified the data gathered in the study, integrating multibeam echosounder data, backscatter echosounder data, side-scan sonar morpho-bathymetric surveys, and acoustic sub-bottom profiling, with the addition of ground-truthing and sediment analyses. This led to the successful classification of the bottom sediments using the object-based image analysis method. Additional inputs to the multibeam echosounder data improved the segmentation of the seafloor classification, geology, and morphology of the surveyed area. This study uncovered and precisely defined distinct geomorphological features, specifically submerged tufa barriers and carbonate mounds active during the Holocene warm periods, analogous to recent tufa barriers that still exist and grow in the upstream part of the Krka River. Fine-grained sediments, classified as estuarine sediments, hold more organic carbon than coarse-grained sediments sampled on barriers. A good correlation of organic carbon with silt sediments allowed the construction of a prediction map for marine sedimentary carbon in this estuarine/lake environment using multibeam echosounder data. Our findings highlight the importance of additional inputs to multibeam echosounder data to achieve the most accurate results.

A new tool for the determination of humic substances in natural waters: Pulsed voltammetry approach

Humic substances (HS) in natural waters can be determined with a new, simple and sensitive method based on their influence on the background current in a differential pulse - adsorptive cathodic stripping voltammetry. The proposed method, termed PB-HS (pulsed background - humic substances) is discussed in detail, including its application in natural samples from the Krka River estuary. The method was additionally compared with absorbance measurements as well as with the typical electrochemical HS quantification in natural waters based on HS complexation with molybdenum (Mo). A good correlation between methods was observed, with PB-HS showing slightly better sensitivity to humic compounds than classical spectrophotometry. Higher HS concentrations measured with the Mo-method may be due to the enhanced hydrophobicity reached at pH 2 that is required by the method. Advantages of the proposed PB-HS method, compared to existing voltammetric methods for HS quantification, are that it does not require any reagent addition (except buffer) and that it can be used at the natural pH of water as well as in a wide salinity range, which is crucial for its application in estuarine waters.

Microplastics assessment in the Krka river estuary surface water

Microplastics (MPs), commonly defined as particles less than 5 mm, are a persistent ubiquitous anthropogenic contaminant that can be found in every environment, making it a global environmental, health, and socioeconomic problem. Due to their high surface area, MPs adsorb toxic pollutants that become bioavailable to organisms upon ingestion as they are often mistaken for food leading to biomagnification (Bule et al., 2020). The sampling area represents the lower part of the Krka River Estuary and is under direct anthropogenic influence from the city of Šibenik runoff waters, nautical and communal ports, city harbor, tourism, mariculture, and fishing. Estuaries and harbors have been recognized as hotspots and transfer pathways for MPs primarily because of the vicinity of the urban environment that emits contaminants from various sources (Miller et al., 2021). The main focus of this research was to determine MPs size, shape, color, surface area, and abundance in surface water using volume-reduced samples collected by a net. Laboratory protocol included sieving, wet peroxidation (H2O2), density separation (saturated NaCl solution), sonication, and filtration. Filter papers were then visually inspected for MPs. Image processing and measurements were carried out with ImageJ/Fiji open-source software.

Microplastic Distribution through the Salinity Gradient in a Stratified Estuary

Despite the extensive and rapidly growing literature on microplastics in oceans and coastal seas, little information exists on microplastic distribution through the salinity gradient. This study is the first one to evaluate microplastic distribution through the salinity gradient of a highly stratified estuary. A total of 910 microplastic particles were collected from 12 different sampling events in the Krka River estuary, Croatia. The number of detected particles ranged from 389 in the surface layer to 63 in the deepest marine layer. The highest plastic abundance was found in the surface layer (3.68 particles/m3) and the lowest in the marine layer (0.13 particles/m3). The measured values of the cross-sectional area indicated an ellipsoidal cross-sectional shape of the particles. It was also found that the majority of microplastic particles belonged to the small microplastic class (<1 mm). The Nile Red (NR) staining method was used to visualize fluorescent microplastic particles, while quantification was performed using ImageJ/Fiji software. The strong salinity stratification in the studied estuary did not alter the usual distribution of microplastic particles in the water column, and there was no significant accumulation on the halocline.

Trace Metal Partitioning in the Salinity Gradient of the Highly Stratified Estuary: A Case Study in the Krka River Estuary (Croatia)

A size partitioning of several trace metals (Zn, Cd, Pb, Cu, Ni, Co, Mn, Fe and Al) between five size fractions (<3 kDa, 3 kDa–0.1 µm, 0.1 µm–1.2 µm, 1.2 µm–5 µm and >5 µm) was studied in the vertical salinity gradient of the highly stratified Krka River estuary. The results indicated a dominant river source for Zn, Co, Mn, Fe and Al and a diluting effect on Cd, Pb and Ni. The truly dissolved fraction (<3 kDa) dominated the Zn, Cd, Cu, Ni and Co pool, and a large part of Pb, Mn, Fe and Al was present in >5 µm particles. Pb, Mn, Fe and Al were closely related, showing a precipitation and colloidal aggregation in the surface layers and dissolution in the seawater layer. The highest percentage (30–37%) of colloids (3 kDa–0.1 µm) in the dissolved pool was found for Pb, Cu, Fe and Al. Differences in size distribution between low and high river flow periods revealed that Zn, Pb, Co, Mn, Fe and Al are introduced by the river mostly in the 3 kDa–5 µm size range. Therefore, a low percentage of colloidally bound metals compared to other coastal areas can be explained by a limited riverine input of terrigenous material, characteristic for this estuary. Correlation with PARAFAC components revealed associations of Cu with protein-like substances and Co with humic-like substances. The accumulation of Cu at the freshwater-seawater interface coupled with an increase of its colloidal fraction was observed, apparently governed by biologically produced organic ligands.

Tracing Nutrients and Organic Matter Changes in Eutrophic Wenchang (China) and Oligotrophic Krka (Croatia) Estuaries: A Comparative Study

Estuaries modify the concentration and composition of riverine nutrients and organic matter (OM), which eventually determine the riverine flux effect to coasts. Nutrients, organic carbon (OC), pigments, and amino acids (AAs) from the samples collected in the eutrophic Wenchang River Estuary (WRE) in China and the oligotrophic Krka River Estuary (KRE) in Croatia were analyzed in order to have a better understanding of how estuaries regulate terrestrial materials. We found a clear increase of dissolved inorganic nitrogen (DIN) concentration and its subsequent decrease due to the removal of DIN (over 100 μM) in the WRE, whereas DIN showed minor variation lengthwise in the KRE, i.e., with the salinity changes, ranging between 1.0 and 5.8 μM. The elevated algae-derived OC, dissolved organic nitrogen, and particulate AAs nitrogen suggest that the OM assimilation may explain approximately one-third of the DIN removal in the WRE, whereas in the oligotrophic KRE, such inorganic to organic transformation is not likely to be significant. Due to the prominent estuarine nitrogen removal/assimilation process, DIN/dissolved inorganic phosphorus (DIP) ratio was as high as 425 in the upper WRE under strong riverine influence, but it declined to as low as 5.4 at the mouth of WRE, that is even lower than DIN/DIP ratio at the mouth of oligotrophic KRE (12). When compared with other rivers worldwide, the Wenchang River showed high nutrients and organic carbon yields. Given the contrasting estuarine process (e.g., DIN removal) between the KRE and the WRE, apparent high nutrient yield from eutrophic rivers should be viewed with caution in ocean studies as the final impact to coastal zone could be similar to the oligotrophic rivers like the KRE.

Redox Speciation of Vanadium in Estuarine Waters Using Improved Methodology Based on Anion Exchange Chromatography Coupled to HR ICP-MS System.

An improved methodology was developed for V redox speciation in estuarine waters using a hyphenated technique consisting of ion chromatograph (IC) with an anion exchange column and a high-resolution inductively coupled plasma mass spectrometer (HR ICP-MS). This approach enables the direct determination of V(V), whereas reduced species (mainly V(IV)) are calculated by subtracting V(V) concentrations from the measured total V concentration. Based on the “on-column” V(V) chelation mechanism by EDTA, with the eluent composed of 40 mmol L−1 ammonium bicarbonate, 40 mmol L−1 ammonium sulphate, 8 mmol L−1 ethylenediaminetetraacetic acid and 3% acetonitrile, the method was successfully used for analyses of V redox speciation in samples taken in the vertical salinity gradient of the highly stratified Krka River estuary. Due to the matrix effects causing different sensitivities, a standard addition method was used for V(V) quantification purposes. The limit of detection (LOD) was also found to be matrix related: 101.68 ng L−1 in the seawater and 30.56 µg L−1 in the freshwater. Performed stability tests showed that V redox speciation is preserved at least 7 days in un-treated samples, possibly due to the stabilization of V-reduced species with natural organic matter (NOM). The dominant V form in the analysed samples was V(V) with the reduced V(IV) accounting for up to 26% of the total dissolved pool. The concentration of V(IV) was found to correlate negatively with the oxygen concentration. Significant removal of dissolved V was detected in oxygen depleted zones possibly related to the particle scavenging.

High proliferation of Pseudo-nitzschia cf. arenysensis in the Adriatic Sea: ecological and morphological characterisation

The aim of the present study isto characterise the diatom Pseudo-nitzschia community during a bloom period together with environmental conditions. High proliferation of Pseudo-nitzschia spp. was observed in September 2017 at the shellfish breeding area in the Krka River estuary (Central eastern Adriatic Sea). The peak of abundance (1.8 x 106 cells L-1) was recorded at 7 m depth, and the increased abundance persisted for four weeks.Morphological analyses of field samples based on scanning electron microscopy (SEM) revealed that Pseudo-nitzschia cf. arenysensis was prevailing (94%) in the Pseudo-nitzschia assemblage. Several strains were successfully isolated from net samples in order to better define morphological features and phylogenetic characterisation. The isolated Pseudo-nitzschia strains corresponded morphologically to the P. cf. arenysensis from the field samples, based on our SEM observations. Phylogenetic analysis demonstrated that the Croatian strains grouped with P. arenysensis using the ITS and LSU rDNA sequences. Spearman rank correlation showed that salinity was an important environmental factor affecting the vertical distribution of Pseudo-nitzschia spp. in this highly variable area. Availability of increased concentration of orthophosphates and ammonium and low Si: TIN ratio may have promoted the bloom of P. cf. arenysensis in the estuary.

Impact of environmental conditions on phospholipid fatty acid composition: implications from two contrasting estuaries

Phospholipid (PL) composition has a tremendous influence on the cell integrity and physiological competency. At the same time, plankton PL make important metabolic fuels for higher trophic levels. The goal of this study was to identify environmental control on PL production and their molecular identity of the suspended particles in two different estuaries. We conducted research in subtropical, eutrophic Wenchang River Estuary in China and temperate pristine, mesotrophic Krka River Estuary in Croatia. In agreement with the more abundant phytoplankton, PL concentrations were much higher in the Wenchang River Estuary (30.3–178.2 μg L−1) than in the Krka River Estuary (8.4–18.8 μg L−1). Given that six PL classes investigated (phosphatidylcholine (PC), phosphatidylglycerol (PG), phosphatidylethanolamine (PE), phosphatidic acid (PA), phosphatidylinositol (PI), and phosphatidylserine (PS)) have different roles in the cell, we expected their different fatty acid composition in different environments. We found small differences in the fatty acid composition of PC, PG, and PI between two estuaries. These results suggest that the essential fatty acid compositions of these PL in estuarine plankton are relatively constant in order to preserve membrane functions and/or cell processes in which they are involved regardless of environmental conditions. In contrast, PE, PA and PS fatty acid composition substantially differed between two estuaries as well as throughout the salinity gradient in each estuary. This suggests the adaptability of plankton to remodel these PL depending on the environmental conditions and the plankton community structure. Good environmental conditions (favorable N/P ratio, temperature) are important for increased PL content (% in POC and total lipids) in estuarine plankton and increased essential polyunsaturated fatty acid content in PL, which is beneficial to higher trophic levels.

Phytoplankton Dynamics in the Middle Adriatic Estuary, with a Focus on the Potentially Toxic Genus Pseudo-nitzschia

The Krka River estuary is a karstic, permanently stratified estuary due to the strong freshwater inflow. It is a special environment in which to study the phytoplankton community, especially because this area is an important aquaculture site. Among other potentially toxic phytoplankton species, the diatom genus Pseudo-nitzschia occurs frequently and is a potential source of domoic acid (DA), causing shellfish toxicity and human intoxication. The main objective was to examine the dynamics of the phytoplankton community and, in particular, the genus Pseudo-nitzschia in the upper part of the Krka estuary, through monthly sampling over two years. The phytoplankton community was analysed using light microscopy and scanning electron microscopy to determine the diversity of Pseudo-nitzschia species and characterise the environmental parameters associated with a high abundance of Pseudo-nitzschia species. Seven Pseudo-nitzschia species were identified in the investigation, with higher frequencies and abundances in the less variable layer, at a 7 m depth. Blooms of Pseudo-nitzschia were noted in the late summer/early autumn, dominated by P. delicatissima/arenysensis. Winter assemblages were characterised by P. pseudodelicatissima/cuspidata, P. calliantha, and P. subfraudulenta, and were associated with domoic acid occurrence in shellfish.

Dissolved organic matter dynamics in the pristine Krka River estuary (Croatia)

The karstic Krka River is characterized by having lower dissolved organic carbon (DOC) concentrations (~30 μM) than coastal seawater (~60 μM). This peculiarity, together with the pristine nature of this area, makes the Krka River estuary a natural laboratory where it is possible to discriminate among the different dissolved organic matter (DOM) sources (riverine, marine and produced in-situ) and to study the main processes of DOM production and removal. The hypothesis behind this work is that in winter, due to the high discharge of the river, most of the DOM has a terrestrial signature, whereas in summer autochthonous DOM compose the main fraction of the DOM pool because of the reduced discharge, the high temperature and primary production. Our data shows that DOM in the river mainly consists of terrestrial molecules, as suggested by the high chromophoric content and low spectral slope (S275–295) values, as well by the predominance of humic-like substances. DOM in the seawater features the concentration and optical properties of the “typical” marine DOM from open sea waters. In summer, low riverine discharge and high temperature promote the intense biological activity, with an increase in DOC concentrations of up to 148 μM, resulting in a non-conservative behavior of DOM in the estuary. The high stratification combined with a decoupling between production and removal processes can explain the observed DOM accumulation. In the bottom layer DOM was released and quickly removed when oxygen was available, whereas in hypoxic waters the production of DOC, chromophoric DOM (CDOM) and fluorescent DOM (FDOM) was linearly related to oxygen consumption. Our work highlights the need of further studies combining chemical and biological information in order to gain new insights into the main processes responsible for DOM dynamics in this system.

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 ± SD): 92 ± 3%, 64 ± 2%, 23 ± 5%, 61 ± 3% and 57 ± 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 0.042-57.8mgkg-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 Šibenik. 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.