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A capacity to determine the provenance of high- value food products is of high scientific and economic interest. With the aim to develop a tool for geographical traceability of Croatian extra virgin olive oils (EVOO), multielement composition and 13C/12C isotope ratio in EVOO as well as the geochemistry of the associated soils were analysed in samples collected from three regions along the Croatian Adriatic coast. Soil geochemistry was shown to influence the transfer and elemental composition of EVOO. The most discriminating variables to distinguish EVOO from different regions were S, Mo, Rb, Mg, Pb, Mn, Sn, K, V and δ13C. The predictive models achieved high sensitivity and specificity, especially when carbon isotope composition was added. The results suggest that interregional geographical traceability of Croatian EVOO is possible based on matching their multielement composition with that of the soils in the provenance area.

Aims A potential of rare earth elements (including yttrium) (REY) accumulation in olives is increasing due to enhanced use of REY in human activities. REY transfer to extra virgin olive oil (EVOO) is little studied, and characterising the relationships between soil properties and REY concentrations in olive leaves, pomace and EVOO can enhance our understanding of soil-plant interactions. Methods Three different soil types (reclaimed karst, rendzina and cambisols), with the sum of REY concentrations (54–364 μg g−1) among the highest in European soils, were characterized for their pH, organic carbon, total carbonates and the applied agronomic practice. Aluminium, calcium, iron, phosphorus and REY were determined in soil (total and plant-available), olive leaves, pomace and EVOO. Results REY were mainly excluded from plant uptake and only small amounts of REY were transferred to leaves (0.2– 652 ng g−1), pomace (0.001–10 ng g−1) and EVOO (

This study presents an analytical procedure for measuring the 87Sr/86Sr isotopic ratio in olive oil and pomace using multicollector-inductively coupled mass spectrometry (MC-ICPMS). The developed method combines liquid-liquid extraction with an acid solution and degradation of organic residues in the extract by dry ashing and oxidation by H2O2 and HNO3. The method enabled 87Sr/86Sr ratios to be obtained in olive oil with Sr content as low as 0.2 ng g􀀀 1, with a precision of 54 ppm. The method’s validity was confirmed by an interlaboratory comparison using NIST SRM 2387, providing the first data on its elemental Sr (2380 ± 230 ng g􀀀 1; n = 10), and 87Sr/86Sr isotopic composition (0.70908 ± 0.00004; n = 14). The procedure was applied to olive oil and pomace samples, showing that they have an identical 87Sr/86Sr ratio, which was consistent with that determined in soils from the same orchards. The results thus revealed that Sr isotopic ratios of olive oil and pomace can both be used in geographical traceability studies of olive oil, which means that, instead of processing large volume of oil, characteristic 87Sr/86Sr signatures of olive oil can be more easily obtained by analyzing small quantities of pomace obtained by centrifuging the oil. &nbsp

Recognizing multiple anthropogenic pressures in marine coastal zones, countries of the Mediterranean region have implemented several directives focused on sustainable management of the Mediterranean Sea coastal zones. One of the essential directives is the Marine Strategy Framework Directive (MSFD), challenging countries, including Croatia, to achieve and maintain Good Environmental Status of their marine environment. The health of the marine environment is undeniably influenced by microorganisms which play a key role in functioning of marine food webs and biogeochemical cycling. The MSFD neglects the importance of microbial communities and possible changes in their function and structure under the anthropogenic influence influencing stability of the whole marine ecosystem. Project MicroLink, funded by the Croatian Science Foundation, aims to highlight the significance of microbial communities in monitoring and consequently preserving the quality of marine environment with the final goal to propose incorporation of the selected microbial attributes among MSFD Quality Descriptors. Sampling of 67 sediments was performed in seven harbors along the eastern Adriatic coast, which were previously identified as pollution “hot spots”. Sediments were comprehensively analyzed and parameters such as metal concentrations, Hg, TP, TN, TC, TBT, toxicity testing etc. were measured. To find the correlation between anthropogenic pollution and changes in the microbial communities, the project MicroLink integrates different approaches: i) multi-domain approach (analyzing changes in Bacteria, Archaea, Protists, and Fungi) and ii) multi-layer approach (changes in structure, microbial networks, abundance of functional genes and biodegradation potential). Due to continuous accumulation of pollutants, sediments and benthic microbial communities could be reliable indicators of the persisting exposure of the marine environment to anthropogenic pressures. Microbial communities should not be neglected in future strategies and measures for conservation of coastal and marine environments.

This study presents the first assessment of butyltins (BuTs) pollution of the Montenegrin coast. The distribution of tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) was investigated in mussels, sediments and water overlying sediment after the sediment resuspension. The results showed that the investigated sites (marinas, ports, shipyards) are contaminated with BuTs (19–402 ng (Sn)/g in mussels ; 43–20, 641 ng (Sn)/g in sediments ; 9–566 ng (Sn)/L in overlying waters). The measured TBT concentrations indicate that toxic effects on marine organisms are expected at most locations. The simultaneous analysis of BuTs and total Sn in sediment cores allowed the assessment of TBT historical input, while it was demonstrated that resuspension of contaminated sediments leads to the release of all BuTs into the water column. This study shows that, despite the ban of TBT based antifouling paints more than a decade ago, pollution of the marine environment with TBT is still a problem and regular monitoring remains essential.

Rare earth elements, i.e., lanthanides, are important components of many recently developed technology applications. However, their increasing use in the industrial sector, medicine, and agriculture over the last few decades has provided them with the title of “new pollutants”. Different methods are now applied for the removal of various pollutants from wastewaters, whereby the emphasis is placed on adsorption due to its simplicity, high efficiency, and low cost. In the present study, geopolymers prepared from coal ash were examined regarding their capacity for the adsorption of lanthanides from model solutions. The obtained results indicate the efficient removal of lanthanides by prepared geopolymers, depicting them as effective adsorbents for this group of elements.

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.

The development of new analytical techniques enabled the precise determination of the expanded set of stable isotopes and provided new insight into the existing geological issues. This review outlines recent studies of non-traditional isotope signatures in geological matrices, summarizing in one place new data for stable isotopes of Ca, Mg, Sr, Li, Ni, Cr, and Cu and their application in the interpretation of environmental processes. Although some of them, such as δ44Ca and δ26Mg, have been previously used to track changes in seawater chemistry throughout geological history, recent studies report their application as geochemical proxies of post- depositional processes. Similarly, isotopic signatures of strontium, previously used in radioactive isotope chronology, and δ7Li, used in tracing plate subduction and crust/mantle material cycling, found a new application in studies of weathering patterns. The use of δ53Cr and δ 65Cu isotope signatures, on the other hand, reflects their fractionation under different redox conditions, whereas δ60Ni, due to its adsorption and co-precipitation with sulfide species and Fe-Mn phases, is used in interpreting the contributions of different material sources. And while the isotopic signatures of all these elements indicate certain environmental conditions and processes (e.g. post-depositional processes, redox conditions, organic matter input, the contribution of sources, etc.), by combining them a more comprehensive insight into the investigated environment can be achieved.

The present study aims to discuss the data on levels and distribution of rare earth elements, including Y, (REYs) in leaves of three different citrus species (lemon, orange, and tangerine) and provide additional information about the major, minor and trace elements in two biological certified reference materials (CRMs), Apple leave (NIST SRM 1515) and Rye grass (ERM CD281). In all samples, element concentrations were determined by High Resolution Inductively Coupled Plasma Mass Spectrometry. The obtained data display substantial variability in the distribution of REY elements, not only between different citrus species but also between different genera of plants indicating their different uptake and accumulation abilities. Measured concentrations of REYs in citrus leaves were substantially lower compared to the literature values, although the fractionation indices were comparable. The data for CRMs provide additional information for the 14 elements in NIST SRM 1515 and the 30 elements in ERM CD281, including rare earth elements. This work is licensed under a Creative Commons Attribution 4.0 International License.

The Rasa coal from Istria belongs to a special type of superhigh-organic-sulfur coals, with organic sulfur content of 11%. This study encompasses culm and coal ashes from old landfills left behind after many decades of the Rasa coal use with regards to their rare earth element geochemistry. Regarding the studied coal ashes, obtained results suggest a substantial variability in the content of rare earth elements and Y (REY) in coal combustion products generated from the Rasa coal. Although samples of coal ash and culm of the Rasa coal have REO (oxide of REY) content (up to 464 mg kg−1) below the level considered as the cut-off grade for beneficial recovery of these metals (1000 ppm, ash basis), they contain relatively high share of critical REY (>30%). The coutl values (outlook coefficient of REY ores; based on Seredin-Dai's criterion) range from 0.78 to 1.45 while Eu and Ce anomaly display slightly positive and negative values, respectively. With LaN/SmN ratios below unity, from 0.65 to 0.88, and LaN/LuN and GdN/LuN ratios ranging from 0.53 to 1.17 and from 0.80 to 1.41, respectively, they dominantly correspond to M-type of enrichment and only sporadically to H-type of enrichment. Previous studies attributed the formation of superhigh-organic-sulfur Rasa coal to the seawater percolation. However, the geochemical data presented in this study suggest that the Rasa coal-bearing strata, representing the Upper Paleocene lacustrine and brackish facies, were influenced by both the seawater and the hydrothermal solutions under conditions which led not only to sulfur enrichment but also to REY accumulation. From the economic standpoint and currently available data, Rasa coal ash cannot be considered as the secondary raw material for rare earth elements, but its significantly variable composition and relatively high REO found in culm highlights the need for future studies of Rasa coal and related combustion products.

In this work, a simple, sensitive and affordable analytical method for the simultaneous determination of nine organotin compounds (butyltins, phenyltins and methyltins) in seawater using solid-phase extraction (SPE) and gas chromatography-pulsed flame photometric detection (GC-PFPD) was developed and validated. The performance of three different SPE cartridges (Envi C18, Oasis HLB and Oasis MCX) and three elution solvents of different polarity (hexane, methanol and acetonitrile) was evaluated. The extraction parameters, such as solvent volume, presence of complexing and ion-pairing reagents, sample volume and pH and breakthrough volume, were also investigated. Tributyltin (TBT), as the organotin compound of special interest, was efficiently extracted using any of the cartridges and solvents tested. However, the simultaneous extraction of all nine organotin compounds was the most efficient using reversed-phase Envi C18 cartridge and 0.1 % (w/v) tropolone in methanol as eluent. The optimised method resulted in good recovery, precision and linearity for all compounds, particularly for tri- and disubstituted species. Method detection limits ranged from 0.22 to 1.27 ng(Sn) L-1 for butyltins, 0.37 to 4.91 ng(Sn) L-1 for phenyltins and 0.45 to 1.16 ng(Sn) L-1 for methyltins. The accuracy of butyltins determination was further verified by the comparison with purchased derivatised standards. The developed method was successfully applied to the environmental samples.

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.

Analysis of elements in Extra Virgin Olive Oil (EVOO) is challenging due to the complex oil matrix as well as very low element concentrations in oil. We postulate that inadequate sample preparation (in particular, the presence of pomace residue in oil) may significantly contribute to variations in EVOO element concentrations. In order to confirm this hypothesis, EVOO and pomace samples were analysed for content of 29 elements by ultrasonic acid extraction and ICP-MS detection. Comparative analyses of non-centrifuged and centrifuged EVOO samples confirmed significant influence of pomace residues on element concentrations. Ranges of macronutrients (25–286 ng g−1), micronutrients (0.3–1.1 ng g−1) and trace elements (0.001–0.2 ng g−1) in centrifuged EVOO samples were up to 1000 times lower than in non-centrifuged oils. We have shown that pomace residue, even when present in very small quantity (1 g of pomace in 1 kg of oil), significantly altered concentrations and relative proportions of many elements in EVOO. Therefore, adequate sample pre-treatment (removal of pomace residue via centrifugation) is essential for determining real multi-element composition of olive oil. This is critical in application of EVOO multi-element composition in traceability studies and determination of geographic origin of olive oil.

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.

This study aims to investigate the geochemical characteristics of waters of the highly stratified Zrmanja River estuary (eastern Adriatic coast, Croatia). For that purpose, data on salinity and distribution of 16 elements in surface and bottom water of the Zrmanja River estuary was used to assess the spatial variation of trace elements in the estuary water and to identify the main processes governing these variations. The composition of the investigated water was found to be determined primarily by natural factors. Mass concentration levels of dissolved elements were relatively low and typical for unpolluted waters and are considered to primarily reflect the geological and hydrogeological background of the catchment area. The distribution of element mass concentrations along the water column was found to primarily reflect different water masses, the river on the surface and sea at the bottom. Deviation from conservative behaviour for some elements in the bottom water is due to adsorption and desorption processes from the particulate phases. This work is licensed under a Creative Commons Attribution 4.0 International License.

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.