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Per- and polyfluoroalkyl substances (PFAS) are of high concern for the environment, wildlife, and human health due to their persistence and potential to cause adverse health effects. Despite political measures to restrict the production and distribution of PFAS and to limit the exposure of populations, PFAS can be measured at commonly high detection frequencies in human samples. Thus, this pilot study aimed to determine the serum concentrations of PFPA, PFHpA, PFOA, PFNA, PFDA, PFUnDA, PFHxS, PFHpS, PFOS, PFHxA, PFDoDA, and PFBS in 113 girls and 112 boys (age 7-10 and 12-15) from Northeastern Slovenia - a rural area characterized by agricultural activities - and to identify potential sources of exposure using questionnaire data. PFAS were analysed by liquid chromatography coupled to mass spectrometry after phospholipid removal. 9 out of 12 analytes were detected at detection frequencies above 30%, with the highest geometric means (GM) being observed for PFOS (GM 1.9 ng/mL) > PFOA (GM 1.0 ng/mL) > PFHxS (GM 0.3 ng/mL) = PFNA (GM 0.3 ng/mL). We identified the participants' socio-economic status, age, sex, sampling region, public water supply, and the consumption of fish and seafood, cereals, and locally produced fruits, vegetables, and mushrooms as the predominant determinants of exposure. Furthermore, we compared our results with the serum and plasma concentrations reported for similar age groups in other studies and concluded that PFAS exposure in this highly agricultural area in Slovenia is notably low. This is the first study systematic HBM study of PFAS exposure in Slovenia, although it was conducted on a limited number of participants representative of rural and agricultural areas, it represents a good basis for upgrading the approach to a nationwide HBM study., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Bio-monitoring of mercury (Hg) in air using transplanted and in-situ lichens was conducted at three locations in Slovenia: (I) the town of Idrija in the area of the former Hg mine, where Hg contamination is well known; (II) Anhovo, a settlement with a cement production plant, which is a source of Hg contamination, and (III) Pokljuka, a part of a national park. Lichens from Pokljuka were transplanted to different sites and sampled four times-once per season, from January 2020 to February 2021. Lichens were set on tree branches, fences, and under cover, allowing them to be exposed to different environmental conditions (e.g., light and rain). The in-situ lichens were sampled at the beginning and the end of the sampling period. The highest concentrations were in the Idrija area, which was consistent with previous research. Significant mass-dependent fractionation has been observed in transplanted lichens during summer period. The δ 202 Hg changed from -3.0‰ in winter to -1.0‰ in summer and dropped again to the same value in winter the following year. This trend was observed in all samples, except those from the most polluted Idrija sampling site, which was in the vicinity of the former Hg ore-smelting plant. This was likely due to large amounts of Hg originating from polluted soil close to the former smelting plant with a distinct isotopic fingerprint in this local area. The Δ 199 Hg in transplanted lichens ranged from -0.5‰ to -0.1‰ and showed no seasonal trends. These findings imply that seasonality, particularly in summer months, may affect the isotopic fractionation of Hg and should be considered in the sampling design and data interpretation. This trend was thus described in lichens for the first time. The mechanism behind such change is not yet fully understood., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Every day we are exposed to a cocktail of anthropogenic compounds many of which are biologically active and capable of inducing negative effects. The simplest way to monitor contaminants in a population is via human biomonitoring (HBM), however conventional targeted approaches require foreknowledge of chemicals of concern, often have compound specific extractions and provide information only for those compounds. This study developed an extraction process for human biomarkers of interest (BoE) in urine that is less compound specific. Combining this with an ultra-high resolution mass spectrometer capable of operating in full scan, and a suspect and non-targeted analysis (SS/NTA) approach, this method provides a more holistic characterization of human exposure. Sample preparation development was based on enzymatically hydrolysed urine spiked with 34 native standards and extracted by solid-phase extraction (SPE). HRMS data was processed by MzMine2 and 80% of standards were identified in the final data matrix using typical NTA data processing procedures., (Copyright © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Phthalates and 1,2-Cyclohexane dicarboxylic acid diisononyl ester (DINCH), bisphenols (BPs), parabens (PBs), and triclosan (TCS) are high-production-volume chemicals of pseudo-persistence that are concerning for the environment and human health. This study aims to assess the exposure to 10 phthalates, DINCH, and environmental phenols (3 BPs, 7 PBs, and TCS) of Slovenian men (n = 548) and lactating primiparous women (n = 536). We observed urinary concentrations comparable to studies from other countries and significant differences among the sub-populations. In our study, men had significantly higher levels of phthalates, DINCH, and BPs, whereas the concentrations of PBs in urine were significantly higher in women. The most significant determinant of exposure was the area of residence and the year of sampling (2008-2014) that mirrors trends in the market. Participants from urban or industrialized sampling locations had higher levels of almost all monitored analytes compared to rural locations. In an attempt to assess the risk of the population, hazard quotient (HQ) values were calculated for individual compounds and the chemical mixture. Individual analytes do not seem to pose a risk to the studied population at current exposure levels, whereas the HQ value of the chemical mixture is near the threshold of 1 which would indicate a higher risk. We conclude that greater emphasis on the risk resulting from cumulative exposure to chemical mixtures and additional studies are needed to estimate the exposure of susceptible populations, such as children., (Copyright © 2021 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Isotopic composition of mercury (Hg) in marine organisms and sediment cores was used to identify sources and reconstruct historical trends of contamination in the coastal-marine area of Rosignano Solvay (Italy), affected by Hg pollution from a chlor-alkali plant on the near land. Sediments show a wide range of Hg concentration and Hg isotope signatures. Particularly, coupled Hg concentration and δ 202 Hg values trace inputs from different sources. The two depth-profiles clearly indicate three distinct periods: "pre-industrial" (before 1941), "industrial" (between 1941 and 2007) and "post-industrial" (after 2007) ages. This is also corroborated by sediment chronology, using 210 Pb dating method, validated through 137 Cs. Marine organisms are characterized by Hg isotope signatures comparable to "post-industrial" surface sediments. Notably, specimens of Mullus spp. evidence isotope composition comparable to the "industrial" sediments, thus suggesting a still active role of those sediments as source of Hg for the benthic fish compartment. The small amount of MIF and the Δ 199 Hg/Δ 201 Hg ratio recorded in organisms are reasonably consistent with limited processes of MMHg demethylation in the water column., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

The quantity and composition of fatty acids (FAs) in milk can influence an infant's growth and development through maternal diet. Therefore, associations between maternal diet and FA composition in 74 mature human milk samples were investigated. This study aimed to obtain FA patterns in mature milk arising from different dietary habits in two geographically different areas in Slovenia: Koper (KP), a coastal area, and Pomurje (MS), an inland area. The results revealed statistically significant differences in the dietary intake of game, freshwater fish, and fresh and frozen seafood between the study areas. Among the mean percentages of 35 individual FAs in milk, 19 were higher in KP and 16 were higher in MS. In KP, despite the higher intake of fresh seafood, the levels of saturated and monounsaturated FAs were higher and the levels of PUFAs, ω-3, and ω-6 were lower compared to those in MS. The ω-6:ω-3 ratio did not differ significantly between the study areas. This finding was not expected and indicates a discrepancy between the measured and self-reported data - the latter lack reliable data on dietary supplements. Therefore, determination of FA profile is important as a promising biomarker of dietary intake in environmental health studies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Lake Nahuel Huapi (NH) is a large, ultraoligotrophic deep system located in Nahuel Huapi National Park (NHNP) and collecting a major headwater network of Northwestern Patagonia (Argentina). Brazo Rincón (BR), the westernmost branch of NH, is close to the active volcanic formation Puyehue-Cordón Caulle. In BR, aquatic biota and sediments display high levels of total Hg (THg), ranging in contamination levels although it is an unpolluted region. In this survey, Hg species and fractionation were assessed in association with dissolved organic matter (DOM) in several aquatic systems draining to BR. THg varied between 16.8 and 363 ng L -1 , with inorganic Hg (Hg 2+ ) contributing up to 99.8% and methyl mercury (MeHg) up to 2.10%. DOC levels were low (0.31-1.02 mg L -1 ) resulting in high THg:DOC and reflecting in high Hg 2+ availability for binding particles (partitioning coefficient log K d up to 6.03). In streams, Hg fractionation and speciation related directly with DOM terrestrial prints, indicating coupled Hg-DOM inputs from the catchment. In the lake, DOM quality and photochemical and biological processing drive Hg fractionation, speciation and vertical levels. Dissolved gaseous Hg (Hg 0 ) reached higher values in BR (up to 3.8%), particularly in upper lake layers where solar radiation enhances the photoreduction of Hg 2+ and Hg-DOM complexes. The environmental conditions in BR catchment promote Hg 2+ binding to abiotic particles and bioaccumulation and the production of Hg 0 , features enhancing Hg mobilization among ecosystem compartments. Overall, the aquatic network studied can be considered a "natural Hg hotspot" within NHNP., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The distributions of the total mercury (T-Hg), methylmercury (MeHg), and ethylmercury (EtHg) concentrations in soil and their relationship to chemical composition of the soil and total organic carbon content (TOC, %) were investigated. Core samples were collected from hill slope on the right and left riverbanks of the Idrija River. Former smelting plant is located on the right bank. The T-Hg average in each of the core samples ranged from 0.25 to 1650 mg kg -1 . The vertical T-Hg variations in the samples from the left bank showed no significant change with depth. Conversely, the T-Hg varied with depth, with the surface, or layers several centimeters from the surface, tending to show the highest values in the samples from the right bank. Since the right and left bank soils have different chemical compositions, different pathways of mercury delivery into soils were suggested. The MeHg and EtHg concentrations ranged from n.d. (not detected) to 444 μg kg -1 and n.d. to 17.4 μg kg -1 , respectively. The vertical variations of MeHg and EtHg were similar to those of TOC, except for the near-surface layers containing TOC greater than 20%. These results suggest that the decomposition of organic matter is closely related to organic mercury formation., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

An inter-laboratory study was conducted to compare results from different analytical methods for monomethylmercury (MeHg) concentrations in 17 soil and sediment samples. The samples were collected from mercury-contaminated areas, including Minamata Bay and Kagoshima Bay in Japan, the Idrija mercury mine in Slovenia, and an artisanal small-scale gold mining area in Indonesia. The Hg in these samples comes from several different sources: industrial waste from an acetaldehyde production facility, volcanic activity, Hg mining activity, and artisanal and small-scale gold mining activity (ASGM). MeHg concentrations in all the samples were measured in four separate laboratories, using three different determination methods: Kagoshima University (Japan), using high-performance liquid chromatography-chemiluminescence detection (HPLC-CL); National Institute for Minamata Disease (Japan), using gas chromatography-electron capture detection; and Metropolitan Council Environmental Services (USA) and Jozef Stefan Institute (Slovenia), both using alkylation-gas chromatography-atomic fluorescence spectrometry detection. The methods gave comparable MeHg results for most of the samples tested, but for some samples, the results exhibited significant variability depending on the method used. The HPLC-CL method performed poorly when applied to samples with elevated sulfur concentrations, producing MeHg concentrations that were much lower than those from the other methods. Additional analytical work demonstrated the elimination of this sulfur interference when the method was modified to bind sulfur prior to the analytical step by using Hg 2+ as a masking agent. These results demonstrate the value of laboratory intercomparison exercises in contributing to the improvement of analytical methods., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Despite located far from point sources of Hg pollution, high concentrations were recorded in plankton from the deep oligotrophic Lake Nahuel Huapi, located in North Patagonia. Native and introduced top predator fish with differing feeding habits are a valuable economic resource to the region. Hence, Hg and Se trophic interactions and pathways to these fish were assessed in the food web of this lake at three sites, using stable nitrogen and carbon isotopes. As expected based on the high THg in plankton, mercury did not biomagnify in the food web of Lake Nahuel Huapi, as most of the THg in plankton is in the inorganic form. As was observed in other aquatic systems, Se did not biomagnify either. When trophic pathways to top predator fish were analyzed, they showed that THg biomagnified in the food chains of native fish but biodiluted in the food chains of introduced salmonids. A more benthic diet, typical of native fish, resulted in higher [THg] bioaccumulation than a more pelagic or mixed diet, as in the case of introduced fish. Se:THg molar ratios were higher than 1 in all the fish species, indicating that Se might be offering a natural protection against Hg toxicity., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Mercury presents a potential risk to the environment and humans, especially in its methylated form. It is among the highest priority environmental pollutants. River Idrijca (Slovenia) is highly contaminated with mercury due to past mercury mining. The aim of this work was to investigate whether the periphyton community in rivers such as Idrijca is a suitable indicator of Hg pollution and of changes in mercury methylation and could serve as an early warning system of increased input of MeHg in the food chain. Periphyton is the only site of primary production in temperate torrential rivers such as Idrijca and is therefore an important link in the food chain. It is also a potential site of Hg accumulation and its introduction to higher trophic levels. Our aim was to assess the response of the periphyton to seasonal and spatial variations in mercury levels and to evaluate its potential as an early warning system of changes in mercury reactivity and mobilization The results indicate that periphyton in a torrential river is too complex and unpredictable to be used as a sole indicator of mercury concentrations and changes in the river. Nevertheless, it can complement environmental measurements due to its importance in the riverine food web., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

A good quality control/quality assurance programme should be implemented in all environmental or health related studies on mercury and its organic compounds, particularly, for monomethylmercury (MeHg) which is the most toxic mercury compound. This can be achieved initially by analysing suitable certified reference materials (CRMs), which are available from various producers such as the National Institute of Standards and Technology (NIST) from USA, National Institute of Environmental Studies (NIES), National Research Council of Canada (NRCC), Standards, Measurements and Testing programme (SM&T) of the European Commission, and the International Atomic Energy Agency (IAEA). It is well understood that these materials are not covering present needs, as most of them are of the marine origin, while many laboratories are conducting research and monitoring in terrestrial ecosystems and fresh water environment. In addition, CRMs for human exposure assessment, such as blood, urine, and hair at several levels of concentrations are still lacking. Therefore, many other actions should be undertaken to achieve, improve and/or maintain quality of data, including participation in interlaboratory studies, proficiency testing and production of laboratory reference materials. A review of these actions has shown that MeHg compounds determination in samples such as soil, sediment and water is rather difficult and the results are also method dependent. In addition, it has been shown that some of the most frequently employed analytical methods may be a subject to spurious MeHg formation in the presence of high concentrations of inorganic mercury and organic matter. These findings have put a number of previous data on MeHg in question and consequently prompt actions were undertaken by a number of well experienced laboratories and producers of CRMs. So far, it is shown that the results obtained by various laboratories using different analytical techniques agree well with certified values in all RMs certified for MeHg. This suggests that comparability of data can be achieved, which however is not a guarantee of the true values.