Efficiency of clustering methods and self-organizing maps of Adriatic sardines and anchovies regarding organochlorine and fatty acid burden.

The Adriatic Sea plays a crucial role as both a significant fishing ground and a thriving trading market for small pelagic edible fish. Recognized for their nutritional value, these fish are esteemed for their high protein content and abundance of polyunsaturated omega-3 and omega-6 fatty acids, making them a sought-after and healthful food choice. Nevertheless, pelagic species can also serve as a reservoir for lipophilic organochlorine pollutants, posing potential risks to human health. In this study, we compared traditional classification methods traditional principal component analysis (PCA) and Ward's clustering with an advanced self-organizing map (SOM) algorithm in determining distribution patterns of 24 organochlorines and 19 fatty acids in sardine and anchovy samples taken from the eastern Adriatic. The outcomes reveal the strengths and weaknesses of the three approaches (PCA, Ward's clustering, and SOM). However, it is evident that SOM has proven to be the most effective in offering detailed information and data visualization. Although sardines and anchovies exhibit similar distribution patterns for p,p'-DDE, PCB-28, PCB-138, PCB-153, PCB-118, and PCB-170, they differ in the concentrations of fatty acids such as stearic, palmitic, myristic, oleic, docosapentaenoic, and docosahexaenoic acid. Our findings supply valuable insights for environmental authorities and fish consumers concerning the potential risks associated with organochlorines in these two types of fish.

Polychlorinated biphenyls in mussels, small pelagic fish, tuna, turtles, and dolphins from the Croatian Adriatic Sea waters: an overview of the last two decades of monitoring.

This review summarises our two decades of polychlorinated biphenyl (PCB) monitoring in different marine organisms along the eastern Adriatic Sea. The aim was to gain an insight into the trends of PCB distribution in order to evaluate the effectiveness of past and current legislation and suggest further action. Here we mainly focus on PCB levels in wild and farmed Mediterranean mussels, wild and farmed bluefin tuna, loggerhead sea turtles, common bottlenose dolphins, and small pelagic fish. The use of artificial intelligence and advanced statistics enabled an insight into the influence of various variables on the uptake of PCBs in the investigated organisms as well as into their mutual dependence. Our findings suggest that PCBs in small pelagic fish and mussels reflect global pollution and that high levels in dolphins and wild tuna tissues raise particular concern, as they confirm their biomagnification up the food chain. Therefore, the ongoing PCB monitoring should focus on predatory species in particular to help us better understand PCB contamination in marine ecosystems in our efforts to protect the environment and human health.

Bedload sediment transport model for revealing the multi-year trend of polychlorinated biphenyl contamination in the river sediment (Kupa, Croatia).

This article investigated the multi-year polychlorinated biphenyl (PCB) burden of the sediment collected along the Kupa River flow in Croatia using the bedload sediment transport model. Kupa, as the natural border between Croatia and Slovenia, belongs to the water system Krupa (Slovenia) → Lahinja (Slovenia) → Kupa (Croatia) → Sava → Danube → Black Sea. From 1962 to 1985, the total quantity of waste calculated for pure PCBs, released by a capacitor manufacturer into the environment within various locations of the Krupa River in Slovenia, was 70 tons. Krupa River (Slovenia) has become one of the most PCB-polluted rivers in Europe, and consequently, PCBs have been detected in the Kupa River (Croatia). Model application revealed that contamination of the Kupa River (Croatia) started significantly earlier than 1983, when a high concentration of PCB was detected for the first time in the Krupa River (Slovenia), with probably significantly higher sediment concentrations at the upstream boundary of the Kupa. A slow concentration changes and PCB accumulation in the sediment should be expected downstream compared to the upstream boundary, governed mainly by high flow events. The PCBs in sediments from 2020/2021 are markedly different after the Lahinja confluence with Kupa (0.2-0.6 µg kg-1 vs. 1.4-34.3 µg kg-1). Measurements of PCBs in Kupa sediment suggest that the intake of PCB has not yet been completely stopped, which should be confirmed by detailed monitoring in the future. The contamination situation observed in the Kupa River represents an excellent example of the persistency of PCBs in the environment.

Persistent organic pollutants in Croatian breast milk: An overview of pollutant levels and infant health risk assessment from 1976 to the present.

This review article summarizes our research of persistent organic pollutants (POPs) in human milk from Croatian mothers over the last few decades. Our studies make up the bulk of all POPs research in human milk in Croatia and show a state-of-the art in the research area. The first investigations were made in 1970's. Aim of our review article is to document the comprehensive results over several decades as the best tool to: 1.) contribute to understanding of POPs and their potential health risks, 2.) evaluate effectiveness of legislative bans and restrictions on human exposure to POPs in Croatia, and 3.) to suggest further actions. In our review we discuss: 1.) Human milk between 2011 and 2014 - evaluation of interrelations of organochlorine pesticides (OCP) and polychlorinated biphenyls (PCB) in human milk and their association with the mother's age and parity using artificial intelligence methods; and our yet unpublished research data on health risks for infants assessed through daily PCB and OCP intake. 2.) Time trends of PCB and OCP in human milk between 1976 and 2014. 3.) polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofuran (PCDD/F) in human milk in 2000., and yet unpublished data on PCDD/F and polybrominated diphenyl ethers (PBDE) in 2014.

Fatty acids, persistent organic pollutants, and trace elements in small pelagic fish from the eastern Mediterranean Sea.

Fatty acids (FAs) composition, 24 persistent organic pollutants (POPs), and 16 trace elements were examined in small pelagic fish (sardine, anchovy, round sardinella, chub and horse mackerels) caught by a fishing fleet for more than three years in the eastern Mediterranean Sea. Five Unmix source profiles associated with both sources, such as overlapping diet, including low-niche marine organisms and inputs from the surrounding environmental compartments were resolved. Inorganic compounds were notably more abundant in fish tissue than organochlorine xenobiotics. Comparison with the values of toxicological parameters revealed that the examined fish species are safe for human consumption, while the content of FAs emphasized the studied species as a valuable source of nutrients. A significant linear correlation was not observed between the 18 FAs and lipophilic organochlorines. Based on the obtained database, future assessments of the quality of edible fish species and the aquatic environment of the eastern Mediterranean Sea, which is known as an important fishing ground, could be significantly improved.

Organochlorines burden in moss H. cupressiforme and topsoil across Serbia.

Following up-to-date initiatives of the Stockholm Convention, its global monitoring plan, and the International Cooperative Programme on Natural Vegetation and Crops (ICP Vegetation 2015) under the convention on long-range transboundary air pollution, this study examined 17 polychlorinated biphenyls (PCBs) and seven organochlorine pesticides (OCPs) in the moss Hypnum cupressiforme Hedw. and topsoil sampled across Serbia. In the topsoil, OCPs ranged from 0.0158 to 9.6804 ng g-1 while concentrations of individual PCB congeners were in the range between 0.0185 and 0.3107 ng g-1. The levels of OCPs and PCBs in the moss H. cupressiforme ranged from 2.7785 to 23.9501 ng g-1, and from 0.4325 to 15.8013 ng g-1, respectively. POP relationships between topsoil and moss investigated by fugacity model equations indicated that the moss POP enrichment was a result of atmospheric long-range transport rather than secondary reemissions from soil.

Persistent organic pollutants in tissues of farmed tuna from the Adriatic Sea.

This study investigated the levels and distribution of polychlorinated biphenyls (PCBs) and organochlorine pesticides in three tissue types of farmed Bluefin tuna (Thunnus thynnus): muscle, liver and branchiae. Seven adult species were caught in 2015 at a tuna farm in the Croatian Adriatic. The organochlorine compound levels decreased in the following order: liver > muscle > branchiae while contaminant distribution in all three tissues followed the same order: ΣPCB ≫ ΣDDT > ΣHCH ~ HCB. The found POP levels indicated moderate pollution of farmed tuna and were below all limits set by current laws. Furthermore, no cytotoxic effect of the POP mixture extracted from tuna liver samples on human neuroblastoma cells was observed.

Legacy persistent organic pollutants (POPs) in archive samples of wild Bluefin tuna from the Mediterranean Sea.

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were quantified in archive samples of dorsal white muscle of the wild Bluefin tuna (BFT) (n = 9) collected in the central Adriatic. PCBs were the predominant organochlorine (OC) compounds (60.8-69.4% of the total OC load) found. The contribution of HCB and ΣHCHs was significantly lower, ranging from

Levels and distribution of polybrominated diphenyl ethers in humans and environmental compartments: a comprehensive review of the last five years of research.

Polybrominated diphenyl ethers (PBDEs) are a class of brominated flame retardants (BFRs), present in the environment, animals, and humans. Their levels, distribution, and human exposure have been studied extensively, and over the last decade, various legal measures have been taken to prohibit or minimize their production and use due to the increasing amount of evidence of their harmful effects on human and animal health.Our aim here was to make a comprehensive and up-to-date review of the levels and distribution of PBDEs in the aquatic environment, air, and soil, in indoor dust, and in humans. To fulfill this, we searched through Web of Science for literature data reported in the last five years (2015-2019) on levels of at least six key PBDE congeners in abovementioned matrices. According to our summarized data, significant PBDE mass concentrations/fractions are still being detected in various sample types across the world, which implies that PBDE contamination is an ongoing problem. Secondary sources of PBDEs like contaminated soils and landfills, especially those with electronic and electrical waste (e-waste), represent a particular risk to the future and therefore require a special attention of scientists.

Persistent organic pollutants (POPs) in edible fish species from different fishing zones of Croatian Adriatic.

High-risk contaminants, OCPs and PCBs, were investigated in marine fish from the Adriatic Sea, from which retail fish in Croatia is commonly sourced. The pollutant levels in sardine, horse and chub mackerel, anchovy and round sardinella were analysed based on a two-year sampling and the joint use of generally accepted statistics and advanced clustering methods - self-organizing maps (SOM) and decision tree analysis (DT). Both the SOM and DT suggested fish mass and length rather than fat along with α-HCH, p,p'-DDT, PCB-74 and PCB-189 to cause variable pollutant uptake among species. Main distinctions of sardines occur in coastal and off coast regions rather than in a particular fishing zone and they are associated with both fish characteristics, levels of γ-HCH and PCBs: -60, -105, -150, -170, and -189. The results, mutually compatible or in agreement, could be useful for the design and implementation of the abatement strategies of fish pollution.

Assessment of multiple anthropogenic contaminants and their potential genotoxicity in the aquatic environment of Plitvice Lakes National Park, Croatia.

In this study, the influence of anthropogenic pollution on the aquatic environment of Plitvice Lakes National Park (PLNP) was investigated during 2011-2012 using a combination of chemical and cytogenetic analyses. Four groups of major contaminants [(volatile organic compounds: benzene, toluene, ethylbenzene, and xylenes (BTEX); persistent organochlorine pollutants: organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs); major and trace elements; anthropogenic radionuclides (90Sr, 134Cs, and 137Cs)] were determined in three aquatic compartments (water, sediment, fish). Mass fractions of inorganic constituents in different compartments reflected the geological background of the area, indicating their origin from predominantly natural sources. Levels of volatile and persistent organic compounds in water and fish, respectively, were very low, at levels typical for remote pristine areas. Analysis of anthropogenic radionuclides in water and sediment revealed elevated activity concentrations of 137Cs in water, and measurable 134Cs in the upper sediment layers from April 2011, possibly as a consequence of the Fukushima nuclear accident in March 2011. The potential genotoxicity of river and lake water and lake sediment was assessed under laboratory conditions using the alkaline comet assay on human peripheral blood lymphocytes, and measured levels of primary DNA damage were within acceptable boundaries. The results showed that despite the protected status of the park, anthropogenic impact exists in both its terrestrial and aquatic components. Although contaminant levels were low, further monitoring is recommended to make sure that they will not rise and cause potentially hazardous anthropogenic impacts.

Persistent Organochlorine Pollutants in Placentas Sampled from Women in Croatia and an Evaluation of Their DNA Damaging Potential In Vitro.

This study investigated the levels and distribution of 17 polychlorinated biphenyls (PCBs) and organochlorine pesticides (HCB, α-HCH, ß-HCH, γ-HCH, p,p'-DDE, p,p'-DDD, and p,p'-DDT) in placenta samples from women living in the coastal area of Croatia. During November 2012 to February 2013, 51 placenta samples were collected from healthy mothers. This study presents the first report about Croatian placenta samples. Each of the analysed compounds were found in all of the samples; all of the maximum values were < 1 ng g-1 w.w., and the highest median value found for PCB-28 was 11.2 pg g-1 w.w. PCBs and organochlorine pesticide (OCPs) present in placenta samples were tested for their genotoxic potential using the alkaline comet assay. The alkaline comet assay is one of the most reliable methods in assessing the DNA lesions that occurs in direct interaction of a chemical and the genome. The detected levels of PCBs and OCPs in the placenta did not pose a significant risk to the children's DNA during embryonic and foetal growth following short-term exposure. PCB and OCP concentrations in the placenta samples did not induce any significant primary damage to DNA in terms of DNA strand breaks and changes in the primary chemical structure, which could be detected by the alkaline comet assay.

The impact of multiple anthropogenic contaminants on the terrestrial environment of the Plitvice Lakes National Park, Croatia.

The anthropogenic impact on the terrestrial environment of the Plitvice Lakes National Park (PLNP) was investigated through the analysis of three groups of major contaminants (persistent organochlorine pollutants including 15 organochlorine pesticides (OCPs) and 17 polychlorinated biphenyls (PCBs), trace elements/heavy metals (6 major and 23 trace constituents), and anthropogenic radionuclides ((90)Sr, (134)Cs, and (137)Cs)) in three terrestrial compartments (soil, air, and bioindicators of air contamination) during 2011-2013. The correlation coefficients of element mass fractions with soil properties indicated that total Fe and Al minerals, soil organic matter (OM), and organic carbon (OC) content affected the mass fractions of most trace elements in the topsoils. The annual and spatial distributions of heavy metals in total deposited matter (TDM) indicated that the metals came from natural sources and long-range transfer of particulate matter. The PCB and OCP levels found in soil and conifer needles corresponded to global environmental pollution levels by persistent organic pollutants and represented the lower end of the mass fraction ranges reported in the relevant literature. Analyses of anthropogenic radionuclides in bioindicators (conifer needles, lichens, and mosses) showed low but measurable activity concentrations of (134)Cs (for the first time after the Chernobyl accident), which indicated origin from the March 2011 Fukushima Nuclear Power Plant accident. Our overall results indicated that human activity inside or near the PLNP had no significant impact either on contaminant spread by air or on their content in topsoils.

Organochlorine pesticides and polychlorinated biphenyl congeners in wild terrestrial mammals from Croatia: Interspecies comparison of residue levels and compositions.

In this pilot study, we investigated levels of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in the adipose tissues of two free-ranging terrestrial carnivores from Croatia sampled in 2010 and 2011: the brown bear (Ursus arctos; N=32) and the grey wolf (Canis lupus; N=29). Concentrations of ∑OCPs and ΣPCBs ranged from 0.45 to 4.09 ng g(-1) lipid mass (lm) and from 0.93 to 8.52 ng g(-1) lm in brown bear, and from 1.18 to 5.67 ng g(-1) lm and 2.68 to 48.9 ng g(-1) lm in grey wolf adipose tissues, respectively. PCBs were dominant accounting for over 72% of total analyzed persistent organic pollutants (POPs). The sum of six indicator non-dioxin-like PCBs (Σ6IndNDL PCBs) made up 60-93% and 58-85% of the total congener concentrations in brown bears and wolves, respectively. Although the levels of the measured parameters were significantly higher in grey wolves than in bears, the contaminant profiles of the two species were similar, with γ-HCH, HCB, ß-HCH and DDE as major OCP contaminants, and PCB-153>PCB-180≈PCB-170>PCB-138 as the dominant congeners. The sum of hexachlorocyclohexanes (ΣHCHs) and 8 toxicologically relevant dioxin-like PCBs (Σ8ToxDL PCBs) was higher in the males than in the females of the brown bear. Concentrations of ΣDDTs, HCB, ΣOCP, ΣPCBs, Σ6IndNDL PCBs, and toxicologically relevant non-dioxin-like PCBs (ΣToxNDL PCBs) were significantly positively correlated with lipid content in the grey wolf. Concentrations of OCPs and PCBs in brown bears and wolves from Croatia were low and normal for large terrestrial mammals.

Chlorinated compounds in the muscle tissue of fish from the Croatian Adriatic: preliminary data on contamination and the associated health risks.

Levels of 17 polychlorinated biphenyl congeners (PCBs) and seven organochlorine pesticides (OCPs) were measured in the muscle tissue of 18 commercially important fish species from the eastern Adriatic Sea. PCBs [

Distribution of persistent organic pollutants (POPs) in cultured mussels from the Croatian coast of the Adriatic Sea.

In this study we investigated the distribution of 7 organochlorine pesticides (OCPs) and 17 polychlorinated biphenyl (PCBs) congeners in the edible tissue of the blue mussels (Mytilusgalloprovincialis) collected at 15 shellfish breeding farms and 1 harvesting area along the Croatian Adriatic coast. All analyzed OCPs were found in all samples (0.011-1.47 ng g(-)(1) w.wt.). Concentrations of PCB congeners in positive samples ranged between 0.007 and 7.66 ng g(-)(1) w.wt. The most abundant compounds were γ-HCH, PCB-138 and PCB-153. Overall levels of PCBs and OCPs were in the lower end of the concentration ranges reported in literature. Significant differences of all contaminants were recorded between seasons, with higher values in the warmer part of the year. Results of the evaluation of the risks to human health associated with consumption of the mussels containing organic contaminants suggest that the levels of these compounds in mussels do not pose any threat for consumers of cultivated mussels.

Organochlorine compounds in red deer (Cervus elaphus L.) and fallow deer (Dama dama L.) from inland and coastal Croatia.

Polychlorinated biphenyl (PCB) and organochlorine pesticide (OCP) levels in fat tissue of red and fallow deer (Cervus elaphus L. and Dama dama L.) from two inland and an Adriatic area were established. Of 17 analysed PCBs, PCB-28, PCB-138, PCB-153, PCB-180 and PCB-118 were found in all samples, whilst PCB-101 and PCB-170 were found in more than 50% of samples. They ranged between 0.03 and 5.98 ng g(-1) fat weight. Of seven analysed OCPs, HCB, γ-HCH and 1,1-dichloro-2,2-di(4-chlorophenyl)ethylene (DDE) were found in all samples, whilst ß-HCH was found in more than 50% of samples. They ranged between 0.17 and 22.14 ng g(-1) fat weight. The dominating compounds were DDE, PCB-138, PCB153, PCB-118 and PCB-180. According to the Duncan multistage test, the levels of PCB-138, PCB-153, PCB 170 and PCB-180 were significantly higher in perirenal fat samples of specimens taken from the Adriatic area. DDE was significantly higher in the inland deer samples. Some species differences were determined and were mostly related to higher PCB and ß-HCH levels in fallow deer samples and higher DDE levels in red deer samples. No sex difference was established. As for age, significantly higher levels of PCB-118 and PCB-52 were found in fawns.

Distribution of polychlorinated biphenyls and organochlorine pesticides in wild mussels from two different sites in central Croatian Adriatic coast.

Levels of 24 organochlorine compounds were investigated in wild mussels collected at two locations (Krka estuary and Kastela Bay) on the Croatian Adriatic coast in 2003, 2005, 2006, 2007, and 2008. PCB and OCP ranges found at the two locations overlapped and followed similar profiles despite the differences between the two locations indicating that they share a common pollutants source. Among organochlorine pesticides, the dominant compound was DDT. Among indicator PCBs, the dominant compound was PCB-153, while PCB-118 was dominant among the remaining 11 congeners. Generally, the sum of six indicator PCBs was constantly greater than the sum of 11 congeners at both locations. α-HCH/γ-HCH and DDE/DDT ratios were below 1, indicating recent input of γ-HCH and DDT into the marine environment. In the investigated period, almost all organochlorine compounds reached the highest values in 2006. The levels of PCBs and OCPs in this study were considerably below the Croatian maximum permissible levels, confirming that they do not pose any threat for human health.

Biomonitoring of organochlorine compounds and trace metals along the Eastern Adriatic coast (Croatia) using Mytilus galloprovincialis.

The paper presents the results of monitoring trace organic contaminants (17 PCBs and 7 OCPs) and 6 trace metals (Cd, Cr, Cu, Hg, Pb and Zn) in the coastal waters of the eastern Adriatic in 2006 using Mytilus galloprovincialis as indicator species. OCPs were found in all samples (0.07-14.3 ng g(-1)d.wt.), while in positive samples concentrations of PCBs ranged between 0.16 and 20.5 ng g(-1)d.wt. The α-HCH/γ-HCH and DDE/DDT ratios indicated recent input of γ-HCH and DDT. Spatial distributions of HCB, PCBs, DDTs and Hg were significantly correlated with population density. Although elevated concentrations of all trace metals and organic contaminants were recorded in the densely populated and industrialized areas, overall data point to relatively low level of contamination of the eastern Adriatic coast. Evaluation of the risks to human health associated with consumption of the mussels suggested that there is no health risk for moderate shellfish consumers.