The PM2.5-bound polycyclic aromatic hydrocarbon behavior in indoor and outdoor environments, part I: Emission sources.

The previous research, aimed at exploring the relationships between the indoor and outdoor air quality, has evidenced that outdoor PM2.5-bound polycyclic aromatic hydrocarbons (PAH) levels exhibit significant daily and seasonal variations which does not necessary corresponds with PAH indoor dynamics. For the purpose of this study, a three-month measurement campaign was performed simultaneously at indoor and outdoor sampling sites of a university building in an urban area of Belgrade (Serbia), during which the concentrations of O3, CO, SO2, NOx, radon, PM2.5 and particle constituents including trace metals (As, Cd, Cr, Mn, Ni and Pb), ions (Cl-, Na+, Mg2+, Ca2+, K+, NO3-, SO42- and NH4+) and 16 US EPA priority PAHs were determined. Additionally, the analysis included 31 meteorological parameters, out of which 24 were obtained from Global Data Assimilation System (GDAS1) database. The Unmix and PAH diagnostic ratios analysis resolved the source profiles for both indoor and outdoor environment, which are comparable in terms of their apportionments and pollutant shares, although it should be emphasized that ratio-implied solutions should be taken with caution since these values do not reflect emission sources only. The highest contributions to air quality were attributed to sources identified as coal combustion and related pyrogenic processes. Noticeable correlations were observed between 5- and 6-ring high molecular weight PAHs, but, except for CO, no significant linear dependencies with other investigated variables were identified. The PAH level predictions in the indoor and outdoor environment was performed by using machine learning XGBoost method.

Introducing of modeling techniques in the research of POPs in breast milk - A pilot study.

This study used advanced statistical and machine learning methods to investigate organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in breast milk, assuming that in a complex biological mixture, the pollutants emitted from the same source or with similar properties are statistically interrelated and possibly exhibit non-linear dynamics. The elaborated analyses such as Unmix source apportionment characterized individual source groups, while guided regularized random forest indicated the pollutant dependence on the ortho-chlorine atom attached to the congener's phenyl ring and mother's age. Mutual associations among PCBs were further discussed, but the results implied they were mostly not related to child delivery. PCB congeners -153, -180, -170, -118, -156, -105, and -138 appeared to be compounds of the outmost importance for mutual prediction with reference to their interrelations regarding chemical structure and metabolic processes in the mother's body. Finally, machine learning methods, which provided prediction relative errors lower than 30% and correlation coefficients higher than 0.90, suggested a possible strong non-linear relationship among the pollutants and consequently, the complexity of their pathways in the breast milk.

Organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in Cyprinidae fish: Towards hints of their arrangements using advanced classification methods.

To tackle the ever-present global concern regarding human exposure to persistent organic pollutants (POPs) via food products, this study strived to indicate associations between organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in lake-fish tissue depending on the species and sampling season. Apart from the monitoring initiatives recommended in the Global Monitoring Plan for POPs, the study discussed 7 OCPs and 18 PCB congeners determined in three Cyprinidae species (rudd, carp, and Prussian carp) from Vransko Lake (Croatia), which are widely domesticated and reared as food fish across Europe and Asia. We exploit advanced classification algorithms, the Kohonen self-organizing maps (SOM) and Decision Trees (DT), to search for POP patterns typical for the investigated species. As indicated by SOM, some of the dioxin-like and non-dioxin-like PCBs (PCB-28, PCB-74, PCB-52, PCB-101, PCB-105, PCB-114, PCB-118, PCB-156 and PCB-157), α-HCH and ß-HCH caused dissimilarities among fish species, but regardless of their weight and length. To support these suggestions, DT analysis sequenced the fish species and seasons based on the concentration of heavier congeners. The presented assumptions indicated that the supplemental application of SOM and DT offers advantageous features over the usually rough interpretation of POPs pattern and over the single use of the methods.

Presence of polycyclic aromatic hydrocarbons and persistent organochlorine pollutants in human Milk: Evaluating their levels, association with Total antioxidant capacity, and risk assessment.

Breastfeeding provides numerous health benefits for both infants and mothers, promoting optimal growth and development while offering protection against various illnesses and diseases. This study investigated the levels of polychlorinated biphenyls (PCB), organochlorine pesticides (OCP) and polycyclic aromatic hydrocarbons (PAH) in human milk sampled in Zadar (Croatia). The primary objectives were twofold: firstly, to evaluate the individual impact of each compound on the total antioxidant capacity (TAC) value, and secondly, to assess associated health risks. Notably, this study presents pioneering and preliminary insights into PAH levels in Croatian human milk, contributing to the limited research on PAH in breast milk worldwide. PCB and OCP levels in Croatian human milk were found to be relatively lower compared to worldwide data. Conversely, PAH levels were comparatively higher, albeit with lower detection frequencies. A negative correlation was established between organic contaminant levels and antioxidative capacity, suggesting a potential link between higher antioxidative potential and lower organic contaminant levels. Diagnostic ratio pointed towards traffic emissions as the primary source of the detected PAH. The presence of PAH suggests potential health risk, underscoring the need for further in-depth investigation.

Human health risk assessment based on direct and indirect exposure to endocrine disrupting herbicides in drinking, ground, and surface water in Croatia.

The recognition of certain herbicides as endocrine disrupting compounds has raised concerns due to their ability to interfere with the normal functioning of the endocrine system, which regulates various physiological processes in organisms. The objective of this study was to assess the possible human health risks associated with terbuthylazine and endocrine-disrupting herbicides atrazine, acetochlor, and metolachlor in the drinking, surface, and groundwater of the Zagreb city region, Croatia. We relied on advanced statistical methods and principal component analysis (PCA), which revealed higher levels of atrazine and acetochlor in drinking and groundwater samples and higher presence of metolachlor and terbuthylazine in surface waters. To evaluate the danger to human health, various exposure scenarios have been assessed. The risk of direct human exposure to analyzed herbicides through drinking or bathing with drinking (tap) or groundwater, as well as from recreational activities like swimming in rivers, streams, and lakes, has been quantified. In addition to these direct exposure scenarios, indirect ones based on consumer goods, fruits, and vegetables, treated with surface and groundwater for irrigation, were assessed to investigate the danger to human health. Judging by the reported herbicide levels there was no significant risk of carcinogenic (CR ≤ 1 × 10-6) or non-carcinogenic (HI < 1) diseases, not even when we assessed the so-called "cocktail effect" of combined the herbicide exposure in different waters.

Organochlorine compounds in pine needles from Croatia.

Levels of seven organochlorine pesticides and 17 congeners of polychlorinated biphenyls (PCBs) were analysed in pine needles collected at eight sites along eastern Adriatic coast (Croatia). The concentration of organochlorine pesticides and PCBs ranged between 0 (below determination limit) and 7.44 ng g(-1) in 1-year-old needles and between 0 (below determination limit) and 15.57 ng g(-1) dry weight in 2-year-old needles. Organochlorine levels were compared with those found in urban and mountain areas.

Human health risks and benefits assessment based on OCPs, PCBs, toxic elements and fatty acids in the pelagic fish species from the Adriatic Sea.

Benefits and risks of the fish consumption should be assessed to balance the ingestion of healthy omega-3 fatty acids and adverse chemicals. Persistent organic pollutants-POPs (organochlorine pesticides-OCPs and polychlorinated biphenyls-PCB), macro- and micro-elements and fatty acid contents were determined in six fish species from the Adriatic Sea to assess health risks for consumers (worst-case scenario, diseases development risks and benefit-risk). 16 element, 24 POPs and 14 fatty acid contents were determined in six pelagic species which can be used in human diet. Element concentrations were determined by inductively coupled plasma mass spectrometry (ICP-MS), POPs by high-resolution gas chromatography and fatty acid content by gas-liquid chromatography. Diet based on chub mackerel and round sardinella showed lower daily intake (DI) of POPs and highest DI of essential omega-3 fatty acids than other investigated species. Lower ingestion of toxic elements can be observed by consuming anchovy and round sardinella. Based on POP concentrations, there was not observed non-carcinogenic (HI) nor carcinogenic (CR) risks for consumers. Based on element concentrations, there was low HI (0.1 ≥ HI ≥ 1), while the maximum HIs and outlier values (horse mackerel and anchovy samples) implied the presence of HI (HI > 1). The most significant contributor to total non-carcinogenic and carcinogenic risks was inorganic arsenic (inorganic As). Acceptable CR for consumers was assessed, but maximum CR for consumers of horse mackerel and anchovy (CR ≥ 1 × 10-6) showed adverse effects on human health. There were low HIs for developing cardiovascular, nervous, and reproductive diseases, and maximum HIs were higher than 1. Acceptable (1 × 10-4≥CR ≥ 1 × 10-6) risks were observed for developing cancer of nervous system and reproductive organs. Among investigated fish samples, those with higher Æ©BR (benefit-risks) and BR for arsenic (As) than median value have a higher risk than benefits in the human diet.

The PM2.5-bound polycyclic aromatic hydrocarbon behavior in indoor and outdoor environments, part II: Explainable prediction of benzo[a]pyrene levels.

Among the polycyclic aromatic hydrocarbons (PAH), benzo[a]pyrene (B[a]P) has been considered more relevant than other species when estimating the potential exposure-related health effects and has been recognized as a marker of carcinogenic potency of air pollutant mixture. The current understanding of the factors which govern non-linear behavior of B[a]P and associated pollutants and environmental processes is insufficient and further research has to rely on the advanced analytical approach which averts the assumptions and avoids simplifications required by linear modeling methods. For the purpose of this study, we employed eXtreme Gradient Boosting (XGBoost), SHapley Additive exPlanations (SHAP) attribution method, and SHAP value fuzzy clustering to investigate the concentrations of inorganic gaseous pollutants, radon, PM2.5 and particle constituents including trace metals, ions, 16 US EPA priority PM2.5-bound PAHs and 31 meteorological variables, as key factors which shape indoor and outdoor PM2.5-bound B[a]P distribution in a university building located in the urban area of Belgrade (Serbia). According to the results, the indoor and outdoor B[a]P levels were shown to be highly correlated and mostly influenced by the concentrations of Chry, B[b]F, CO, B[a]A, I[cd]P, B[k]F, Flt, D[ah]A, Pyr, B[ghi]P, Cr, As, and PM2.5 in both indoor and outdoor environments. Besides, high B[a]P concentration events were recorded during the periods of low ambient temperature (<12 °C), unstable weather conditions with precipitation and increased soil humidity.

Organochlorine contaminants and quality of olive oil collected from olive oil growers along the Croatian Adriatic coast.

In this study we assessed 48 samples of virgin olive oil collected along the Croatian Adriatic coast for quality control, and for the presence of residues of seven organochlorine pesticides and 17 congeners of polychlorinated biphenyls (PCBs). Organochlorine pesticide levels ranged between below the limit of determination and 3.7 ng g(-1) of oil, while PCBs ranged between below the limit of determination and 1.8 ng g(-1) of oil. A larger problem than the presence of organochlorine compounds was that the seven tested oils (out of 48) did not meet some quality standards.

Levels of organochlorine compounds in the Mediterranean blue mussel from the Adriatic Sea.

The distribution of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) was investigated in Mediterranean blue mussel collected at four locations in Mali Ston Bay few times a year in 2005­2007. OCPs were found in all samples and levels ranged between 0.07 and 7.58 ng g−1 dry wt. Levels of PCBs ranged between 0 (below detection limit) and 21.55 ng g−1 dry wt. For most analyzed compounds there were no significant level changes between the 3 years. Exceptions are decreased levels of ß-HCH, DDD, and PCB-138 and increased levels of γ-HCH and DDT in 2007. However, mussels from this area are applicable for human diet.

Self-organizing maps for indications of airborne polychlorinated biphenyl (PCBs) and organochlorine pesticide (OCPs) dependence on spatial and meteorological parameters.

This paper investigates the relation of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in air samples with meteorological parameters (temperature, atmospheric pressure and relative humidity) using the Kohonen self-organizing map (SOM). Both gas- and particle-adsorbed phase of 20 PCB congeners and 7 OCPs including the three new ones (α-HCH, ß-HCH, and γ-HCH) listed in the Stockholm Convention were collected during a one-year period at urban locations in Zagreb (Croatia). Moving beyond existing studies, the SOM analysis showed that the meteorological characteristics of transient seasons such as spring had no influence on the dissimilarities in the behavior of PCBs and OCPs. Towards the identification of pollutant spatial patterns, the SOM did not isolate a clear phenomenon probably due to the absence of local pollution sources contributing to the elevated concentrations of these compounds. Overall, our results have shown that the SOM method, by recognizing significant differences among PCB and OCP seasonality, could be recommended in the analysis of pollutant distribution depending on temperature and atmospheric pressure.

Are pine needles bioindicators of air pollution? Comparison of organochlorine compound levels in pine needles and ambient air.

Levels of six PCB congeners and seven organochlorine pesticides were investigated and compared in ambient air and in pine needle samples. The applied methods are suitable for the analysis of PCBs and organochlorine pesticides in environmental samples and for their detection in recent intakes. DDE, HCB, lindane, PCB-28, PCB-52, PCB-101, PCB-138 and PCB-153 were found in all pine needle and air samples. The highest median values were found for PCB-28, PCB-101 and gamma-HCH, and the lowest for PCB-180 and DDD. The median value of alpha-HCH/ gamma-HCH ratios was 0.2 in both matrices. DDE/DDT ratios were close to or below 1 in some pine needle and ambient air samples. The results showed a correspondence between air and pine needle pollution; the same compounds were present in the highest or in the lowest levels in both types of matrices. These results suggest that pine needles are passive biomonitors of air pollution.

[Chemical methods for determination of hydroxylated metabolites of polycyclic aromatic hydrocarbons and polychlorinated biphenyls in biological material]. / Kemijske metode odredivanja hidroksiliranih metabolita policiklickih aromatskih ugljikovodika i poliklorbifenila u bioloskome materijalu.

This review presents methods for the analysis of hydroxylated metabolites of polycyclic aromatic hydrocarbons and polychlorinated biphenyls in humans and animals. These metabolites serve as biomarkers of human and animal exposure to the mentioned pollutants, but some metabolites also have toxic properties. Most are analysed in urine, which is the most accessible sample, but they can also be analysed in human and animal liver, bile, and adipose tissue.Their analysis is important for assessing bioavailability of aromatic pollutants and their toxicity in human organism, but also the toxicity of metabolites themselves. Advancements in analytical methods have made it possible to analyse multiple metabolites in a sample at the same time. New extraction techniques and more precise and selective qualitative and quantitative analyses can now detect very low metabolite concentrations. An extra advantage is that these simple techniques require less chemicals and time.

Accumulation of organochlorine contaminants in loggerhead sea turtles, Caretta caretta, from the eastern Adriatic Sea.

We analyzed 15 polychlorinated biphenyls (PCBs) and five organochlorine pesticides (OCPs) in fat tissue of 27 loggerhead sea turtles (Caretta caretta) from eastern Adriatic Sea with the curved carapace length ranging from 25.0 to 84.5 cm. The PCB profile was dominated by hexa- and hepta-chlorinated congeners, with PCB-153 (median: 114.9 ng g⁻¹ wet mass), PCB-138 (80.0 ng g⁻¹ w.m.), and PCB-180 (26.7 ng g⁻¹ w.m.) detected with the highest levels. Toxic mono-ortho congeners PCB-118, PCB-105 and PCB-180 with dioxin-like toxicity were found in > 70% samples. 4,4'-DDE (81.0 ng g⁻¹ w.m.) prevailed the OCP signature, accounting for 80% of the total DDTs. A significant increasing trend in accumulation with size was found for PCB-52 (r(s) = 0.512, p < 0.01) and PCB-114 (r(s) = 0.421, p < 0.05). Comparison of our results with organochlorine contaminant (OC) pattern in some prey taxa suggest that contamination occurs primarily through the food web, with biomagnification factors of 0.14-6.99 which were positively correlated with the octanol-water partition coefficient (logK(ow); p < 0.05). This study, based upon a fairly large sample size collected mostly from incidentally captured animals over a short time period (June 2001-November 2002), present a temporal snapshot of OC contamination in wild, free-ranging loggerheads from Adriatic feeding grounds and provide a baseline for monitoring the regional OC trends in this endangered species.

[Levels and distribution of PCBs and organochlorine pesticides in the air, pine needles, and human milk]. / Razine i raspodjela PCB-a i organoklorovih pesticida u zraku, borovim iglicama i majcinu mlijeku.

This review presents the findings on the distribution and levels of 20 congeners of polychlorinated biphenyls (PCBs) and 7 organochlorine pesticides (OCPs) all over the world, based on measurements in samples of air, human milk and pine needles. The Institute for Medical Research and Occupational Health has been conducting research in all three matrices for many years, and this review summarises its results too. Significant decrease in concentrations of organochlorine compounds has been seen after the legal ban of their use, but that decresing trend has been slowed down and they are still found in all samples. In general, higher PCB levels are found in samples from urban locations, pesticides levels are higher in samples from locations where has been their probable usage in agriculture, while HCB levels are usually indicator of industrial activity.γ-HCH has been found in the highest concentration in air and pine needles samples, while in humans DDE and ß-HCH are the most abundant compounds. Indicator PCB congeners are also differently present in environment and humans: in air and pine needles lower-chlorinated, more volatile PCB congeners have higher concentrations while in humans that goes for more persistent higher-chlorinated PCB congeners. Among toxic ortho-substituted PCB congeners in human and environmental samples the most abundant is PCB-118 while three non-ortho substituted congeners (PCB-77, PCB-126 and PCB-169) that are the most toxic ones are rarely detected. From organochlorine pesticides, DDD is found in lowest concentrations in all samples.

[Analysis of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in soil and sediment]. / Analiza polikloriranih dibenzo-p-dioksina i polikloriranih dibenzofurana u tlu i sedimentu.

This review presents methods for the analysis of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), called dioxins, in soil and sediment. These compounds are produced as by-products of different combustion processes, and because of their persistency and toxicity they present a threat for animal and human health. Due to their high organic matter content, soil and sediment can accumulate dioxins and have become important secondary emission sources. Determining dioxins in these samples is complex because dioxins are present in trace levels and have to be separated from interferences whereas other classes of organic contaminants are present in higher concentrations. After sampling, follows extraction of compounds with a suitable solvent, extract clean-up from unwanted compounds, and qualitative and quantitative analysis. At the end of this review, we gave levels of PCDD/PCDFs found in soil and sediment samples.

Distribution of organochlorine compounds in pine needles collected in Zagreb.

The distribution of polychlorinated biphenyls and organochlorine pesticides was investigated in one- and two-year-old pine needles collected at eight locations in Zagreb in 2006. Concentration medians for most analyzed compounds in two-year-old needles were higher or similar to the concentration medians of the same compounds in one-year-old needles, with the exception of PCB-28, PCB-52, PCB-153, and PCB-138. The pollution profiles seems to have remained the same over the 2 years. These results were compared to those obtained in samples collected at the same locations in 1998.