Bioaccumulation of potentially toxic elements in leafy and tuberous vegetables: a comparison based on meta-analysis studies with a cumulative health risk assessment.

Seventy seven research papers published from 1986 to 2018 were observed. These papers investigated PTEs (Pb, Cd, Cu, As, Fe, Zn, Ni, and total Cr) in leafy (mint, spinach, coriander, and lettuce) and tuberous (potato, carrot, radish, and onion) vegetables irrigated by wastewater. The studies observed in our paper were conducted in 19 countries. The PTEs concentrations were compared among studies and the human health risk was observed. According to the obtained meta-analysis results, PTEs concentrations (mg/kg) in vegetables were found in the following order Zn (34.216)> Cu (22.581)> Ni (14.056)> Pb (10.173)> Cr (8.308)> Fe(8.130)> As(1.881)> Cd (1.763). Hazard index for children was higher than that for adults and for both groups, the calculated HQ was higher than 1, which indicates that there is a health risk for the consumers. This study provides a comprehensive analysis that demonstrates the urgent necessity for treating PTE pollution in agricultural areas worldwide.

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.

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.

Non-destructive techniques for the determination of magnetic particle and element contents in grapevine leaves and soil as an eco-sustainable tool for environmental pollution assessment in the agricultural areas.

The concentration of magnetic particulate matter (PM) on the leaf surface (an indicator of current pollution) and topsoil (an indicator of magnetic PMs which have geogenic natural signal or historical pollution origin) was assessed in agricultural areas (conventional and organic vineyards). The main aim of this study was to explore whether magnetic parameters such as saturation isothermal remanent magnetization (SIRM) and mass-specific magnetic susceptibility (χ) can be a proxy for magnetic particulate matter (PM) pollution and associated potentially toxic elements (PTEs) in agricultural areas. Besides, wavelength dispersive X-ray fluorescence spectroscopy (WD-XRF) was investigated as a screening method for total PTE content in soil and leaf samples. Both magnetic parameters (SIRM and χ) pinpoint soil pollution, while SIRM was more suitable for evaluating magnetic PM accumulated on leaves. The values of both magnetic parameters were significantly (p < 0.01) correlated within the same type of sample (soil-soil or leaf-leaf), but not between different matrixes (soil-leaf). Differences between magnetic particles' grain sizes among vegetation seasons in vineyards were obtained by observing the SIRM/χ ratio. WD-XRF was revealed to be an appropriate screening method for soil and leaf total element contents in agricultural ambient. For a more precise application of WD-XRF leaf measurements, specific calibration using a similar matrix to plant material is required. In parallel, measurements of SIRM, χ, and element content (by WD-XRF) can be recommended as user-friendly, fast, and eco-sustainable techniques for determining magnetic PM and PTE pollution hotspots in agricultural ambient.

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.

Environmental pollution influence to soil-plant-air system in organic vineyard: bioavailability, environmental, and health risk assessment.

This study was performed in organic vineyard to assess integrated pollution in soil-plant-air system by potentially toxic elements (PTE). Concentrations of 26 PTE were determined in soil, grapevine, and air biomonitors (moss bags) using ICP-OES and ICP-MS. Environmental implication assessment of soil did not show pollution by PTE, except for B in samples collected in the middle of grapevine season (July). Despite low total Cd concentrations in soil, it has the highest influence on increase of environmental risk. Based on biological accumulation concentration (BAC), grapevine is not hyperaccumulator of PTE from soil. Advanced classification algorithm, Kohonen self-organizing map (SOM), was applied to compare environmental implications in organic with conventional vineyards. PTE concentrations were significantly lower in organic than conventional grapevine. PTE concentrations were higher in the outer (leaf and petiole) than in the inner grapevine parts (skin, pulp, and seed). Some airborne elements have an influence on outer grapevine parts, especially on leaves (ratio factor-RF > 1). Moss bag technique testified about lower enrichment of airborne elements compared with the conventional vineyard and urban microenvironments. Environmental and health risk assessments confirmed that organic production is harmless for field workers and grape consumers.

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.

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.

Integrated approach to environmental pollution investigation - Spatial and temporal patterns of potentially toxic elements and magnetic particles in vineyard through the entire grapevine season.

An integrated approach to the investigation of potentially toxic elements (PTEs) was applied to the soil and grapevine leaf samples collected from vineyard environment through the grapevine season. To investigate mobile and bioavailable concentrations of PTEs, six single extraction procedures and pseudo-total digestion were applied to the samples. The element concentrations in the samples were measured using inductively coupled plasma-optical emission spectrometry (ICP-OES) and inductively coupled plasma-mass spectrometry (ICP-MS). To assess atmospheric particle deposition, saturation isothermal remanent magnetisation (SIRM) was applied to the leaf samples. The obtained PTE concentrations in samples were used for calculating various ecological implications in the vineyard environment. The notable environmental pollution implications were estimated for As, B, Cd, Co, Cr, Cu, Mn, Ni and Sr. The environmental risk (RI) of the elements soluble under low-acid conditions influenced soil bioavailability risk. The most bioavailable elements from soil to leaves were Mn, Ni and Sr, followed by Cr and Cu. Cadmium and Co were strongly-bonded in the soil and were not bioavailable. The most suitable extractants for assessing bioavailability in the soil-leaf system were chelating agent Na2EDTA, and weak salt solutions CaCl2 and NH4NO3. The biological accumulation concentrations (BACs) of B, Ba, Cd, Co, Ni and Zn were decreasing in the leaves through the grapevine growing phases, that is contributed to the decreasing agrochemical application through the season. The BACs of Co, Cr, Sb and Pb, in July (veraison), were higher than in other phases, which indicate anthropogenic activities. According to correlations between biogeochemical index (BGI) and BAC, Cu and Na were mostly bioaccumulated from soil to leaves due to agrochemical applications, while bioaccumulation of B, Cd, Sb and Sr could be influenced by the other anthropogenic sources. Significant correlations between PTE concentrations and SIRM imply that leaves indicate Co, Cr and Ni air pollution in the vineyard environment.

Bioavailability of potentially toxic elements in soil-grapevine (leaf, skin, pulp and seed) system and environmental and health risk assessment.

Monitoring of potentially toxic elements in agricultural soil represents the first measure of caution regarding food safety, while research into element bioavailability should be a step forward in understanding the element transportation chain. This study was conducted in the grapevine growing area ("Oplenac Wine Route") for investigating element bioavailability in the soil-grapevine system accompanied by an assessment of the ecological implications and human health risk. Single extraction procedures (CH3COOH, Na2EDTA, CaCl2, NH4NO3 and deionised H2O) and digestion were performed to estimate the bioavailability of 22 elements (Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Ni, Pb, Sb, Sr, V and Zn) from the topsoil (0-30 cm) and subsoil (30-60 cm) to the grapevine parts (leaf, skin, pulp and seed) and wine. The extractants were effective comparing to the pseudo-total concentrations in following order Na2EDTA ˃ CH3COOH ˃ NH4NO3 ˃ CaCl2, H2O 2 h and 16 h. The most suitable extractants for assessing the bioavailability of the elements from the soil to the grapevine parts were CaCl2, NH4NO3 and Na2EDTA, but deionised H2O could be suitable, as well. The results showed that Ba was the most bioavailable element in the soil-grapevine system. Contamination factor implied a moderate contamination (1 < CF < 3) of the soil. The concentrations of Cr, Ni and Cd in the soil were above the maximum allowed concentrations. According to the biological accumulation coefficient (BAC), the grape seeds and grapevine leaves mostly accumulated Cu and Zn from the soil, respectively. Based on ratio factor (RF > 1), the influence of atmospheric deposition on the aerial grapevine parts (leaves and grape skin) was observed. Nevertheless, low adverse health risk effects (HI < 1 and R ≤ 1 × 10-6) were estimated for farmers and grape and wine consumers.

Assessment of species-specific and temporal variations of major, trace and rare earth elements in vineyard ambient using moss bags.

Since the methodological parameters of moss bag biomonitoring have rarely been investigated for the application in agricultural areas, two mosses, Sphagnum girgensohnii (a species of the most recommended biomonitoring genus) and Hypnum cupressiforme (commonly available), were verified in a vineyard ambient. The moss bags were exposed along transects in six vineyard parcels during the grapevine season (March‒September 2015). To select an appropriate period for the reliable 'signal' of the element enrichment in the mosses, the bags were simultaneously exposed during five periods (3 × 2 months, 1 × 4 months, and 1 × 6 months). Assuming that vineyard is susceptible to contamination originated from different agricultural treatments, a wide range of elements (41) were determined in the moss and topsoil samples. The mosses were significantly enriched by the elements during the 2-month bag exposure which gradually increasing up to 6 months, but Cu and Ni exhibited the noticeable fluctuations during the grapevine season. However, the 6-month exposure of moss bags could be recommended for comparative studies among different vineyards because it reflects the ambient pollution comprising unpredictable treatments of grapevine applied during the whole season. Although higher element concentrations were determined in S. girgensohnii than H. cupressiforme, both species reflected the spatio-temporal changes in the ambient element content. Moreover, the significant correlation of the element (Cr, Cu, Sb, and Ti) concentrations between the mosses, and the same pairs of the elements correlated within the species, imply the comparable use of S. girgensohnii and H. cupressiforme in the vineyard (agricultural) ambient. Finally, both the moss bags and the soil analyses suggest that vineyard represents a dominant diffuse pollution source of As, Cr, Cu, Ni, Fe, and V.

Assessment of major and trace element bioavailability in vineyard soil applying different single extraction procedures and pseudo-total digestion.

A different single extraction procedures (CH3COOH, Na2EDTA, CaCl2, NH4NO3, deionized water), and pseudo-total digestion (aqua regia) were applied to determine major (Al, Fe, K, Mn, Na, P, S, and Si) and trace (Cd, Co, Cr, Cu, Mo, Ni, Pb, V, and Zn) element bioavailability in a topsoil from the experimental vineyard ("Radmilovac", Belgrade, Serbia). For the first time, the extraction with deionized water during 16 h was tested as an alternative method for isolating bioavailable major and trace elements from the soil. Concentrations of the elements were determined by inductively coupled plasma - optical emission spectroscopy (ICP-OES). The extraction of Cu and S from the soil by deionized water during 16 h extracting, NH4NO3, and CaCl2 indicated that these elements could originate from the anthropogenic sources, such as fungicide. In addition according to the soil - plant experiment, performed as a preliminary experiment for future studies in vineyards, deionized water was recommended for isolation of bioavailable elements from grape seed and grape pulp; CH3COOH, Na2EDTA, CaCl2 and NH4NO3 for grape skin, while for assessment of leaf bioavailable elements from soil fraction, aqua regia was recommended. In addition, identification of similarities between the plant parts and the plant species were performed. Applying environmental risk assessment formulas, the most polluted vineyard parcel in the vineyard region "Radmilovac" was determined. The leaves of some grapevine species showed the high ability for accumulation some of the potentially toxic trace elements from the soil.

Moss bag biomonitoring of airborne toxic element decrease on a small scale: A street study in Belgrade, Serbia.

A database of potentially hazardous substances, necessary for estimating the exposure of humans to air pollutants, may be deficient because of a limited number of regulatory monitoring stations. This study was inspired by undeniably harmful effects of human long-term exposure to intense traffic emissions in urban area. Moss bag biomonitors were used to characterize spatial variation of airborne toxic elements near crossroads and two- and one-lane streets. The Sphagnum girgensohnii and Hypnum cupressiforme moss bags were exposed for 10 weeks to 48 sampling sites across Belgrade (Serbia) during the summer of 2014. In addition, oven-drying pretreatment of the moss bags was tested. During the experimental period, traffic flows were estimated at each site by counting the number of vehicles during the rush hours. The concentrations of 39 elements were determined in the moss samples. There was no significant difference between the results obtained for nontreated and oven-dried moss bags. For the majority of elements, the moss bags identified a common pattern of decrease in the concentration from crossroads to two- and one-lane streets. The exposed moss bags were enriched with Sb, Cu and Cr. The correlation coefficients (r=0.65-0.70) between the moss concentrations of Cr, Cu, Fe and Sb and the site-counted traffic flows also confirmed a dependence of the airborne element content on traffic emissions. A strong correlation with traffic flows makes Sb, Cu and Cr reliable traffic tracers.