Explainable extreme gradient boosting tree-based prediction of toluene, ethylbenzene and xylene wet deposition.

Current research suggests that, apart from photochemical reactions, toluene, ethylbenzene and xylene (TEX) removal from ambient air might be affected by atmospheric precipitation, depending on the concentrations and water solubility of the compounds, Henry's law, physico-chemical properties of the water, as well as the frequency and intensity of precipitation events. Nevertheless, existing knowledge of the role that wet deposition plays in biogeochemical cycles of volatile species remains insufficient, and this topic requires more scientific effort to be explored and understood. In this study, we employed the eXtreme Gradient Boosting tree ensemble for revealing TEX transfer from ambient air to rainwater, and applied a novel SHapley Additive exPlanations feature attribution framework to examine the relevance of the monitored parameters and identify key factors that govern wet deposition of TEX. According to the results, main impacts, including ambient air TEX concentrations, and rainwater and air temperatures, and occasional, but less important impacts, including wind speed, air pressure, turbidity, and total organic carbon, NO3-, Cl- and K+ rainwater concentration, shaped TEX partition between gaseous and aqueous phases during rain events.

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.

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.

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.

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.

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.

The first survey of airborne trace elements at airport using moss bag technique.

Air traffic represents an important way of social mobility in the world, and many ongoing discussions are related to the impacts that air transportation has on local air quality. In this study, moss Sphagnum girgensohnii was used for the first time in the assessment of trace element content at the international airport. The moss bags were exposed during the summer of 2013 at four sampling sites at the airport 'Nikola Tesla' (Belgrade, Serbia): runway (two), auxiliary runway and parking lot. According to the relative accumulation factor (RAF) and the limit of quantification of the moss bag technique (LOQT), the most abundant elements in the samples were Zn, Na, Cr, V, Cu and Fe. A comparison between the element concentrations at the airport and the corresponding values in different land use classes (urban central, suburban, industrial and green zones) across the city of Belgrade did not point out that the air traffic and associated activities significantly contribute to the trace element air pollution. This study emphasised an easy operational and robust (bio)monitoring, using moss bags as a suitable method for assessment of air quality within various microenvironments with restriction in positioning referent instrumental devices.

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.

Residential heating contribution to level of air pollutants (PAHs, major, trace, and rare earth elements): a moss bag case study.

In areas with moderate to continental climates, emissions from residential heating system lead to the winter air pollution peaks. The EU legislation requires only the monitoring of airborne concentrations of particulate matter, As, Cd, Hg, Ni, and B[a]P. Transition metals and rare earth elements (REEs) have also arisen questions about their detrimental health effects. In that sense, this study examined the level of extensive set of air pollutants: 16 polycyclic aromatic hydrocarbons (PAHs), and 41 major elements, trace elements, and REEs using Sphagnum girgensohnii moss bag technique. During the winter of 2013/2014, the moss bags were exposed across Belgrade (Serbia) to study the influence of residential heating system to the overall air quality. The study was set as an extension to our previous survey during the summer, i.e., non-heating season. Markedly higher concentrations of all PAHs, Sb, Cu, V, Ni, and Zn were observed in the exposed moss in comparison to the initial values. The patterns of the moss REE concentrations normalized to North American Shale Composite and Post-Archean Australian Shales were identical across the study area but enhanced by anthropogenic activities. The results clearly demonstrate the seasonal variations in the moss enrichment of the air pollutants. Moreover, the results point out a need for monitoring of air quality during the whole year, and also of various pollutants, not only those regulated by the EU Directive.

Active moss biomonitoring for extensive screening of urban air pollution: Magnetic and chemical analyses.

In this study, active magnetic biomonitoring of moss for particulate air pollution and an assessment of heavy metals and polycyclic aromatic hydrocarbons (PAHs) were performed for the entire metropolitan area of Belgrade. Two mosses, Sphagnum girgensohnii (a species of the most recommended biomonitoring moss genus) and Hypnum cupressiforme (a common moss in the study area), were used. During the summer of 2013, moss bags were exposed at 153 sampling sites, forming a dense network of sites. A type II regression model was applied to test the interchangeable use of the two moss species. Significantly higher levels of all measured pollutants were recorded by S. girgensohnii in comparison with H. cupressiforme. Based on the results, the mosses could not be interchangeably used in urban areas, except for the biomonitoring of Cu. Nevertheless, according to the relative accumulation factors obtained for both moss species, similar city zones related to high, moderate and low levels of air pollution were distinguished. Moreover, new pollution hotspots, omitted by regulatory monitoring, were identified. The results demonstrate that moss magnetic analysis represents an effective first step for obtaining an overview of particulate air pollution before more expensive chemical analyses. Active moss biomonitoring could be applied as a pragmatic approach for optimizing the representativeness of regulatory monitoring networks.

Active moss biomonitoring of small-scale spatial distribution of airborne major and trace elements in the Belgrade urban area.

In urban environments, human exposure to air pollutants is expected to be significantly increased, especially near busy traffic streets, street canyons, tunnels, etc. where urban topography and microclimate may additionally cause poor air conditions giving rise to pollution hotspots. As a practical and cost-effective approach, active moss biomonitoring survey of some major and trace element air pollution was performed in the Belgrade street canyons and city tunnel in 2011 with the aim to evaluate possibility of using Sphagnum girgensohnii moss bags for investigation of the small-scale vertical and horizontal distribution patterns of the elements. In five street canyons, the moss bags were hung at heights of about 4, 8 and 16 m, during 10 weeks, and also, for the same time, the moss bags were exposed in the tunnel, in front of and out of it. After the exposure period, the concentrations of Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sr, V and Zn in the moss were determined by inductively coupled plasma optical emission spectrometry. According to the results, in all street canyons, the vertical distribution patterns of the moss elements concentration (Al, Ba, Co, Cr, Cu, Ni, Pb, Sr, V and Zn) showed statistically significant decrease from the first to the third heights of bags exposure. In the tunnel experiment, from inner to out of the tunnel, for Al, Ba, Cd, Co, Cr, Cu, Fe, K and Zn, decreasing trend of concentrations was obtained. Significantly higher concentration of the elements was pronounced for the tunnel in comparison with the street canyons. The results indicate that the use of S. girgensohnii moss bags is a simple, sensitive and inexpensive way to monitor the small-scale inner city spatial distribution of airborne major and trace element content.