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.

The Effect of Heavy Industry on Air Pollution Studied by Active Moss Biomonitoring in Donetsk Region (Ukraine).

The active moss biomonitoring technique was applied to assess the environmental pollution in the Donetsk region and to compare the biomonitoring capacity of acrocarpous (Ceratodon purpureus) and pleurocarpous (Brachythecium campestre) moss transplants. Moss bags were exposed for 6 months in the surroundings of two steelworks, a power station, and two parks. The concentrations of 19 elements were determined in the moss transplants by neutron activation analysis and atomic absorption spectrometry. Various environmental indices-relative accumulation factor, contamination factor, pollution load index, enrichment factor, and ecological risk index-were used to quantitatively assess the degree of ambient contamination. The RAF values indicate that the most prevalent elements in Brachythecium campestre and Ceratodon purpureus were Na, Al, Ca, Fe, Ti, V, Cr, Mn, Co, Ni, Zn, Ba, Sr, Pd, and Cd. The results showed a significant difference between metal accumulation by Ceratodon purpureus and Brachythecium campestre indicating various mechanisms of uptake. All elements were highly correlated in Ceratodon purpureus. The main air pollution sources in the region are the Zuivska power station (Zuivska TES), Donetsk Metallurgical Plant, and Yenakiieve Iron and Steel Works.

Elemental characterization of general aviation aircraft emissions using moss bags.

In light of growing concern and insufficient knowledge on the negative impact of aircraft emissions on environmental health, this study strives to investigate the air burden of major and trace elements caused by general aviation, piston-engine, and turboprop aircraft, within the vicinity of Eskisehir Hasan Polatkan Airport (Eskisehir, Turkey). The levels of 57 elements were investigated, based on moss bag biomonitoring using Sphagnum sp., along with chemical analyses of lubrication oil and aviation gasoline fuel used in the aircraft's operations. Five sampling sites were selected within the vicinity of the airport area to capture spatial changes in the concentration of airborne elements. The study demonstrates that moss bag biomonitoring is a useful tool in the identification of differences in the air burden by major and trace elements that have concentrated downwind of the aircraft emission sources. Moreover, pollutant enrichment in the Sphagnum moss bags and elemental characterization of oil/fuel are in agreement suggesting that Pb, followed by Cd, Cu, Mo, Cr, Ni, Fe, Si, Zn, Na, P, Ca, Mg, and Al are dominant elements that shaped the general aviation aircraft emissions.

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.

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.

Chemometrics in biomonitoring: Distribution and correlation of trace elements in tree leaves.

The concentrations of 15 elements were measured in the leaf samples of Aesculus hippocastanum, Tilia spp., Betula pendula and Acer platanoides collected in May and September of 2014 from four different locations in Belgrade, Serbia. The objective was to assess the chemical characterization of leaf surface and in-wax fractions, as well as the leaf tissue element content, by analyzing untreated, washed with water and washed with chloroform leaf samples, respectively. The combined approach of self-organizing networks (SON) and Preference Ranking Organization Method for Enrichment Evaluation (PROMETHEE) aided by Geometrical Analysis for Interactive Aid (GAIA) was used in the interpretation of multiple element loads on/in the tree leaves. The morphological characteristics of the leaf surfaces and the elemental composition of particulate matter (PM) deposited on tree leaves were studied by using scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS) detector. The results showed that the amounts of retained and accumulated element concentrations depend on several parameters, such as chemical properties of the element and morphological properties of the leaves. Among the studied species, Tilia spp. was found to be the most effective in the accumulation of elements in leaf tissue (70% of the total element concentration), while A. hippocastanum had the lowest accumulation (54%). After water and chloroform washing, the highest percentages of removal were observed for Al, V, Cr, Cu, Zn, As, Cd and Sb (>40%). The PROMETHEE/SON ranking/classifying results were in accordance with the results obtained from the GAIA clustering techniques. The combination of the techniques enabled extraction of additional information from datasets. Therefore, the use of both the ranking and clustering methods could be a useful tool to be applied in biomonitoring studies of trace elements.

The novel approach to the biomonitor survey using one- and two-dimensional Kohonen networks.

To compare the applicability of the leaves of horse chestnut (Aesculus hippocastanum) and linden (Tilia spp.) as biomonitors of trace element concentrations, a coupled approach of one- and two-dimensional Kohonen networks was applied for the first time. The self-organizing networks (SONs) and the self-organizing maps (SOMs) were applied on the database obtained for the element accumulation (Cr, Fe, Ni, Cu, Zn, Pb, V, As, Cd) and the SOM for the Pb isotopes in the leaves for a multiyear period (2002-2006). A. hippocastanum seems to be a more appropriate biomonitor since it showed more consistent results in the analysis of trace elements and Pb isotopes. The SOM proved to be a suitable and sensitive tool for assessing differences in trace element concentrations and for the Pb isotopic composition in leaves of different species. In addition, the SON provided more clear data on seasonal and temporal accumulation of trace elements in the leaves and could be recommended complementary to the SOM analysis of trace elements in biomonitoring studies.

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.