Sandra Škrivanj

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.

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.

Comparison of single extraction procedures and the application of an index for the assessment of heavy metal bioavailability in river sediments

Metals in sediments are present in different chemical forms which affect their ability to transfer. The objective of this body of work was to compare different extraction methods for the bioavailability evaluation of some elements, such as Ba, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Ni, Pb, V and Zn from Serbian river sediments. A bioavailability risk assessment index (BRAI) was used for the quantification of heavy metal bioavailability in the sediments. Actual and potential element availability was assessed by single extractions with mild (CaCl2 and CH3COONH4) and acidic (CH3COOH) extractants and complexing agents (EDTA). Aqua regia extraction was used for the determination of the pseudo-total element content in river sediments. In different single extraction tests, higher extraction of Cd, Cu, Zn and Pb was observed than for the other elements. The results of the single extraction tests revealed that there is a considerable chance of metal leaching from the sediments assessed in this study. When the BRAI was applied, the results showed a high risk of heavy metal bioavailability in Serbian river sediments.

Heavy Metals Fractionation in Agricultural Soils of Pb/Zn Mining Region and Their Transfer to Selected Vegetables

Improved understanding of the relationships between heavy metals fractionation in agricultural soils and biological uptake could be obtained by analysing samples of biota in parallel with sequential extraction of their grown media. The overall goals of this study were to identify the characteristics of metal fractions and their bioavailability to maize and potato plants in the agricultural land of the Ibar River in southern Serbia and northern Kosovo. The concentrations of Pb, Zn, Cd, Ni, Cr and Cu in soil and vegetable samples were determined by the ICP-OES method. Pb/Zn production and industrial waste disposal significantly increased the pseudo-total concentrations of heavy metals in the soil together with their mobile and potentially bioavailable amounts. The Pb concentrations in the vegetable samples were generally above the EU maximum permitted concentrations in foodstuffs. However, the concentrations of Zn, Ni, Cr and Cu in the vegetables were below the critical levels. The results of the present study indicated that the intensive industrial production of Pb/Zn over the years and permanent pollution were responsible for the environmental contamination by heavy metals in the study area, particularly by Pb and Zn. The quantity of the mobile and potentially bioavailable heavy metals in the studied soils threatens the quality of Zea mays L. and Solanum tuberosum L. crops, with a real risk that these elements could enter the food chain.

Distribution and mobility of heavy elements in floodplain agricultural soils along the Ibar River (Southern Serbia and Northern Kosovo). Chemometric investigation of pollutant sources and ecological risk assessment.

This work investigates the influence of a high-magnitude flood event on heavy elements (HEs) pollution and mobility in the agricultural soils along Ibar River in Southern Serbia and Northern Kosovo. The study area was one of the most important Pb/Zn industrial regions in Europe. Soil samples (n = 50) collected before and after the floods in May 2014 were subjected to the sequential extraction procedure proposed by the Community Bureau of Reference (BCR). The results indicated that the floods significantly increased not only the pseudo total concentrations of HEs in the soil but also their mobile and potentially bioavailable amounts. Moreover, higher concentrations (both pseudo total and potentially bioavailable) were found in the agricultural soils closer to the industrial hotspots. Principal component analysis and hierarchical cluster analysis successfully grouped the analyzed elements according to their anthropogenic or natural origin. The floods significantly increased the potential ecological risk of HEs associated with Pb/Zn industrial activities in the study area. The potential ecological risk of Cd after the floods was highest and should be of special concern.

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.

Arsenic in Agricultural Soils of a Historically Mined and Industrial Region of Southern Serbia and Northern Kosovo: Bioavailability and Uptake by Plants Species Zea mays L. and Solanum tuberosum L.

This article reports the results of a study focused on the presence and bioavailability of arsenic in agricultural soil in the mining and industrial regions of northern Kosovo and southern Serbia, as well as uptake and bioaccumulation of arsenic in two commonly cultivated plant species (Zea mays L. and Solanum tuberosum L.). This area was one of the most important mining districts in Europe. The collected soil samples were subjected to a modified BCR three-step sequential extraction procedure in order to investigate the chemical partitioning of arsenic in the soils. The general distribution of arsenic in various fractions was: exchangeable < reducible < oxidizable fractions. Highest concentrations of total arsenic in soil were found close to industrial facilities and tailing ponds. In addition, fluvisols were significantly more enriched with arsenic than soils at a distance from the river flows. The edible parts of the plant specimen showed different As contents, suggesting that these plant species have different propensities for the uptake and bioaccumulation of arsenic from soil.

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.