Trace elements in soils and food chains of the Balkan region

Abstract

The present review summarizes the available data on the concentration of trace elements (TEs) in soils and their availability to plants with a view to reflect the quality and safety of food and fodder crops. Most soils in western Balkan countries are not contaminated. However, soils around industrial centers and historical mining sites do create concern for food and feed safety. Also high concentrations of TEs are related to their geochemical original. For example, ultrabasic rocks and serpentinites in western Serbia and western Bosnia are very rich in chromium, nickel, magnesium, iron (Fe), and cobalt, and cover an area of 5200 km². High TE concentrations caused by anthropogenic activities are also reported. In vineyard soils in Croatia, concentrations of cadmium, copper (Cu), and zinc (Zn) were much higher than their background concentrations. On the other hand, TE deficiency in plants is also prevalent in the regions. For example, Zn and Fe deficiencies in eastern parts of Croatia and northern parts of Serbia, Cu deficiency in pasture and sheep's blood at Nisici Plateau of Bosnia and Herzegovina, and selenium (Se) deficiency almost in the whole region have been observed. Therefore, information on TEs' behavior and soil factors affecting their mobility and availability is highly needed in order to separate the areas of contamination and then propose agrotechnical measures to protect the entry of TEs into the food chain. Research is also required to assess the influence of agronomic management on TE supply to plants and for achieving a better utilization of essential TEs. Concentrations of Se in wheat in Serbia are so low that if people were fed exclusively with wheat, their daily requirements for Se would not be met. There is also a need for full implementation of new food safety regulations in the Balkan countries in accordance with the legislations of the European Union.     

Effects of root exudates and humic substances on weathering kinetics

The effect of complex natural organic ligands on the weathering kinetics of aluminum oxide was investigated in laboratory experiments. A peat-derived humic substance and root exudates obtained from ectomycorrhizal (Picea abies — Hebeloma crustuliniforme) and non-mycorrhizal Norway Spruce trees; and γ-Al₂O₃ were used as a model system. The experimental weathering rates are in accordance with a surface-controlled dissolution mechanism. The effect of the humic material on dissolution rates appears to depend on the degree of protonation of the humic (macro)molecules: we observed dissolution-enhancement or -inhibition at pH 3 and 4, respectively. Ectomycorrhizal exudates proved to be effective weathering agents at pH 4, as opposed to humic material and non-mycorrhizal exudates. Our results suggest that (i) the role of humic materials in mineral weathering and podzolization is different from what is commonly thought, and (ii) mineral weathering rates in the rhizosphere may be higher than in the bulk soil.     

Principal component analysis of trace elements in Serbian wheat

Trace elements (Cu, Fe, Pb, Hg, Cd, As, Mn, Zn) were analyzed quantitatively in 14 wheat samples collected from fields in all Serbian growing regions, harvested in 2002. Microelements were determined according to an atomic absorption spectrophotometric method. Principal component analyses (PCA) were performed on data matrices consisting of contents of trace elements in wheats (columns) and all Serbian wheat-growing regions (rows). It was found that four principal components account for 87.2% of the total variance in the data. The plot of component loadings showed significant groupings for concentration of some microelements. The component scores indicated the similarities among the Serbian wheat-growing regions. The loading plot reveals that there is no need to measure all of the variables to achieve the same classification. It is enough to measure one variable per group. Naturally, this conclusion is valid only within the limits of the present study of wheat grain samples from different parts of Serbia.     

How the deadwood of different tree species in various stages of decomposition affected nutrient dynamics?

Purpose

The aim of the study was to estimate how the deadwood of different tree species in various stages of decomposition affected nutrient dynamics.

Materials and methods

The deadwood of eight species (common alder, common aspen, common ash, silver fir, pedunculate oak, Norway spruce, common hornbeam and silver birch) was selected. Three logs from each species in the third, fourth and fifth decay classes were chosen for analysis. Wood in the third decay class was characterised by larger hard fragments, fragmented bark and no branches; in the fourth decay class, it was characterised by small pieces and a fragmented bark; and in the fifth decay class, it was characterised by a soft texture and no bark. The investigation was carried out in the Czarna Rózga Reserve in Central Poland. Tension lysimeters were installed under each log in the humus horizon. The water samples collected from tension lysimeters were chemically analysed in the laboratory. The water chemistry was analysed by means of ion chromatography using a DIONEX ICS 5000 unit.

Results and discussion

The leachate obtained from different tree species contained different ion concentrations. The high similarity of the concentration of total anions and statistically significant differences in the content of total cations were determined in the leachate from the wood of coniferous and deciduous species. The concentration of the cations increases with the advancement of the decomposition level. A general linear model analysis demonstrates that wood species and the decomposition classes are of equal importance in defining the ion composition of the filtrate leaching from deadwood.

Conclusions

Wood at the highest decomposition stage releases more ions to the surface soil layers than wood at the lower decay class. An exception from the rule is the wood of birch, which in the III decay class releases more ions than in its higher decay classes. When comparing the ionic composition of leachate released from wood of coniferous and deciduous tree species, the latter are characterised by higher cation concentrations in comparison with coniferous species. Among the deciduous species, wood of such species as ash, hornbeam, aspen, birch and alder has the most favourable effects on the soil surface horizons through its supply with ionic substances. The ash wood releases high amounts of calcium, hornbeam wood releases magnesium and sodium, and aspen releases calcium, potassium and nitrate anion. From the analysed coniferous species, fir wood has a more favourable effect in terms of ion release to soil than spruce wood.

     

Assessing heavy metal contamination in soils of the Zagreb region (Northwest Croatia) using multivariate geostatistics

The assessment of soil contamination and location of pollution sources represent a crucial issue in soil remediation. Topsoil samples were collected in the Zagreb area (Northwest Croatia) and the total contents of trace and major elements were determined. A multivariate geostatistical analysis was used to estimate soil chemical composition variability. Factorial Kriging Analysis (FKA) was used to investigate the scale-dependent correlation structure of some variables by modelling co-regionalization of ten chemical variables, co-kriging specific factors and mapping them. The FKA provided two regionalized factors at different spatial scales of variability: the first factor at shorter range for Zn, Pb, Cd, Cu and Ni indicated different sources of anthropogenic contamination, whereas Ca (mainly loading on the longer range factor) was related to the lithology and parent material composition. The methodology used has proved to be a useful tool to separate geological and anthropogenic causes of variation in soil heavy metal content and to identify common pollution sources.     

Chromosomal interchanges and phylogeny of some accessions of Triticum aestivum subsp. spelta

Summary The occurrence of chromosomal interchanges was studied in F1 hyrids in two diallel schemes, including nine accessions of Triticum aestivum subsp. spelta, originating from Iran, Europe and North Africa, and the common wheat variety Chinese Spring as a reference. Seven accessions of subsp. spelta differed in one translocation from Chinese Spring. The European accession Grey differed in one or perhaps two interchanges from the reference variety, and Iran 417a showed a difference of three interchanges with Chinese Spring. In total six or perhaps seven interchanges were observed. Thus the number of translocation events in subsp. spelta appeared to be low. One translocation was unique and occurred only in the accession from North Africa. Also one accession from Europe, the landrace Schwarzwald, possibly carried a unique translocation. In both diallels an interchange with a relatively low coefficient of multivalent realisation at first meiotic metaphase was observed in most accessions. The two extra translocations in Iran 417a are considered to be the result of more recent translocation events, whereas the possible second translocation in accession Grey showed such a low coefficient of multivalent realisation that its existence could be doubted.     

Potentially toxic elements in the riparian soils of the Sava River

Purpose

Riparian zone contamination is a growing problem for several European catchments due to high anthropogenic pressures. This study investigates As, Cd, Cr, Cu, Ni, Pb, and Zn concentrations in the Sava River riparian zone, characterized by wide agricultural areas, various geological substrates, and different types of industrial pollution. The accumulation and mobility of these elements were studied because they are listed as priority substances in the Water Framework Directive and environmental objectives for surface waters.

Materials and methods

Sampling was performed during the sampling campaign of the EU 7th FW-funded GLOBAQUA project in September 2015 during a low-water event. Soil samples were collected along the Sava River at 12 selected sampling sites, from a depth of 0–30 cm, at a distance of 10–15 m from the river bank. The extent of pollution was estimated by determining total and readily soluble element concentrations in the soils. Potential ecological risk and the source of the selected elements in the soils was determined using the enrichment factor (EF), potential ecological risk index (RI), and statistical methods such as the principal component analysis (PCA) and multiple linear regression analysis (MLRA).

Results and discussion

This study showed that concentrations of the selected elements increase along the Sava. In terms of origin, PCA and MLRA indicated that Cr and Ni in soils are predominantly lithogenic, while As, Cd, Pb, and Zn are both lithogenic and anthropogenic (ore deposits, industry, and agriculture). PCA singled out Cu since its origin in soil is most probably from specific point-source pollution. EF was generally minor to moderate for most of the examined elements, apart from Cu, for which the EF was significant at one sampling site. Overall ecological risk (RI) fell within the low-risk category for most sites, apart from Belgrade sampling site (BEO), where high total Cd content affected individual and overall ecological risk indicators, indicating Cd could represent a considerable ecological risk for the downstream riparian zone.

Conclusions

At downstream sites, there was a noticeable increase in PTE content, with Cd, Cr, Ni, and Zn exceeding the proposed threshold values for European soils, indicating rising contamination in riparian soils. In terms of the ecological risk, only Cd could pose a potential ecological threat for the downstream riparian zone.

     

Cabbage (Brassica oleracea var. capitata) as possible indicator of wartime metal and metalloid contamination in eastern Croatia (ICP-MS method)

Biomonitoring of the local population and environmental monitoring in eastern Croatia have revealed abnormalities in metal and metalloid distribution that could be related to war activities during the 1990s. The goal of this study was to determine whether there are differences in the concentrations of metals and metalloids by comparing locations of high and low-intensity combat activity; we also evaluated a possible connection between metal contamination in soil and in humans. We sampled 14 locations and measured the concentrations of 20 war related metals and metalloids (Al, As, B, Ba, Cd, Co, Cr, Cu, Fe, Hg, Li, Mg, Ni, Pb, Sb, Si, Sr, U, V and Zn). The results of principal components analysis showed two main clusters: locations Dopsin and Dalj (both characterized by high-intensity combat activity), where the concentrations of most elements (except Hg) were increased. Although the concentrations of metals and metalloids in cabbage samples collected in eastern Croatia did not exceed the maximum allowed values, the results of our study confirmed existance of environmental ‘hotspot’ with higher concentrations of war metals and metalloids. Our findings indicate that there is a possible common source and mechanism of transferring metals from the environment to the population.     

Spatial and vertical distribution of <Superscript>137</Superscript>Cs in soils in the erosive area of southeastern Serbia (Pčinja and South Morava River Basins)

Purpose

The area of southeastern Serbia, the P?inja and South Morava River Basins, is under the influence of very strong erosion, and the aim of this study was to investigate the vertical and spatial distribution of the ¹³⁷Cs in the eroded soils of this area.

Materials and methods

Vertical soil profiles were collected with 5-cm increments from the uppermost layer down to 20, 25, 30, 40, and 50 cm of depth, depending on the thickness of the soil layers, i.e., down to the underlying parent rocks. Measurements of ¹³⁷Cs activity concentration were performed by using the HPGe gamma-ray spectrometer ORTEC-AMETEK (34 % relative efficiency and high resolution 1.65 keV at 1.33 MeV for ⁶⁰Co), from its gamma-ray line at 661.2 keV.

Results and discussion

The mean ¹³⁷Cs activity concentration across all 18 soil profiles (for all soil layers) was found to be 20 Bq kg^?1. In the greatest number of soil profiles, the ¹³⁷Cs activity concentration was generally highest in the first soil layer (0–5 cm) and decreased with soil depth, while in a few soil profiles, the peak of either the ¹³⁷Cs activity concentration occurred in the second soil layer (5–10 cm) or the ¹³⁷Cs activity concentration was almost equal throughout the entire soil profile. The mean ¹³⁷Cs activity concentration in the first soil layer (0–5 cm) was found to be 61 Bq kg^?1, and the high coefficient of variation of 92 % pointed out high spatial variability and large range of the ¹³⁷Cs activity concentrations in the study area.

Conclusions

The obtained results indicate that in the greatest number of soil profiles, ¹³⁷Cs is present in the upper layers, with concentration decreasing with depth, as is typical in uncultivated soil. Its spatial distribution was very uneven among the surface soil layers of the investigated sites. One of the main reasons for such pattern of ¹³⁷Cs in the study area may be soil erosion. Additional investigations which would support this hypothesis are required.