Analysis of mosses and topsoils for detecting sources of heavy metal pollution: multivariate and enrichment factor analysis

In order to assess the contribution of emission sources to the pollution of areas remote from industrial facilities, a combined approach of enrichment factor analysis and multivariate statistics was used for detecting the origin of heavy metal pollution in the Zlatibor ecosystem, in Serbia. Samples of moss (Pleurozium schreberi, Hylocomium splendens, Scleropodium purum, Hypnum cupressiforme and Thuidum delicatulum) and of topsoil (0-5 cm) were collected in 2005. The concentrations of seven heavy metals (Cd, Cr, Cu, Mn, Ni, Pb and Zn) were determined in moss and soil samples by atomic absorption spectrometry. The results obtained by enrichment factor analysis and two multivariate statistical methods, principal component analysis and cluster analysis, enabled discrimination of the lithologic and anthropogenic sources of heavy metals in the mosses. Enrichment factors, calculated to evaluate the contribution to the metal content in moss from anthropogenic sources, revealed pollution of the investigated area by Cd and Pb, originating from long-range transport and fossil fuel burning.     

Trampling impact on vegetation of embryonic and stabilised sand dunes in Montenegro

Trampling is one of the human activities that are harmful for plant species and communities of sand dune ecosystems. The aim of this study was to compare the vegetation of embryonic and shifting Ammophila sand dunes with and without fencing to limit trampling. Fenced sand dunes appeared to be richer in species but differences were more prominent in embryonic sand dunes. Some species (Cakile maritima, Pancratium maritimum) were missing on trampled embryonic dunes. The positive impact of trampling exclusion on embryonic sand dunes was indicated by a lowered slope in a Whittaker graph as well as by rarefaction curves that showed higher species richness on the lower slope. Changes in the vegetation of more stabilised shifting Ammophila sand dunes due to trampling are not evident, although species composition is also impoverished. Fencing of parts of sand dunes proved to be an effective measure for vegetation conservation. In addition to physical exclusion of visitors, fences can also have symbolic value for raising public awareness.     

Sugar beet ( L.) growth reduction caused by hydrochar is related to nitrogen supply

Hydrothermal carbonization allows rapid conversion of biomass into a carbon-rich, lignite-like product (hydrochar). It is assumed to have beneficial effects on soil properties and plant growth, but detailed studies are lacking, especially in the field. The objective of our study was to investigate the effect of hydrochar incorporated into arable soils on soil mineral nitrogen (N) content and sugar beet growth. In 2010-2011, a field and a pot trial were conducted. Hydrochars (field: 10 Mg ha; pot: equivalent to 30 Mg ha) processed from sugar beet pulp (HSP) and beer draff (HBD) were tested against an untreated control. As a second factor, mineral nitrogen (N) fertilizer level (field: 0, 50, 100, 150 kg N ha; pot: 0, 100, 200 mg N kg soil) was varied. In both trials, hydrochars reduced initial sugar beet growth, especially when hydrochar with a high C/N ratio (38, HSP) was combined with a low N fertilizer level; high N supply partly compensated for the reduced seedling growth. Without N fertilization, no extractable N was present at the end of the pot trial in the HSP treatment, whereas in HBD even more N was extracted than in the control. This suggests remineralization of previously immobilized N when hydrochar with a low C/N ratio was applied (16, HBD). In the field, beet yield was equal at the high N fertilizer level in HSP and at all N levels in HBD treatment. Our results suggest that hydrochar can decrease plant-available N due to N immobilization. Other potential causes for the observed early growth reduction need to be studied more in detail.     

The electronic properties of trimethylnaphthalenes as properties for the prediction of biodegradation rates: ab initio and DFT study

There is little information on trimethylnaphthalenes (TMNs) which are constituents of diesel fuel and bitumen emissions. In this study, a theoretical investigation of the electronic properties of all trimethylnaphthalene (TMN) isomers and their relation to biodegradation are presented. Equilibrium geometries, ionization potentials (IPs), electron affinities (EAs), dipole moments and electronic dipole polarizabilities of TMN isomers calculated by ab initio and Density Functional Theory (DFT) methods are reported. Polarizability and dipole moment computations have been performed in gas and in water solution using the polarizable continuum model (PCM). The results obtained show that the IP value varies little along the series of isomers while averaged static dipole polarizabilities (〈α〉) increase on passing from α,α,α-TMN to β,β,β-TMN isomers. This indicates that the binding affinity between TMNs and active site of bacterial enzymes is mainly determined by dispersive and inductive effects. Therefore, the computed polarizability values of TMNs can be used as predictors of the rates of biodegradation of TMNs.     

Seasonal and spatial variations of Po and Pb activity concentrations in Mytilus galloprovincialis from Croatian coast of the Adriatic Sea

Results of 2 years monitoring of ²¹⁰Po and ²¹⁰Pb activity concentrations in soft tissue of the species Mytilus galloprovincialis from Croatian part of the Adriatic coast are presented. The samples were collected at thirteen coastal stations (some of which are also a part of the Mediterranean Mussel Watch Project) in spring and autumn of 2010 and 2011. The collected mussels were ranging between 4 cm and 6 cm in shell length. After sample pre-treatment lead and polonium were radiochemically separated on Sr resin. ²¹⁰Po was determined by alpha-particle spectrometry and ²¹⁰Pb was determined, via ²¹⁰Bi, by a low-level gas proportional counter. The results of ²¹⁰Po activity concentrations were found to vary between (104 ± 11) and (1421 ± 81) Bq kg⁻¹ dry weight while ²¹⁰Pb activity concentrations were much lower and in range (8.2 ± 5.3)–(94.1 ± 29.8) Bq kg⁻¹ dry weight. Higher ²¹⁰Po and ²¹⁰Pb activity concentrations were determined in spring period. The inter-site differences seen in their activity concentrations can be due to natural background levels of sites. The ²¹⁰Po/²¹⁰Pb activity concentration ratios in all cases exceeded unity for all mussel samples and ranged between 4.0 and 47.9.     

Assessment of GC–MS response of selected pesticides in apple matrices related to matrix concentration

A uniform analyte response is required for GC–MS analysis in order to obtain acceptable quantitative results. The response of pesticides in complex matrices is susceptible to variation due to the interactions of co-extractives, both with pesticides or with GC–MS system. This study was conducted to determine the magnitude of the interactions, called matrix effect, and their behavior with the matrix dilution. The response of pyrimethanil (4,6-dimethyl-N-phenylpyrimidin-2-amine), cyprodinil (4-cyclopropyl-6-methyl-N-phenylpyrimidin-2-amine), trifloxystrobin (methyl-(2Z)-2-methoxyimino-2-[2-[[(E)-1-[3(trifluoromethyl)phenyl]ethylidene amino]oxymethyl]phenyl]acetate) and bifenthrin(2-methyl-3-phenylphenyl)methyl-3-[(Z)-2-chloro-3,3,3-trifluoroprop-1-enyl]-2,2-dimethylcyclopropane-1-carboxylate), used in apple crops protection, was evaluated in different concentrations of peel and flesh extracts of Granny Smith, Golden Delicious and Demi Rouge, selected as representatives of different matrix types. The matrix effect ranged from ?0.05 to 146.14%, depending on matrix type and pesticide. The highest response variation was observed in extracts of Granny Smith—an enhancement in flesh and suppression in peel extract. With the dilution, the matrix effect decreased with different magnitudes, but for Granny Smith peel extract an inverted effect was observed. The presence of the matrix effect in GC–MS pesticides analysis was obvious, requiring the application of matrix-matched calibration in quantification procedures for each variety, with calibration standards matched by the matrix concentration.     

Multi-criteria forest road network planning in fire-prone environment: a case study in Serbia

This paper presents a multi-criteria selection of the best forest road network with the aim of achieving effective preventive and timely repressive protection against forest fires. The research was carried out in national park (NP) “Tara” at a site which is under constant threat of fire. Four variants of the forest road network were designed and analyzed against seven criteria, and the best variant was selected using entropy weight coefficients (EWC) method. The importance of these seven criteria was studied by the management of the NP “Tara.” The greatest importance was given to the criteria relating to the cost of construction and maintenance of permanent and temporary roads (47% of the total value of all criteria). The EWC method did not select the variant based on the lowest costs of construction and maintenance as the best option, but the variant whose location was the most suitable for effective defense against forest fires.     

Direct N2O emission from agricultural soils in Poland between 1960 and 2009

Nitrogen fertilization (N) is commonly known as a main source of direct nitrous oxide (N₂O) emission from agricultural soils. An area of 38 % of the total land surface of Poland was covered by agricultural soils in 2009. In this paper, we aimed at analyzing data regarding the land exploitation for 13 selected subareas of Poland between 1960 and 2009. Seven out of the 13 subareas studied are located in the West (area A), and six subareas are located in southeast of Poland (area B). The total area covered by large farms (>20 ha) differed largely, between area A (10.6 %) and area B (0.9 %) in 2009. Both areas varied in terms of the amount of fertilizers used annually, average crop yield and crop structure. Average direct emissions of N₂O from agricultural soils were 1.66 ± 0.09 kg N₂O–N ha^?1 a^?1 for area A, 1.39 ± 0.07 kg N₂O–N ha^?1 a^?1 for area B and 1.46 ± 0.07 kg N₂O–N ha^?1 a^?1 for the whole country between 1960 and 2009.     

Malondialdehyde and heavy metal concentrations in tissues of wild boar (Sus scrofa L.) from central Croatia

The aim of this research was to assess the degree of heavy metal (cadmium, lead and mercury) contamination of wild boars from central Croatia and thereby conduct further tests to connect the contamination to oxidative stress occurrence. The highest cadmium concentration was noticed in the kidneys of older boars, the lead concentration was approximately the same in the liver and kidneys, but it was much higher than the concentration in the muscles, while the highest mercury concentration was measured in the kidneys of all wild boars. The correlation between the malondialdehyde (MDA) and the heavy metal concentrations was higher in tissue samples taken from younger animals (1 to 3 years of age) than in the tissue samples taken from older animals (5 to 6 years of age). In the kidneys of all wild boars there was a statistically significant connection between the MDA and cadmium concentration; in the kidneys of younger wild boars there was a statistically significant connection between the MDA and lead concentration. Further research on this topic should focus on MDA potential to find its use, not only as a contamination biomarker in the area of ecotoxicology, but also in the evaluation of the hygienic acceptability of animal products.     

Cadmium effects on the fitness-related traits and antioxidative defense of Lymantria dispar L. larvae

Cadmium, like many other pollutants, is nondegradable and can be accumulated by Lymantria dispar at a level that affects fitness components, physiology, and development, which could indicate presence of environment pollution by heavy metals. The cadmium effect on fitness-related traits in the third, fourth, fifth, and sixth instar of L. dispar L. was determined. Furthermore, activities of the following antioxidative defense components after the larvae had been fed on the artificial cadmium-supplemented diet (50 μg Cd/g dry food) were assessed: superoxide dismutase (SOD), catalase (CAT), ascorbate peroxidase (APOX), total glutathione amount (GSH), glutathione-S-transferase (GST), glutathione reductase (GR), and the amount of free sulfhydryl (SH) groups. Statistically significant delay of development in the fourth, fifth, and sixth instar and decrease of the larval mass in the third and fourth instar were estimated after the exposure to cadmium through food in comparison to the control. There were no changes in SOD activity of cadmium-treated larvae. Significantly lower CAT, APOX, and GR activities were recorded in the third, fifth, and in the third instar, respectively. At the same time, higher activity was recorded in the sixth instar, while GST activity was higher in the third. GSH content was significantly lower during all instars after treatment but the amount of SH groups was higher in older larvae. The strategy of antioxidative defense and the adjustment or modulation of fitness-related traits in presence of cadmium was dependent on the age of larvae in L. dispar, which might be used in early metal risk assessment in Lepidoptera and other insects.