Determination of traces of copper and zinc in honeys by the solid phase extraction pre-concentration followed by the flame atomic absorption spectrometry detection

A simple and fast solid phase extraction procedure was developed to pre-concentrate traces of Cu and Zn prior to their determination in honey samples by flame atomic absorption spectrometry. The sample preparation included dissolution of honey samples and the passage (at 20 ml/min) of resulting 10 % m/v solutions (100 ml) through Dowex 50W?×?8-400 resin beds in order to quantitatively retain Cu and Zn and separate them from the glucose and fructose matrix. Enriched Cu and Zn traces were recovered with 5.0 ml of a 3.0 mol/l HCl solution and quantified by flame atomic absorption spectrometry. The procedure proposed was used to analyze sixty nine commercially available and freshly ripened honey samples coming from the Lower Silesia region (Poland). It enabled to measure Cu and Zn within the range of 0.01–1.42 and 0.03–15.38 μg/g, respectively, with precision better than 4 %. Accuracy, assessed on the basis of the recovery test and the comparison of results with those obtained using wet digestion and inductively coupled plasma optical emission spectrometry, was ranged from ?4 % to +6 %. Detection limits of Cu and Zn achieved with this method were 5 and 7 ng/g, respectively.     

A field screening test for the assessment of concentrations and mobility of potentially toxic elements in soils: a case study on urban soils from Rome and Novi Sad

The increasing demand for environmental pollution control results in the development and use of new procedures for the determination of dangerous chemicals. Simple screening methods, which can be used directly in the field for a preliminary assessment of soil contamination, seem to be extremely advantageous. In our laboratory, we developed and optimized a rapid test for a preliminary evaluation of both the concentration and the mobility of some potentially toxic metals in soils. This screening test consists of a single extraction of the soil sample with a buffer solution, followed by the titration of the extracted solution with dithizone to determine the contents of bi-valent heavy metals (such as Pb, Cu, Zn, and Cd). This screening method was then directly applied in the field during the sampling campaign in the framework of an Italian–Serbian collaborative project, finalized in the study of metal availability in soils. The results obtained in the field with the rapid test were compared with those obtained in the laboratory following the conventional procedure commonly used to evaluate metal bioavailability (diethylenetriaminepentaacetic extraction). Moreover, selected samples were analyzed sequentially in the laboratory using the standardized BCR three-step sequential extraction procedure. The screening test gave results conceptually in good agreement with those obtained via the BCR procedure. These preliminary data show that the proposed screening test is a reliable method for the preliminary rapid evaluation of metal total concentrations and of potential metal mobility in soils, supporting sampling activities directly in the field.     

Exposure to mixtures of organohalogen contaminants and associative interactions with thyroid hormones in East Greenland polar bears (Ursus maritimus)

We investigated the multivariate relationships between adipose tissue residue levels of 48 individual organohalogen contaminants (OHCs) and circulating thyroid hormone (TH) levels in polar bears (Ursus maritimus) from East Greenland (1999-2001, n=62), using projection to latent structure (PLS) regression for four groupings of polar bears; subadults (SubA), adult females with cubs (AdF_N), adult females without cubs (AdF_S) and adult males (AdM). In the resulting significant PLS models for SubA, AdF_N and AdF_S, some OHCs were especially important in explaining variations in circulating TH levels: polybrominated diphenylether (PBDE)-99, PBDE-100, PBDE-153, polychlorinated biphenyl (PCB)-52, PCB-118, cis-nonachlor, trans-nonachlor, trichlorobenzene (TCB) and pentachlorobenzene (QCB), and both negative and positive relationships with THs were found. In addition, the models revealed that DDTs had a positive influence on total 3,5,3'-triiodothyronine (TT3) in AdF_S, and that a group of 17 higher chlorinated ortho-PCBs had a positive influence on total 3,5,3',5'-tetraiodothyronine (thyroxine, TT4) in AdF_N. TH levels in AdM seemed less influenced by OHCs because of non-significant PLS models. TH levels were also influenced by biological factors such as age, sex, body size, lipid content of adipose tissue and sampling date. When controlling for biological variables, the major relationships from the PLS models for SubA, AdF_N and AdF_S were found significant in partial correlations. The most important OHCs that influenced TH levels in the significant PLS models may potentially act through similar mechanisms on the hypothalamic-pituitary-thyroid (HPT) axis, suggesting that both combined effects by dose and response addition and perhaps synergistic potentiation may be a possibility in these polar bears. Statistical associations are not evidence per se of biological cause-effect relationships. Still, the results of the present study indicate that OHCs may affect circulating TH levels in East Greenland polar bears, adding to the "weight of evidence" suggesting that OHCs might interfere with thyroid homeostasis in polar bears.     

Aporrectodea caliginosa, a suitable earthworm species for field based genotoxicity assessment?

There is a growing interest for the application of biomakers to field-collected earthworms. Therefore we have evaluated the usability of native populations of endogeic, widely distributed earthworm Aporrectodea caliginosa in the assessment of soil genotoxicity using the Comet assay. Validation of the Comet assay on earthworm coelomocytes has been established using commercially available Eisenia fetida exposed to copper, cadmium, and pentachlorophenol, along with A. caliginosa exposed to copper in a filter paper contact test. Neutral red retention time (NRRT) assay was conducted on copper exposed and field-collected earthworms. Significant DNA and lysosomal damage was measured using Comet and NRRT assays in native populations of A. caliginosa sampled from the polluted soils in the urban area in comparison to the earthworms from the reference site. The results of this study confirm the employment of A. caliginosa as a suitable species for the in situ soil toxicity and genotoxicity field surveys.     

Radionuclides in some edible and medicinal macrofungal species from Tara Mountain,Serbia

Edible and medicinal macrofungi used in human diet represent not only important sources of nutritive elements but toxic substances as well (heavy metals and radionuclides). Radioactivity levels of four radionuclides (⁴⁰K, ¹³⁷Cs, ²²⁶Ra, ²²⁸Ra) were determined in the basidiomata (fruiting bodies of a Basidiomycetes) of six lignicolous (Fomitopsis pinicola, Ganoderma applanatum, Hericium clathroides, Megacollybia platyphylla, Pluteus cervinus, Trametes gibbosa) and three mycorrhizal (Boletus luridus, Boletus sp. 1, Boletus sp. 2) species as well as their soil (wood) substrates by gamma spectrometry (high-resolution high-purity germanium (HPGe) detector). The aim was to investigate their ability for radionuclide absorption according to transfer factors (from soil and wood), to predict potential bioindicator species as well as species with potential risk for human use. Samples were taken during years 2011 and 2012, at two sites in forest ecosystem of Tara Mountain (Serbia). Observed concentration ranges per dry weight were as follows: 29–3,020 Bq/kg (⁴⁰K), 21.9–735 Bq/kg (¹³⁷Cs), 3–39 Bq/kg (²²⁶Ra), and 2.0–18 Bq/kg (²²⁸Ra). Obtained results indicate that the type of basidiome (fleshy/tough), most likely due to a different metabolic rate, has a very important role in radionuclide accumulation. The highest activity concentrations of all analyzed radionuclides were found in species with fleshy basidiomata—P. cervinus, H. clathroides, M. platyphylla, and Boletus species. A species-specific influence on radionuclide uptake was more prominent comparing to habitat differences and the role of fungal trophic mode. No significant variations were observed regarding radionuclide activity among the same fungal species from different sampling sites.