Monitoring of trace elements in honey from the Republic of Macedonia by atomic absorption spectrometry

Contents of Zn, Cu, Fe, Mn, Cd, Na, K, Ca and Mg in 123 honey samples from different regions of the Republic of Macedonia were determined by atomic absorption spectrometry. A microwave digestion system was applied for digestion of the samples. The mean content for the elements determined was found to be: 2.252, 0.696, 1.885, 1.752, 0.004, 29.52, 984.8, 40.11, 18.24 mg kg(-1) for Zn, Cu, Fe, Mn, Cd, Na, K, Ca and Mg, respectively. Based on a comparison of statistical parameters, the spatial distribution of particular elements in Macedonian honey and the results of factor analysis, two natural and one anthropogenic geochemical associations were identified. The natural geochemical associations (Mg, Mn, Ca, K and Fe, Zn, Ca, -K, -Na) are influenced mainly by lithology. The anthropogenic associations (Cd and -Cu) are mostly a result of metallurgical activities, namely lead production in the town of Veles.     

Organochlorine pesticides and polychlorinated biphenyls in surface soils of Novi Sad and bank sediment of the Danube River

The contents of 16 organochlorine pesticides (OCPs) and six so-called indicator polychlorinated biphenyls (PCBs) were determined in the surface zone (0–5 cm) of soil and sediment samples, taken from different locations in the city of Novi Sad, capitol of Vojvodina Province (North of the Serbia) covering residential and commercial area, recreational and arable zone. The total organochlorine pesticides concentration in soil varied from 2.63 to 31.78 ng g^?1 dry weight, while the level in sediment was 10.35 ng g^?1 dry weight. Maximum content of identified individual organochlorine pesticide in soil samples was 10.40 ng g^?1 dry weight for p, p-DDE in the market garden and 6.31 ng g^?1 dry weight for p, p'-DDT in sediment of the Danube River, although their application is restricted in Serbia. Some of investigated PCBs were identified only in the soil samples from a park-school backyard in the city downtown (0.32 ng g^?1 dry weight) and market garden (0.22 ng g^?1 dry weight), and also in sediment sample from left bank of the Danube River (0.41 ng g^?1 dry weight). Data of the OCPs and PCBs present in this study were compared with the ones found for soils and river sediments throughout the world, and with limit values set by soil and sediment quality guidelines. Also, correlation between the levels of certain pesticides and soil characteristics (organic matter, pH and clay content) was investigated.     

Changes of metal-induced toxicity by H2O2/NO modulators in Scenedesmus quadricauda (Chlorophyceae)

Effect of nitric oxide donor (sodium nitroprusside, SNP, 500 μM) or hydrogen peroxide scavenger (dithiothreitol, DTT, 500 μM) on cadmium (Cd) or copper (Cu) uptake (150 μM solutions) and toxicity using Scenedesmus quadricauda was studied. Combined treatments (Cd or Cu + DTT or SNP) usually ameliorated metal-induced toxicity at the level of pigments, proteins, and mineral nutrients in comparison with respective metal alone. Viability tests (MTT and TTC) showed the lowest values preferentially in Cu treatments, indicating higher toxicity in comparison with Cd. Cd showed low impact on amino acids while strong Cu-induced depletion was mitigated by DTT and SNP. Amount of ROS and NO showed the most pronounced responses in SNP variants being rather reciprocal than parallel and regulated ascorbate peroxidase activity. Blot gel analyses of hsp70 protein did not reveal extensive changes after given exposure period. Phenols were elevated by DTT alone while all Cu treatments revealed depletion. Total Cu content decreased while total Cd content increased in metal + SNP or metal + DTT. Subsequent experiment using lower Cd, SNP or DTT doses (10 and 100 μM) revealed concentration-dependent impact on Cd uptake. Overall, DTT was found to be more suitable for the amelioration of metal-induced toxicity.     

Geochemical investigation of potentially harmful elements in household dust from a mercury-contaminated site,the town of Idrija (Slovenia)

A comprehensive geochemical investigation of potentially harmful elements (PHEs) in household dust from the town of Idrija (Slovenia), once a world-famous Hg mining town that is now seriously polluted, was performed for the first time. After aqua regia digestion, the content of mercury (Hg), arsenic (As), cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), molybdenum (Mo), nickel (Ni), lead (Pb) and zinc (Zn) was measured. PHE-bearing particles were recognised and observed by scanning electron microscopy and energy-dispersive spectrometry before and after exposure to simulated stomach acid (SSA). Mercury binding forms were identified by Hg thermal desorption technique and gastric bioaccessible Hg was estimated after SSA extraction by ICP-MS. With regard to rural and urban background values for Slovenia, high Hg content (6–120 mg/kg) and slightly elevated As content (1–13 mg/kg) were found. Mercury pollution is a result of past mining and ore processing activities. Arsenic content is potentially associated with As enrichment in local soils. Four Hg binding forms were identified: all samples contained Hg bound to the dust matrix, 14 samples contained cinnabar, two samples contained metallic Hg (Hg⁰), and one sample assumingly contained mercury oxide. After exposure to SSA, Hg-bearing phases showed no signs of dissolution, while other PHE-bearing phases were significantly morphologically and/or chemically altered. Estimated gastric Hg bioaccessibility was low (<0.006–0.09 %), which is in accordance with identified Hg binding forms and high organic carbon content (15.9–31.5 %) in the dust samples.     

Lead,cadmium and mercury contents and bioaccumulation potential of wild edible saprophytic and ectomycorrhizal mushrooms,Croatia

ABSTRACT

Lead (Pb), cadmium (Cd), and mercury (Hg) contents in ten species of edible mushrooms in Trako??an, Croatia were determined. In addition, the similarity between the studied species was determined by cluster analysis. The caps and stipes of the fruiting bodies were analysed separately. The analyses were carried out by inductively coupled plasma - optical emission spectrometry (ICP-OES). The greatest mean lead concentrations of 1.91 and 1.60 mg kg ^?1 were determined in caps and stipes of Macrolepiota procera. The greatest mean concentrations of cadmium (3.23 and 2.24 mg kg^?1) were determined in caps and stipes of Agaricus campestris and of mercury (2.56 and 2.35 mg kg^?1) in Boletus edulis. In terms of the anatomical parts of the fruiting body (cap-stipe), a considerably greater concentration of the analysed elements was found in the cap for all mushroom species. According to calculated bio-concentration factors, all the examined species were found to be bio-accumulators of Cd and Hg. On the basis of the accumulation of the studied metals, great similarity of mushroom species belonging to the same genus and partial similarity of species of the same ecological affiliation was obtained by cluster analysis.     

Zero-valent iron particles for PCB degradation and an evaluation of their effects on bacteria,plants, and soil organisms

Two types of nano-scale zero-valent iron (nZVI-B prepared by borohydride reduction and nZVI-T produced by thermal reduction of iron oxide nanoparticles in H₂) and a micro-scale ZVI (mZVI) were compared for PCB degradation efficiency in water and soil. In addition, the ecotoxicity of nZVI-B and nZVI-T particles in treated water and soil was evaluated on bacteria, plants, earthworms, and ostracods. All types of nZVI and mZVI were highly efficient in degradation of PCBs in water, but had little degradation effect on PCBs in soil. Although nZVI-B had a significant negative impact on the organisms tested, treatment with nZVI-T showed no negative effect, probably due to surface passivation through controlled oxidation of the nanoparticles.

     

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.     

Characteristics and origin of the hydrogen sulphide spring water from the Split spa (Southern Croatia)

The objective of this paper is to study the hydrological characteristics and origin of the hydrogen sulphide spring water from the Split spa in Southern Croatia in 1987, 1988 and 2003. This paper presents the results of monitoring the content of chlorides and hydrogen sulphide as well as the temperature of the hydrogen sulphide spring water. Since the hydrogen sulphide content during the dry periods significantly differs from the hydrogen sulphide content during rainy periods, this paper also compares the results obtained for those two periods. Under the influence of great quantities of rainfall during cold periods (winter and the beginning of spring) the ratio between seawater and surface water changes and thus the reduction of chlorides and other minerals occurs. The lowered temperature also reduces hydrogen sulphide which can disappear completely. The concentration of 12‰ chlorides (76–94.4% days/year) and 12 mg/L hydrogen sulphide (66.7–88.9% days/year) has been taken as a limit value between water with a normal typical content and water in cold rainy periods. According to the monitoring results it can be concluded that hydrogen sulphide spring water consists of seawater and hydrogencarbonate surface water with a fairly constant content during dry periods while the hydrogencarbonate content increases during rainy periods.     

The Rengen Grassland experiment: bryophytes biomass and element concentrations after 65 years of fertilizer application

The Rengen Grassland Experiment in Germany, established in 1941, consists of the following fertilizer treatments applied under a two cut management: control, Ca, CaN, CaNP, CaNP-KCl, and CaNP-K₂SO₄. The aim of this study was (1) to identify effects of fertilizer application on biomass and species composition of bryophytes and (2) to investigate the impact of fertilizer application on macro- (N, P, K, Ca, Mg), micro- (Cu, Fe, Mn, Zn), and toxic (As, Cd, Cr, Pb, Ni) element concentrations in bryophyte biomass. In June 2006, Rhytidiadelphus squarrosus was the only bryophyte species recorded in the control. In treatment Ca, R. squarrosus was the dominant bryophyte species whereas Brachythecium rutabulum occurred sporadically only in a single plot of that treatment. The latter was the only bryophyte species collected in CaN, CaNP, CaNP-KCl, and CaNP-K₂SO₄ treatments. Dry matter accumulation of bryophytes was highest in the control (180 g m^???2) followed by Ca (46 g m^???2), CaNP (25 g m^???2), CaNP-KCl (15 g m^???2), CaNP-K₂SO₄ (9 g m^???2), and CaN (2 g m^???2) treatments. A negative correlation between biomass production of bryophytes and dry matter production of vascular plants was revealed up to a threshold value of 400 g m^???2. Above this limit, biomass production of bryophytes remained obviously unaffected by further increase in biomass production of vascular plants. A significant effect of treatment on As, Cd, Cr, Fe, Mn, Ni, Pb, P, Ca, Mg, K, and N concentrations was revealed. Concentrations of these elements were a function of amount of elements supplied with fertilizers. Bryophytes seem to be promising bio-indicators not only for airborne deposition of toxic element but also for fertilizer introduced as well.     

Distribution of heavy elements in urban and rural surface soils: the Novi Sad city and the surrounding settlements, Serbia

Concentrations of ten heavy elements (Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, and Zn), as well as the pH values, organic matter contents, and electrical conductivities were measured in the surface soil samples collected from 21 sites of urban areas in the city of Novi Sad, the second largest city in Serbia, its suburban settlement and the nearby villages. Range of the heavy element concentrations was from 0.16 mg/kg (for Hg) to 18,994 mg/kg (for Fe). Significantly higher Hg and Mn concentrations were observed in subgroups with rural and market garden samples in comparison to the subgroups with urban and grassland samples, respectively, while the contents of Pb found in the grasslands subgroup were significantly higher than in the subgroup with market garden soils. Only one sample of urban soil exceeded the maximum permissible value for Zn set by the relevant Serbian legislation. According to the Dutch soil quality standard, the Cd and Co concentrations in majority of the examined soils were higher than the target values for unpolluted soil. The content of Hg was above the target value in 52% of the samples, most of them belonging to the subgroup of market garden soils. The results for the Novi Sad city area were compared to the relevant data available for other cities in the Western Balkan Countries. Principal component analysis of data revealed seven outlying samples, while the rest of the analyzed samples were grouped together indicating similar heavy element patterns most probably due to mixed emission sources.