Water as a mild extractant of metals and metalloids from the samples of the selected certified reference materials and subsequent multi-elemental quantification by ICP-AES.

An assessment of mobility and bioavailability of trace elements present in the soil requires the determination of these elements in soil samples by an appropriate methodology. In such a context, the use of mild extraction reagents-such as water-is considered to be appropriate. On the other hand, performing an analysis of a reference material together with real samples is recommended in order to control the quality of analytical procedure. The quantification of 27 analytes in aqueous extracts of the soil CRMs samples is described. The methodology consisted of single-step extraction of analytes by deionized water (m/v = 1/10) with their subsequent direct determination by inductively coupled plasma-atomic emission spectrometry (ICP-OES). Three certified reference materials (CRM) for soils have been selected as model samples: NCS DC 77302 (alias GBW 07410), Metranal-31, and Metranal-33. Although the recoveries of the selected elements obtained by water extractions are very low (i.e., the values usually do not exceed 1%), the results obtained in this study reveal the elements that by means of ICP-OES can be quantified in the water extracts of unpolluted soils are as follows: Al, Ba, Ca, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, P, S, Sr, Ti, and V. However, ICP-OES is not sensitive enough to quantify the elements As, Be, Cd, Co, Pb, Sb, Se, Tl, and Zn that are present in the water extracts of clean soil samples in too low mass fractions. The results obtained in this paper are useful for future uses of the three tested CRMs, in the cases of the extraction of the analytes by deionized water at room temperature.

Assessment of the trace element distribution in soils in the parks of the city of Zagreb (Croatia).

This paper presents the results of the preliminary testing of the selected trace elements in the soils of several parks in the city of Zagreb, Republic of Croatia. In each park, the samples were taken from several points-at various distances from the roads. The samples were taken at two different depths: 0-5 and 30-45 cm. Composite samples were done for each sampling point. Microwave-assisted wet digestion of the soil samples was performed and the determination by ICP-AES technique was done. Results obtained for Al, As, Ba, Mn, Ti, V, and K are in a good agreement with the results published in the scientific literature so far. The mass fraction values of Cd, Cr, Cu, Ni, Pb, and Zn are somewhat higher than the maximum values given in the Croatian Directive on agricultural land protection against pollution. Be, Mo, Sb, Se, and Tl in the samples were present in the concentrations that are lower than their method detection limit values.

Multi-elemental Analysis, Pattern Recognition Techniques of Wild and Cultivated Rosehips from Serbia, and Nutritional Aspect.

Twenty-six major and trace elements, in the seed and the mesocarp of wild and cultivated rosehips from different locations in Serbia, were quantified by means of inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The cultivated rosehip was investigated for the first time. In both wild and cultivated rosehips, the most abundant elements were K and Ca. Among trace elements, Mn (in both seed and mesocarp); Fe (in seeds); and B, Ba, and Sr (in mesocarp) were quantified in the highest concentrations. The higher content of Cu, K, Mn, P, and S in the seed of cultivated rosehip, as well as Ca, Mg, and Sr in the mesocarp of wild rosehip, was observed, both significant at p < 0.05. Additionally, differences between the seed and the mesocarp of studied rosehip were noticed in the content of B, Cu, Fe, K, Ni, P, S, Sr, and Ti (p < 0.05). Nutritional assessment revealed that both wild and cultivated rosehips are a valuable source of essential elements (Ca, Cu, K, Mg, Mn, and P). The absence of toxic and potentially toxic elements additionally contributes to the quality of studied Serbian rosehip. A high impact of factors such as variety, location, as well as their interaction on the content of elements in cultivated rosehip mesocarp and seed was observed. Pattern recognition techniques, principal component analysis (PCA), and hierarchical cluster analysis (HCA) were applied in order to provide insight into similarities among the analyzed samples.

Ecotoxicological effects of aluminum and zinc on growth and antioxidants in Lemna minor L.

The present study aimed at investigating effects of zinc and aluminum (0.15 and 0.3mM) in duckweed (Lemna minor L.) over a 15-day period. High bioaccumulation of both metals was accompanied by an increase in dry weight under higher metal treatments. Antioxidant response was observed under both metal stresses, with large increases in superoxide dismutase and peroxidases. Catalase activity declined only in duckweed exposed to Zn while lipid peroxidation as well as H(2)O(2), proline and ascorbate levels increased. The results suggest induction of oxidative stress under both aluminum and zinc toxicity, and also demonstrate duckweed's capacity to upregulate its antioxidative defense. Additionally, Zn was found to be more toxic than Al to duckweed for the concentrations applied. Due to its high bioaccumulation potential and tolerance via increased antioxidant capacity, duckweed has a potential for phytoremediation of water bodies polluted by low levels of zinc and aluminum.

Oxidative stress and DNA damage in broad bean (Vicia faba L.) seedlings induced by thallium.

Thallium (Tl) is a metal of great toxicological concern because it is highly toxic to all living organisms through mechanisms that are yet poorly understood. Since Tl is accumulated by important crops, the present study aimed to analyze the biological effects induced by bioaccumulation of Tl in broad bean (Vicia faba L.) as well as the plant's antioxidative defense mechanisms usually activated by heavy metals. Thallium toxicity was related to production of reactive oxygen species in leaves and roots of broad bean seedlings following short-term (72 h) exposure to thallium (I) acetate (0, 0.5, 1, 5, and 10 mg/L) by evaluating DNA damage and oxidative stress parameters as well as antioxidative response. The possible antagonistic effect of potassium (K) was tested by combined treatment with 5 mg/L of Tl (Tl+) and 10 mg/L of potassium (K+) acetate. Accumulation of Tl+ in roots was 50 to 250 times higher than in broad bean shoots and was accompanied by increase in dry weight and proline. Despite responsive antioxidative defense (increased activities of superoxide dismutase, ascorbate peroxidase, and pyrogallol peroxidase), Tl+ caused oxidative damage to lipids and proteins as evaluated by malondialdehyde and carbonyl group levels, and induced DNA strand breaks. Combined treatment caused no oxidative alternations to lipids and proteins though it induced DNA damage. The difference in Tl-induced genotoxicity following both acellular and cellular exposure implies indirect DNA damage. Results obtained indicate that oxidative stress is involved in the mechanism of Tl toxicity and that the tolerance of broad bean to Tl is achieved, at least in part, through the increased activity of antioxidant enzymes.

Preliminary assessment of total dissolved trace metal concentrations in Sava River water.

This study provides the preliminary data set for total dissolved trace metal concentrations in the surface water of the Sava River in Croatia and the assessment of Sava River water quality status. The highest levels of total dissolved metals were observed for Fe, Mn, and Zn (12.6 +/- 7.8 mirog L(-1), 3.44 +/- 3.95 mirog L(-1), and 2.27 +/- 1.53 mirog L(-1), respectively), the intermediate concentrations for Ni, Cu, and Cr (0.59 +/- 0.14 mirog L(-1), 0.54 +/- 0.14 mirog L(-1), and 0.32 +/- 0.06 mirog L(-1), respectively), and the lowest levels for Co, Pb, and Cd (0.064 +/- 0.022 mirog L(-1), 0.055 +/- 0.051 mirog L(-1), and 0.011 +/- 0.004 mirog L(-1), respectively). The results refer to the grab water samples taken at five sites in the period from March to June, 2006. For four trace metals (Mn, Pb, Zn, and Fe), the high temporal variability within one season was observed. It can present a problem for reliable evaluation of total dissolved concentrations of these metals in the river water, if the assessment is based on the occasional grab water sampling. The comparison of results obtained in this study with previously reported data for several unpolluted rivers indicated that Sava River water reflects a certain anthropogenic impact. However, according to the levels proposed by European regulations, it still can be classified as water containing total dissolved trace metals in concentrations not significantly above the natural level.

The first example of multi-elemental analysis of water samples from urban monumental fountains-a case study from Zagreb (Croatia).

Water fountains are usually present in the urban public places and often draw the attention of citizens and tourists. Their water is often, in various ways, used by adults and children, but water from fountains is not usually a subject of researchers' interest. This paper describes the analytical procedure and the results of the multi-elemental characterisation of the waters from the selected public water fountains in the city of Zagreb, Republic of Croatia. Twenty-eight chemical elements (Al, As, B, Ba, Be, Cd, Co, Cr, Cu, Fe, Li, Mn, Mo, Ni, P, Pb, S, Sb, Se, Sr, Ti, Tl, V, Zn and Ca, K, Mg and Na) were quantified by means of ICP-AES technique. In addition to the multi-elemental analysis, determination of pH values was performed too. Pearson's correlation coefficients suggest that Al, Cu, Fe, Mn and Pb originate from the plumbing system and their leaching is strongly negatively correlated with the pH values of the tested samples. On the other hand, alkali and alkaline-earth metals as well as Mo, Ti, Zn and B, P and S are most probably of a natural origin in the water samples tested in this study. The results lead to the conclusions that (i) trace and major element content in squirt of a monumental water fountain is analogous to their content in water of the same origin and (ii) a pool of a fountain which is made of a high-quality stone, in the context of the herein performed testings, generally does not affect the quality of water which is contained in it.

alpha(v)beta(3) Integrin-mediated drug resistance in human laryngeal carcinoma cells is caused by glutathione-dependent elimination of drug-induced reactive oxidative species.

As a model for determination of the role of integrins in drug resistance, we used alpha(v)beta(3) integrin-negative human laryngeal carcinoma cell line (HEp2) and three HEp2-derived cell clones with a gradual increase of alpha(v)beta(3) integrin expression. The alpha(v)beta(3) integrin expression protects cells from cisplatin, mitomycin C, and doxorubicin. In HEp2-alpha(v)beta(3) integrin-expressing cells, the constitutive expression of Bcl-2 protein and the level of glutathione (GSH) were increased compared with HEp2 cells. Pretreatment of HEp2-alpha(v)beta(3) integrin-expressing cells with an inhibitor of GSH synthesis, buthionine sulfoximine (BSO), decreased the level of GSH and partially reverted drug resistance to all above-mentioned drugs, but it did not influence the expression of Bcl-2. Sensitivity to selected anticancer drugs did not change with overexpression of Bcl-2 in HEp2 cells, nor with silencing of Bcl-2 in HEp2-alpha(v)beta(3) integrin-expressing cells, indicating that Bcl-2 is not involved in resistance mechanism. There was no difference in DNA platination between HEp2 and HEp2-alpha(v)beta(3) integrin-expressing cells, indicating that the mechanism of drug resistance is independent of cisplatin detoxification by GSH. A strong increase of reactive oxidative species (ROS) formation during cisplatin or doxorubicin treatment in HEp2 cells was reduced in HEp2-alpha(v)beta(3) integrin-expressing cells. Since this increased elimination of ROS could be reverted by GSH depletion, we concluded that multidrug resistance is the consequence of GSH-dependent increased ability of alpha(v)beta(3)-expressing cells to eliminate drug-induced ROS.

The effect of hazardous pollutants from coal combustion activity: Phytotoxicity assessment of aqueous soil extracts.

Airborne fly ash and related hazardous particles derived from coal combustion contaminate soil and groundwater, negatively affecting ecosystems. The aim of this study was chemical and toxicological evaluation of aqueous extracts of soil collected from the vicinity of a coal-fired Plomin power plant (PPP), using Lemna (Lemna minor L.) bioassay and additional biochemical indicators - photosynthetic pigments, lipid peroxidation, antioxidative enzymes and glutathione. Topsoil samples were collected from distances of 200, 300, 400 and 800 m from the PPP in accordance with the prevailing SW wind direction. Elevated levels of polycyclic aromatic hydrocarbons (up to 15,765 ng L-1) and potentially toxic trace elements were detected in the Plomin soil extracts (PEs) in comparison to control soil extract (CE). Trace elements accumulated in L. minor were mostly in accordance with their concentrations in PEs. The results demonstrate that PEs induced significant growth inhibition and other phytotoxic effects. Those effects can be related to damage caused by increased production of reactive oxygen species and impaired antioxidant levels. The connection among the phytotoxicity, a distribution of analyzed contaminants, and distances from the PPP is clearly established.

Mercury in aquatic sediments and soils from Croatia.

Mercury is one of the most toxic and hazardous pollutant which occurs in the environment in different chemical forms, of which methylmercury is the most dangerous. Recently it was recognised that long-term anthropogenic inputs of mercury into environment resulted in the global mercury pollution and it was concluded that action should be taken to quantify the pollution sources and reduce human-generated releases of mercury. This paper presents new data on mercury levels in aquatic sediments from about 15 Croatian rivers, lakes and estuaries. It also brings data on mercury concentrations in soils from eight different regions of Croatia. Distribution of mercury species is discussed in more details for the Sava River, the Krka estuary and the Kastela Bay on the eastern Adriatic coast. Results show that sediments and soils from Croatia are generally not contaminated by mercury, except for some rivers and coastal locations under direct anthropogenic influence.

Determination of lanthanides by source excited energy dispersive X-ray fluorescence (EDXRF) method after preconcentration with ammonium pyrrolidine dithiocarbamate (APDC).

A new analytical procedure for determination of lanthanides in environmental samples after chemical separation from major matrix elements on DOWEX 50W-X8 resin followed by preconcentration with chelating agent ammonium pyrrolidine dithiocarbamate (APDC) and analyses of thin targets by energy dispersive X-ray fluorescence (EDXRF) method using 109Cd as the source of excitation was presented. Characteristic Lalpha X-ray lines of the lanthanides were used for calculations of the net peak area and mass concentrations. The influence of pH value of the solution and addition of organic matter on the complexation was investigated. Percentage of recovery of each lanthanide after separation on DOWEX 50W-X8 resin was also determined. Accuracy of the method was tested on standard reference materials and real environmental samples (red mud material). For that purpose samples of standard reference materials and red mud were prepared as thick targets and directly analyzed (without the separation step) by EDXRF method using 241Am as the excitation source. In that case lanthanides concentrations were determined over their characteristic Kalpha X-ray lines and results were compared with those obtained after separation/preconcentration step described above. Results showed that selected lanthanides made stable complexes with APDC in the alkaline medium with the maximum recovery at pH=8. The presence of organic matter slightly modified the complexation by means of somewhat higher recovery percentage at pH lower than 7 and approx. 20% lower recovery at pH higher than 7. Recovery of the elements after separation on DOWEX 50W-X8 resin and preconcentration with APDC at pH=8 varied from 91.4% (Pr) to only 24.9% in the case of Dy. Concentrations of lanthanides measured in standard reference material and environmental samples of red mud after microwave digestion, separation on DOWEX 50W-X8 resin, preconcentration with APDC at pH=8 and recalculation on the percentage of recovery were in good agreement with certified values in the case of SRM as well as with the concentrations obtained by direct determination over Kalpha lines using 241Am excitation source in the case of red mud leading to the conclusion that presented method was applicable for the determination of lanthanides in real environmental samples.

Bis{1-[N-(2-methoxyphenyl)iminomethyl]naphthalen-2(1H)-onato-kappa3O,N,O'}zinc(II) ethanol solvate.

In the crystal structure of the title compound, [Zn(C18H14NO2)2].C2H6O, the Zn atom displays a highly distorted octahedral coordination involving the O and N atoms of two molecules of the Schiff base 1-[N-(2-methoxyphenyl)iminomethyl]naphthalen-2(1H)-one, which acts as an O,N,O'-tridentate ligand. The ethanol molecule is bound to the methoxy group of one ligand molecule via a hydrogen bond.