Abstract: In this study we investigated cytotoxic, mutagenic and genotoxic effects of different concentrations of wastewater from the phosphoric gypsum depot near the factory for fertilizing agents 'INA Petrokemija' (Kutina, Croatia). The Ames test was performed on Salmonella typhimurium TA98 and TA100 strains, in the presence of S9 mix, glutathione and buffer, respectively. Cytotoxicity was studied on human laryngeal carcinoma cells (HEp2) and human cervical cells (HeLa). The level of lipid peroxidation in these two cell lines was evaluated in parallel. To establish the levels of primary DNA damage, the alkaline comet assay was performed on treated human peripheral blood leukocytes. No mutagenic effects of phosphoric gypsum on Salmonella typhimurium strains in the presence of S9 mix, GSH or PBS were observed. However, strong cytotoxic effect was observed on both human cell lines when they were treated with different concentrations of wastewater. Lipid peroxidation was induced and increased by prolonged time of incubation, highlighting that the damage was not repaired, but increased with the time of incubation. The results of the alkaline comet assay indicate significant DNA damaging potential of wastewater for human leukocytes. Since phosphoric gypsum transport water in its present composition and acidity is highly toxic and acts as prooxidant, causing free radicals formation and DNA damage, urgent neutralization/purification of the wastewater to a level acceptable for disposal into the environment is mandatory. Copyright (c) 2008 John Wiley & Sons, Ltd.

Abstract: Optimum measurement parameters for analysis of soil and sediment samples with the compact MiniPal 4 (MP4)EDXRF spectrometer (PANalytical, Almelo, The Netherlands) were presented. The following elements were considered: K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As and Pb. Since the elements from low Z to medium Z region were covered, three measurement conditions (sequences) were defined. The following parameters were selected for measurement of the elements K, Ti, and V: voltage = 12 kV; current = 750 mu A; filter material: Al_thin. Cr, Mn and Fe were measured at 20 kV; 300 mu A with Al filter while for measurements of Ni, Cu, Zn, As, Pb, Rb, and Sr an Ag filter was selected and tube voltage and current were 30 kV and 300 AA. Each sequence was measured for 200 s and measurements were done in the air. MP4 spectrometer was characterized with acceptable precision, long-term stability and satisfactory minimum detection limit for the analyses of soil and sediment materials. For the elements K, Mn, Fe, and Ti the precision of the analysis was better than 0.5%, and for all the other elements better than 50%. Detection limits for sediment samples were 20 ppm for K, 6.1 ppm for Ti, 5.2 for Mn, 4 ppm for Fe, 4.2 ppm for As and less than 2 ppm for all the other elements. These values were significantly lower compared to typical concentrations of the same elements found in unpolluted soil and sediments. Copyright (c) 2008 John Wiley & Sons, Ltd.

Abstract: Spatial distributions of trace elements in the coastal sea sediments and water of Maslinica Bay (Southern Adriatic), Croatia and possible changes in marine flora and foraminifera communities due to pollution were investigated. Macro, micro and trace elements' distributions in five granulometric fractions were determined for each sediment sample. Bulk sediment samples were also subjected to leaching tests. Elemental concentrations in sediments, sediment extracts and seawater were measured by source excited energy dispersive X-ray fluorescence (EDXRF). Concentrations of the elements Cr, Cu, Zn, and Pb in bulk sediment samples taken in the Maslinica Bay were from 2.1 to over six times enriched when compared with the background level determined for coarse grained carbonate sediments. A low degree of trace elements leaching determined for bulk sediments pointed to strong bonding of trace elements to sediment mineral phases. The analyses of marine flora pointed to higher eutrophication, which disturbs the balance between communities and natural habitats.

Abstract: Variations in the elemental composition of different carp (Cyprinus corpio) organs (liver, kidney, eggs, intestine, spleen and skin + muscle) from three Croatian fish farms were investigated. Sediments and water samples were also taken from each pond. All measurements were carried out by the source excited Energy Dispersive X-Ray Fluorescence method (EDXRF). Significant difference was found in the sediment and water composition among the three fish farms (p < 0.01). Compared to fish farm 1, concentrations of heavy metals in sediments and water from fish farm 2 were between 2 and 6 times higher and from fish farm 3 between 2 and 5 times higher. The following concentrations ranges (expressed as wet weight) were measured in different carp organs: Pb (0.11-1.45 mg/kg); Cr (0.10-3.72 mg/kg); Mn (1.70-28.47 mg/kg); Fe (8.09-117.21 mg/kg); Cu (0.41-4.09 mg/kg) and Zn (4.61-171.53 mg/kg). Significant difference was found in selected heavy metal concentrations of selected organs at each location as well as among the three locations (p < 0.05). Generally, carp from fish farm 2 had the highest concentration of the majority of elements (Pb, Cr, Mn, Fe Cu, Zn), while carp from fish farm I had the lowest concentration, demonstrating an impact of the geochemical environment on heavy metal concentrations in carps.

Abstract: To investigate whether occupational exposure to tobacco dust is genotoxic, a group of employees in a tobacco factory was tested for structural chromosome aberrations (CA), cytokinesis-block micronucleus assay (CBMN) and sister chromatid exchanges (SCE) that are well established as indicators of early biological effects. The study group consisted of 40 tobacco workers and an equal number of matched controls. The results obtained in the exposed group showed a significant increase in chromosome aberrations (R = 0.26), micronucleus frequency (R = 0.56) and in sister chromatid exchanges (R = 0.75), which was additionally influenced by smoking. A significant increase in high frequency cells (HFC) in the exposed group was also observed. Like the SCE frequency, the HFC frequency increased significantly in smokers of the control and exposed smokers. The study indicates that occupational exposure to tobacco dust induces genome damage. A higher risk was observed in women. The micronucleus frequency and sister chromatid exchange tests seem to be more reliable indicators of genome damage than chromosome aberrations in monitoring chronically exposed subjects. Copyright (C) 2008 John Wiley & Sons, Ltd.

Abstract: Concentrations of heavy metals (Pb, Cr, Mn, Fe, Cu, and Zn) were measured in water, mud and different organs (liver, kidney, intestine, spleen, skin and muscle) of bighead carp (Hypophthalmichthys molitrix), grass carp (Ctenepharyngodon idella), wels (Siluris glanis) and pike (Esox lucius) from three Croatian fish farms. All measurements were carried out by the source excited Energy Dispersive X-Ray Fluorescence method (EDXRF). Significant difference was found in the mud and water composition among the three fish farms. Compared to the fish farm 1, concentrations of heavy metals in mud and water from the fish farm 2 were between 2 and 6 times higner and from fish farm 3 between 2 ana 5 times higher. The concentrations of heavy metals (expressed as wet weight) were measured in different organs of herbivore and predatory fish species and significant difference was found in selected heavy metals concentration in organs of two group fish species with varied modality of alimentation.

Abstract: To investigate the genotoxic potential of atorvastatin on human lymphocytes in vitro standard comet assay was used in the evaluation of basal DNA damage and to investigate possible oxidative DNA damage produced by reactive oxygen species (ROS) Fpg-modified version of comet assay was also conducted. In addition to these techniques the new criteria for scoring micronucleus test were applied for more complete detection of baseline damage in binuclear lymphocytes exposed to atorvastatin 80 mg/day in different time periods by virtue of measuring the frequency of micronuclei, nucleoplasmic bridges and nuclear buds. All parameters obtained with the standard comet assay and Fpg-modified comet assay were significantly higher in the treated than in control lymphocytes. The Fpg-modified comet assay showed a significantly greater tail length, tail intensity, and tail moment in all treated lymphocytes than did the standard comet assay, which suggests that oxidative stress is likely to be responsible for DNA damage. DNA damage detected by the standard comet assay indicates that some other mechanism is also involved. In addition to the comet assay, a total number of micronuclei, nucleoplasmic bridges and nuclear buds were significantly higher in the exposed than in controlled lymphocytes. Regression analyses showed a positive correlation between the results obtained by the comet (Fpg-modified and standard) and micronucleus assay. Overall, the study demonstrated that atorvastatin in its highest dose is capable of producing damage on the level of DNA molecule and cell. (c) 2008 Elsevier Inc. All rights reserved.

Abstract: The cytokinesis-block micronucleus assay (CBMN) was used to assess the variability and determine possible influences of external and internal factors on the background levels of cytogenetic damage in peripheral blood lymphocytes (PBL) of 50 healthy volunteers selected at random from the general population of Croatia. The mean MN frequency for all subjects was 4.74+/-0.31 per 1000 cells and the mean cytokinesis-block proliferation index (CBPI) was 1.82+/-0.01. The mean frequency of nucleoplasmic bridges (NPB) for all subjects was 0.06+/-0.04 and of nuclear buds (NB) 0.12+/-0.05. The canonical correlation analyses indicate a positive non-significant correlation between the MN frequency and age, gender and smoking habits. Results of factor structure and canonical weights showed that age and gender rather than smoking habits control the incidence of MN in PBL of healthy volunteers. The lowest median value of MN was observed in subjects younger than 30 years (both smoking and non-smoking). Generally, non-smokers had lower median values of MN compared to smokers. In non-smokers, males showed lower micronucleus incidence than females. Within the non-smokers smaller differences in the median values of MN between subgroups (male and female; age subgroups) were observed. Among smokers, females had a two-fold higher median value of MN frequency than males, but this difference was not significant (p=0.2643, Mann-Whitney U test). Canonical correlation analyses indicate a strong and significant correlation between cell proliferation parameters (M1-M4 and CBPI) and age, gender and smoking habits. The most sensitive parameters were M3 and M4. Age had the strongest effect on M3, while M4 was highly influenced by smoking habits. Gender had an equal non-significant effect on both parameters. The usefulness of the new criteria for the cytokinesis-block MN assay measuring DNA damage as a sensitive biomarker in biomonitoring studies is confirmed.

Abstract: DNA sensitivity in peripheral blood leukocytes of radar-facility workers daily exposed to microwave radiation and an unexposed control subjects was investigated. The study was carried out on clinically healthy male workers employed on radar equipment and antenna system service within a microwave field of 10 muW/cm(2)-20 mW/cm(2) with frequency range of 1,250-1,350 MHz. The control group consisted of subjects of similar age. The evaluation of DNA damage and sensitivity was performed using alkaline comet assay and chromatid breakage assay (bleomycin-sensitivity assay). The levels of DNA damage in exposed subjects determined by alkaline comet assay were increased compared to control group and showed inter-individual variations. After short exposure of cultured lymphocytes to bleomycin cells of subjects occupationally exposed to microwave (MW) radiation responded with high numbers of chromatid breaks. Almost three times higher number of bleomycin-induced chromatid breaks in cultured peripheral blood lymphocytes were determined in comparison with control group. The difference in break per cell (b/c) values recorded between smokers and non-smokers was statistically significant in the exposed group. Regression analyses showed significant positive correlation between the results obtained with two different methods. Considering the correlation coefficients, the number of metaphase with breaks was a better predictor of the comet assay parameters compared to b/c ratio. The best correlation was found between tail moment and number of chromatid with breaks. Our results indicate that MW radiation represents a potential DNA-damaging hazard using the alkaline comet assay and chromatid breakage assay as sensitive biomarkers of individual cancer susceptibility.

Abstract: The purpose of this work was development of an appropriate procedure for the neutralization/purification of electroplating wastewater (EWW) with alkaline solid residue (ASR) by-product of the alkaline extraction of zinc and lead from electric arc furnace dust (EAFD). Removal efficiency of ASR at optimum purification conditions (pH 8 and mixing time; 20 minutes) for the elements Pb, Cr (VI), Cr (III), Fe, Ni, Cu and Zn were 94.92%, 97.58%, 99.59%, 99.48%, 97.25% and 99.97%, respectively. The concentrations of all elements in the purified wastewater were significantly lower in relation to the upper permissible limit for wastewaters suitable for discharge into the environment. The remaining waste mud was regenerated in the strong alkaline medium and successfully applied once again for the neutralization/purification of EWW. Removal efficiencies of heavy metals accomplished with regenerated waste mud were comparable to these achieved by original ASR. Elemental concentrations in the leachates of the waste mud were in accordance with regulated values.

Abstract: Literature data on carbofuran genotoxicity in vitro and in vivo are very scarce. There are few papers indicating that occupational exposure to this AChE inhibiting insecticide might be connected to increased risk of developing non-Hodgkin's lymphoma and lung cancer. Other authors showed its genotoxicity in vitro. We used comet and CBMN micronucleus assay combined with centromere probes to evaluate genome damage in lymphocytes of workers employed in carbofuran production. Also, the level of AChE activity in blood and plasma was measured. Only few workers exhibited AChE activity below 85%. Comet assay parameters were slightly but significantly elevated compared to control subjects, especially the long-tailed nuclei ratio. We found poor correlation between AChE activity and comet assay parameters, but significant effect of smoking and alcohol intake on the latest. In binucleated lymphocytes of workers significantly increased number of micronuclei, nuclear buds, and nucleoplasmic bridges was detected. Proportion of micronuclei with centromere, DAPI signal positive micronuclei was also elevated. Micronucleus assay parameters also appeared to be significantly influenced by duration of exposure to carbofuran. Together with published data on carbofuran's effect on health our results might indicate the need for further evaluations of its genotoxicity using a range of different cytogenetic techniques. (c) 2007 Elsevier Ltd. All rights reserved.

Abstract: To determine current radiation background of the environment at the "Giricic" location in Kastel Gomilica, Croatia, in situ measurement of radon concentration (Rn-222 and Rn-220) in an open atmosphere on a ground level and at the height of 1.5 in has been made as well as total gamma radiation at the height of I in in an energy range of 15 keV to 2 MeV. The researched location was divided in three specific parts: (i) regulated area with the bottom ash and flying ash in the basis ("old" depot), (ii) unregulated area with waste materials, including bottom ash and flying ash, in the basis ("new" depot), (iii) uncontaminated area with no waste materials deposited on. Average radon concentration on a ground level was 213 Bq/M-3 for the "old" depot, 214 Bq/M3 for the "new" depot and 59 Bq/M3 for the uncontaminated area and at the height of 1.5 m 20 Bq/M3 for the "old" depot, 34 Bq/M3 for the "new" depot and 26 Bq/M3 for the uncontaminated area. Average total gamma radiation values in selected energy range were 109.92 cps (counts per second) for the "old" depot, 357.76 cps for the "new" depot and 65.97 cps for the uncontaminated area. For selected radionuclides (Pb-214, (137)cS, Ac-228, Pa-234m K-40 and Bi-214) average gamma radiation values at characteristic energies have been determined as well. (C) 2007 Elsevier B.V. All rights reserved.

Abstract: The discharge of untreated electroplating wastewaters directly into the environment is a certain source of heavy metals in surface waters. Even though heavy metal discharge is regulated by environmental laws many small-scale electroplating facilities do not apply adequate protective measures. Electroplating wastewaters contain large amounts of various heavy metals (the composition depending on the facility) and the pH value often bellow 2. Such pollution diminishes the biodiversity of aquatic ecosystems and also endangers human health. The aim of our study was to observe/measure the toxic effects induced by a mixture of seven heavy metals on a bioindicator species Lemna minor L. Since artificial laboratory metal mixtures cannot entirely predict behaviour of metal mixtures nor provide us with informations relating to the specific conditions in the realistic environment we have used an actual electroplating wastewater sample discharged from a small electroplating facility. In order to obtain three more samples with the same composition of heavy metals but at different concentrations, the original electroplating wastewater sample has undergone a purification process. The purification process used was developed by Orescanin et al. [Orescanin V, Mikeli� L, Luli� S, Nad K, Rubci� M, Pavlovi� G. Purification of electroplating wastewaters utilizing waste by-product ferrous sulphate and wood fly ash. J Environ Sci Health A 2004; 39 (9): 2437-2446.] in order to remove the heavy metals and adjust the pH value to acceptable values for discharge into the environment. Studies involving plants and multielemental waters are very rare because of the difficulty in explaining interactions of the combined toxicities. Regardless of the complexity in interpretation, Lemna bioassay can be efficiently used to assess combined effects of multimetal samples. Such realistic samples should not be avoided because they can provide us with a wide range of information which can help explain many different interactions of metals on plant growth and metabolism. In this study we have primarily evaluated classical toxicity endpoints (relative growth rate, Nfronds/Ncolonies ratio, dry to fresh weight ratio and frond area) and measured guaiacol peroxidase (GPX) activity as early indicator of oxidative stress. Also, we have measured metal accumulation in plants treated with waste ash water sample with EDXRF analysis and have used toxic unit (TU) approach to predict which metal will contribute the most to the general toxicity of the tested samples.

Abstract: In order to estimate the influence of a nuclear power plant and other industrial and agricultural anthropogenic sources on the quality of Sava River sediments, samples taken from seven locations (one upstream and six downstream of the Krsko NPP) were characterized. Seasonal variations in the sediment composition were determined on the basis of four samplings taken during the year 2004 (in February, May, October and December). Total concentrations of the elements Cr, Mn, Fe, Cu, Zn, Co and Pb in the sediment fractions less than 0.5 mm have been measured by source excited energy dispersive X-ray fluorescence (EDXRF), while K-40, Cs-137, I-131, Be-7, Th-228. Th(Ra-228), U(Th-234), Ra-226 and Pb-210 were determined by gamma spectrometry. Mineralogical examinations of the samples were performed using the X-ray diffraction (XRD) method. (C) 2007 Elsevier B.V. All rights reserved.

Abstract: This paper presents comparison of two methods for the determination of Fe-55 activity of waste waters discharged from the Krsko nuclear power plant (KNPP). Research was conducted on 12 composite samples of waste water collected in the waste monitor tank (WMT) during each month as well as on Analytics, Inc. cross-check sample. Results showed that the complicated and time-consuming method proposed by the Environmental Measurements Laboratory (EML) could be successfully replaced with a simple and fast based on the extraction of Fe-55 from waste water by non-specific chelating agent ammonium-pyrrolidinedithiocarbamate (APDC) at pH 4 after separation from cobalt, and activity measurement by X-ray fluorescence spectroscopy (XRS). Results obtained by the XRS method were approximately 8.6% lower than those obtained by liquid scintillation spectrometer (LSC). The mean deviation of the XRS results from the activity of cross-check sample was 2.47%, which ensures that this method is accurate enough for environmental monitoring. (C) 2007 Elsevier B.V. All rights reserved.

Abstract: This study was carried out to determine the appropriate treatment of electric arc furnace (EAF) dust prior to permanent disposal. The total heavy metal content as well as heavy metal leaching from EAF dust was investigated in five composite samples obtained from three Croatian and Slovenian steelworks. In order to recover zinc and reduce its leaching from the dust, all five samples were submitted to alkaline extraction with 10 M NaOH. Reduction of Cr (VI) to Cr(III) was conducted using FeSO4 x 7H2O solution. The elements Mn, Fe, Cu, Ni, and notably Zn and Pb, exhibited highest mobility during toxicity characteristic leaching procedure (TCLP). Comparing to TCLP extracts of initial EAF dust, zinc was found to be over 15 times lower and lead over 200 times lower in TCLP extracts of EAF dust processed by the alkaline leaching method. Since Cr (VI) exceeded its permissible level in the DIN 38414-S4 extracts of both initial and alkaline digested dust, its reduction to Cr (III) prior to permanent disposal is necessary. The recovery of zinc from EAF dust treated with alkaline agent ranged from 50.3% to 73.2%. According to phase analysis, recovery yield showed dependence on zincite/franklinite ratio. The results of the study indicate that permanent disposal of EAF dust require the following procedure: alkaline digestion (followed by leachate purification and alkaline zinc electrolyses), chromate reduction (if necessary), solidification of leaching residue and its testing using the leaching analyses.

Abstract: Production of the coagulant using bauxite waste (red mud and waste base) as raw material and the results of the testing of this new product in laboratory and field condition (pilot plant, full scale plant) were presented. Results showed that red mud could be used as a low-coast solution for heavy metals removal from its own waste base and other industrial wastewaters after partial dissolution with diluted sulphuric acid and neutralization with the waste base. This coagulant is especially suitable for the treatment of the wastewaters generated from the pressure washing of boats in the marinas. The coagulant produced from the red mud has few advantages compared to the commercial Fe and Al salts: (1) Coagulation /flocculation process could be done in one step without coagulant aid or any other chemical addition. (2) pH measurement during the purification could be avoided due to the negligible pH variations of the treated solution. (3) Allow one step removal of the cationic and anionic species from the wastewater. (4) One dose of coagulant is sufficient for five repeated treatment cycles. (5) Negligible leaching of heavy metals from the waste mud under normal environmental conditions. (6) Safe for the transport, storage and handling.

Abstract: Results of two years monitoring of heavy metals and arsenic concentrations in soft tissue of Mediterranean blue mussel Mytilus galloprovincialis are presented. Samples were taken at six localities (five exposed to various pollution Sources and one control site) on the east coast of the Middle Adriatic in October 2003 and 2004 and in April 2004 and 2005. All measurements were carried out with source excited Energy Dispersive X-ray Fluorescence Method (EDXRF). Measured concentrations were in the following ranges: Pb (2-7 mg/kg); As (4-30 mg/kg); Cr (1-2.9 mg/kg); Mn (2-13 mg/kg); Fe (53.4-719 mg/kg); Ni (0.8-5 mg/kg); Cu (3.7-11.1 mg/kg) and Zn (59.1-273 mg/kg). Maximum values of the most elements were measured in samples from the most polluted Vranjic region. Statistically significant difference among six localities (p = 0.05) was found for As, Fe and Zn while Mn, Fe and Cu showed significantly higher concentrations in spring period. None of the selected elements showed significant difference between the control and exposed regions. (c) 2005 Elsevier B.V. All rights reserved.

Abstract: The objective of this study was to chemically characterize the soil samples affected by the dust emission and slag dumping from ferrochromium smelter, as well as uptake of metals by vegetation growing on that soil. There were 38 samples collected altogether, including unpolluted background soil samples, polluted soil samples taken in the vicinity of the factory, slag material, bottom and fly ash. Grass material was also taken from both polluted and unpolluted soil. All samples were analyzed with energy dispersive X-ray fluorescence (EDXRF). The results showed (especially for chromium and manganese) metal concentrations in soil samples taken in the vicinity of the factory increased up to 56 times in relation to normal background soil concentrations. Slag material, fly and bottom ash were highly enriched with chromium, manganese and nickel. There was a significant chromium uptake by vegetation growing on the contaminated soil.

Abstract: 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.

Abstract: The objective of this study was to determine the chemical, radiological and leaching properties of slag and ash produced by a thermoelectric unit of a former factory Adriavinil and deposited in the area of Kasktel Gomilica near Split, Croatia. A total of 33 samples were analysed. The bioavailable fraction of the slag and ash was estimated using different leaching tests. The waste material was characterized by a high activity of naturally occurring radionuclides 238U, 235U and 226Ra and by elevated concentrations of heavy metals. The concentrations of most heavy metals were three to four times as high as in the common soil. Uranium slag and ash concentration was almost 40 times higher than in control soil. More than 37% of the total U could be removed from the slag and ash with the sea water.

Abstract: Iron-containing antianemic drug ferric-sorbitol-citrate (FSC) inhibits the proliferation of various cancer cell lines in vitro and causes a regression of experimental murine tumors in vivo but does not affect the proliferation of nonmalignant cells. Growth modification caused by FSC iron involves a diminished expression of Bcl-2 and an overexpression of p53 proto-oncogene, accompanied by an increased incidence of apoptosis. Aiming to evaluate further the activity principle of the anticancer effects of this antianemic drug, in this study, we analyzed the utilization of iron from FSC and the effects of FSC iron on transferrin receptor 1 (TfR1) and ferritin expression. Without FSC iron, all the cell lines had an equal expression of TfR1, but if cultured in FSC-supplemented medium, human colon SW620 and laryngeal carcinoma Hep cells exhibited a lower expression of TfR1-positive cells than nonmalignant Wi38 fibroblasts and pancreatic carcinoma MiaPaCa2 cells. The most sensitive to FSC iron were colon carcinoma SW620 cells, whereas Wi38 fibroblasts were not sensitive at all. Increased iron uptake by colon carcinoma cells was noticed in the first 3 hours of the incubation with FSC iron, whereas higher FSC iron concentrations and longer incubation also impaired ferritin expression in SW260 colon carcinoma cells. Thus, the anticancer ability of FSC could result from its higher initial utilization of iron and consecutive negative signal for the expression of TfR1 in tumor cells. Tumor cells containing lower amounts of ferritin are probably more sensitive to oxidative stress caused by iron overload, whereas FSC iron itself was proven to be chemically stable and did not induce lipid peroxidation.

Abstract: This paper attempts to determine the impact of former Pb-Zn- Ba mining activities in Slovenian drainage basin on overbank sediments of the Sava river (West Croatia). Among the four studied sequences (S7, S8, S9, S10), the most upstream profile S7 showed the most pronounced impact of ore mining. Mercury was enriched more than 100-fold; Pb and Zn had a strong positive correlation (r > 0.99). Two factor models clearly revealed the Pb-Ba-Hg association in the lower-lying carbonate (CA) population of all four profiles, but only in the overlying silicate (SI) population of profile S7. Factor analysis confirmed this association in the total sediment (90 samples) as well as separately in the CA (33 samples) and SI (57 samples) populations. Based on a comparison with an undisturbed soil profile, the vertical distribution of Cs-137 in profile S7 was interpreted to be the combination of caesium deposition caused by a flood in 1964 and by post-depositional redistribution.

Abstract: The concentrations of the elements Pb, Rb, Sr, Y, Zr, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn and Co were determined in the ash-samples of writing, copying and computer printing papers by energy dispersive X-ray fluorescence (EDXRF). Non-coloured white papers of various manufactures and grammages were considered. Ashes of copying papers printed with black toner and black ink by laser and ink jet printers were also analyzed. Most of the elements measured in papers showed the lowest concentrations in the ashes of Navigator and Copier papers (Sorpocel S.A., Portugal). Fabriano paper contains significantly higher amount of lead, strontium and zirconium compared to the papers of other manufactures. The concentrations of the elements Co, Mn, Fe, Cr and Ti in the Navigator paper printed by laser printers are significantly higher compared to the non-printed papers. In Fabriano papers the concentrations of the elements Cr, V and Cu as well as organic content increases with paper grammage from 80 to 160 g/m(2), while opposite was found for the amount of Pb, Rb, Sr, Y, Zr, K, Ca, Ti, Fe, Ni and Zn. (C) 2004 Elsevier B.V. All rights reserved.

Abstract:

Abstract: In the paper, the results of wastewater treatment (water before treatment in Krofta flotation clarifier, after flotation and passing through sand filters) in the company of papermaking PAN, Croatia, are presented. The results obtained after removal with clinoptilolite-rich tuff were compared with removal of metals by means of coagulation with iron (III) chloride and using activated red mud. The results proved that iron (III) chloride and activated red mud are more efficient in removal of metals from wastewaters. It is to assume that wastewaters of paper industry contain complex agents which bind a part of metal ions and that way influence efficiency of ion exchange on zeolite.

Abstract: The objective of this study was chemical/mineralogical characterization of soil samples affected by the dust emission and slag dumping from ferro-manganese smelter and ex-aluminium factory as well as uptake of metals by vegetation growing on that soil. Energy dispersive X-ray fluorescence (EDXRF) was used for the determination of elemental concentrations in soil, vegetation and different soil extracts while mineralogical composition of soil samples was determined by XRD analysis. Results of chemical and statistical analyses together with calculated enrichment factors indicate that smelter and aluminium factory caused the severe heavy metal pollution of its surroundings which is still visible thirteen years after the production was ceased. Iron was the main component of metallurgical slag deposited near the smelter. Slag material was highly enriched in Zn, Cr, Cu, Co and Pb. Enrichment of the elements in soil samples taken in the vicinity of the smetler ranging from 3.5 to approximatly 166 times compared to background soil samples. Fortunately, elements taken from contaminated soil are strongly bound to the mineral soil components resulting in low degree of leaching and low heavy metal uptake by vegetation growing on that soil.

Abstract: The objective of this study was set on three goals: (i) Chemical and radiological characterization as well as leaching properties of the mixture of fly and bottom ash produced in thermo electric unit of former "Adriavinil" factory and deposited in Kastel Gomilica region, Croatia, (ii) Chemical, radiological and mineralogical characterization of the Kastela Bay sediments under the influence of past industrial activity and its waste by products, and (iii) Estimation of the influence of TENORM deposition on the quality of Kastela Bay sediments. Kastela Bay sediments are exposed to numerous sources of pollution like fly and bottom ash enriched in radionuclides and heavy metals, chemical plant, cement plant, iron plant, shipyard, electroplating facility, untreated industrial and domestic waste waters as well as to heavy traffic. High activity of naturally occuring radionuclides U-238, U-235 and Ra-226 present in the ash was the reason for its classification as TENORM (Technologically Enhanced Naturally Occuring Radioactive Material). Besides, this material was highly enriched in heavy metals. To obtain a preliminary data about the present state of researched area, 33 samples of the mixture of fly and bottom ash, 12 sediment cores ranging from 0 to 40 cm and nine surface sediment samples were analyzed. Enrichment with heavy metals in the mixture of fly and bottom ash ranged from 1.5 to 36 times compared to flisch soil while Ra-226 and 238U were up to 50 times enriched compared to average activities characteristic for surrounding soils developed on the Middle and Upper Eocene flisch. Most of the measured heavy metals in the ash were 3-4 times those in the surrounding soil. It was found that over 37% of the total U could be removed from the ash by the sea water. Bioavailable fraction of the ash was estimated by conducting different leaching tests. According to mean values of the elemental concentrations for each sediment segment, the elements could be divided into five groups with similar distribution patterns. The highest enrichment in sediment cores compared to background values were found for Zn (35.6 times), Pb (16 times), Cr (9.1 times) and Ni (4 times). The highest concentrations of total uranium were determined at positions 1 and 2 situated in the vicinity of the ash deposit site and under the constant influence of ash dumping into the sea and leaching from the ash deposit. Observed concentrations of Zr, Fe and Co point out a larger input of terrestrial material, like the mixture of fly and bottom ash and flisch material, into predominant carbonate sediments. Maximum concentrations of heavy metals were found in deeper sediment segments deposited in the period of the highest industrial production and the negligible care to the environment.

Abstract: The objective of this study was chemical and radiological characterization of Kastela Bay sediments exposed to numerous anthropogenic sources like deposition of fly and bottom ash enriched in radionuclides and heavy metals, chemical plant, cement plant, iron plant, shipyard, electroplating facility, untreated industrial and domestic waste waters as well as heavy traffic. Totally, 33 samples of the mixture of fly and bottom ash, 12 sediment cores ranging from 0 to 40 cm and nine surface sediment samples were analyzed. Enrichment in heavy metals in the mixture of fly and bottom ash was ranging from 1.5 to 36 times compared to flysch soil while Ra-226 and U-238 were up to 50 times enriched compared to average activities characteristic for surrounding soils developed on the Middle and Upper Eocene flysch. Maximum U-238 activity was approximately 32 times higher and Ra-226 approximately 40 times higher in the Kastela Bay sediment compared to mean value determined for Adriatic sediments. The highest enrichment in sediment cores compared to background values were found for Zn (35.6 times), Pb (16 times), Cr (9.1 times) and Ni (4 times)

Abstract: Toxicological safety of the new purification method for electroplating wastewaters (EWW) has been assessed. Method utilizes waste by-product ferrous sulfate and wood fly ash to scavenge heavy metals from EWW. Energy dispersive X-ray fluorescence (EDXRF) analysis of all samples met the law requirements for safe depositing of waste into the environment. The toxicity study consisted of determination of frequency of bacterial and human cell lines survival and the Ames assay (plate incorporation assay and the preincubation assay). Unexpectedly, data obtained indicate cytotoxicity and slight mutagenic potential of purified water. Ames assay showed that combination of alkalis and heavy metals present in the water purified with original fly ash and eluates of fly and waste ash were metabolically activated and conjugated with glutathione, resulting in new metabolites active and toxic for the cell. In order to reduce this effect pretreatment of fly ash (partial removal of highly soluble compounds) are necessary prior to its usage for neutralization /coagulation/flocculation processes.

Abstract: A rapid, sensitive and selective procedure for determination of Cr(III) and Cr(VI) in environmental and industrial liquid samples via preconcentration with ammonium pyrrolidine dithiocarbamate (APDC) and determination by means of the EDXRF was described. The effect of pH in the range of 3-11 on the recovery of Cr(III) and Cr(VI) has been investigated separately and in combination of these two species. The influence of organic matter, carbonate species and elements V, Mn and Fe on the recovery of each chromium specie (separately/in combination) over whole pH range was also tested in order to simulate condition occurring in natural waters that usually contain certain amount of dissolved organic matter and carbonate ions. Cr(VI) and Cr(III) have shown different behaviors in reaction with APDC at different pH ranges and therefore it is possible to separate those two species. It was found that Cr(VI) creates complex with APDC only in the pH range from 3 to 5 with quantitative recovery (app. 98%) at pH 3, but there was no recovery of Cr(III) at that pH. On the contrary, in pH range from 6 to 11, reaction with Cr(III) and APDC reviled that the only reaction product is Cr(OH)(3) instead of the expected Cr(III)-APDC complex. All reaction products were characterized by IR spectroscopy. (C) 2004 Elsevier B.V. All rights reserved.

Abstract:

Abstract: Total concentrations of 13 elements (K Ca, Ti, Cr, Mn, Fe, Cu, Zn, Rb, Sr, Y, Zr, Pb) in the size-fractionated Sava River sediments upstream and downstream of the Krsko nuclear power plant together with metal speciation within bulk sediment have been investigated. Trace metals generally increase with decreasing particle size, however, because of entrapment of organic matter in the 0.63-1 mm fraction, concentrations in the coarser sediment fraction are higher than expected. Exchangeable Pb, Zn, Cu, Mn, Cr and Fe are generally found to represent a negligible fraction of the total metal concentration of the bulk sediment. Seasonal variations of the Pb, Zn and Cu concentrations in the <0.5 mm. fraction reflect decreased values during the spring period. Heavy metal concentrations in the 2003 waste water discharges from the Krsko nuclear power plant released into the Sava River were much lower than their maximum allowed values. Combined rubidium and organic matter normalization of the Zn, Pb and Cu concentrations, which was applied on the minus 0.063 mm fraction, indicated three potential sources of contaminants.

Abstract: The fate of heavy metals (Cu, Pb, Zn) from their sources to the final sink was analysed. Investigations included the identification of sources, the input from each source as well as transport towards their temporary (soil, vegetation, and marine water) and final sink (marine sediments). Research was conducted in the catchment area of Punat Bay on the island of Krk (Northern Adriatic, Croatia). Four sources were identified: long-range transport, traffic, antifouling paints and eroded material which annually introduced about 158 kg of Cu, 175 kg of Pb and 666 kg of Zn into the Bay. Antifouling paints were significant but not the main source of pollution in this area as was considered in previous investigations. Due to long-range transport, the input of Zn was almost four times greater, whereas the input of Pb was almost six times greater than the input from antifouling paints. Aerosols emitted from motor vehicles still represent the mayor source of Pb in this area. Cu originates mostly from antifouling paints and long-range transport. It was estimated that only around 30% of analysed elements introduced into the water column would be deposited in their final sink, i.e. marine sediments.

Abstract: The objective of this study was chemical and radiological characterization of soil samples affected by the dust emission and slag dumping from ferro-manganese smelter as well as uptake of metals by vegetation growing on that soil. Iron was the main component of metallurgical slag deposited near the smelter. Slag material was highly enriched in Zn, Cr, Cu, Co, and Pb. V and Cr were enriched in the soil taken near the smelter approximately by a factor of two, Pb and Cu were increased fivefold whereas the mean content of Mn was about 130 times higher than the levels in background soil samples. Activities of agricultural soil samples were typical for the soil developed on late Cretaceous carbonate surface. K-40, Th-232, and Cs-137 showed somewhat lower activities in background soil compared to the soil taken near the smelter while the opposite was found for Ra-226 and U-238. Plot of factor I against factor 2, obtained by Principal component analysis, showed perfect separation of the samples taken in the vicinity of the smelter, slag material, and normal background agricultural soil. Perfect correlation (Canonical R=0.992) was obtained between chemical composition of soil and vegetation samples taken from the same spots. The content of Mn was approximately 36 times higher in vegetation taken from the vicinity of the smelter compared to the background values.

Abstract: Water extracts genotoxicity of the coagulant produced from industrial waste (red Mud and waste base) and its waste mud remained after waste water treatment by the coagulation/flocculation process were studied. Tests were conducted in order to confirm nontoxicity of this new product prior to commercial production and usage and also to recommend a safe way for a handling and disposal of the remaining waste material. The toxicity investigation included (i) determining frequency of the cell survival, (ii) the Ames assays, (iii) micronucleus assay, and (iv) cell proliferation kinetics (expressed as mitotic index). These techniques were also employed in toxicity testing of the different concentrations of metal salts. zinc chloride, and lead nitrate in this case since these two elements were present in high concentrations in the waste water intended for the purification with the new coagulant. Mixture of metal salts in the concentrations that represent maximum allowed values for water extracts of technological waste was also tested. Two strains of Salmonella typhimurium, TA98, and TA 100 were used for determining cytotoxicity and for the Ames test, while the cytogenetic investigations were performed on human peripheral blood lymphocytes. Water extracts of the coagulant and its waste mud did not induce a significant increase of the micronuclei in human peripheral blood lymphocytes. They also did not disturb lymphocyte proliferation kinetics in vitro. As regards lead nitrate it proved not to be cytotoxic on bacterial strains in the tested concentration range (1-100 mg/L), whereas zinc chloride showed cytotoxic effect for the concentrations above 25 mg/L. The Ames test results for the noncytotoxic concentrations of these metals were negative. Comparing to the negative control a significantly higher number of the micronuclei was determined after the treatment of the whole blood with 100 mg/L of zinc chloride. as well as with 10 and 100 mg/L of lead nitrate. A linear, dose dependent increase was obtained for both salts. Similar results were obtained on the basis of the mitotic index.

Abstract: A new procedure for electroplating wastewater treatment using waste by-product (ferrous-sulfate) and waste (wood fly ash) is presented. Ferrous-sulfate was employed for Cr(VI) reduction whereas neutralization and heavy metal removal from electroplating wastewaters was performed using wood fly ash. Heavy metal removal efficiency varied from 97.5% for Cu to 99.973% for Zn. Satisfying results can be achieved already at the pH 8. The method is suitable for the purposes of wastewater treatment and disposal in compliance with environmental laws. Furthermore, it is technically simple, cost-efficient and requires less space compared to the classical methodology. According to the composition of its water extractable fraction remaining waste ash could be safely deposited on domestic waste repositories.

Abstract: This study was undertaken to investigate the suitability of applying the conventional method of chemical deinking flotation of digital offset prints and ecological implications of the disposal of digital offset prints, with special emphasis on the content of heavy metal cations. The EDXRF method was used to determine the concentrations of Pb, Zr, Sr, As, Co, Zn, Cu, Ni, Fe, Mn, Cr, V, Ti, Ca, and K cations in handsheet ashes after flotation as well as in ashes of foams separated from cellulose suspension in the flotation phase. The same method was applied to determine the concentrations of Pb, Cr, Mn, Fe, Ni, Cu, Zn, and Co in process water filtrates obtained from the cellulose suspension after flotation and in foam filtrates. Centrifuging and coagulation previously treated flotation process water, while foam filtrates were centrifuged. Concentrations of Pb, As, Sr, Zr, K, Ca, Ti, V, Cr, Mn, Fe, Cu, and Zn were determined in the sediments obtained by centrifuging process water. The trials were done with unprinted substrates without deinking chemicals, with unprinted substrates in the presence of deinking chemicals and with printed substrates in the presence of deinking chemicals. Cation analysis revealed that deinking chemicals facilitate release of cations from the substrate and their transition into process water. Concentrations of most cations in the flotation process water, in foam water as well as in the sediment of the process water of printed substrate flotation deinking were lower than those obtained by flotation of unprinted substrate suspension. Polymer particles of ElectroInk incompletely separated from cellulose fibers prevent release of cations from cellulose fibers into process water. Deinking chemicals do not affect release of cations from ElectroInk particles, so the substrate is the main source of increased concentration of cations in the water of digital offset print deinking. The major part of cations in process water is bound to the colloid particles of the filler (CaCO3) released by substrate disintegration and to particles of fine fibers.

Abstract: Samples of soil, plant material and water collected on the Croatian island Krk in northern Adriatic sea were analyzed for a number of elements (Ca, Ti, Mn, Fe, Ni, Cu, Zn, As, Br, Rb, Sr, Zr, Pb) by using energy dispersive X-ray fluorescence (EDXRF) as an analytical tool. Some of these data have been previously used to produce geochemical map of the island.(1) In addition, trace element contents of hair from children, attending elementary and secondary schools, has been investigated using the same analytical method for Mg, S, Ca, Cr, Mn, Fe, Ni, Cu, Zn, As, Hg and Pb elements. Concentrations of the twelve elements and nine variables from the questionnaire, i.e., age, sex, living place, transportation, medication, hair colour, hair type, type of shampoo used and hair treatment, were considered in the statistical analysis. The observed differences for the seven island's communes have also been discussed.

Abstract: The waste disposal site of the abandoned alumina plant near Obrovac, Croatia, contains two basins filled with red mud and waste base in total amounts estimated at 0.85 x 10(6) and 0.65 x 10(6) m(3), respectively. The Red mud was analyzed for its major components, heavy metals content, free base content and leaching properties under different conditions of pH and temperature. Concentrations of 15 elements (Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, As, Rb, Sr, Y, Zr, and Pb) were measured using tube excited EDXRF. The major compounds were determined by XRD, and AAS and XRF methods were used for elemental concentration determinations in different types of leachates. It was found that a possible threat to the environment from red mud under normal environmental conditions could be caused only by leaching of alkalis and V. On the other hand, the concentrations of V, Cr, Cu, As and Se in the waste base and the pH are much higher than allowed for technical waste waters discharged directly into the environment. Waste base treatment (neutralization and heavy metal removal) can be achieved in a one-step process. During this process, neutralization of acidic red mud would result in the production of a gel-like coagulant. Copyright (C) 2004 John Wiley Sons, Ltd.

Abstract: Water extracts genotoxicity of the coagulant produced from industrial waste (red mud and waste base) and its waste mud remained after waste water treatment by the coagulation/flocculation process were studied. Tests were conducted in order to confirm nontoxicity of this new product prior to commercial production and usage and also to recommend a safe way for a handling and disposal of the remaining waste material. The toxicity investigation included (i) determining frequency of the cell survival, (ii) the Ames assays, (iii) micronucleus assay, and (iv) cell proliferation kinetics (expressed as mitotic index). These techniques were also employed in toxicity testing of the different concentrations of metal salts, zinc chloride, and lead nitrate in this case since these two elements were present in high concentrations in the waste water intended for the purification with the new coagulant. Mixture of metal salts in the concentrations that represent maximum allowed values for water extracts of technological waste was also tested. Two strains of Salmonella typhimurium, TA98, and TA100 were used for determining cytotoxicity and for the Ames test, while the cytogenetic investigations were performed on human peripheral blood lymphocytes. Water extracts of the coagulant and its waste mud did not induce a significant increase of the micronuclei in human peripheral blood lymphocytes. They also did not disturb lymphocyte proliferation kinetics in vitro. As regards lead nitrate it proved not to be cytotoxic on bacterial strains in the tested concentration range (1-100 mg/L), whereas zinc chloride showed cytotoxic effect for the concentrations above 25 mg/L. The Ames test results for the noncytotoxic concentrations of these metals were negative. Comparing to the negative control a significantly higher number of the micronuclei was determined after the treatment of the whole blood with 100 mg/L of zinc chloride, as well as with 10 and 100 mg/L of lead nitrate. A linear, dose dependent increase was obtained for both salts. Similar results were obtained on the basis of the mitotic index.

Abstract: Vegetation samples were collected at 112 locations on the Croatian island Krk in the northern Adriatic sea. The collected samples were analyzed for 12 chemical elements (Ca, Cr, Mn, Fe, Ni, Cu, Zn, As, Br, Rb, Sr, Pb) by EDXRF method. For all of the measured elements concentration maps for the island were produced using kriging gridding methodology. This was done in order to relate variations in chemical composition of vegetation with that of soils as well as to the soil type, local environment, prevalent use of soil, and other antropogenic influences. Concentrations maps for the chemical elements have also been used in the evaluation of chemical elements transfer from plants to grazing animals, and eventually to the inhabitants of the island. Elemental transfer from the soil to the plants was confirmed by canonical correlation analysis. Good positive correlation between elemental concentration in soil and grass samples (canonical R = 0.647) was found.

Abstract: A system for waste water cleaning using activated red mud is described in this paper. This system was originally developed for heavy metals and turbidity removal from the waste water generated by pressure washing of the boats coated with antifouling paints. The major parts of the system are described. After the treatment clear water can be discharged directly into the sea and the remaining waste mud with high amount of Cu, Zn, and Pb is filtered through the filter bag and stored. It is possible to carry out five cycles with the same dose of coagulant. Untreated water and sediment analysis was done and concentrations of heavy metals in the treated water are lower than the allowed concentrations prescribed for the technological waste water that could be discharged into the environment.

Abstract: The elemental concentrations of nine elements (V, Cr, Mn, Fe, Ni, Cu, Zn, As and Pb) were determined in soil, grape and wine samples taken from the wine producing area of Vrbnik on the island Krk in the northern Adriatic) using the tube excited energy dispersive X-ray fluorescence, EDXRF method. Extensive grape cultivation in Vrbnicko polje through the years approximately doubled the Cu content in the soil from this area compared to the background level determined on Krk. Most of this total Cu is exchangeable and thus available to plants. The concentrations of all other elements are similar to those found in the Krk soil. Canonical analysis showed that the main source of heavy metals in grape was absorption from the soil. Statistically significant differences in elemental composition between red and white wine were found. All elements showed greater concentrations in red grape. In spite of the elevated Cu level in the soil, the content of this metal in wine was much lower than the allowed value.

Abstract: The physical, chemical and genotoxic properties of the activated red mud and its waste mud remained after waste water treatment were studied. The sequential leaching of waste mud under different conditions was investigated, as well as the toxic effect of its water extract, in order to discover a safe way for the handling and disposal of this waste material. Furthermore, in order to reduce the amount of waste material, the possibility of its regeneration and re-usage was also studied. Heavy metals content and other parameters, as well as the genotoxicity of water extract of new coagulant produced for industrial waste water treatment, were investigated to confirm its non-toxicity before its commercial production and usage. For the toxicity investigation, two strains of Salmonella typhimurium, TA98 and TA100 were used as a test system. Tested samples were not cytotoxic or mutagenic for S. typhimurium TA98/TA100 in the presence/absence of the metabolic activation. Promising results were also obtained in the field of waste mud regeneration and re-usage.

Abstract: Distributions of trace elements in the coastal sea sediments of Punat Bay in the Northern Adriatic have been investigated. The concentrations of 16 elements (Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Br, Rb, Sr, Y, Zr and Pb) were measured by energy dispersive XRF. Two predominant types of sediments were observed: the first (sediment "A"), which consists of 87% pelitic fraction and the second (sediment "B"), where coarse-grained fraction (0.315-0.1 mm) prevails. Enrichment factors had elevated values in two upper-most segments for the elements Cu, Zn and Pb in sediment "A." The highest percentage of exchangeable fraction with respect to the total composition was characteristic for Cr, Cu and Zn in both types of sediments. By means of the linear regression analysis it was established that metals present in the antifouling paints were dispersed all over the bay because of an inefficient cleaning mechanism, poor communication with the open sea, and the good mixing of water and suspended mater in the bay by tide and wind currents.

Abstract: Disposal of the dredged material from the harbor to the sea bottom represents a route through which many contaminants could be transported towards open sea and enter the food chain. In this study, five sediment samples were taken from different depths and locations within the Plomin bay (Istria Peninsula, Northern Adriatic Sea, Croatia). Water sediment extracts were prepared, analyzed for chemical and physical properties and subject to cytotoxic and mutagenic investigation. We used two strains of Salmonella typhimurium, TA98 (determination of frameshift mutations) and TA100 (detection of base pair substitutions) as a test system. The insensitivity of bacteria to heavy metals cytotoxicity and mutagenicity was avoided by changing the classical Ames assay with a modified preincubation. Cytotoxicity screening was made by spot test and by determination of frequency of the cell survival. For the mutagenic assay, sediment extracts and bacterial strains were preincubated for 24 hours at 37 degreesC (with and without metabolic activation) and incorporated on the minimal medium. After 72 hours the number of revertant colonies was counted. Concentrations of heavy metals measured in extracts represent exchangeable fraction and are 500-1000 times smaller than the content of the same elements in the solid mud. Nine elements were determined in extracts: V, Cr, Mn, Fe, Ni, Cu, Zn, As and Pb. None of the sediment sample extracts was cytotoxic or mutagenic for Salmonella typhimurium TA98 or TA100 in the presence/absence of metabolic activation.

Abstract: Coagulant production using red mud and waste base as raw material is described together with phase and chemical composition changes in red mud during coagulant production and usage. Investigation of phase and chemical composition was carried out using X-ray diffraction analysis (XRD) and sequential extraction. Acid treatment of the red mud resulted in the removal of the exchangeable fraction, carbonates and alkalis. Base addition into acid treated and centrifuged red mud caused its flocculation and sorption by surface enlargement. Mineral phase transition in coagulant (activated red mud) with time was not found. An amount of 1g of this coagulant was able to sorb 99.347mg of Cu, 95.002mg of Zn and 98.695mg of Pb from aqueous solution containing 100mg/l of those metals. Among three metals investigated, Zn sorption was the most affected with changes in pH value of treated solution. The sorption of metal cations (Cu(II), Zn(II) and Pb(Il)) from the metal-EDTA solution onto the activated red mud (ARM) for different metal-EDTA concentrations (1-100mg/l) was also investigated. It was found that, among the three tested metals, the sorption of Cu onto the ARM was most affected by EDTA. The removal of these three metals from the metal-EDTA mixture solution was also studied by using two other types of coagulants: ferric chloride and polyaluminium chloride (PAC). In the case of the FeCl3, the addition of EDTA had a slight influence on the Cu removal and none on the Pb and Zn removal, while in the case of the PAC, the greatest influence was found for all these metals.

Abstract: Disposal of the dredged material from the harbour to the sea bottom represents a route through which many contaminants could be transported towards the open sea and enter to the food chain. In this study, five sediment samples were taken from different depths and locations within Plomin bay (Istria Peninsula, Northern Adriatic Sea, Croatia). Water sediment extract were prepared and analysed for chemical and physical properties, and subjected to cytotoxic and mutagenic investigation. We used two strains of Salmonella typhimurium, TA98 (determination of frameshift mutation) and TA100 (detection of base pair substitution) as a test system. Result showed that concentrations of heavy metals measured in extracts represent exchangeable fraction and are 500-1000 times smaller than the content of the same elements in solid mud. Nine elements were determined in extract: V, Cr, Mn, Fe, Ni, Cu, Zn, As and Pb. None of sediment sample extracts were cytotoxic or mutagenic for S. typhimurium TA98 nor TA100 in presence/absence of metabolic activation.

Abstract: Soil samples were collected at 112 locations on Croatian island Krk in the northern Adriatic sea. The collected samples were analyzed for 14 chemical elements (Ca, Ti, Mn, Fe, Ni, Cu, Zn, As, Br, Rb, Sr, Y, Zr, Pb) by using EDXRF as an analytical tool. For all of the measured elements concentration maps for the island are produced using kriging gridding methodology. This is done in order to relate geochemical variations in soils to underlying differences in geology, soil type, local environment, prevalent use, and antropogenic influences. Concentration maps for the chemical elements measured could tie also used in the evaluation of chemical elements transfer from soils to plants, and eventually through food chain to the inhabitants of the island.

Abstract: Proposal for coagulant production using red mud and waste base as row material, by-products of abandoned alumina factory near Obrovac in Croatia, is described. Basic physico-chemical characteristics of red mud and waste base were also given. Elemental concentrations of red mud, waste base and wastewaters before and after treatment were measured using tube excited EDXRF method. Coagulant production consist of partial dissolution of red mud with diluted sulphuric acid (30% wt), separation of liquid from residual red mud by centrifugation or filtration through the filter press, and neutralisation of acid red mud (pH = 0) with the waste base to pH = 8. This process of red mud neutralisation results in heavy metals removal and also neutralisation of waste base to pH = 8, which could be, after treatment, discharged directly into the environment. Resulting red mud, after neutralisation, is in gel-like state and is suitable for heavy metals and turbidity removal from industrial wastewaters. As an example, wastewaters from pressure washing of boats coated with antifouling paints were used and promising results were obtained. With one dose of coagulant (activated red mud), five cycles of heavy metals removal could be done.