Toxicity assessment of untreated/treated electroplating sludge using human and plant bioassay.

The purpose of this work was to assess the risk to the environment arising from the electroplating sludge from both chemical and toxicological point of view. Both approaches were used for the assessment of the treatment efficiency which consisted of CaO based solidification followed by thermal treatment at 400°C. The elemental composition was determined in the bulk samples and the leachates of untreated sludge. The toxicity of the leachate was determined using two human colorectal adenocarcinoma cell lines (Caco-2 and SW 480) and Hordeum vulgare L. based plant bioassay. The same toxicity tests were employed to the leachate of the treated sludge. Untreated sludge showed extremely high cytotoxic effect to both human and plant bio-system in dose-dependent manner. The percentages higher than 0.5% and 0.05% of the leachate caused significant cytotoxic effect on Caco-2 and SW 480 cells, respectively. The percentages of the leachate higher than 0.05% also showed significant toxic effect to H. vulgare L. bio-system with complete arrest of seed germination following the treatment with 100% to 5% of the leachate. The leachate of the treated sludge showed no toxicity to any of the test systems confirming the efficiency and justification of the employed procedures for the detoxification of electroplating sludge.

Electroplating wastewater treatment by the combined electrochemical and ozonation methods.

This article presents a pilot-plant study of the electroplating wastewater treatment by the processes of electroreduction with iron electrode plates, and electrocoagulation/ozonation with aluminum electrode set, followed by the process of ozonation. The initial effluent was found to be highly enriched in heavy metals and to possess the elevated levels of organic contaminants. The values of Cr(VI), Fe, Ni, Cu, Zn, Pb, TOC, and COD exceeded the upper permissible limits of 63, 220.2, 1.1, 7, 131.3, 1.7, 12.3, and 11.4 times, respectively. The heavy metal removal was forced either by the coagulation/flocculation using Fe(II), Fe(III), and Al(III) ions released into the treated solution by the electrochemical corrosion of the sacrificial iron and aluminum electrodes, or the precipitation of the metal hydroxides as well as co-precipitation with iron and aluminum hydroxides. The principle organic matter destruction mechanisms were ozone oxidation and the indirect oxidation with chlorine/hypochlorite formed by the anodic oxidation of chloride already present in the wastewater. Following the combined treatment, the removal efficiencies of Cr(VI), Fe, Ni, Cu, Zn, Pb, TOC, and COD were 99.94%, 100.00%, 95.86%, 98.66%, 99.97%, 96.81%, 93.24%, and 93.43%, respectively, thus complying with the regulated values.

Treatment of winery wastewater by electrochemical methods and advanced oxidation processes.

The aim of this research was development of new system for the treatment of highly polluted wastewater (COD = 10240 mg/L; SS = 2860 mg/L) originating from vine-making industry. The system consisted of the main treatment that included electrochemical methods (electro oxidation, electrocoagulation using stainless steel, iron and aluminum electrode sets) with simultaneous sonication and recirculation in strong electromagnetic field. Ozonation combined with UV irradiation in the presence of added hydrogen peroxide was applied for the post-treatment of the effluent. Following the combined treatment, the final removal efficiencies of the parameters color, turbidity, suspended solids and phosphates were over 99%, Fe, Cu and ammonia approximately 98%, while the removal of COD and sulfates was 77% and 62%, respectively. A new approach combining electrochemical methods with ultrasound in the strong electromagnetic field resulted in significantly better removal efficiencies for majority of the measured parameters compared to the biological methods, advanced oxidation processes or electrocoagulation. Reduction of the treatment time represents another advantage of this new approach.

The determination of the extractability of selected elements from agricultural soil.

Concentrations of Ag, Al, Ba, Cd, Co, Cr, Cu, Fe, K, Mn, Na, Ni, Pb, Sr, and Zn-isolated by sequential extraction steps from apple orchard soil-were analyzed by inductively coupled plasma-atomic emission spectroscopy and compared to the total amount of metal in soil determined by XRF. The extractable amount of each metal was calculated by the extraction yields of the four steps. The LODs of the different elements in all extracts ware below 3 µg/L except for Ba (steps 1 and 2), Cu (step 1), Fe (all steps), K (steps 1-3), Mn (step 2), Na (steps 1-3), Ni (step 1), Pb (steps 1 and 4), and Zn (steps 1 and 2). The highest LOD (>10 µg/L) was found for Fe, K, and Na (step 1). The recovery of all metals after four sequential extraction steps was 90-112%. The repeatability (<1.1%), the intermediate precision (<5.3%), the day-to-day reproducibility (<6.2%), and the overall uncertainty of measurement (approximately 4-8.5%) for all analyzed metals supports the choice of the method used.

Chemical and radiological characterization of fly and bottom ash landfill of the former sulfate pulp factory Plaski and its surroundings.

The subject of this study was chemical and radiological characterization of the fly and bottom ash, by-product of the combustion of coal used as an energy source in the former sulfate pulp factory in Plaski. The research involves determination of the concentration of macro, micro and trace elements and activities of the radionuclides in: (i) ash from different positions of the landfill; (ii) soil samples in the zone of the influence of the landfill; (iii) control soil samples and (iv) sediment sample from the river Dretulja. Besides, in situ measurement of an effective dose rate above ash/soil was also determined. In relation with the control soil the average increase of the concentrations of the elements Ca, Cd, Hg, Ni, Se, Sr, Th and U in the samples taken from the fly and bottom ash landfill as well as soil samples within the radius of 300 m from the landfill was 38.3, 6.7, 9.9, 8.5, 9.4, 7.2, 3.6 and 5.7 times, respectively. In these samples, the concentrations of the above mentioned elements were in the following ranges: calcium from 7.94 to 19.7 %; cadmium from 0.33 to 1.66 mg/kg; mercury from 0.18 to 0.49 mg/kg; nickel from 260 to 1500 mg/kg; selenium from 2.7 to 21 mg/kg; strontium from 176 to 542 mg/kg; thorium from 8 to 55 mg/kg and uranium from 5.6 to 19.7 mg/kg. Compared to the world's average soil concentration, uranium and thorium values increased 3.7 and 1.7 times, respectively. The mean value of the total effective dose rate measured in the air at the height of 1 m for all samples of ash and soil under the influence of the landfill was 1.60 mSv/yr. Compared to the Croatian average (0.7015 mSv/yr), the determined mean value for the Plaski landfill is two times higher. However, compared to the local background (0.14 mSv/yr), the mean value of the total effective dose rate measured above the Plaski landfill is 11.4 times higher. In the samples of ash and contaminated soil regardless of the sampling location the activity concentrations of the radionuclides in Bq/kg vary in the following ranges: (226)Ra from 82.10 to 314.90 (mean value 145.99), (232)Th from 32.50 to 223.60 (mean value 76.76) and (238)U from 69.10 to 243.20 (mean value 134.38). Compared to the mean values found in the background soil (226)Ra and (238)U mean activity concentrations increased from 1.6 to 6.4 times and (232)Th from 1.4 to 4.3 times. In order to reduce total effective dose rate to the local "background" values and to prevent redistribution of the radionuclides and heavy metals from the deposited material into the environment fly and bottom ash landfill must be sealed with 10 cm thick layer of the material with low permeability.

Characterization and treatment of water used for human consumption from six sources located in the Cameron/Tuba City abandoned uranium mining area.

The purpose of this research was the characterization and improvement of the quality of water used for human consumption of unregulated/regulated water sources located in the Cameron/Tuba City abandoned uranium mining area (NE Arizona, western edge of the Navajo Nation). Samples were collected at six water sources which included regulated sources: Wind Mill (Tank 3T-538), Badger Springs and Paddock Well as well as unregulated sources: Willy Spring, Water Wall and Water Hole. Samples taken from Wind Mill, Water Wall and Water Hole were characterized with high turbidity and color as well as high level of manganese, iron and nickel and elevated value of molybdenum. High level of iron was also found in Badger Spring, Willy Spring, and Paddock Well. These three water sources were also characterized with elevated values of fluoride and vanadium. Significant amounts of zinc were found in Water Wall and Water Hole samples. Water Wall sample was also characterized with high level of Cr(VI). Compared to primary or secondary Navajo Nation Environmental Protection Agency (NNEPA) water quality standard the highest enrichment was found for turbidity (50.000 times), color (up to 1.796 times) and manganese (71 times), Cr(VI) (17.5 times), iron (7.4 times) and arsenic (5.2 times). Activities of (226)Ra and (238)U in water samples were still in agreement with the maximum contaminant levels. In order to comply with NNEPA water quality standard water samples were subjected to electrochemical treatment. This method was selected due to its high removal efficiency for heavy metals and uranium, lower settlement time, production of smaller volume of waste mud and higher stability of waste mud compared to physico-chemical treatment. Following the treatment, concentrations of heavy metals and activities of radionuclides in all samples were significantly lower compared to NNEPA or WHO regulated values. The maximum removal efficiencies for color, turbidity, arsenic, manganese, molybdenum and nickel were 100.0%. Maximum removal percentage of Cu, F(-), V, Zn, (137)Cs, (226)Ra, (232)Th, (238)U were as follows: 98.0%; 82.7%; 99.9%; 95.6%; 75.0%; 76.9%; 80.0% and 99.2%. From the results presented it could be concluded that electrochemical treatment is a suitable approach for the purification of drinking water with complex mixture of contaminants, especially those with high turbidity and color.

A combined treatment of landfill leachate using calcium oxide, ferric chloride and clinoptilolite.

The aim of this research was development of appropriate procedure for treatment of landfill leachate taken from old sanitary landfill Piskornica (Koprivnica, Croatia). Due to complex nature of the effluent a combined treatment approach was applied. Samples were treated with calcium oxide followed by ferric chloride and finally with clinoptilolite. The optimum amount of treating agents and contact time were determined. Application of calcium oxide (25 g/L, 20 min. contact time) resulted in the reduction of color, turbidity, suspended solids and ammonia for 94.50%, 96.55%, 95.66% and 21.60%, respectively, while the removal efficiency of Cr (VI), Fe, Ni, Cu, Zn and Pb was 75.00%, 95.34%, 56.52%, 78.72%, 73.02% and 100.00%, respectively. After addition of ferric chloride (570 mg Fe(3+)/L, 20 min. contact time) removal efficiency of color, turbidity, suspended solids and ammonia increased to 96.04%, 99.27%, 98.61%, and 43.20%, respectively. Removal of ammonia (81.60%) increased significantly after final adsorption onto clinoptilolite (25 g/L, 4 h contact time). Removal of COD after successive treatment with calcium oxide, ferric chloride and clinoptilolite was 64.70%, 77.40% and 81.00%, respectively.

Carbon isotope fractionation in karst aquatic mosses.

Radiocarbon activity (a14C) and 13C composition (δ13C) were measured in hygrophyte and mesophyte (land) mosses collected in the natural habitat of the Plitvice Lakes and along the Zrmanja and Krupa Rivers (typical continental and Mediterranean climates, respectively), Croatia. a14C and δ13C values of mosses, of atmospheric CO2 and dissolved inorganic carbon (DIC) were compared with contemporary data and with data from 30 years ago at the Plitvice Lakes when 14C activity of atmospheric CO2 was ∼30% higher. A positive correlation between a14Cmoss and δ13Cmoss was observed for all data reflecting the change of carbon isotopic composition in DIC along the water flows and in atmospheric CO2 regardless of the climatic regions and historic period. Fraction of the atmospheric carbon in moss (ωatm.C) and carbon fractionation factor from aquatic CO2 (DIC) to moss tissue (εmoss/g-aq) were calculated for each individual moss. Three species of mosses had ωatm.C ∼ 0 % implying that they turn to anabiosis during dry periods. The relation εmoss/g-aqvs.ωatm.C differentiates true aquatic and amphiphyte mosses. The first had a statistically significant negative correlation between εmoss/g-aq and ωatm.C. The amphiphyte mosses had lower εmoss/g-aq with higher water flow rates.

Ecotoxicological assessment of industrial effluent using duckweed (Lemna minor L.) as a test organism.

This study aimed at assessing the toxic effects of industrial effluents using duckweed (Lemna minor L.) plants as a test system. Growth inhibition test according to standardized protocol (ISO 20079) was performed. The suitability of the Comet assay (indicates DNA damage) and certain parameters such as peroxidase activity and lipid peroxidation level, as biomarkers for environmental monitoring was evaluated. The water samples were collected monthly over a 3-month period from the stream near the industrial estate of Savski Marof, Croatia. All samples caused inhibition of growth rates based on frond number and biomass as well as decrease of chlorophylls content. In contrast, peroxidase activity, malondialdehyde content and tail extent moment (measure of DNA strand breaks) markedly increased. Obtained data demonstrate the relevance of duckweed as sensitive indicators of water quality as well as the significance of selected biological parameters in the reliable assessment of phyto- and genotoxic potential of complex wastewaters.

Boat pressure washing wastewater treatment with calcium oxide and/or ferric chloride.

The aim of this study was to investigate the efficiency of (1) chemical precipitation by calcium oxide, (2) coagulation/flocculation by ferric chloride (FC), and (3) the combination these two methods in reducing the toxicity of wastewater generated by boat pressure washing. All three methods gave satisfactory results in the removal of colour, turbidity, Cr, Fe, Cu, Zn, and Pb. The concentrations of heavy metals were lowered below national limits with 1 g of CaO, 2.54 mg of Fe3+ in the form of FeCl3x6H2O, and the combination of 0.25 g of CaO and 5.08 mg of Fe3+ per 50 mL of wastewater. Both CaO (1.50 g per 50 mL of wastewater) and FC proved efficient, but their combination yielded a significantly better performance: 99.41 %, 100.00 %, 97.87 %, 99.09 %, 99.90 %, 99.46 % and 98.33 % for colour, turbidity, Cr, Fe, Cu, Zn, and Pb respectively. For colour, Cr, Cu, Zn, and Pb removal efficiencies increased in the following order: FC

The bulk composition and leaching properties of electroplating sludge prior/following the solidification/stabilization by calcium oxide.

Eighteen samples of electroplating sludge were taken from three vertical profiles of waste storage pond of the zinc plating facility. Dry matter and organic matter content, pH value, bulk concentrations and leachate composition were determined. A sludge sample with the highest zinc value in the leachate was treated with calcium oxide (10% to 70%) and the obtained solidificate was repeatedly tested. There were found significant variations of all measured parameters among the profiles of untreated waste. Dry matter content varied from 125 to 455 mgg(-1), organic matter varied from 94.3 to 293.9 mgg(-1), and pH value varied from 3.42 to 5.90 (mean 4.34). Iron content ranged from 38.4 to 191.4 mgg(-1) (mean 136 mgg(-1); RSD 0.25), while zinc ranged from 10.9 to 58.2 mgg(-1) (mean 33.4 mgg(-1); RSD 0.38). According to its DIN38414-S4 leachate composition, this material was not suitable for landfilling of inert waste since zinc and nickel mean values were 10 and 1.5 times higher, respectively, and maximum values 27 and 2.5 times higher, respectively, compared to the upper permissible limit. Maximum values of Cr(VI), Fe, Ni, Cu, and Zn in the DIN38414-S4 leachate were 0.183 mgL(-1), 34.085 mgL(-1), 1.052 mgL(-1), 0.829 mgL(-1) and 107.475 mgL(-1)L, respectively. Following the solidification/stabilization procedure with CaO (sample/CaO = 90/10), concentrations of Cr(VI), Fe, Cu and Zn were reduced 92, 44, 66 and 57 times, respectively, compared to the untreated sample. The addition of 50% of CaO into the sludge reduced zinc and nickel concentrations 79 and 45 times, respectively, in the DIN38414-S4 leachate of the solidified waste compared to the original sludge, thereby converting an hazardous waste into the inert material suitable for landfilling or reuse in the construction processes.