Gordana Medunić

ICP-AES determination of minor- and major elements in apples after microwave assisted digestion

The aim of this paper was to determine the content of minor and major elements in apples by inductively coupled plasma atomic emission spectrometry (ICP-AES). Prior to ICP-AES measurement, dried apples were digested in a microwave assisted digestion system. The differences in the measured element concentrations after application of open and closed microwave system as sample preparation procedures are discussed. In whole apples, flesh and peel Ag, Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sr and Zn were analysed after optimisation and validating the analytical method using ICP-AES. The accuracy of the method determined by spiking experiments was very good (recoveries 88-115%) and the limits of detection of elements of interest were from 0.01 up to 14.7 μg g(-1). The reference ranges determined in all apple samples are 39-47 mg g(-1) for K, 9-14 mg g(-1) for Na, 3-7 mg g(-1) for Mg, 3-7 μg g(-1) for Zn, 0.7-2.8 μg g(-1) for Sr. The range of Mn in peel 4-6 μg g(-1) is higher compared to whole apple from 0.7 to 1.7 μg g(-1). Cd is found only in peel, in the concentration range of 0.4-1.1 μg g(-1).

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−1L, 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.

Leaching properties of electric arc furnace dust prior/following alkaline extraction

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· 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.

Toxic airborne S, PAH, and trace element legacy of the superhigh-organic-sulphur Raša coal combustion: Cytotoxicity and genotoxicity assessment of soil and ash.

This paper presents the levels of sulphur, polycyclic aromatic hydrocarbons (PAHs), and potentially toxic trace elements in soils surrounding the Plomin coal-fired power plant (Croatia). It used domestic superhigh-organic-sulphur Raša coal from 1970 until 2000. Raša coal was characterised by exceptionally high values of S, up to 14%, making the downwind southwest (SW) area surrounding the power plant a significant hotspot. The analytical results show that the SW soil locations are severely polluted with S (up to 4%), and PAHs (up to 13,535ng/g), while moderately with Se (up to 6.8mg/kg), and Cd (up to 4.7mg/kg). The composition and distribution pattern of PAHs in the polluted soils indicate that their main source could be airborne unburnt coal particles. The atmospheric dispersion processes of SO2 and ash particles have influenced the composition and distribution patterns of sulphur and potentially toxic trace elements in studied soils, respectively. A possible adverse impact of analysed soil on the local karstic environment was evaluated by cytotoxic and genotoxic methods. The cytotoxicity effects of soil and ash water extracts on the channel catfish ovary (CCO) cell line were found to be statistically significant in the case of the most polluted soil and ash samples. However, the primary DNA-damaging potential of the most polluted soil samples on the CCO cells was found to be within acceptable boundaries.

Influence of soil characteristics on rare earth fingerprints in mosses and mushrooms: Example of a pristine temperate rainforest (Slavonia, Croatia)

The present study aims to investigate levels and distribution of rare earth elements (REE) in soils, mosses and mushrooms of a pristine temperate rainforest, a non-polluted natural system, in order to characterise their environmental availability and mobility. The multielement analysis of digested soil, moss and mushroom samples was performed by High Resolution Inductively Coupled Plasma Mass Spectrometry. The distribution of rare earths in mosses and mushrooms was found primarily affected by local pedological setting. Mosses displayed a consistent lithological signature with an almost insignificant REE fractionation compared to soils. Mushrooms showed differences in REE concentrations in certain parts of the fruiting body with regard to their main physiological function and indicated a significant impact of soil organic content on the overall REEs uptake. Results of our work highlight the importance of substrate characteristics on the initial levels of REEs in mosses and mushrooms. Moreover, this study provides baseline data on the rare earth element levels in mosses and mushrooms growing in a pristine forest area characterised by naturally elevated REE levels in the soil.

Removal of Cr(VI) from aqueous solution by a commercial carbon black

AbstractHexavalent chromium is classified as a human carcinogen of high carcinogenic hazard according to the US EPA. Therefore, batch adsorption experiments aiming at Cr(VI) removal from an aqueous solution were carried out using a commercial carbon black (CB) as an adsorbent. The CB was characterized by the Brunauer–Emmett–Teller and Barrett–Joyner–Halenda, scanning electron microscopy with energy dispersive X-ray spectroscopy, and Fourier transform infrared spectroscopy methods. Various parameters were tested, including adsorbent dose, solution pH, contact time, initial metal concentration, and temperature, so as to determine their relation to the adsorption yield. The results showed that an initial solution of pH 2.4 was most favorable for the Cr(VI) removal. The equilibrium data were analyzed by the Freundlich, Langmuir, and Temkin isotherm models. The equilibrium data best fitted according to the Freundlich isotherm model. The CB maximum adsorption capacity was found at 33.22 mg/g, thus proved to be ...

Inertisation of galvanic sludge with calcium oxide, activated carbon, and phosphoric acid

In this study we compared three methods for the treatment of electroplating sludge highly loaded with zinc and iron: (1) calcium oxide-based solidifi cation/stabilisation; (2) conversion into inert material by adsorption of organic and inorganic pollutants onto activated carbon; and (3) conversion of mobile waste components into insoluble phosphates. All three methods proved highly effi cient in the conversion of hazardous waste into inert material. Under optimum treatment conditions zinc concentration in the leachate of solidifi ed waste was reduced by 99.7 % compared to untreated sludge. Zinc retention effi ciency in the waste treated with activated carbon and phosphoric acid was 99.9 % and 98.7 %, respectively. The advantages of electroplating sludge treatment with activated carbon over the other two methods are high sorption capacity, insignifi cant pH and volume changes of the sludge, and simple use.

Characterization and treatment of the phosphoric gypsum transport water

This paper presents a new treatment procedure applied on phosphogypsum transport water. Untreated transport water is highly acidic (pH 1.79), having fluoride content of 1540 mg/L and elevated values of phosphates (215 mg/L) and heavy metals (Fe = 25.8 mg/L; Zn = 5.7 mg/L; Mn = 2.7 mg/L, V = 1.7 mg/L). Neutralization/purification of the transport water was carried out with wood fly ash, otherwise a rich source of calcium, composed of calcite, dipotassium calcium carbonate and hydroxylapatite. Maximum removal efficiency of fluoride was observed at pH 7 (99.99%) and phosphate at pH 9 (96.29%). The removal of fluorides was a consequence of the formation of fluorite and fluorapatite mineral phases derived from the reaction of calcium (released from the fly ash minerals) and fluorides (from the transport water). The removal of phosphates resulted from the formation of fluorapathite and hydroxilapatite. At the optimum conditions removal efficiencies for the elements Pb, V, Cr(VI), Mn, Fe, Ni, Cu, and Zn were 95%, 98.14%, 91.11%, 100%, 99.71%, 96.33%, 97.24%, and 99.65%, respectively. Optimal heavy metal removal occurred in major cases at pH 7.

Geochemistry of Croatian superhigh-organic- sulphur Raša coal, imported low-S coal, and bottom ash: their Se and trace metal fingerprints in seawater, clover, foliage, and mushroom specimens

The Labin city area has represented the major Croatian coal mining, metal industry, and coal- fired electricity centre for more than two centuries. Th

Multi-element composition of soil, mosses and mushrooms and assessment of natural and artificial radioactivity of a pristine temperate rainforest system (Slavonia, Croatia)

This study investigates multi-element composition of soil, mosses and mushrooms from a pristine temperate rainforest (Prašnik, Croatia). Additionally, the activity levels of natural (238U, 235U and 232Th decay chains, 40K and 7Be) and anthropogenic (137Cs and 134Cs) radionuclides in the investigated soil samples, obtained by gamma spectrometry, provide baseline of environmental radioactivity levels in this area. The aim of investigation was to explore the uptake of metal(loid)s by bioindicator species (mosses, mushrooms) growing in a pristine environment characterized by naturally elevated concentration of metals. The calculated enrichment and bioaccumulation factors, correlations between different groups of elements and similar multi-element patterns in mosses, mushrooms and soil samples revealed the prevailing influence of the local substrate geochemistry on element concentrations in mosses and mushrooms. The results suggest atmospheric deposition of Bi, Cd and Pb, while radionuclide activities point to atmospheric fall-out (including global contamination by radiocaesium) and influence of the pedological substrate. The confined area of investigation, with limited variations in soil characteristics and geological composition, allowed clearer insight into the origin of metal(loid)s in mosses and mushrooms. On the other hand, using bioindicator species with different element uptake mechanisms enabled distinction between different sources of elements.