Štefica Kampić

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.

Influence of digested wastewater sludge on early growth of the perennial ryegrass (Lolium perenne L.)

Effects of residual wastewater sludge, amended with zeolites, on the early growth of perennial ryegrass (Lolium perenne L.) were investigated. For that purpose growth parameters, content of photosynthetic pigments, substrate characteristics, levels of macro- and micronutrients, as well as toxic elements in plant tissue, plant inorganic matter and substrates, sewage sludge and soil, were determined. Among the growth indicators, only protein content and inorganic matter in plant tissue were found to be influenced by the type and composition of the substrate. Sewage sludge was found to contain elevated levels of Mo, Ni, Pb, Sb, Se, Sr and Zn, while Cu and Sn were found in an order of magnitude higher levels compared to the control sample. Application of sewage sludge, however, modified only the content of Cu and Zn in the plant tissue, inducing accumulation of these elements by a factor of 2. Despite the fact that all other measured elements (Al, As, Ba, Ca, Cd, Co, Cr, Cs, Fe, K, Li, Mg, Mn, Na, Ti, U and V) were found in plant tissue at similar level regardless of the substrate metal loading, accumulation indices point to overall lower bioavailability of elements from digested sludge in comparison with control substrate. Moreover, metal concentrations in all analyzed plant samples were below legally established limits.

Environmental geochemistry of the polymetallic ore deposits: Case studies from the Rude and the Sv. Jakob historical mining sites, NW Croatia

This paper presents the results of the sampling surveys carried out in order to evaluate the environmental impact of the Rude and the Sv. Jakob historical mining sites, NW Croatia. The studied polymetallic ore deposits are differing in the mineralogical and geochemical features as well as in the host rock lithology. The Rude Fe-Cu-Pb-Zn-Ba deposit is hosted by Permian siliciclastic sediments. Siderite, hematite, galena, sphalerite, chalcopyrite, pyrite, barite and gypsum are the major ore minerals, whereas quartz is the principal gangue mineral. The Sv. Jakob Pb-Zn-Ag deposit occurs in the Middle Triassic dolostone. The most abundant ore minerals are galena, sphalerite and pyrite. Calcite and quartz represent the principal gangue minerals. Although the deposits represent the potential sources of numerous toxic metals, the pollution of the drainage streams and associated stream sediments was not recorded. The studied mining sites are characterized by the high carbonate/sulfide ratios responsible for the alkaline character of the drainage streams. Consequently, the mining sites have very low potential for generation of acid mine drainage as well as very low potential for leaching of heavy metals into the drainage systems. Furthermore, the presented study revealed that the populated areas (stream waters with decreased redox potential, increased organic matter content, high NO 3 - , NH 4 + and PO 4 3- concentrations; stream sediments enriched in exchangeable Pb and Zn) and the Sava river alluvium (overflowing streams enriched in Hg) represent bigger environmental threat than the investigated polymetallic ore deposits.

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

Copper and Zinc Fractionation in Apple Orchard Soil in the Village of Bukevje (Croatia) Using the Revised Four-Step BCR Extraction Procedure

Abstract The aim of this study was to establish the fractionation of copper and zinc in a small apple orchard using the revised (four-step) Bureau Communautaire de Reference (BCR) sequential extraction procedure and assess their potential mobility in soil. Soil samples were collected at the depth of 10 cm to 25 cm, sixteen from the orchard and five control samples from a meadow located some 200 m away from the orchard. As the distribution of trace-element concentrations in the control samples was normal, they were used for comparison as background levels. We also determined soil mineralogical composition, carbonate content, soil pH, cation exchange capacity, and soil organic matter. The extraction yields of Cu and Zn from the control soil were lower than from the orchard soil (25 % vs. 34 % and 47 % vs. 52 %, respectively), which pointed to natural processes behind metal bonding in the control soil and greater influence of man-made activities in the orchard soil. Compared to control, the orchard soil had significantly higher concentrations of total Cu (P=0.0009), possibly due to the application of Cu-based fungicides. This assumption was further supported by greater speciation variability of Cu than of zinc, which points to different origins of the two, Cu from pesticides and Zn from the parent bedrock. Copper levels significantly better (P=0.01) correlated with the oxidisable fraction of the orchard soil than of control soil. Residual and organically bound copper and zinc constituted the most important fractions in the studied soils. However, the use of Cu-based fungicides in the apple orchard did not impose environmental and health risk from Cu exposure. Sažetak Analizirani su uzorci tla iz obiteljskog voćnjaka u selu Bukevju kako bi se utvrdilo ponašanje metala u tragovima u okolišu u kontekstu poljoprivrednih postupaka proteklih nekoliko desetljeća. Unos kemijskih sredstava za zaštitu bilja navodno je nizak. Nakon provedene tzv. BCR sekvencijske ekstrakcijske analize, kemijski oblici bakra i cinka razmotreni su iz geokemijskoga/geološkoga gledišta. Uzeto je šesnaest uzoraka tla iz voćnjaka te pet uzoraka kontrolnog tla s obližnje livade. Analize su obuhvaćale određivanje mineralnog sastava tla, kationsko izmjenjivačkog kompleksa (KIK), pH tla i gubitka žarenjem. Koncentracije mjerenih varijabli u kontrolnim uzorcima, određene XRF metodom, upućuju na njihove prirodne razine na temelju normalnosti raspodjela. Tlo iz voćnjaka neznatno je onečišćeno bakrom, moguće od primjene fungicida na bazi bakra, što je utvrđeno Mann-Whitneyevim U testom, koji je pokazao statistički značajno više koncentracije ukupnog Cu (P = 0.0009) u tlu voćnjaka u usporedbi s uzorcima kontrolnog tla. Učinkovitost BCR ekstrakcije bakra i cinka izračunata za kontrolno tlo (25 % odnosno 47 %) bila je niža nego ona izračunata za tlo iz voćnjaka (34 % odnosno 52 %). Bakar, potječući djelomice od fungicida, pokazao je veću specijacijsku varijabilnost u istraživanim tlima u usporedbi s cinkom, za koji se pretpostavlja da potječe uglavnom od trošenja stijenske podloge. Mann-Whitneyev U test pokazao je statistički značajno (P = 0,01) više vrijednosti Cu povezane s frakcijom tla iz voćnjaka podložnoj oksidaciji u odnosu na istu frakciju kontrolnih uzoraka. Bakar i cink u istraživanim tlima čvrsto su vezani za rezidualnu i organsku frakciju, a ukupne im vrijednosti ne premašuju maksimalno dopuštenu količinu onečišćujućih tvari u poljoprivrednom zemljištu, pa ne bi trebali predstavljati toksikološku opasnost za ljudsko zdravlje.