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.

Retrieving planktonic foraminifera from lithified rocks, examples from the Eocene limestones and marls (External Dinarides, Croatia).

Paleoecologic (paleoclimatologic) and biostratigraphic studies of pelagic and deep-water deposits rely on the identification of planktonic foraminifera. Here we report and compare the results of planktonic foraminiferal assemblages from the Middle Eocene indurated limestones and marls collected in the External Dinarides extracted with acetic acid of different concentrations (50%, 60%, 70% and 80%) and different reaction (exposure) times. The deposits originated within the Dinaric foreland basin, have been assigned to the so-called Transitional beds and Flysch, and are characterized by different ratio of carbonate content and degree of lithification. The aim of this paper is to compare the efficiency of the laboratory procedures for obtaining isolated specimens and to evaluate the impact of preparation procedure on the quality of tests (complete test vs. secondary dissolution effects). For each acetic concentration we assessed:(1)the effectiveness of the treatment in terms of the time required for successful extraction of planktonic foraminifera, and(2)the degree of dissolution by analyses of dissolution proxies, including the weight percentage of sieved residues after disaggregation and preservation features of the tests. Our results indicate that accurate taxonomic analysis of carbonate rocks requires the use of 60% acetic acid for a shorter reaction time, and hydrogen peroxide methods for marls.

Copper and zinc fractionation in apple orchard soil in the village of Bukevje (Croatia) using the revised four-step BCR extraction procedure.

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 Référence (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.

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(-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.

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.