Soil pollution assessment in the Baia Mare area after partial closure of ore processing activities

The paper presents the assessment of the soil pollution with Cu, Pb and Zn in the Baia Mare area, historically polluted with metals resulted from mining and processing of non-ferrous ores. Despite the closure of mines and reducing the activity related to ore processing, Baia Mare is still a highly polluted site with Pb, Cu and Zn. The Tessier extraction scheme carried out on soil samples recently collected revealed the residual fraction as dominant for all three metals, followed by the reducible fraction bound to Fe and Mn oxides. The exchangeable fraction, considered as the most mobile fraction and that bound to carbonates, which can be mobilized under acidic conditions, were lower. The presence of the oxidisable metal fraction was also observed

Characterization and assessment of potential environmental risk of tailings stored in seven impoundments in the Aries river basin, Western Romania

BACKGROUND: The objective of this study was to examine the potential environmental risk of tailings resulted after precious and base metal ores processing, stored in seven impoundments located in the Aries river basin, Romania. The tailings were characterized by mineralogical and elemental composition, contamination indices, acid rock drainage generation potential and water leachability of hazardous/priority hazardous metals and ions. Multivariate statistical methods were used for data interpretation. RESULTS: Tailings were found to be highly contaminated with several hazardous/priority hazardous metals (As, Cu, Cd, Pb), and pose potential contamination risk for soil, sediments, surface and groundwater. Two out of the seven studied impoundments does not satisfy the criteria required for inert wastes, shows acid rock drainage potential and thus can contaminate the surface and groundwater. Three impoundments were found to be highly contaminated with As, Pb and Cd, two with As and other two with Cu. The tailings impoundments were grouped based on the enrichment factor, geoaccumulation index, contamination factor and contamination degree of 7 hazardous/priority hazardous metals (As, Cd, Cr, Cu, Ni, Pb, Zn) considered typical for the studied tailings. Principal component analysis showed that 47% of the elemental variability was attributable to alkaline silicate rocks, 31% to acidic S-containing minerals, 12% to carbonate minerals and 5% to biogenic elements. Leachability of metals and ions was ascribed in proportion of 61% to silicates, 11% to acidic minerals and 6% to the organic matter. A variability of 18% was attributed to leachability of biogenic elements (Na, K, Cl(-), NO(3)(-)) with no potential environmental risk. Pattern recognition by agglomerative hierarchical clustering emphasized the grouping of impoundments in agreement with their contamination degree and acid rock drainage generation potential. CONCLUSIONS: Tailings stored in the studied impoundments were found to be contaminated with some hazardous/ priority hazardous metals, fluoride and sulphate and thus presents different contamination risk for the environment. A long term monitoring program of these tailings impoundments and the expansion of the ecologization measures in the area is required

Assessing the bioavailability and translocation efficiency of mineral elements in Lycium barbarum species from R. Macedonia and R. China

Goji berries or wolfberries (Lycium barbarum L.) have been traditionally used as food and a medicinal plant. The interest in the chemical composition of goji berries has intensified because of an increased awareness of their possible health benefits. On the other hand, the toxic elements can also be interacting in the plant tissue through the bioavailable pathway of the root-soil system. The present work reports the results obtained by the proposed method for the simultaneous determination of metals (Na, Mg, K, Ca, Mn, Fe, Cu and Zn) and nonmetals (P and S) in goji berries by using inductively coupled plasma–optical emission spectrometry (ICP-OES), following digestion using a diluted oxidant mixture in a closed-vessel microwave oven. Determinations of Cr, As, Pb, Cd and Ni were realized using the graphite furnace atomic absorption spectrometer (GFAAS). Mercury quantification was realized on the solid samples by the TDAAS method, with the automated direct mercury analyzer hydra-C. The obtained data for element contents reports the multi-element characterization of different plant parts, and variation in multi-elements content between Macedonian and Chinese species. Bioaccumulation and bioconcentration factor scores revealed the translocation efficiency of metals and nonmetals across the Lycium barbarum plant parts

Figures of Merit and Fundamental Processes in the Analysis of Ca from Liquid Samples Using an r.f. CCP Torch with Tubular and Ring Electrodes

A radiofrequency capacitively coupled Ar plasma, obtained with a molybdenum tubular electrode placed inside a quartz tube and one or two copper ring electrodes placed outside the tube, was used as spectral source for determination of atoms, ions and molecular radicals of calcium. A simultaneous spectrometer equipped with a photodiode array was used for detection of emission spectra. The atomization and ionization processes of Ca species were studied in the presence and absence of NaCl and H3PO4 matrix, with both single ring and two rings electrode torches. The limits of detection are 250 ng mL–1 for CaII 393 nm, 100 ng mL–1 for CaI 423 nm, 230 and 100 ng mL–1 for CaOH 555 nm and 622 nm. The recovery degree for certified plasma serum samples was 99.4 ± 4.4% and the RSD was between 3.8–4.9%. For 5 blood samples the RSD of Ca content is 2.9–4.4%

Figures of Merit and Fundamental Processes in the Analysis of Ca from Liquid Samples Using an r.f. CCP Torch with Tubular and Ring Electrodes

A radiofrequency capacitively coupled Ar plasma, obtained with a molybdenum tubular electrode placed inside a quartz tube and one or two copper ring electrodes placed outside the tube, was used as spectral source for determination of atoms, ions and molecular radicals of calcium. A simultaneous spectrometer equipped with a photodiode array was used for detection of emission spectra. The atomization and ionization processes of Ca species were studied in the presence and absence of NaCl and H3PO4 matrix, with both single ring and two rings electrode torches. The limits of detection are 250 ng mL–1 for CaII 393 nm, 100 ng mL–1 for CaI 423 nm, 230 and 100 ng mL–1 for CaOH 555 nm and 622 nm. The recovery degree for certified plasma serum samples was 99.4 ± 4.4% and the RSD was between 3.8–4.9%. For 5 blood samples the RSD of Ca content is 2.9–4.4%

Traces of Cu, Mn and Zn in Aquatic Animals, Water and Sediments from the Cris River Basin West Romania. Part II: Distribution Study

The paper presents the determination of Cu, Mn and Zn (TRT r.f.CCP-AES, FAAS) in water, sediment and aquatic animals (fish fillet, freshwater molluscs gills and muscles) collected in the basin of the Cris rivers (White Cris and Black Cris) in West Romania. The concentrations in water were in the range: 1-15 pg Lr1 (Cu), 10-1500 pg L-1 (Mn), 3-100 pg L-1 (Zn). Metal contents, as dry mass fractions, w^m x IO6, were: 5-380 (Cu), 225-2000 (Mn), 23-1140 (Zn) in sediment; 1-11 (Cu), 4-40 (Mn), 8-130 (Zn) in fish fillet, and 5-34 (Cu), 100-600 (Mn) and 50-130 (Zn) in mollusc muscles with higher values for the White Cris samples. Among the seven sample collection sites only one was identified as having concentrations of Mn and Zn in water higher than the admitted levels, but the limits of tolerance for aquatic organisms were not exceeded in either river. In mollusc gills, the metal contents expressed as wdm x IO6 were: 8-60 (Cu), 11000-16000 (Mn), 190-1200 (Zn), and similar for both rivers in the case of Mn

Rapid Determination of Trace Elements in Macedonian Grape Brandies for Their Characterization and Safety Evaluation

A graphite furnace atomic absorption spectrometry (GFAAS) was used for determination of trace elements (Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) in Brakija^ samples, a grape brandy traditionally produced in Republic of Macedonia by distillation of grape pomace or wine, for characterization and safety evaluation. Cd, Pb, Cr, and Ni were determined directly, while Cu, Fe, Mn, and Zn were quantified after appropriate dilution. The calibration curves of all elements were linear with correlation coefficients (R 2 ) ranging from 0.9995 to 0.9998. The accuracy of the method was checked with a standard addition method showing good repeatability and reproducibility (relative standard deviation (RSD) <10 %). Relationship between several metal concentrations (Cu, Fe, Mn, Zn) in brandies and distillation system (homemade/industrial) on one side and aging mode (oak barrels/oak chips) on the other side were demonstrated. Two homemade brandies showed Cu, Fe, and Zn concentrations higher than industrial distillates and thus were found to be not safe for consumption because of Cu and Zn over the maximum allowed values. For the industrially produced brandies, Mn was identified to be a suitable marker related to aging with oak chips regardless variety, while Cu a marker for the influence of oak chip type

Fatty acids composition of selected Macedonian goji berries determined by GC-FID

Goji berries or wolfberries (Lycium barbarum L.) have been used in traditional Chinese medicine for over 2000 years. They are known as anti-aging fruits, fat-free and a good source of fibers and antioxidants. This study, for the first time, presents the fatty acids composition of Macedonian goji berries determined using GC-FID technique. Oil extraction of seeds was performed by sonication with petroleum eter [1], followed by transmethylation of the fatty acids, under alkali-catalysed conditions [2]. Twelve different types of fatty acids (FAs) were found in the samples, including caplrylic (C8:0), capric (C10:0), lauric (C12:0), myristic (C14:0), pamitic (C16:0), pamitoleic (C16:1), stearic (C18:0), oleic (C18:1), linoleic (C18:2n6), linolenic (C18:3n3), arachidic (C20:0) and behenic (C22:0) acids. In all the analyzed fruit samples, the predominant fatty acid was linoleic, followed by oleic, palmitic and stearic acids. The erucic (C22:1n9) and lignoceric (C24:0) acids were not detected in any of the analyzed samples. The fatty acid percentage composition of goji berries, total percentage of saturated fatty acids (SFAs), monounsaturated fatty acids (MUFAs) and polyunsaturated fatty acids (PUFAs) were determined. The analyzed fruits were mainly constituted by PUFAs (59.25–73.98%), followed by SFAs (13.02–26.27%), and finally by MUFAs (13.00–18.29%). The total unsaturated fatty acids (UFAs=MUFAs+PUFAs) varied between 73.73% and 86.98%, with average of 82.33%

Traces of Cu, Mn and Zn in Aquatic Animals and Sediments from the Cris River Basin West Romania. Part I: Statistical Evaluation of Data Obtained by Atomic Emission Spectrometry with Radiofrequency Capacitively Coupled Plasma Source and Flame Atomic Absorption Spectrometry

The limits of detection in r.f.CCP-AES were 2 (Cu), 6 (Mn) and 3 (Zn) pg g_1. Statistic evaluation of the results was based on 31 samples collected in the basin of the Cris rivers, Romania. After removing the samples with a metal concentration lower than the limit of determination in TRT r.f.CCP-AES, the F-test (95% confidence level) showed similar precision in the two methods, with one exception in the case of Mn and one in the case of Zn. From 21, 28 and 31 determinations of Cu, Mn and Zn, statistical correlation and regression as well as the analysis of Bland and Altman (95% confidence level) showed systematic errors in TRT r.f.CCP-AES versus FAAS only in one case for Cu, two cases for Mn and one case for Zn. The metal content amounted to: 10-400 pg g-1 (Cu), 20-16000 pg g-1 (Mn) and 20-1200 pg g-1 (Zn)