Use of the BCR three-step sequential extraction procedure for the study of the partitioning of Cd, Pb and Zn in various soil samples

A slightly modified three-step sequential extraction procedure proposed by the Community Bureau of Reference (BCR) for analysis of sediments was successfully applied to soil samples. Contaminated soil samples from the lead and zinc mining area in the Mezica valley (Slovenia) and natural soils from a non-industrial area were analysed. The total concentrations of Cd, Pb and Zn and their concentrations in fractions after extraction were determined by flame or electrothermal atomic absorption spectrometry (FAAS, ETAAS). Total metal concentrations in natural soils ranged from 0.3 to 2.6 mg kg^-1 for Cd, from 20 to 45 mg kg^-1 for Pb and from 70 to 140 mg kg^-1 for Zn, while these concentrations ranged from 0.5 to 35 mg kg^-1 for Cd, from 200 to 10000 mg kg^-1 for Pb and from 140 to 1500 mg kg^-1 for Zn in soils from contaminated areas. The results of the partitioning study applying the slightly modified BCR three-step extraction procedure indicate that Cd, Pb and Zn in natural soils prevails mostly in sparingly soluble fractions. Cd in natural soils is bound mainly to Fe and Mn oxides and hydroxides, Pb to organic matter, sulphides and silicates, while Zn is predominantly bound to silicates. In contaminated soils, Cd, Pb and Zn are distributed between the easily and sparingly soluble fractions. Due to the high total Cd, Pb and Zn concentrations in contaminated soil close to the smelter, ! and their high proportions in the easily soluble fraction (80% of Cd, 50% of Pb and 70% of Zn), the soil around smelters represents an environmental hazard.     

Determination of ultratrace cadmium in food and environmental samples by ETAAS after vapor generation and in situ preconcentration

A method is described for the determination of ultratrace cadmium by coupling a continuous flow vapor generation system with in situ preconcentration technique and electrothermal atomic absorption spectrometry (ETAAS). A graphite tube coated with Ir as permanent chemical modifier was used for trapping cadmium vapor species. The effects of the flow rates of carrier gas and sample injection in vapor generation systems on the trapping measurement for cadmium were respectively investigated. Graphite tubes with different characteristic surfaces were comparatively studied for trapping cadmium vapor. The experimental results showed that the permanent chemical modifier of Ir is an alternative to the thermolabile modifier of Pd for simplifying the trapping measurement. The trapping efficiency of cadmium on the graphite tube coated with Ir was estimated. The trapping temperature and time were also investigated. A detection limit (3σ) of 0.005 μg·L⁻¹ was obtained for this proposed method. The relative standard deviation (RSD) was 1.4% for 0.5 μ·L⁻¹ of Cd (n = 11). This method can be applied to the determination of ultratrace cadmium in food and environmental samples with good agreement between the certified and found values.     

Heavy Metal Contents of Vegetables Grown in Soil, Irrigated with Mixtures of Wastewater and Sewage Sludge in Pakistan, using Ultrasonic-Assisted Pseudo-digestion

The success of risk assessment of metal‐contaminated soils depends on how precisely one can predict the bio‐availability of trace and toxic metals in soil and transfer to the human food chain. A field experiment was carried out from 2004 to 2005 to evaluate the long‐term effect of sewage sludge application in agricultural lands where mostly vegetables are grown. The aim of this study was to predict the uptake of Cd, Cu, Cr, Ni, Pb and Zn by different vegetables grown on agricultural soil irrigated for long period with untreated domestic waste water and sewage sludge (SIDWS) as test samples and for comparative purposes, same vegetables grown on agricultural soil irrigated with fresh canal water (SIFW), collected as control samples. A sample preparation method based on ultrasound‐assisted pseudo‐digestion (UASD) of soil, sewage sludge and vegetable samples in ultrasonic bath was developed. A conventional wet acid digestion method was used for comparison purposes. The EDTA‐extractable metal in SIFW and SIDWS was also studied. The extracts and digests were analysed by flame atomic absorption spectrometer/electrothermal atomic absorption spectrometer (FAAS/ETAAS). Analytical results for six metals and metalloid by UASD in bath and conventional wet digestion methods showed a good agreement, thus indicating the possibility of using low mass and minimum quantity of digesting acid mixture in less time when compared with the conventional digestion method (CDM). The validation of the proposed UASD method was assessed by using certified reference materials BCR 483 and (whole meal flour) BCR 189. Recoveries ranging from 95.5 % to 102.3 % for understudied metals were obtained for different samples (soils and vegetables). The average relative standard deviation of UASD method varied between 2.3 % and 7.9 % for N = 12, depending on the analyte. The vegetables grown in SIDWS showed high level of heavy metals when compared with control samples. This investigation highlights the increased danger of growing vegetables in the agricultural land, continuously irrigated and dressed with waste water and solid sewage sludge.