Changes in chemical forms of lead in temperate and semiarid soils in sterile and unsterile conditions

Sequential extraction has been used as a suitable method for fractionation of chemical forms of trace elements and study of their plant availability. Surface soils were sampled from Guilan and Hamadan provinces in north and northwest of Iran with temperate and semiarid climates. The chemical forms of Pb in the Pb(NO₃)₂-treated (400 μg Pb g⁻¹) soils have been studied in solid state incubation (FC) at 27°C in sterile and unsterile conditions. After 20 min and 3600 h a sequential extraction scheme was also used to fractionate Pb of incubated samples into soluble-exchangeable (Sol-Exch), carbonates associated (ACar), organic matter associated (AOM), Mn oxide associated (AMnOx), Fe oxide associated (AFeOx), and residual (Res) forms. Temperate soil samples had higher clay content, cation exchange capacity (CEC), dichromate oxidable organic carbon (OC), total Kjeldahl-nitrogen (TN), biological activity, amorphous and crystalline Fe and Al, but semiarid soil samples had higher sand content, pH, equivalent calcium carbonate (ECC), available P and K. Soil lead fractionation revealed that in both groups of soils Pb largely changed to exchangeable, carbonates associated and organic associated forms after 20 min. The chemical forms of Pb differed widely among soils after 3600-h incubation. The conversion rate of Pb from more available forms to less available forms was higher in temperate soils with higher Fe–Mn oxides and OM contents compared to semiarid soils. In temperate soils after 3600-h incubation, greater content of Pb was observed in Res (68%), AOM (14%), ACar (7%), and AMnOx (5%) fractions. However, in semiarid soils greater content of Pb was observed in Res (61%), ACar (16%), Sol-Exch (8%), and AOM (8%) fractions. The sum of AMnOx and AFeOx chemical forms for Pb in semiarid soils compared to temperate soils was lower. It was only 7% against 9% in temperate soils. Soil microorganisms in unsterile soils had significant effect on AOM, AFeOx and Res fractions of Pb. They not only increased AOM and AFeOx fractions of Pb in soils but also decreased Res fraction of Pb significantly.     

Distribution and availability of potentially toxic metals in soil in central area of Belgrade,Serbia

Belgrade, capital city of Serbia, has over 1,600,000 inhabitants and over 400,000 vehicles trafficking every day on its streets. The investigation of soil pollution was performed by sequential extraction analysis to investigate the availability of potentially toxic metals (Zn, Cd, Pb, Co, Ni, Cu, Cr and Mn) under different oxidation and pH conditions. All investigated metals were mainly extracted from soils with neutral or acidic extractants. Serious pollution was observed along roads and streets with high traffic frequency, but Pb and Ni pollution was the highest since their concentrations exceed both soil Serbian standard and Canadian guidance values and is characteristic for all investigated sites. Cd, Cu, Cr and Zn concentrations are moderately high since they are between Canadian guideline and Serbian standard.     

Photochemical reaction of nitro-polycyclic aromatic hydrocarbons: effect by solvent and structure

Photochemical degradation of 1-nitropyrene, 2-nitrofluorene, 2,7-dinitrofluorene, 6-nitrochrysene, 3-nitrofluoranthene, 5-nitroacenaphthene, and 9-nitroanthracene was examined in CHCl₃, CH₂Cl₂, DMF, DMF/H₂O (80/20), CH₃CN, or CH₃CN/H₂O (80/20). The degradation mostly follows the first order kinetics; but a few follow second order kinetics or undergo self-catalysis. The photodegradation rates follow the order: CHCl₃ > CH₂Cl₂ > DMF > DMF/H₂O > CH₃CN > CH₃CN/H₂O. DMF is an exceptional solvent because three of the seven compounds undergo self-catalytic reaction. 9-Nitroanthracene, which has a perpendicular nitro group, is the fastest, while the more compact 1-nitropyrene and 3-nitrofluoranthene are the slowest degrading compounds.     

Quantification of singlet oxygen and hydroxyl radicals upon UV irradiation of surface water

We measured the formation rate and the steady-state concentration of hydroxyl radicals and of singlet oxygen upon irradiation of lake water. There is controversy about the importance of singlet oxygen in the environmental photochemistry, but here we show that the steady-state concentration of ¹O₂ under irradiation can be higher by about two orders of magnitude compared to the hydroxyl radical. The higher occurrence of singlet oxygen in surface waters is mainly due to a higher rate of formation, because the transformation rate constants of ¹O₂ (collision with the solvent) and of ^·OH (reaction with dissolved compounds) are comparable.     

Removal of chelated copper from wastewaters by Fe<Superscript>2+</Superscript>-based replacement–precipitation

We studied the removal mechanism and affecting factors of Fe²⁺-based replacement–precipitation process for treating CuEDTA-containing wastewaters. Since Fe²⁺ was easily oxidized to Fe³⁺ in the presence of oxygen, the chelated copper was removed by the synergetic effect of Fe³⁺ replacement and NaOH precipitation. Our experiments showed that the copper removal efficiency was considerably dependant on pH conditions of the solution and molar ratio of Fe²⁺/Cu²⁺.     

Screening of phthalic acid esters in raw materials,premixes and feed additives

Phthalates are animal carcinogens and may cause death or tissue deformities. Samples of feedstuffs collected in 2005 and 2006 from industrial feed manufacturers in the Czech Republic were analysed for contamination with phthalic acid esters (PAEs), specifically di-2-ethylhexyl phthalate (DEHP) and di-n-butyl phthalate (DBP). Samples of feed additives, premixes and raw materials were collected (year 2005, n = 26). For soybean oil, the total volume of phthalates measured (DBP + DEHP) reached a level of 131.42 mg kg⁻¹; for rapeseed oil, fish meal and animal fats, the levels measured were 15.00, 7.96 and 58.87 mg kg⁻¹, respectively. The lowest level of DBP + DEHP was found in corn (2.03 mg kg⁻¹). Since phthalates were detected, samples of feed additives (n = 28) and raw materials (n = 28) were collected again in 2006. The highest levels of DBP + DEHP were found in raw materials containing fat. Phthalate levels in rapeseed oil samples ranged from 1.38 to 32.40 mg kg⁻¹ DBP + DEHP. For feed additives, contamination levels in vitamins and amino acids ranged from 0.06 to 3.15 and 1.76 to 4.52 mg kg⁻¹ DBP + DEHP, respectively. Here, we show that the levels of PAEs found in cereals such as wheat, barley and corn may be regarded as being alarmingly high, because cereals make up the largest proportion of compound feed of farm animals.     

Evaluation of metabisulfite and a commercial steel wool for removing chromium(VI) from wastewater

Efficiency of metabisulfite and a commercial steel wool as reducing agents in the removal of Cr(VI) from wastewaters was evaluated. Chromium(VI) was converted to Cr(III), precipitated with NaOH, and removed by filtration. A reduction of more than 1.0 × 10⁵ and 4.0 × 10⁵ fold in total Cr and the Cr(VI) concentrations, respectively, was observed by employing steel wool masses as low as 0.4420 g to 30-mL solutions of wastewater. Chromium(III) hydroxide obtained after the treatment was recycled and used as marker in cattle nutrition studies. The liquid residue obtained after the treatment was reused as precipitation agent replacing NaOH.     

Removal of malachite green from water samples by cloud point extraction using Triton X-100 as non-ionic surfactant

A surfactant mediated cloud point extraction (CPE) procedure has been developed to remove color from wastewater containing malachite green using Triton X-100 as non-ionic surfactant. The effects of the concentration of the surfactant, temperature and salt concentration on the different concentrations of dye have been studied and optimum conditions were obtained for the removal of malachite green. The concentration of malachite green in the dilute phase was measured using UV–Vis spectrophotometer. It was found that the separation of phases was complete and the recovery of malachite green was very effective in the presence of NaCl as an electrolyte. The results showed that up to 500 ppm of malachite green can quantitatively be removed (>95%) by CPE procedure in a single extraction using optimum conditions.     

Photo-polymerization of triclosan in aqueous solution induced by ultraviolet radiation

The formation of 2,8-dichlorodibenzo-p-dioxin and other harmful degradation products in the photo-degradation process of triclosan is of increasing concern. Here we worked on the identification of polymerized products at high triclosan concentration and on the mechanism of photoreaction. Five dimmers and two trimers of triclosan were detected by liquid chromatography-mass spectrum analysis. 2,8-dichlorodibenzo-p-dioxin was also identified by comparing with an authentic standard. Relatively low pH and high concentration favored the polymerization of triclosan. Three main routes of photoreaction were postulated, namely dechlorination, ring closure and polymerization.