Macrocapsules, composed of a pH-sensitive polymer and phosphate buffer, offer a novel remediation alternative for acidic ground waters. To test their potential effectiveness, laboratory experiments were carried out followed by a field trial within a coal pile runoff (CPR) acidic contaminant plume. Results of traditional limestone and macrocapsule treatments were compared in both laboratory and field experiments. Macrocapsules were more effective than limestone as a passive treatment for raising pH in well water from 2.5 to 6 in both laboratory and field experiments. The limestone treatments had limited impact on pH, only increasing pH as high as 3.3, and armoring by iron was evident in the field trial. Aluminum, iron and sulfate concentrations remained relatively constant throughout the experiments, but phosphate increased (0.15-32 mg/L), indicating macrocapsule release. This research confirmed that macrocapsules may be an effective alternative to limestone to treat highly acidic ground water. Encapsulated phosphate buffer macrocapsules were more effective than limestone for passive treatment of acidic coal pile runoff (CPR) contaminated ground water, increasing pH from 2.5 to 6 in laboratory and field experiments.

The aims of the present study were to optimize and validate methods for esterase activity (EA), total oxidant status (TOS) and total antioxidant capacity (TAC) determination in mussel' gills, and to establish the relationships between these biomarkers and Pb, Cd and Cu pollution, in single form and ternary mixture. Two different buffers for sample homogenization, the need of ultracentrifugation, and analytical validation were evaluated. Coefficients of variation, when buffer without additives and ultracentrifugation were used, were <15%, and recovery were 97%–109% in all cases. The EA response tends to decrease with treatments, TOS decreased significantly in Cd and ternary groups, while TAC tended to increase in treatments with Pb, Cd and ternary groups. In conclusion, the methods for EA, TOS and TAC measurements in gills of mussel were precise and accurate and could be interesting resources in biomonitoring programmes.

Albendazole (ALB) belongs to a group of benzimidazoles - classified as antiparasitic pharmaceuticals. Its widespread application results in the presence of this pharmaceutical in natural environment (water and soil). In this paper a suitable pretreatment method was established including sampling, freeze-drying and extraction. Vicia faba was used as model organism. ALB accumulation by plant tissues was observed in hydroponic culture as well as in soil. The range of pharmaceutical concentrations was 1.7 × 10-5 mol/L (in hydroponic culture) and 1.7 × 10-5 to 1.7 × 10-4 mol/kg air dry soil (in soil). Observations were conducted for 14 days. After this time biological material was freeze-dried and after homogenization, dimethyl sulfoxide (DMSO) extraction was performed. The recovery of ALB for the roots was 93 % while for the shoots 86 %. After cleaning, the samples were subjected to further analysis by HPLC system. Phosphate buffer and acetonitrile (50:50) were used as a mobile phase. Drug retention time was 6.3 min. Results obtained in this experiment indicate higher drug accumulation in roots rather than in the hypocotyl part of the plant, cultivated both in soil and in hydroponic culture. © 2013 The Author(s).

Extraction and analysis methods have been developed for the detection of the following four antibacterial agents and two natural estrogens in treated municipal wastewater sludge and commercial compost: sulfamethoxazole (SMX), sulfadimethoxine (SDM), tetracycline (TET), oxytetracycline (OXY), estrone (E1), and 17β-estradiol (E2). The antibiotics and estrogens were extracted from secondary sludge and mixed compost using ultrasonic solvent extraction. Citric acid (pH 4.7) and methanol were used as extraction buffer, followed by tandem-solid-phase extraction cleanup, strong anion exchange + hydrophilic–lipophilic balance for antibiotics and CarboPrep/NAX for estrogens. For quantification, two different methods were employed, using HPLC–MS/MS, with an electrospray ionization source for antibiotics and an atmospheric-pressure chemical ionization source for estrogens. Recoveries were 11–31% for the sulfonamides (SMX and SDM) and tetracyclines (TET and OXY) and 30–59% for the estrogens (E1 and E2) over the entire method. Limits of detection for the extraction method were in the nanogram per gram range for dry weight sludge and compost samples. Neither of the two sulfonamide antibiotics was detected in secondary sludge or mixed compost samples. Estrogens were found in compost in amounts of 160 ± 65 ng/g (E1) and 21 ± 3 ng/g (E2), but not in sludge. The tetracyclines, as well as what is believed to be the 4-epimer of OXY, were found in both sludge and compost in amounts of 1.57 ± 0.67 and 2.95 ± 0.42 μg/g (TET), 0.56 ± 0.12 and 6.51 ± 0.52 μg/g (OXY), and 7.60 ± 1.68 and 1.35 ± 0.24 μg/g (4-epi-OXY), respectively. These results indicate that sorption-prone compounds are not removed during the wastewater treatment process and can persist through sludge digestion and that the composting process does not sufficiently eliminate these particular contaminants. Thus, biosolids (even composted) are an additional source of drug residues leaching into the environment, and it must be considered while using biosolids as fertilizer.

The use of multiwall carbon nanotubes (MWCNT) as an efficient solid extractor in preconcentration/cleanup studies for tin determination in water samples by electrothermal atomic absorption spectrometry (ETAAS) is proposed. In the proposed method, tin adsorption onto MWCNT was carried out by percolating the solution previously buffered (pH 4.79 with 0.24 mol L−1 acetic acid/acetate buffer) at 4.0-mL min−1 flow rate, followed by elution with 1.0 mL of 2.7 mol L−1 HNO3. Factors such as sample pH, preconcentration/cleanup flow rate, type and concentration of eluent, and buffer concentration were appraised and optimized from chemometric tools based on fractional factorial design and Doehlert design. A limit of detection of 0.73 μg L−1 and precision (n = 8) assessed as relative standard deviation of 8.6% and 7.0% for tin concentration of 8.0 and 43.0 μg L−1, respectively, were achieved. Foreign metallic ions (Ni2+, Pb2+, Co2+, Zn2+, Cd2+, Mn2+, and Fe3+) were checked as potential interferents, and no interference was observed up to an analyte/interference ratio of 1:10 (m/v). Direct tin determination by ETAAS in water samples containing high salt amount is drastically affected by background signal. However, previous cleanup of sample by MWCNT has promoted a significant improvement and makes the method useful for tin monitoring in water samples (mineral, lake, mine, and natural waters) by ETAAS. Quantitative recovery values ranging from 91.5% to 103.0% attested the applicability of the proposed preconcentration/cleanup for tin determination in water samples.

The decolorization and degradation of anionic sulphonated azo dye (Reactive orange 16 (RO16)), which is suspected to be carcinogenic, were investigated using ozone. The decolorization process of the reactive dye was carried out by bubbling ozone at the bottom of a bubble column reactor containing the dye solution. The effect of pH, reaction time, dye concentration, ozone concentration, and decolorization time was studied. Also, degradation products and possible degradation mechanism were investigated. The results showed that ozonation was a highly effective way to remove color from wastewater. The color of a synthetic waste solution containing water-soluble reactive dye was reduced to 69.69 % under the basic condition (pH 12), with complete RO16 degradation occurring in 8 min. Ozone consumption continued for a further 16 min after which time most of the degradation reactions were complete. Kinetic studies showed that direct ozonation of the aqueous dyes represented a pseudo-first-order reaction with respect to the dye. The apparent rate constant increased with both the applied ozone dose and higher pH values and declined logarithmically with the initial dye concentration. Intermediates such as 6-acetylamino-3-aminonaphthalene-2-sulfonic acid, 2-(4-nitrosophenyl) sulfonylethyl hydrogen sulfate, and 6-acetamido-4-hydroxy-3-nitroso naphthalene-2-sulfonic acid were detected by gas chromatograph coupled with mass spectrometry in the absence of pH buffer, while nitrate and sulfate ions and formic, acetic, and oxalic acids were detected by ion chromatography.

Peroxidase from fenugreek (Trigonella foenum-graecum) seeds was highly effective in the decolorization of textile effluent. Effluent was recalcitrant to the action of fenugreek seeds peroxidase (FSP). However, in order to effectively decolorize effluent by peroxidase, the role of six redox mediators has been investigated. The maximum decolorization of textile effluent was observed in the presence of 1.0 mM 1-hydroxybenzotrizole, 0.7 mM H₂O₂, and 0.4 U ml⁻¹ of FSP in the buffer of pH 5.0 at 40°C in 2.5 h. The decolorization of textile effluent in a batch process by peroxidase was 85% in 5 h, whereas the complete decolorization of textile effluent by membrane-entrapped FSP was observed within 11 h of its operation. The absorption spectra of treated effluent exhibited a marked diminution in the absorbance at different wavelengths compared to untreated effluent.

Analytical procedure for the determination of exchangeable Cr(VI) was developed. In order to optimise the extraction procedure, the efficiency of extraction of exchangeable Cr(VI) in soil samples was investigated in KH₂PO₄-K₂HPO₄ buffer solutions (0.015 up to 0.2 mol l-¹), adjusted to the pH of the soil. Phosphate buffer was used to efficiently desorb Cr(VI) from soil particles. The extraction time (mechanical shaking) ranged from 1 up to 72 h. Cr(VI) in soil extracts was determined by anion-exchange fast protein liquid chromatography with electrothermal atomic absorption detection (FPLC-ETAAS). The study was performed on soil samples from the field treated with the tannery waste for seventeen years. Samples were analysed in the 16 year after the last waste application. It was experimentally proven that the optimal phosphate buffer concentration was 0.1 mol l-¹ and extraction time 16 h. An additional experiment was done to confirm that during the extraction, soluble Cr(III) was not oxidised to Cr(VI) by Mn(IV) oxides present in soil samples. For this purpose soil with the same characteristics, but not treated with tannery waste, was spiked with Cr(III) and the analytical procedure performed. No measurable Cr(VI) concentrations were detected. The repeatability of measurement was 2.5%, while the reproducibility of measurement was 6.9%. The accuracy of the analytical procedure was tested by spiking of soil samples with Cr(VI). The recoveries were better than 95%. The analytical procedure with limit of detection (LOD) 15 ng g-¹ of Cr(VI) was sensitive enough for the determination of exchangeable Cr(VI) in soils. In field soil samples analysed the concentrations of exchangeable Cr(VI) were found to be about 200 ng g-¹.