Investigation of Acidithiobacillus ferrooxidans in pure and mixed-species culture for bioleaching of Theisen sludge from former copper smelting.

AIMS: The aim of this study was to investigate the potential of bioleaching for the treatment of an environmentally hazardous waste, a blast-furnace flue dust designated Theisen sludge. METHODS AND RESULTS: Bioleaching of Theisen sludge was investigated at acidic conditions with Acidithiobacillus ferrooxidans in pure and mixed-species culture with Acidiphilium. In shaking-flask experiments, bioleaching parameters (pH, redox potential, zinc extraction from ZnS, ferrous- and ferric-iron concentration) were controlled regularly. The analysis of the dissolved metals showed that 70% zinc and 45% copper were extracted. Investigations regarding the arsenic and antimony species were performed. When iron ions were lacking, animonate (Sb(V)) and total arsenic concentration were highest in solution. The bioleaching approach was scaled up in stirred-tank bioreactors resulting in higher leaching efficiency of valuable trace elements. Concentrations of dissolved antimony were approx. 23 times, and of cobalt, germanium, and rhenium three times higher in comparison to shaking-flask experiments, when considering the difference in solid load of Theisen sludge. CONCLUSIONS: The extraction of base and trace metals from Theisen sludge, despite of its high content of heavy metals and organic compounds, was feasible with iron-oxidizing acidophilic bacteria. In stirred-tank bioreactors, the mixed-species culture performed better. SIGNIFICANCE AND IMPACT OF THE STUDY: To the best of our knowledge, this study is the first providing an appropriate biological technology for the treatment of Theisen sludge to win valuable elements.

Volatile organic compounds effective diffusion coefficients and fluxes estimation through two types of construction material.

UNLABELLED: Accumulation of volatile organic compounds (VOCs) that migrate inside buildings from underlying contaminated soils and groundwater poses human health risks. VOCs intrusion into buildings driven only by diffusion was reproduced by a laboratory-scale experiment. Effective diffusion coefficients and fluxes of a group of selected chlorinated solvents and BTEX through two types of isolation material - that is, concrete (anhydrite screed) and geo-membrane - were estimated. The laboratory experiment indicated that the diffusive transfer of pollutants through sediments into indoor air of buildings cannot be prevented by building sealing material, but it could be attenuated to a certain degree by concrete and up to non-detectable levels by the geo-membrane. Effective diffusion coefficients through concrete and geo-membrane ranged from 3.17 × 10(-2) to 5.90 × 10(-5) cm(2) /s and from 5.47 × 10(-6) to 5.50 × 10(-8) cm(2) /s, respectively. PRACTICAL IMPLICATIONS: The vapor intrusion of volatile organic compounds (VOCs) into buildings has special relevance in human health risk assessment. Prediction of indoor air VOCs concentration by applying numerical or analytical models eventually fails due to the lack of input parameters, such as the VOCs effective diffusion coefficient through building material used as foundation or isolation material. Passive migration of VOCs from contaminated sites into indoor air through construction and isolation materials has not been extensively investigated. Our findings showed that the mass flux through building material is not negligible, but it could be reduced partly, and to a minimum, with the utilization of concrete and geo-membranes, respectively. As a result of our investigation, effective diffusion coefficients of BTEX and chlorinated solvents, as well as the correlation between specific compounds' parameters and the estimated effective diffusion coefficient, are provided.

Impact of arsenic on uptake and bio-accumulation of antimony by arsenic hyperaccumulator Pteris vittata.

Individual uptake of As and Sb species in Pteris vittata have been investigated, but little information is available how uptake is affected if both metalloids are simultaneously present in different amounts. We investigated the uptake of antimony and its speciation in Pteris vittata cultivated in quartz substrate with, versus without, co-contamination with arsenic and a contaminated soil for 7 weeks. Applying HPLC-ICP-MS technique Sb(V), Sb(III), As(III), and As(V) could be identified as main species in aqueous extracts of roots and fronds with up to 230 mg kg(-1) of total Sb in the roots. Adding increasing amounts of As to the quartz substrate resulted in increasing uptake of Sb. In contrast to As, which is readily transferred to the fronds, Sb is primarily accumulated in the roots with Sb(V) being the dominant species (>90% of Sb). The addition of As doesn't result in enhanced translocation of Sb into the fronds.

Sorption of aqueous antimony and arsenic species onto akaganeite.

Two akaganeite materials were tested for the removal of antimonate, trimethyl antimonate, arsenate, arsenite, and dimethyl arsenate from water: a commercial product (GEH) and a synthesized akaganeite. The two materials show similar q(max) values, but differ in their K(L) values. This could be a result of their different crystal sizes indicated by sharper XRD reflections of the synthesized akaganeite compared with GEH. Batch experiments were carried out using all species to investigate the influence of the pH on their sorption onto the commercial material. The best results for the removal of antimonate and arsenate were achieved under acidic conditions, while the sorption of arsenite has an optimum at pH 7. The maximum loadings vary from 450 mg g(-1) (antimonate at pH 2.2.) to 2 mg g(-1) (trimethyl antimonate at pH 7). Competition reactions (up to a 10-fold excess of the competitor ion) were studied with antimonate, arsenate, and phosphate. The sorption capacity of arsenate decreases up to 12.5% by adding phosphate (ratio 1:10), but the addition of antimonate did not influence the sorption of arsenate. Conversely, the sorption of antimonate decreases due to the addition of 10-fold concentration of arsenate (31%) or phosphate (27%).

Analytical investigations of phenyl arsenicals in groundwater.

Phenylic arsenic compounds are the main contaminants in groundwater at abandoned sites with a history of arsenic containing chemical warfare agents (CWA). A fast and sensitive HPLC-ICP-MS method was developed to determine inorganic arsenic compounds like arsenite and arsenate as well as the degradation products of the arsenic containing warfare agents (phenylarsonic acid, phenylarsine oxide, diphenylarsinic acid). Beside these arsenic species the groundwater samples contained also high iron contents (up to 23 mg/l as Fe(II)) which led to precipitates in the samples after coming into contact with the atmosphere. Preservation immediately after sampling by phosphoric acid has shown that a successful avoidance of any losses of any arsenic species between sampling and analysis was possible. The suggested analytical method was applied to groundwater samples taken from different depths at a polluted site. The main contaminant in the water samples was diphenylarsinic acid (up to 2.1 mg/l) identified by ESI-MS, but also elevated concentrations of inorganic arsenic (up to 240 microg/l) were found.

Preservation of arsenic species in water samples using phosphoric acid--limitations and long-term stability.

The preservation of arsenic species in water samples is an indispensable method to avoid their changes during storage, if it is not possible to analyse them immediately. The aim of this investigation was to demonstrate the limitations of the suggested method by using phosphoric acid as a preservation agent. The samples remain stable for 3 months, even if they show evidence of high concentrations of iron or manganese. Critical is an increasing pH>3. Theoretically, a precipitation of strengite (Fe(3)(PO(4))(2)) could occur, which should be avoided. Phosphoric acid with a final concentration of 10mM is recommended as a preservation agent, combined with keeping the samples cool (6 degrees C) and dark. Filtration of samples before preservation may be carried out with respect to the analytical aim to distinguish between the total and soluble fraction (without colloids). It was shown that filtered and non-filtered samples can be preserved by utilising the above mentioned scheme.

Kinetics of the arsenite oxidation in seepage water from a tin mill tailings pond.

The kinetic of the oxidation of trivalent arsenic was investigated in synthetic as well as in natural samples of a tin mill seepage water. The influence of ferric ions and solid MnO(2) on the process was studied. To determine the time dependence of the concentrations of the arsenic species, a series of samples were taken sequentially and analysed by coupling of ionchromatographic separation and ICP-MS detection. To investigate the naturally occurring oxidation reaction, original seepage water samples were filtered and spiked with As(III) (1 mg l(-1)) and Fe(II) (10 mg l(-1)) and shaken providing intensive contact with the air. Additional synthetic samples buffered with carbonate were used in similar experiments to simplify the system. The reaction was incomplete in the presence of excess of iron for both types of samples. The oxidation of As(III) was complete within 8 h in the presence of MnO(2) (10 mg), but there was a difference in oxidation rates between the natural and the synthetic samples. The results are discussed with respect to the redox potentials and equilibrium constants.

Determination of flotation reagents used in tin-mining by capillary electrophoresis.

Alkyl xanthates (O-alkyl dithiocarbonates) and phosphonates are important organic collectors for the flotation of metals from crude ore. Leaching from waste dumps into river and ground water, these substances can cause environmental pollution. A capillary electrophoretic method for the routine determination of ethyl, isopropyl, hexyl xanthate, and styrene phosphonate has been developed. Separation within 12 min could be achieved in borate pH 8.8 performing UV detection at 254 and 300 nm simultaneously. To improve the limits of detection obtained with hydrodynamic injection (0.4-1.5 ppm), field amplified sample injection (FASI) and stacking were investigated. An increase in sensitivity up to 4-8 fold could be achieved by pressure assisted FASI. Applying a stacking method to enrich the analytes by filling the capillary with sample solution to one third of its length, the limits of detection could be decreased to 10-40 ppb. Water samples from a former tin ore mining area have been analyzed using the optimized stacking technique. Quantitation was performed by standard addition. Good precision and accuracy were obtained, making this robust capillary electrophoretic method well-suited for routine analysis.

Arsenic speciation in iron hydroxide precipitates.

In this study a special sequential extraction method is proposed to discriminate between arsenic adsorbed and co-precipitated in precipitates arising mainly from iron hydroxides or bound in low solubility mineral phases. Synthetic iron hydroxide precipitates were prepared to investigate the influence of the amount of arsenate, of the manganese additionally added and of the valence state of arsenic on the remobilisation of arsenic. After preparing the precipitates with arsenate no arsenic could be detected in the supernatant solution. About 82% (w/w) of the arsenate is adsorbed to the precipitate and the remaining part can be dissolved by shaking with an oxalate buffer. A significant difference between the amount of arsenic added and the amount analysed in the two steps was not found. Consequently, compounds with a low solubility, such as scorodite, were not formed in the synthesized precipitates. The valence of the arsenic and addition of manganese influence significantly the uptake of arsenic by iron hydroxides. Natural precipitate samples from a percolate water of tin mill tailings were investigated using this method.