Remediation of heavy metal polluted sediment by suspension and solid-bed leaching: estimate of metal removal efficiency.

Remediation of heavy metal polluted sediment by extracting the metals with sulfuric acid can be performed as follows: abiotic suspension leaching, microbial suspension leaching, abiotic solid-bed leaching, and microbial solid-bed leaching. Abiotic leaching means that the acid is directly added, while microbial leaching means that the acid is generated from sulfur by microbes (bioleaching). These four principles were compared to each other with special emphasis on the effectiveness of metal solubilization and metal removal by subsequent washing. Abiotic suspension leaching was fastest, but suspending the solids exhibits some disadvantages (low solid content, costly reactors, permanent input of energy, high water consumption, special equipment required for solid separation, large amounts of waste water, sediment properties hinder reuse), which prevent suspension leaching in practice. Abiotic solid-bed leaching implies the supply of acid by percolating water which proceeds slowly due to a limited bed permeability. Microbial solid-bed leaching means the generation of acid within the bed and has been proven to be the only principle applicable to practice. Metal removal from leached sediment requires washing with water. Washing of solid beds was much more effective than washing of suspended sediment. The kinetics of metal removal from solid beds 0.3, 0.6 or 1.2m in height were similar; when using a percolation flow of 20lm(-2)h(-1), the removal of 98% of the mobile metals lasted 57-61h and required 8.5, 4.2 or 2.3lkg(-1) water. This means, the higher the solid bed, the lower the sediment-mass-specific demand for time and water.

Effect of oxygen limitation on solid-bed bioleaching of heavy metals from contaminated sediments.

The effects of oxygen limitation on solid-bed bioleaching of heavy metals (Me) were studied in a laboratory percolator system using contaminated sediment supplemented with 2% elemental sulfur (So). Oxygen limitation was realized by controlling the gas flow and oxygen concentration in the aeration gas. The oxygen supply varied between 150 and 0.5 mol So (-1) over 28 d of leaching. Moderate oxygen limitation led to temporarily suppression of acidification, rate of sulfate generation and Me solubilization. Lowering the oxygen supply to 0.5 mol O2 mol So (-1) resulted in retarding acidification over a period of three weeks and in poor Me solubilization. Oxidation of So occurred even under strong oxygen limitation at a low rate. High surplus of oxygen was necessary for almost complete oxidation of the added So. The maximum Me solubilization was reached at an oxygen supply of 7.5 mol O2 mol So (-1). Thus, the oxygen input during solid-bed bioleaching can be reduced considerably by controlling the gas flow without loss of metal removal efficiency. Oxygen consumption rates, ranging from 0.4 x 10(-8) to 0.8 x 10(-8) Kg O2 Kg dm (-1) S(-1), are primarily attributed to high reactivity of the sulfur flower and high tolerance of indigenous autotrophic bacteria to low oxygen concentrations. The So related oxygen consumption was calculated assuming a molar yield coefficient Y O2/S of 1.21. The oxygen conversion degree, defined as part of oxygen feed consumed by So oxidation, increased from 0.7% to 68% when the oxygen supply was reduced from 150 to 0.5 mol O2 mol So (-1).

Remediation of heavy metal polluted sediment in the solid bed: comparison of abiotic and microbial leaching.

Basic research on remediation of polluted sediment by leaching has, to date, been carried out exclusively with suspended material. For economic reasons, only solid-bed leaching is applicable to large-scale processes. Abiotic and microbial solid-bed leaching were comparatively studied in a percolator system using ripened and therefore permeable heavy metal polluted river sediment. In the case of abiotic leaching, sulfuric acid was supplied to the sediment by circulating water; the lower the pH of the percolating water, the higher the percolation flow, and the lower the solid-bed height was, the faster the heavy metals were solubilized. However, the pH and percolation flow are subjected to restrictions: strongly acidic conditions result in dissolution of mineral components, and the percolation flow must not exceed the bed permeability. And a high solid bed is an economic requirement. In the case of bioleaching, elemental sulfur added to the sediment was oxidized to sulfuric acid within the package which, in turn, solubilized the heavy metals. Here, the percolation flow and the solid-bed height did not affect the rate of metal solubilization. Solid-bed leaching on a larger scale will thus be much more efficient applying bioleaching with sulfur as the leaching agent than abiotic leaching with sulfuric acid.

Effect of different types of elemental sulfur on bioleaching of heavy metals from contaminated sediments.

The application of two different types of elemental sulfur (S0) was studied to evaluate the efficiency on bioleaching of heavy metals from contaminated sediments. Bioleaching tests were performed in suspension and in the solid-bed with a heavy metal contaminated sediment using commercial sulfur powder (technical sulfur) or a microbially produced sulfur waste (biological sulfur) as substrate for the indigenous sulfur-oxidizing bacteria and thus as acid source. Generally, using biological sulfur during suspension leaching yielded in considerably better results than technical sulfur. The equilibrium in acidification, sulfur oxidation and metal solubilization was reached already after 10-14 d of leaching depending upon the amount of sulfur added. The metal removal after 28 d of leaching was higher when biological sulfur was used. The biological sulfur added was oxidized with high rate, and no residual S0 was detectable in the sediment samples after leaching. The observed effects are attributable to the hydrophilic properties of the biologically produced sulfur particles resulting in an increased bioavailability for the Acidithiobacilli. In column experiments only poor effects on the kinetics of the leaching parameters were observed replacing technical sulfur by biological sulfur, and the overall metal removal was almost the same for both types of S0. Therefore, under the conditions of solid-bed leaching the rate of sulfur oxidation and metal solubilization is more strongly affected by transport phenomena than by microbial conversion processes attributed to different physicochemical properties of the sulfur sources. The results indicate that the application of biological sulfur provides a suitable means for improving the efficiency of suspension leaching treatments by shortening the leaching time. Solid-bed leaching treatments may benefit from the reuse of biological sulfur by reducing the costs for material and operating.

Immobilization of arsenic in a tailings material by ferrous iron treatment.

Weathering and internal dissolution processes in mining waste materials may mobilize elevated levels of arsenic (As), contaminating ground and surface waters. Treating the polluted waters with iron oxyhydroxides is an established remediation method. By contrast, little knowledge is available to stabilize As in source materials by treating it with Fe precipitates and, on this way, to prevent the generation of polluted waters. In the present work the efficiency of Fe(II) treatment on As immobilization in a tailings material (TM) was studied with regard to the Fe:As molar ratio, the influence of CaCO3 amendment, and the As desorption at continued intensive leaching of Fe-treated TM. Fe precipitates were created by aerobic treatment of TM with Fe(II)sulfate at several Fe:As molar ratios with or without adding CaCO3, followed by aging the Fe-treated TM. The As retention in the treated tailings was studied by 4-fold elution with water, and the As desorption kinetics was examined by suspension leaching in laboratory microcosms over 3 weeks. Fe(II) treatment of TM reduced the water-extractable total As to <10 microg/L as the Fe:As molar ratio increased from 0 to 8. The water-soluble As of Fe-treated tailings could be reduced to 10-30 microg/L also under conditions of intensive leaching. Stabilizing the pH with CaCO3 resulted in consistently higher As release. The As desorption data followed the first-order kinetics in the early time stages of the desorption whereas at longer times the parabolic diffusion model was valid.