Zeolite: A single-use sorbent for the treatment of metals-contaminated water and waste streams

Olin, T. J. ; Bricka, R. M.
Organization: Society for Mining, Metallurgy & Exploration
Pages: 6
Publication Date: Jan 1, 1999
Heavy metals contamination is an environmental problem at Army installations engaged in firearms training and munitions production. At these facilities, weathering and corrosion of expended munitions and leaching from wastewater lagoons, landfills and burn pits have resulted in heavy metals contamination of the soil. The principal metals encountered in firing-range soils are lead, copper and zinc. Cadmium and other metals, such as antimony, that are often incorporated in the munitions are sometimes seen in lesser concentrations. Mercury is associated with various propellants and, while present in much smaller concentrations, is of concern because of its acute toxicity. Chromium is primarily associated with plating operations. The transport of metals into groundwater has been confirmed at some locations, which has required treatment of the soil and groundwater at these sites. Certain treatment processes for contaminated soil produce metals-laden extracts, which also require treatment before reuse or disposal. Ion exchange is generally quite effective for removing metals from aqueous streams. However, resins are expensive and must be regenerated, and activated carbon is generally less effective for most metals and also requires regeneration. Therefore, alternative effective and economic sorbents are needed. Twelve sorbents were screened in initial batch testing. These included activated carbon, bark, chitosan, crown ether, corn cob, xanthate, clay (kaolinite and montmorillonite), peat moss, seaweed and reagent-grade zeolite (aluminosilicate, Sigma Product No. Z3125). Of these, zeolite demonstrated the highest capacity for Pb, Cr and Cd. For this reason, zeolite was selected for further testing in batch, kinetic and column studies. Materials and methods Zeolite. The zeolite used in the second-phase batch and column studies was obtained from a natural deposit of clinoptilolite-rich rock located in South Dakota (Rocky Ford SDH) (Desborough, 1996). Large blocks of the material were crushed and sieved into the following three particle size ranges: 0.5 to 1.0, 1.0 to 4.0 and 2.0 to 4.7 mm. This material demonstrates high structural stability in acidic solutions (pH 2.5) (Desborough 1996) and has a measured surface area of 30 m2/g. The measured total cation-exchange capacity (TCEC) was approximately 10 meq/100 g. This is well below what has been indicated for commercially available zeolite, which has been reported to be about 180 to 220 meq/ 100 g. The TCEC test was repeated (Method 9081, SW 846) using sodium acetate. The test resulted in a TCEC of 54.5 meq/100 g. The difference between values obtained for this material and published values for zeolites may be attributable to the greater heterogeneity in the material used in this study, compared to commercially available materials, or to the effect of the relatively large particle sizes utilized. Batch studies. Seven batch studies were conducted using synthetic metal solutions and soil extracts (Table 1). Extract composition: The P-extract was prepared by sequential surfactant extraction of organics from a burnpit soil followed by acid extraction of metals. The pH of this solution is approximately 1.1. A number of metals and organic compounds were present in the soil. Analysis of the extract was restricted to Pb, Zn and Cu concentrations for this study. The FBH extract was produced from a firing-range soil that was oxidized with a 0.01 M CaO solution and then extracted with 0.1 M acetic acid. This was filtered through 0.5-µm Whatman No. 5 filter paper and stored at room temperature. The pH of the FBH extract was approximately 4.5. pH Control: Calcium carbonate (CaCO3) may be present in the zeolite horizon or bed. Calcium ion (Ca") is released from the exchange sites when in contact with solutions containing ions for which it is more selective, such as lead. This results in a rise in solution pH over time. Acid washing removes most of the carbonates, eliminating the need for a buffer. Batch studies were conducted using both acid-washed zeolite (AW) and unwashed zeolite (UW) for performance comparison. The UW zeolite was rinsed with distilled deionized (DDI) water to remove fine soil particles. Both materials were dried at 105°C (220°F) overnight, so that the dry mass could be determined. Column studies. Ten column studies were conducted. Because it was expected to have the best hydraulic properties, the largest particle
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