ABSTRACT
Heavy metals including Cd, Pb, and Zn are prevalent stormwater and groundwater contaminants derived from natural and human activities, and there is a lack of cost-effective treatment for their removal. Recently, biochar has been increasingly recognized as a promising low-cost sorbent that can be used to remediate heavy metal contaminated water. This study evaluates the immobilization/release performance of dairy manure-derived biochar (DM-BC) as a sustainable material for competitive removal of coexisting heavy metal ions from water and explains the underlying mechanism for regeneration/reusability of biochar. Results showed that the metal ions exhibited competitive removal in the order of Pb2+ â« Zn2+ > Cd2+. The pH played a decisive role in influencing metal ion speciation affecting the electrostatic attraction/repulsion and surface complexation. Higher pH led to greater removal for Pb2+ and Cd2+, whereas Zn2+ showed maximum removal at pH ≈ 7.5. Diffuse reflectance infrared spectroscopy, scanning electron microscopy, and X-ray diffraction confirmed the interactions and precipitation reactions of oxygen-containing functional groups (e.g., âOH, CO32-, and SiâO) as key participants in metal immobilization. Langmuir, Freundlich, and Redlich-Peterson isotherm modeling data showed varied and unique results depending on the metal ion and concentration. The removal kinetics and model fitting showed that the three steps of intraparticle diffusion might be more representative for describing the immobilization processes of metal ions on the external surface and internal pores. In the flow-through columns, DM-BC effectively retained the mixed metal ions of Cd2+, Pb2+, and Zn2+ showing 100% removal for the duration of the column run over three cycles of regeneration and reuse.
ABSTRACT
This study investigated the removal of fluoride from water using a calcium-modified dairy manure-derived biochar (Ca-DM500). The Ca-DM500 showed a 3.82 - 8.86 times higher removal of fluoride from water than the original (uncoated) manure-derived biochar (DM500). This is primarily attributed to strong precipitation/complexation between fluoride and calcium. The Freundlich and Redlich-Peterson sorption isotherm models better described the experimental data than the Langmuir model. Additionally, the removal kinetics were well described by the intraparticle diffusion model. The Ca-DM500 showed high reactivity per unit surface area [0.0001, 0.03, 0.16 mg F per m2 for Douglas fir-derived biochar (DF-BC), DM500. and Ca-DM500, respectively] for retention of fluoride reflecting the importance of surface complexation. The copresence of anions reduced removal by Ca-DM500 in the order SO 4 2 - ≈ PO 4 3 - > NO 3 - . The sorption behavior of fluoride in a continuous fixed-bed column was consistent with the Thomas model. Column studies demonstrated that the Ca-DM500 shows a strong affinity for fluoride, a low release potential, and a stable (unreduced) removal capacity through regeneration and reuse cycles.
ABSTRACT
This study investigated the adsorptive removal of fluoride from simulated water pollution using various (hydro)oxide nanomaterials, which have the potential to be used as sorbents for surface water and groundwater remediation. Tested nanomaterials include hematite, magnetite, ferrihydrite, goethite, hematite-alpha, hydroxyapatite (HAP), brucite, and four titanium dioxides (TiO2-A [anatase], TiO2-B [rutile], TiO2-C [rutile], and TiO2-D [anatase]). Among 11 (hydro)oxide nanomaterials tested in this study, ferrihydrite, HAP, and brucite showed two to five times higher removal of fluoride than other nanomaterials from synthetic fluoride solutions. Freundlich and Redlich-Peterson adsorption isotherms better described the adsorptive capacity and mechanism than the Langmuir isotherm based on higher R 2 values, indicating better fit of the regression predictions. In addition, the adsorption kinetics were well described by the intraparticle diffusion model. Column studies in a fixed bed continuous flow through system were conducted to illustrate the adsorption and desorption behavior of fluoride on ferrihydrite, HAP, or brucite. Experimental results fitted well with the Thomas model because of the R 2 values at least 0.885 or higher. By comparisons of the adsorption capacity and the rate constant, columns packed with ferrihydrite exhibited not only faster rates but also higher sorption capacity than those packed with HAP or brucite. Desorption tests in deionized water showed that the adsorbed fluoride could be desorbed at a lower efficiency, ranging from 4.0% to 8.9%. The study implicated that (hydro)oxide nanomaterials of iron calcium and magnesium could be effective sorptive materials incorporated into filtration systems for the remediation of fluoride polluted water.
