Morphologically controlled synthesis of MgFe-LDH using MgO and succinic acid for enhanced arsenic adsorption: Kinetics, equilibrium, and mechanism studies.

In this study, we investigated improving the performance of a layered double hydroxide (LDH) for the adsorption of As(III) and As(V) by controlling the morphology of LDH crystals. The LDH was synthesized via a simple coprecipitation method using barely soluble MgO as a precursor and succinic acid (SA) as a morphological control agent. Doping the LDH crystals with carboxylate ions (RCOO-) derived from SA caused the crystals to develop in a radial direction. This changed the pore characteristics and increased the density of active surface sites. Subsequently, SA/MgFe-LDH showed excellent affinity for As(III) and As(V) with maximum sorption densities of 2.42 and 1.60 mmol/g, respectively. By comparison, the pristine MgFe-LDH had sorption capacities of 1.56 and 1.31 mmol/g for As(III) and As(V), respectively. The LDH was effective over a wide pH range for As(III) adsorption (pH 3-8.5) and As(V) adsorption (pH 3-6.5). Using a combination of spectroscopy and sorption modeling calculations, the main sorption mechanism of As(III) and As(V) on SA/MgFe-LDH was identified as inner-sphere complexation via ligand exchange with hydroxyl group (-OH) and RCOO-. Specifically, bidentate As-Fe complexes were proposed for both As(III) and As(V) uptake, with the magnitude of formation varying with the initial As concentration. Importantly, the As-laden adsorbent had satisfactory stability in simulated real landfill leachate. These findings demonstrate that SA/MgFe-LDH exhibits considerable potential for remediation of As-contaminated water.

Insights on the Contradiction between the Affinity and Capacity of Ferrihydrite toward As(III) and As(V): Surface Reaction Revisited.

Ferrihydrite is omnipresent in nature, and its adsorption of As(III/V) decides the migration of arsenic. Although As(III) is commonly recognized as the more mobile species of inorganic arsenic, it sometimes exhibits less mobility in ferrihydrite systems, which calls for further insights. In this study, we elucidated the adsorption behavior and mechanisms of As(III/V) on ferrihydrite under different loading levels (molar ratio As/Fe = 0-0.38), solution pH (3-10), and coexisting ions [P(V) and Ca(II)] based on batch adsorption experiments, surface complexation modeling, density functional theory calculations, and X-ray photoelectron spectroscopy. Our results show that As(III) exhibits weaker adsorption affinity but a larger capacity compared with that of As(V). On ferrihydrite, As(III) and As(V) are adsorbed mainly as bidentate mononuclear complexes at type-a sites [≡Fe(OH-0.5)2] and bidentate binuclear complexes at type-b sites (2≡FeOH-0.5), respectively. As the dosage increases, As(III) further forms mononuclear monodentate complexes at both surface sites, resulting in a higher site utilization efficiency, while As(V) does not due to repulsive electrostatic interaction. The difference in surface species of As(III/V) also leads to complex responses when coexisting with high concentrations of P(V) and Ca(II). This study helps us to understand environmental behavior of As(III/V) and develop remediation strategy in As(III/V) contaminated systems.

Influence of elevated temperature on the species and mobility of chromium in ferrous sulfate-amended contaminated soil.

Ferrous sulfate (FeSO4) combined with acid pretreatment is usually employed to remediate contaminated soils containing Cr(VI). However, the long-term efficiency of this stabilization method is important for its sustainability. In this study, a gradient temperature-elevating exposure test was employed to investigate the stability of Cr in FeSO4-remediated soil when exposed to elevated temperatures (40 °C, 120 °C, and 500 °C), possibly caused by hot weather and/or wildfires. The results of chemical extraction and X-ray absorption near edge structure spectroscopy (XANES) showed that the Cr(VI) in contaminated soil was successfully transformed to Cr(III) after stabilization, resulting in the dramatic decrease of water-leachable Cr(VI). The stabilization efficiency was further improved under 40 °C treatment after 30 days. Subsequently, the 120 °C treatment (7 days) had relatively little effect on the Cr speciation and mobility in soils. However, even one day of 500 °C calcination resulted in the deterioration of stabilization efficiency, and the water-leachable Cr(VI) re-increased and became higher than the Chinese environmental standards (total Cr 15 mg/L, Cr(VI) 5 mg/L) for the classification of hazardous solid wastes. XANES results reflected that heating at 500 °C facilitate the formation of Cr2O3, which was mainly caused by thermal decomposition and dehydration of Cr(OH)3 in the soil. Besides, the transformation of Cr species resulted in the enhanced association of Cr with the most stable residual fraction (88.3%-91.6%) in soil. Based on chemical extraction results, it was suggested that the oxidation of Cr(III) to Cr(VI) contributed to the re-increased mobility of Cr(VI) in soil. However, the XANES results showed that almost no significant re-oxidization of Cr(III) to Cr(VI) happened after heating at 500 °C, which was probably caused by XANES linear combination fits (LCF) uncertainties. Moreover, the changes in soil properties, including a rise in pH to a slightly alkaline range and/or the decomposition of organic matter, possibly contributed to the enhanced mobility of Cr(VI) in soil. This study contributes to clarifying the mobility and transformation of Cr in contaminated soils and provides a support for the sustainable management of remediated soils.

Waste-Based Ceramsite for the Efficient Removal of Ciprofloxacin in Aqueous Solutions.

Ciprofloxacin (CIP), a compound with bioaccumulation toxicity and antibiotic resistance, is frequently detected in water at alarming concentrations, which is becoming an increasing concern. In this study, a low-cost ceramsite was developed from industrial solid wastes through sintering to remove CIP from wastewater. The effects of adsorbent dosage, initial pH, contact time, initial CIP concentration, and temperature were explored. More than 99% of CIP (20-60 mg/L) was removed at around pH 2-4 by the ceramsite. The kinetic data fitted well with the pseudo-second-order model, revealing that chemisorption was the main rate-determining step. The isotherm data was better described by the Freundlich model, suggesting that CIP was removed by the formation of multiple layers on the heterogeneous surface. Moreover, the removal efficiency was practically higher than 95% during five regeneration cycles, when different regeneration methods were used, including calcination, HCl, and NaOH washing, indicating that the ceramsite exhibited outstanding reusability in removing CIP. The primary mechanism of CIP removal by the ceramsite was found to be the synergism of adsorption and flocculation, both of which depended on the release of Ca2+ from the ceramsite. In addition, strong Ca-CIP complexes could be formed through surface complexation and metal cation bridging between Ca2+ and different functional groups in CIP.

Geochemical Modeling of Heavy Metal Removal from Acid Mine Drainage in an Ethanol-Supplemented Sulfate-Reducing Column Test.

A passive treatment process using sulfate-reducing bacteria (SRB) is known to be effective in removing heavy metals from acid mine drainage (AMD), though there has been little discussion of the mechanism involved to date. In this work, a sulfate-reducing column test was carried out using supplementary ethanol as an electron donor for microorganisms, and the reaction mechanism was examined using geochemical modeling and X-ray absorption fine structure (XAFS) analysis. The results showed that Cu was readily removed from the AMD on the top surface of the column (0-0.2 m), while Zn and Cd depletion was initiated in the middle of the column (0.2-0.4 m), where sulfide formation by SRB became noticeable. Calculations by a developed geochemical model suggested that ethanol decomposition by aerobic microbes contributed to the reduction of Cu, while sulfide produced by SRB was the major cause of Zn and Cd removal. XAFS analysis of column residue detected ZnS, ZnSO4 (ZnS oxidized by atmospheric exposure during the drying process), and CuCO3, thus confirming the validity of the developed geochemical model. Based on these results, the application of the constructed geochemical model to AMD treatment with SRB could be a useful approach in predicting the behavior of heavy metal removal.

Highly Efficient Cd2+ Removal Using Tobermorite with pH Self-Adjustment Ability from Aqueous Solution.

Cadmium (Cd), as a type of heavy metal, can increase the incidence of many diseases, even in low concentrations. In this study, tobermorite was hydrothermally synthesized and then applied to adsorb Cd2+ from an aqueous solution. The physicochemical characteristics of the synthesized tobermorite were detected, and the results indicated that the well-crystallized tobermorite had a lot of mesopores and a large specific surface area of 140.92 m2/g. It acquired a pH self-adjustment ability via spontaneously releasing Ca2+ and OH- into the aqueous solution. The effects of different factors on Cd2+ removal were investigated. For Cd2+, the removal efficiency could reach 99.71% and the maximum adsorption capacity was 39.18 mg/g using tobermorite. The adsorption data was best fitted with the pseudo-second-order kinetic and Langmuir isotherm models. In addition, there was no strict limit on the solution pH in Cd2+ adsorption because the tobermorite could adjust the solution pH to an alkaline atmosphere spontaneously. The efficient removal of Cd2+ using tobermorite was a result of surface complexation and ion exchange.