Adsorption behavior of lead, cadmium, and arsenic on manganese-modified biochar: competition and promotion.

Biochar adsorption of heavy metals has been a research hotspot, yet there has been limited reports on the effect of heavy metal interactions on adsorption efficiency in complex systems. In this study, the adsorbent was prepared by pyrolysis of rice straw loaded with manganese (BC-Mn). The interactions of Pb, Cd and As adsorption on BC-Mn were systematically studied. The results of the adsorption isotherms for the binary metal system revealed a competitive adsorption between Pb and Cd, resulting in decreased Pb (from 214.38 mg/g to 148.20 mg/g) and Cd (from 165.73 mg/g to 92.11 mg/g). A notable promotion occurred between As and Cd, showing an increase from 234.93 mg/g to 305.00 mg/g for As and 165.73 mg/g to 313.94 mg/g for Cd. In the ternary metal system, Pb inhibition did not counteract the promotion of Cd and As. Furthermore, the Langmuir isotherm effectively described BC-Mn's adsorption process in monometallic, binary, and ternary metal systems (R2 > 0.9294). Zeta and FTIR analyses revealed simultaneous competition between Pb and Cd for adsorption on BC-Mn's -OH sites. XPS analysis revealed that As adsorption by BC-Mn facilitated the conversion of MnO2 and MnO to MnOOH, resulting in increased hydroxyl radical production on BC-Mn's surface. Simultaneously, Cd combined with the adsorbed As to form ternary Cd-As-Mn complexes, which expedited the removal of Cd. These results help to provide theoretical support as well as technical support for the treatment of Pb-Cd-As contaminated wastewater.

Cooperative effect of slow-release ferrous and phosphate for simultaneous stabilization of As, Cd and Pb in soil.

The different chemical behavior of anionic As and cationic Cd and Pb makes the simultaneous stabilization of soils contaminated with arsenic (As), cadmium (Cd), and lead (Pb) challenging. The use of soluble, insoluble phosphate materials and iron compounds cannot simultaneously stabilize As, Cd, and Pb in soil effectively due to the easy re-activation of heavy metals and poor migration. Herein, we propose a new strategy of "cooperatively stabilizing Cd, Pb, and As with slow-release ferrous and phosphate". To very this theory, we developed ferrous and phosphate slow-release materials to simultaneously stabilize As, Cd, and Pb in soil. The stabilization efficiency of water-soluble As, Cd and Pb reached 99% within 7d, and the stabilization efficiencies of NaHCO3-extractable As, DTPA-extractable Cd and Pb reached 92.60%, 57.79% and 62.81%, respectively. The chemical speciation analysis revealed that soil As, Cd and Pb were transformed into more stable states with the reaction time. The proportion of residual fraction of As, Cd, and Pb increased from 58.01% to 93.82%, 25.69 to 47.86%, 5.58 to 48.54% after 56 d, respectively. Using ferrihydrite as a representative soil component, the beneficial interactions of phosphate and slow-release ferrous material in stabilizing Pb, Cd, and As were demonstrated. The slow-release ferrous and phosphate material reacted with As and Cd/Pb to form stable ferrous arsenic and Cd/Pb phosphate. Furthermore, the slow-release phosphate converted the adsorbed As into dissolved As, then the dissolved As reacted with released ferrous to form a more stable form. Concurrently, As, Cd and Pb were structurally incorporated into the crystalline iron oxides during the ferrous ions-catalyzed transformation of amorphous iron (hydrogen) oxides. The results demonstrates that the use of slow-release ferrous and phosphate materials can aid in the simultaneous stabilization of As, Cd, and Pb in soil.

Synchronous stabilization of As, Cd, and Pb in soil by sustained-release of iron-phosphate.

Anionic arsenic (As) exhibits geochemical behavior opposite to those of cationic cadmium (Cd), and lead (Pb), which makes the synchronous remediation of As, Cd, and Pb challenging. The synchronous stabilization of As, Cd, and Pb to form Cd/Pb-phosphate and iron­arsenic precipitates is a promising strategy. However, the effectiveness of soluble phosphate or iron-based materials is limited by the activation of Cd, Pb, or As, while low mobility hinders insoluble particles. In this study, we developed an amorphous structure that releases iron and phosphate at a sustained rate. Thus, the stabilization efficiencies of NaHCO3-extractable As, DTPA-extractable Cd and Pb reached 44.6 %, 40.8 %, and 48.1 %, respectively. The proportion of residual fraction of As, Cd, and Pb increased by 12.1 %, 14.5 %, and 36.4 %, respectively, after 28 d. Ferrihydrite was chosen as the soil component to monitor the chemical behavior and speciation transformation of As, Cd, and Pb in the reaction. During the process, the released iron directly reacted with dissolved As to form iron­arsenic precipitation and phosphate directly reacted with Cd/Pb to form Cd/Pb-phosphate precipitation. Simultaneously, phosphate replaced the adsorbed As and transformed into a dissolved state, which could be re-precipitated with the released iron ions. Thus, this study provides a reliable strategy for the remediation of As, Cd, and Pb combined pollution in soil.

Synergistic Cr(VI) reduction and adsorption of Cu(II), Co(II) and Ni(II) by zerovalent iron-loaded hydroxyapatite.

Multi-metal contaminated soil, such as Cr(VI), Cu(II), and Co(II), still challenge the environmental remediation. In this work, zerovalent iron-loaded hydroxyapatite (ZVI/HAP) was first applied to simultaneously adsorb multi-metal in contaminated soil. During the remediation, the co-existing Cu(II), Ni(II), and Co(II) were adsorbed and precipitated onto ZVI/HAP. This "spontaneous deposition" simultaneously achieved the adsorption of the cationic metals and improved the isoelectric point of ZVI/HAP to 4.83 from 1.59, thus significantly alleviating the electronegativity to enhance the capture and reduction efficiency of Cr(VI). The application of ZVI/HAP resulted in the reduction of more than 99% of total Cr(VI) in contaminated soil, and the almost complete adsorption of water-soluble and DTPA-extractable Cu, Ni and Co within 20 d. Based on the sequential extraction and risk reduction assessment, soil Cr, Cu, Ni, and Co speciation was transformed from an unstable state (exchangeable and carbonate-bound fractions) to a relatively stable state, reducing the risk of heavy metals in contaminated soil significantly. This study developed an efficient strategy for the remediation of multi-metal contaminated soil.