RESUMO
Modified biochar used for soil remediation is affected by exposure to the environment and aging process results in changes in its physicochemical properties and As(V) adsorption and immobilization in soil. Herein, the Ce/Mn-modified wheat straw-biochar (MBC) was manufactured and then aged through three artificial aging processes by exposure to soil with additional natural, freeze-thaw, and dry-wet cycles involved. It revealed that the specific surface areas of freeze-thaw-aged MBC reached 214.98 m2/g and was increased more than those of other two aging treatments. In addition, the pH values and C contents of MBC all decreased after aging while the H and O contents increased. Correspondingly, the contents of O-containing functional groups like C-O, -OH, and CO all increased by >16% with aging. The freeze-thaw cycling and alternating dry-wet aging treatments improved adsorption capacities of As(V) onto MBC and were increased by 16.2 and 10.6% at pH 5, respectively and these samples exhibited the best recyclability and adsorption selectivity for As(V). However, natural aging exerted a lower effect for As(V) adsorption by MBC due to its few changes on physicochemical properties. Causally, the freeze-thaw and dry-wet aging activated the Ce/Mn-oxides to generate Mn2+/3+ species and a new mono-Ce that exerted a strong bonding complexation with As(V) to form Ce/Mn-O-As ligands and increased CeAsO4 precipitation. Our results offer a new insight into the alterations expected for modified biochars with aging treatment in terms of As(V) adsorption for its long-term utilization in As contaminated soil.
Assuntos
Poluentes do Solo , Adsorção , Carvão Vegetal , SoloRESUMO
Layered double hydroxides (LDH) are the cost-effective and high-efficiency materials for remediation of potentially toxic elements (PTEs) in contaminated soil and groundwater. Herein, the effectiveness and mechanisms of a ternary Ca-Mg-Al LDH (CMAL) for the synergistic remediation of As, Cd, and Pb were investigated in contaminated soils and simulative groundwaters for the first time. The immobilization efficiencies of As, Cd, and Pb in both black soil (BS) and red soil (RS) amended by CMAL at 5 wt% were all > 75%. CMAL amendment transferred more mobile As, Cd, and Pb fractions in soils to immobile species than did Ca-Al LDH and Mg-Al LDH treatments. Furthermore, using a pump-and-treat technology, 82-98% of these 3 PTEs from contaminated groundwater were successfully immobilized in both CMAL treated BS and RS top-soils. Meanwhile, leaching of Ca, Mg, and Al from CMAL was minimal indicating the material was stable. The excellent immobilization performance of CMAL for these PTEs was attributed to the coating of soil microparticles by CMAL nanosheets that allowed complexation of Ca-O-As/Cd or Mg-O-As/Cd/Pb formation, co-precipitation of Ca/Fe-As and Cd(OH)2, and formation of Ca-bridged ternary complex (FeO-Ca-As/Cd). The adverse effect of oppositive pH/Eh-dependence between As and Cd/Pb was overshadowed by these mechanisms and thus allowed As immobilization. Immobilization of As, Cd, and Pb by CMAL amendment was more favorable for RS soil due to its lower reduction potential and more participation of metal-(hydr)oxides for complexation. Overall, the ternary-LDH is a promising synergistic remediation strategy for multi-PTEs contaminated soil and groundwater.
Assuntos
Recuperação e Remediação Ambiental , Água Subterrânea , Poluentes do Solo , Poluentes do Solo/análise , Cádmio , Chumbo , Solo , Hidróxidos , ÓxidosRESUMO
The impact of multiple preparation protocols on properties and performance of modified biochar remains unclear. This study prepared layered double hydroxide (LDH)-based magnetic biochars (LMBCs) with different LDH loading rates (LLR), pyrolysis temperatures, and biomass sources to explore their performance-characterization relationships toward As(III) and Cd(II). Higher LLR and pyrolysis temperature enhanced LMBCs᾿ adsorption capacities by increasing specific surface area (SSA) and metal/O-containing groups. Hence, LMBC produced at 2:1 LLR (LDH: magnetic biochar) and 800 â pyrolysis exhibited maximum adsorption over 2 times that of LMBC with 0.5:1 LLR and 400 â pyrolysis. Bamboo-sourced LMBC demonstrated superior adsorption than sewage sludge and garlic-sourced LMBCs due to its increased SSA, enabling a higher loading of nano-LDH. Adsorption of As(III) and Cd(II) onto LMBCs was governed by metal-mineral and metal-containing group through co-precipitation and complexation. This study provides a reference for adjusting the preparation protocols to improve sorption performance of modified biochar toward multiple heavy metals.