A Universal Synergistic Rule of Cd(II)-Sb(V) Coadsorption to Typical Soil Mineral and Organic Components

Heavy metals and metalloids are common cooccurrence in contaminated soils, making their behaviors more complex than their individual presences. Adsorption to soil minerals and organic components determines the solubility and mobility of heavy metals. However, little information is available regarding coadsorbing metals (e.g., Cd) and metalloids (e.g., Sb) to soil components, and whether there is a universal coadsorption rule needs to be illuminated. This study investigated the coadsorption behaviors of Cd(II) and Sb(V) to goethite, kaolinite, and bacteria (Bacillus cereus) at both acidic (pH 4.5) and alkaline pH (pH 8.5). Equilibrium adsorption experiments, coupled with scanning electron microscopy- (SEM-) energy-dispersive X-ray spectrum (EDS) and X-ray photoelectron spectroscopy (XPS), were applied to determine the batch adsorption phenomena and possible mechanisms. Batch results showed that Cd(II) adsorption was greater at pH 8.5 whereas Sb(V) adsorption was greater at pH 4.5. The presence of Cd or Sb promoted each other’s adsorption to goethite, kaolinite, and bacteria, but slight differences were that Sb(V) preferred to enhance Cd(II) adsorption at acidic pH, whereas Cd(II) was more able to increase Sb(V) adsorption at alkaline pH. SEM-EDS analyses further showed that the distribution of Cd and Sb was colocalized. The surface FeOH, AlOH, and COOH groups participated in the binding of Cd(II) and Sb(V), probably through the formation of inner-sphere complexes. Two possible ternary complexes, i.e., sorbent-Cd2+-Sb(OH)6– and sorbent-Sb(OH)6–-Cd2+, were possibly formed. Both the charge effect and the formation of ternary complexes were responsible for the collaborative coadsorbing of Cd-Sb. The universal synergistic rule obtained suggests that current models for predicting Cd(II) or Sb(V) sequestration based on single systems may underestimate their solid-to-liquid distribution ratio in a coexistence situation. The results obtained have important implications for understanding the chemical behavior of Sb and Cd in contaminated soils.</jats:p

A Universal Synergistic Rule of Cd(II)-Sb(V) Coadsorption to Typical Soil Mineral and Organic Components

Heavy metals and metalloids are common cooccurrence in contaminated soils, making their behaviors more complex than their individual presences. Adsorption to soil minerals and organic components determines the solubility and mobility of heavy metals. However, little information is available regarding coadsorbing metals (e.g., Cd) and metalloids (e.g., Sb) to soil components, and whether there is a universal coadsorption rule needs to be illuminated. This study investigated the coadsorption behaviors of Cd(II) and Sb(V) to goethite, kaolinite, and bacteria (Bacillus cereus) at both acidic (pH 4.5) and alkaline pH (pH 8.5). Equilibrium adsorption experiments, coupled with scanning electron microscopy- (SEM-) energy-dispersive X-ray spectrum (EDS) and X-ray photoelectron spectroscopy (XPS), were applied to determine the batch adsorption phenomena and possible mechanisms. Batch results showed that Cd(II) adsorption was greater at pH 8.5 whereas Sb(V) adsorption was greater at pH 4.5. The presence of Cd or Sb promoted each other’s adsorption to goethite, kaolinite, and bacteria, but slight differences were that Sb(V) preferred to enhance Cd(II) adsorption at acidic pH, whereas Cd(II) was more able to increase Sb(V) adsorption at alkaline pH. SEM-EDS analyses further showed that the distribution of Cd and Sb was colocalized. The surface FeOH, AlOH, and COOH groups participated in the binding of Cd(II) and Sb(V), probably through the formation of inner-sphere complexes. Two possible ternary complexes, i.e., sorbent-Cd2+-Sb(OH)6– and sorbent-Sb(OH)6–-Cd2+, were possibly formed. Both the charge effect and the formation of ternary complexes were responsible for the collaborative coadsorbing of Cd-Sb. The universal synergistic rule obtained suggests that current models for predicting Cd(II) or Sb(V) sequestration based on single systems may underestimate their solid-to-liquid distribution ratio in a coexistence situation. The results obtained have important implications for understanding the chemical behavior of Sb and Cd in contaminated soils

Sorption of Pb(II) by Nanosized Ferrihydrite Organo-Mineral Composites Formed by Adsorption versus Coprecipitation

Nanosized iron hydroxides and organic matter (OM) are important scavengers of nutrient elements and dissolved trace-metals in geologic systems. Despite this, little is known about the sorption characteristics of metals to the iron–OM nanocomposites formed by adsorption (adsorption of OM on presynthesis ferrihydrite) versus coprecipitation (formation of ferrihydrite in the presence of OM). This study investigates lead (Pb) sorption behaviors on ferrihydrite–humic acid (Fh–HA) composites through batch sorption coupled with Pb-L_III EXAFS. We report that composites formed by coprecipitation have a higher carbon content, smaller specific surface area, and faster Pb sorption rate compared to the equivalent composites formed by adsorption of HA to preformed Fh. Pb sorption on the composites is enhanced at pH < 5 than that on pure Fh, and coprecipitated and adsorbed composites sorb almost equivalent amount of Pb. We identify a bidentate edge-sharing Pb complex on the ferrihydrite surface with a PbFe bond length of 3.33 Å and a bidentate inner-sphere Pb complex on the HA fraction of the composite. More Pb ions are associated with the HA fraction of the composites with the increases of pH from 4 to 6.5. More Pb ions are sequestrated by the organic fraction in the adsorbed than in the coprecipitated composites. This research therefore has important implications for predicting the mobility and fate of Pb in iron and organic rich soils and sediments