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a b s t r a c tThis paper investigates the structural evolution of chitosan-palygorskite (CP) composites in relation to variable mass ratios of their individual components. The composite beads' performance in lead (Pb) adsorption from aqueous solution was also examined. The composite beads were prepared through direct dispersion of chitosan and palygorskite at 1:1, 1:2 and 2:1 mass ratios (CP1, CP2 and C2P, respectively). Analyses by Fourier transform Infrared (FTIR) spectroscopy, Brunauer-Emmett-Teller (BET) surface area, X-ray diffraction (XRD) and scanning electron microscopy (SEM) confirmed the dependence of the composites' structural characteristics on their composition mass ratio. The chitosan-palygorskite composite beads exhibited a better Pb adsorption performance than the pristine materials (201.5, 154.5, 147.1, 27.7 and 9.3 mg g −1 for CP1, C2P, CP2, chitosan and palygorskite, respectively). Adsorption of Pb by CP1 and CP2 followed Freundlich isothermal model, while C2P fitted to Langmuir model. Kinetic studies showed that adsorption by all the composites fitted to the pseudo-second order model with pore diffusion also acting as a major rate governing step. The surface properties and specific interaction between chitosan and palygorskite in the composites were the most critical factors that influenced their capabilities in removing toxic metals from water.

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Bioremediation of polycyclic aromatic hydrocarbon (PAH)-contaminated soils requires a higher microbial viability and an increased PAH bioavailability. The clay/modified clay-modulated bacterial degradation could deliver a more efficient removal of PAHs in soils depending on the bioavailability of the compounds. In this study, we modified clay minerals (smectite and palygorskite) with mild acid (HCl) and alkali (NaOH) treatments (0.5-3 M), which increased the surface area and pore volume of the products, and removed the impurities without collapsing the crystalline structure of clay minerals. In soil incubation studies, supplements with the clay products increased bacterial growth in the order: 0.5 M HCl ≥ unmodified ≥ 0.5 M NaOH ≥ 3 M NaOH ≥ 3 M HCl for smectite, and 0.5 M HCl ≥ 3 M NaOH ≥ 0.5 M NaOH ≥ 3 M HCl ≥ unmodified for palygorskite. AC-tracing study showed that the mild acid/alkali-treated clay products increased the PAH biodegradation (5-8%) in the order of 0.5 M HCl ≥ unmodified > 3 M NaOH ≥ 0.5 M NaOH for smectite, and 0.5 M HCl > 0.5 M NaOH ≥ unmodified ≥ 3 M NaOH for palygorskite. The biodegradation was correlated (r = 0.81) with the bioavailable fraction of PAHs and microbial growth as affected particularly by the 0.5 M HCl and 0.5 M NaOH-treated clay minerals. These results could be pivotal in developing a clay-modulated bioremediation technology for cleaning up PAH-contaminated soils and sediments in the field.

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