In this paper, the adsorption removal characteristic for 10 species of perfluoroalkyl and polyfluoroalkyl substances (PFAS) was investigated using GAC and modified GAC (GAC-Cu). After modification with Cu(II), the amount of copper was to 1.93 and 4.73 mg/g for GAC and GAC-Cu, respectively. The total amount of 10 species of PFAS per specific area was obtained to 0.548 and 0.612 ng/m2 for GAC and GAC-Cu, respectively. A series of batch test confirmed lower efficiency was observed with a smaller number of carbon chain length and the removal efficiency of PFCA (perfluoroalkyl carboxylic acids) was lower than that of PFSA (perfluoroalkyl sulfonic acids) with the same carbon chain length. Regarding the pH effect, the adsorption capacity was decreased with increase of pH due to the increase of electrostatic repulsion. According to pseudo first and second order (PFO and PSO) kinetic models, while the values of equilibrium uptake and time did not show significant difference, a difference in uptake was observed between 24-48h. Furthermore, based on correlation analysis, Log Kow and uptake have a high correlation with molecular weight (M.W.) and initial concentration, respectively. These results show that long-chain PFAS have higher removal efficiency due to their increased hydrophobicity.

The binary oxide adsorbent using Fe and Mn (Fe-Mn) has been prepared by precipitation method to enhance the removal of phosphate. Different amounts of chitosan, a natural organic polymer, were used during preparation of Fe-Mn as a stabilizer to protect an aggregation of Fe-Mn particles. The optimal amount of chitosan has been determined considering the separation of the Fe-Mn particles by gravity from solution and highest removal efficiency of phosphate (Fe-Mn10). The application of Fe-Mn10 increased removal efficiency at least 15% compared to bare Fe-Mn. According to the Langmuir isotherm model, the maximum uptake (qm) and affinity coefficient (b) were calculated to be 184 and 240 mg/g, and 4.28 and 7.30 L/mg for Fe-Mn and Fe-Mn10, respectively, indicating 30% and 70% increase. The effect of pH showed that the removal efficiency of phosphate was decrease with increase of pH regardless of type of adsorbent. The enhanced removal efficiency for Fe-Mn10 was maintained in entire range of pH. In the kinetics, both adsorbents obtained 70% removal efficiency within 5 min and 90% removal efficiency was achieved at 1 h. Pseudo second order (PSO) kinetic model showed higher correlation of determination (R2), suggesting chemisorption was the primary phosphate adsorption for both Fe-Mn and Fe-Mn10.

Perfluorooctanoic acid(PFOA) was one of widely used per- and poly substances(PFAS) in the industrial field and its concentration in the surface and groundwater was found with relatively high concentration compared to other PFAS. Since various processes have been introduced to remove the PFOA, adsorption using GAC is well known as a useful and effective process in water and wastewater treatment. Surface modification for GAC was carried out using Cu and Fe to enhance the adsorption capacity and four different adsorbents, such as GAC-Cu, GAC-Fe, GAC-Cu(OH)2, GAC-Fe(OH)3 were prepared and compared with GAC. According to SEM-EDS, the increase of Cu or Fe was confirmed after surface modification and higher weight was observed for Cu and Fe hydroxide(GAC-Cu(OH)2 and GAC-Fe(OH)3, respectively). BET analysis showed that the surface modification reduced specific surface area and total pore volumes. The highest removal efficiency(71.4%) was obtained in GAC-Cu which is improved by 17.9% whereas the use of Fe showed lower removal efficiency compared to GAC. PFOA removal was decreased with increase of solution pH indicating electrostatic interaction governs at low pH and its effect was decreased when the point of zero charges(pzc) was negatively increased with an increase of pH. The enhanced removal of PFOA was clearly observed in solution pH 7, confirming the Cu in the surface of GAC plays a role on the PFOA adsorption. The maximum uptake was calculated as 257 and 345 μg/g for GAC and GAC-Cu using Langmuir isotherm. 40% and 80% of removal were accomplished within 1 h and 48 h. According to R2, only the linear pseudo-second-order(pso) kinetic model showed 0.98 whereas the others obtained less than 0.870.

The adsorption process using GAC is one of the most secured methods to remove of phosphate from solution. This study was conducted by impregnating Cu(II) to GAC(GAC-Cu) to enhance phosphate adsorption for GAC. In the preparation of GAC-Cu, increasing the concentration of Cu(II) increased the phosphate uptake, confirming the effect of Cu(II) on phosphate uptake. A pH experiment was conducted at pH 4-8 to investigate the effect of the solution pH. Decrease of phosphate removal efficiency was found with increase of pH for both adsorbents, but the reduction rate of GAC-Cu slowed, indicating electrostatic interaction and coordinating bonding were simultaneously involved in phosphate removal. The adsorption was analyzed by Langmuir and Freundlich isotherm to determine the maximum phosphate uptake(qm) and adsorption mechanism. According to correlation of determination(R2), Freundlich isotherm model showed a better fit than Langmuir isotherm model. Based on the negative values of qm, Langmuir adsorption constant(b), and the value of 1/n, phosphate adsorption was shown to be unfavorable and favorable for GAC and GAC-Cu, respectively. The attempt of the linearization of each isotherm obtained very poor R2. Batch kinetic tests verified that ~30% and ~90 phosphate adsorptions were completed within 1 h and 24 h, respectively. Pseudo second order(PSO) model showed more suitable than pseudo first order(PFO) because of higher R2. Regardless of type of kinetic model, GAC-Cu obtained higher constant of reaction(K) than GAC.

Chitosan, natural organic polymer, has been applied in water treatment as adsorbent due to non-toxic for human being. The amino group as functional group, can interacts with cation and anion at the same time. The prepared chitosan bead (HCB) was crosslinked to increase chemical stability (HCB-G) and both HCB and HCB-G were prepared to increase physical strength by drying referred to DCB and DCB-G, respectively. The adsorption effect for crosslinking and drying for four types of chitosan bead was tested using pseudo fist order (PFO), pseudo second order (PSO), and intraparticle diffusion model (ID). Regardless of PFO and PSO, the order of K, rate constant, is as followed: HCB > HCB-G > DCB > DCB-G for Cu(II) and phosphate. Drying leading to contraction of bead significantly reduced adsorption rate due to reduce the porosity of chitosan. In addition, crosslingking also negatively effect on adsorption rate. When compared with Cu(II) using hydrogel bead, phosphate showed higher value than Cu(II) for PFO and PSO. The application of ID showed that both hydrogel beads (HCB and HCB-G) obtained a very low R2 ranging to 0.37 to 0.81, while R2 can be obtained to over 0.9 for DCB and DCB-G, indicting ID is appropriate for low adsorption rate.