The biosensor technology, which makes it possible to detect biomaterial such as protein, pathogen, and small molecules, is useful in such areas as diagnosis, bioprocessing, and food analysis or safety. For the development of a highly sensitive biosensor, immobilization techniques of organic/bio films on solid substrate, and detection methods of protein-protein reactions appearing in a few nanometers region from the sensor surface should be established. In this review, several immobilization techniques and detection methods are reviewed based on the articles reported recently.

Zeolite (FZ) prepared using coal fly ash from an Ulsan industrial complex was immobilized with polysulfone (PS) to fabricate PS-FZ beads. The prepared PS-FZ beads were characterized by scanning electron microscopy and Fourier transform infrared spectroscopy. The optimum ratio for preparing PS-FZ beads was 1 g of PS to 2 g of FZ. The removal efficiencies of Sr and Cu ions by the PS-FZ beads increased as the solution pH increased and nearly reached a plateau at pH 4. A pseudo-second-order model morel fit the adsorption kinetics of both ions by the PS-FZ beads better than a pseudo-first-order model. The Langmuir isotherm model fit the equilibrium data well. The maximum adsorption capacities calculated from the Langmuir isotherm model were 46.73 mg/g and 62.54 mg/g for the Sr and Cu ions, respectively. Additionally, the values of thermodynamic parameters such as free energy (ΔG˚), enthalpy (ΔH˚) and entropy (ΔS˚) were determined. The results implied that the prepared PS-FZ beads could be interesting an alternative material for Sr and Cu ion removal.

Zeolite (FZ), prepared from fly ash, was immobilized with polyacrylonitrile (PAN) to fabricate PAN/FZ beads. The prepared PAN/FZ beads were characterized by scanning electron microscopy, thermogravimetric analysis, and Fourier transform infrared spectroscopy. The optimum ratio to prepare PAN/FZ beads was 0.3 g of PAN to 0.3 g of FZ. The diameter of the prepared PAN/FZ beads was about 3 mm. Sr and Cu ion adsorption experiments were conducted with PAN/FZ beads. A pseudo-second-order model fit the kinetic data for Sr and Cu ion adsorption by PAN/FZ beads well. The equilibrium data fitted well with the Langmuir isotherm model, and the maximum adsorption capacities were 96.5 mg/g and 74.6 mg/g for the Sr and Cu ions, respectively. Additionally, the values of thermodynamic parameters such as Gibbs free energy (ΔGo), enthalpy (ΔHo) and entropy (ΔSo) were determined. The positive values of ΔHo revealed the endothermic nature of the adsorption process and the negative values of ΔGo were indicative of the spontaneity of the adsorption process.

PSf/D2EHPA/CNT beads were prepared by immobilizing di-(2-ethylhexyl)-phosphoric acid (D2EHPA) and carbon nanotubes (CNT) on polysulfone (PSf) and used to remove Cu(II) from aqueous solutions. Optimum pH was in the range of 4 to 6. The removal kinetic of Cu(II) by the prepared PSf/D2EHPA/CNT beads was mainly governed by internal diffusion, and the diffusion coefficient of Cu(II) by PSf/D2EHPA/CNT beads was found to be 2.19×10-4∼2.64×10-4 cm2/s. The Langmuir isotherm model predicted the experimented data well. The maximum removal capacity of Cu(II) obtained from this isotherm was 7.32 mg/g. Calculated thermodynamic parameters such as ΔGo, ΔHo and ΔSo showed that the adsorption of Cu(II) ions onto PSf/D2EHPA/CNT beads was feasible, spontaneous and endothermic at 293–323 K.

The removal of Sr ion and Cs ion was investigated to evaluate adsorption properties by using SAN-Zeolite beads immobilized with styrene acrylonitrile (SAN). The adsorption capacities increased with the decrease of SAN/zeolite ratio (SAR) from 2.5 to 0.83. The relationship of adsorption capacity (qe) and SAR was described by experimental equation such as qe=20.88＋137.81e-1.96SAR (r2=0.9980). The adsorption kinetics of Sr ion and Cs ion with SAN-Zeolite beads were fitted well by the pseudo-second-order model. The maximum adsorption capacities of Sr ion and Cs ion calculated from Langmuir isotherm model were 66.97 mg/g and 81.97 mg/g, respectively.

The objective of this study is to investigate the immobilization properties of arsenic in solidification process using geopolymer binder. Metakaolin and fly ash were used as prime materials for geopolymer that was also called as activated metakaolin cement (or Si + Al cement). The immobilization of As in geopolymer was found to be very limited regardless of the oxidation state of As and the mixing ratio of As to the binders. These results may be ascribed to the low Ca contents in prime materials used and the structural property of geopolymer formed. It was generally accepted that As was immobilized into C-S-H (calcium silicate hydrates) via precipitation and sorption, when it was solidified with ordinary portland cement and/or lime. When Ca(II) or Fe(III) was used as stimulating agents, the As leaching was reduced by15 ~ 25% than that of control experiment. These limited improvements of As immobilization might be resulted from the extremely high pH in geopolymer reaction.

The solid phase extractant (PVC-D2EHPA bead) was prepared by immobilizing di-2-ethylhexyl-phosphoric acid (D2EHPA) with polyvinyl chloride (PVC). The prepared PVC-D2EHPA beads were characterized by using fourier transform infrared spectrometer (FTIR) and scanning electron microscopy (SEM). The removal experiments of Cu(II) by PVC-D2EHPA beads conducted batchwise. The removal kinetics of Cu(II) was found to follow the pseudo-second-order model. The equilibrium data fitted well with Langmuir isotherm model and the maximum removal capacity was 2.6 mg/g at 20℃. The optimum pH region was in the range of 3.5 to 6. and the standard free energy (△Go) was between –4.67 ∼–4.98 kJ/mol, indicating the spontaneous nature of Cu(II) removal by PVC-D2EHPA beads.

Difference in immobilization effect of heavy metal-contaminated soil between two different amendment methods was evaluated; 1) both of steel slag (i.e., consisted in solid phase) and soluble phosphate (i.e., consisted in liquid phase) were simultaneously applied to contaminated soil (i.e., simultaneous amendment methods) and 2) soluble phosphate and steel slag was applied sequentially to the contaminated soil (i.e., sequentially amendment methods). The application rate of stabilizers to soils was determinated based on weight/weight ratio of 5% for steel slag and PO4/Pb molar ratio of 2.0 for phosphates, respectively. To identify difference of immobilization effect to test soil, three different soluble phosphates, such as Na2HPO4·12H2O, Ca(H2PO4)2·H2O and (NH4)2HPO4 were used. The sequential amendment was 6 ~ 27% more effective than the simultaneous amendment in terms of the immobilization efficiency for Pb, Cu, and Cd in the contaminated soil. There was little difference in case of Zn. Among the three phosphates tested, (NH4)2HPO4 was clearly the most effective. Residual form of heavy metals concentration in sequentially methods is higher than those in simultaneously methods. At the same time, more exchangeable and carbonate-bound forms of heavy metals in simultaneously methods were observed than in sequentially case. These result implies that the sequential amendment method was more effective than the simultaneous amendment method in terms of heavy metal immobilization in the contaminated soil.

The objective of this study was to evaluate the immobilization of heavy metals (Cu, Pb, Zn and Cd) in an abandoned mine soil by applying both soluble phosphates and steel slag as stabilizers. The application rate of stabilizers to soils was determinated based on PO4/Pb molar ratio of 2.0 for phosphates and on weight/weight ratio of 2, 5, 10% for steel slag, respectively. Immobilization efficiency of heavy metals in the contaminated soils was evaluated by toxicity characteristics leaching procedure (TCLP). After adding both phosphate and slag, the immobilization efficiencies of Cu, Zn and Cd increased significantly (about 14% - 40%) compared to those of treatment with soluble phosphate alone. The increae in immobilization efficiencies of Cu was the greatest. Whereas, immobilization efficiency of Pb was not significantly different from those with soluble phosphate alone. Among the tested three phosphates (Na2HPO4 ·12H2O, Ca(H2PO4)2 ·H2O, (NH4)2HPO4), the immobilization efficiencies with Na2HPO4 ·12H2O increased more than those of other phosphates. Results of sequential extraction analysis indicated that fraction of reducible form (F3) and residual form (F5) increased, while mobile forms (F1, and F2) decreased after immobilization treatment with both stabilizers resulting in decrease in leachability of heavy meyals in the treated soils. Residual fraction of Cu after treatnment was the highest as 68.5%, it was followed by Cu > Pb > Zn > Cd.

The objective of this study was to evaluate the immobilization efficiency and sequential extraction of soluble phosphates (Na2HPO4 ·12H2O, Ca(H2PO4)2 ·H2O, (NH4)2HPO4) for the stabilization of heavy metals (Cu, Pb, Zn and Cd) in abandoned mine soil. The application rate of stabilizers to soils was determinated PO4/Pbtotal molar ratio of 0.5, 1.0, 2.0, 4.0. The immobilization efficiency was evaluate of TCLP (EPA method 1311) used in a landfill for heavy metals. After processing stabilization, the immobilization efficiency of Pb is more than 95% at molar ratio of 2.0 regardless kind of phosphate. For Cu Zn and Cd, on the other hand, the efficiency has the range of from 30% to 50%, even though molar ratio increase up to 4.0. It is relatively low in comparison with Pb. Leachability of heavy metals was reduced with increasing amounts of added phosphate. Phosphates, Na2HPO4 ·12H2O was more immobilization than Ca(H2PO4)2 ·H2O, (NH4)2HPO4. After sequential extraction, form of heavy metals in soil tends to increase strongly bond like forms of organic matter-bound(F4) and residual (F5). Especially the stable residual form increases in all metals. The growth rate of residual fraction was a little different heavy metals. The growth rate of Zn is greatest increased from 17% to 22% than other metals, it was followed by Zn > Cd > Pb > Cu. Phosphates, Ca(H2PO4)2 ·H2O was the greatest increased for residual fraction.

Fe­석류석인 경우, 사면체 배위를 하는 Fe의 이온반경이 Si보다 크기 때문에 고준위 방사성 폐기물에 다량 함유되어 있는 악티나이드 원소들을 고정화시킬 수 있는 매트릭스로 고려되고 있다. 따라서 본 연구에서는 Ca2,5C e0.5Z r2F e3 O12 및 Ca2CeZrFeF e3 O12인 조성을 가진 석류석을 합성하여 이들의 상평형 관계 및 특성을 연구하였다. 혼합된 시료는 200∼400 kg/ cm2의 압력으로 성형한 후, 1100∼1400℃ 범위에서 온도 및 분위기를 변화시키면서 소결하였으며 합성된 시료는 XRD, SEM/EDS를 사용하여 상분석과 정량분석을 실시하였다. 실험결과, 이들 조성을 가진 석류석들은 1300℃로 가열하였을 때, 최적 합성상을 얻을 수 있었지만 소량의 페롭스카이트 등 부수상이 공존하였다. Ca2,5C e0.5Z r2F e3 O12 및 Ca2CeZrFeF e3 O12인 조성으로부터 합성된 Fe­석류석의 조성이 각각 Ca2.5­3.2C e0.3­0.7Z r1.8­2.8F e1.9­3.2 O12 및 Ca2.2­2.5C e0.8­1.0Z r1.3­1.6F e0.4­.07 F e3­3.2 O12였다. 특히 화학양론적 조성과 비교시, 합성된 석류석의 8배위 자리를 점하고 있는 Ca이 초과된 양상을 보였고, Ce의 함량은 초과 또는 결핍된 양상을 보였다. 이는 8배위 자리에서의 Ca과 Ce의 이온반경의 상대적인 차이 및 전하보상적 차원에서 비롯된 것으로 해석된다.에서 비롯된 것으로 해석된다.석된다.