A continuous process of persulfate oxidation and citric acid washing was investigated for ex-situ remediation of complex contaminated soil containing total recoverable petroleum hydrocarbons (TRPHs) and heavy metals (Cu, Pb, and Zn). The batch experiment results showed that TRPHs could be degraded by Fe2+ activated persulfate oxidation and that heavy metals could be removed by washing with citric acid. For efficient remediation of the complex contaminated soil, two-stage and three-stage processes were evaluated. Removal efficiency of the two-stage process (persulfate oxidation - citric acid washing) was 83% for TRPHs and 49%, 53%, 24% for Cu, Zn, and Pb, respectively. To improve the removal efficiency, a three-stage process was also tested; case A) water washing - persulfate oxidation - citirc acid washing and case B) persulfate oxidation - citric acid washing (1) - citric acid washing (2). In case A, 63% of TRPHs, 73% of Cu, 60% of Zn, and 55% of Pb were removed, while the removal efficiencies of TRPHs, Cu, Pb, and Zn were 24%, 68%, 62%, and 59% in case B, respectively. The results indicated that case A was better than case B. The three-stage process was more effective than the two-stage process for the remediation of complex-contaminated soil in therms of overall removal efficiency.

Amendment of multi-binders was employed for the immobilization of metal(loid)s in field-contaminated soils to reduce the leaching potential. The effect of different types of multi-binders (lime/diammonium phosphate, diammonium phosphate/ladle slag and lime/ladle slag) on the solidification/ stabilization of metal(loid)s (Pb, Zn, Cu and As) from the smelter soil and mine tailing soil were investigated. The amended soils were evaluated by measuring Toxicity Characterization Leaching Procedure (TCLP) leaching concentration of metal(loid)s. The results show that the leaching concentration of metal(loid)s decreased with the immobilization using multi-binders. In terms of TCLP extraction, the mixed binder was effective in the order of lime/ladle slag > diammonium phosphate/ladle slag > lime/diammonium phosphate. When the mixed binder amendment (0.15 g lime+0.15 g ladle slag for 1g smelter soil and 0.05 g lime+0.1 g ladle slag for 1 g mine tailing soil, respectively) was used, the leaching concentration of metal(loid)s decreased by 90%. However, As leaching concentration increased with diammonium phosphate/lime and diammonium phosphate/ladle slag amendment competitive anion exchange between arsenic ion and phosphate ion from diammonium phosphate. The Standard, Measurements and Testing programme (SM&T) analysis indicated that fraction 1 (F1, exchangeable fraction) decreased, while fraction 4 (F4, residual fraction) increased. The increased immobilization efficiency was attributed to the increase in the F4 of the SM&T extraction. From this work, it was possible to suggest that both arsenic and heavy metals can be simultaneously immobilized by the amendment of multi-binder such as lime/ladle slag.

In this study, as a fundamental study for the remediation of the radionuclides-contaminated soil, the adsorption of cobalt, strontium, and cesium on natural soil and kaolin were experimently investigated and adsorption characteristics were evaluated by using several adsorption kinetic and isotherm models. The pseudo-first-order kinetic model (PFOM), pseudo-second-order kinetic model (PSOM), one-site mass transfer model (OSMTM), and two compartment first-order kinetic model (TCFOKM) were used to evaluate the kinetic data and the pseudo-second-order kinetic model was the best with good correlation. The adsorption equilibria of cobalt, strontium, and cesium on natural soil were fitted successfully by Redlich-Peterson and Sips models. For kaolin, the adsorption equilibria of cobalt, strontium, and cesium were fitted well by Redlich-Peterson, Freundlich, and Sips models, respectively. The amount of adsorbed radionuclides on natural soil and kaolin was in the order of cesium > strontium > cobalt. It is considered that these results could be useful to predicting the adsorption behaviors of radionuclides such as cobalt, strontium, and cesium in soil environments.

In Korea, the chemical oxygen demand(CODsed) in freshwater sediments has been measured by the potassium permanganate method used for marine sediment because of the absence of authorized analytical method. However, this method has not been fully verified for the freshwater sediment. Therefore, the use or modification of the potassium permanganate method or the development of the new CODsed analytical method may be necessary. In this study, two modified CODsed analytical methods such as the modified potassium permanganate method for CODMn and the modified closed reflux method using potassium dichromate for CODCr were compared. In the preliminary experiment to estimate the capability of the two oxidants for glucose oxidation, CODMn and CODCr were about 70% and 100% of theoretical oxygen demand(ThOD), respectively, indicating that CODCr was very close to the ThOD. The effective titration ranges in CODMn and CODCr were 3.2 to 7.5 mL and 1.0 to 5.0 mL for glucose, 4.3 to 7.5 mL and 1.4 to 4.3 mL for lake sediment, and 2.5 to 5.8 mL and 3.6 to 4.5 mL for river sediment, respectively, within 10% errors. For estimating CODsed recovery(%) in glucose-spiked sediment after aging for 1 day, the mass balances of the CODMn and CODCr among glucose, sediments and glucose-spiked sediments were compared. The recoveries of CODMn and CODCr were 78% and 78% in glucose-spiked river sediments, 91% and 86% in glucose-spiked lake sediments, 97% and 104% in glucose-spiked sand, and 134% and 107% in glucose-spiked clay, respectively. In conclusion, both methods have high confidence levels in terms of analytical methodology but show significant different CODsed concentrations due to difference in the oxidation powers of the oxidants.

Sorption of chlorinated pesticides such as 2,4-dichlorophenoxyacetic acid (2,4-D) and atrazine onto natural clays (montmorillonite and zeolite) modified with cationic surfactant, hexadecyltrimethyl-ammonium (HDTMA) and a natural soil was investigated using batch adsorbers. The clays were transformed from hydrophilic to hydrophobic by the cation exchange between clay surface and HDTMA up to 100% of the cation exchange capacity (CEC). Physicochemical characteristics of the sorbents such as pH, PZC (point of zero charge), organic carbon content (foc), fourier transform infrared spectroscopy (FT-IR), differential thermogravimetric analysis (DTGA) and X-ray diffraction (XRD) were analyzed. Sorption isotherm models such as Freundlich and Langmuir were fitted to the experimental data, resulting Langmuir model (R2 > 0.986) was fitted better than Freundlich model (R2 > 0.973). Sorption capacity (Q0) for 2,4-D and atrazine was in the order of HDTMA-montmorillonite > HDTMA-zeolite > natural soil corresponding to the increase in organic carbon content (foc). The sorption of the pesticides was also affected by pH. The sorption of 2,4-D decreased with the increase in pH, whereas that of atrazine was not changed. This indicated that the sorption capacity (Q0) of 2,4-D and atrazine was not affected by the solution pH because they exist as anionic (deprotonated) forms at pH above pKa. The results indicate that organoclay has a promising potential to reduce chlorinated pesticides in the effluent from golf courses.

The environmental behaviors of polycyclic aromatic hydrocarbons (PAHs) are mainly governed by their solubility and partitioning properties on soil media in a subsurface system. In surfactant-enhanced remediation (SER) systems, surfactant plays a critical role in remediation. In this study, sorptive behaviors and partitioning of naphthalene in soils in the presence of surfactants were investigated. Silica and kaolin with low organic carbon contents and a natural soil with relatively higher organic carbon content were used as model sorbents. A nonionic surfactant, Triton X-100, was used to enhance dissolution of naphthalene. Sorption kinetics of naphthalene onto silica, kaolin and natural soil were investigated and analyzed using several kinetic models. The two compartment first-order kinetic model (TCFOKM) was fitted better than the other models. From the results of TCFOKM, the fast sorption coefficient of naphthalene (k1) was in the order of silica > kaolin > natural soil, whereas the slow sorbing fraction (k2) was in the reverse order. Sorption isotherms of naphthalene were linear with organic carbon content (foc) in soils, while those of Triton X-100 were nonlinear and correlated with CEC and BET surface area. Sorption of Triton X-100 was higher than that of naphthalene in all soils. The effectiveness of a SER system depends on the distribution coefficient (KD) of naphthalene between mobile and immobile phases. In surfactant-sorbed soils, naphthalene was adsorbed onto the soil surface and also partitioned onto the sorbed surfactant. The partition coefficient (KD) of naphthalene increased with surfactant concentration. However, the KD decreased as the surfactant concentration increased above CMC in all soils. This indicates that naphthalene was partitioned competitively onto both sorbed surfactants (immobile phase) and micelles (mobile phase). For the mineral soils such as silica and kaolin, naphthalene removal by mobile phase would be better than that by immobile phase because the distribution of naphthalene onto the micelles (Kmic) increased with the nonionic surfactant concentration (Triton X-100). For the natural soil with relatively higher organic carbon content, however, the naphthalene removal by immobile phase would be better than that by mobile phase, because a high amount of Triton X-100 could be sorbed onto the natural soil and the sorbed surfactant also could sorb the relatively higher amount of naphthalene.