• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2003.09a
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• pp.168-171
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• 2003

This research was conducted to assess the performance of the mixed reactive materials with sand, iron filings, and HDTMA-bentonite for trichloroethylene (TCE) and chromate removal under controlled groundwater flow conditions. TCE and chromate removal rates with the mixtures of iron filing/HDTMA-bentonite were highest among four columns due to reduction by iron filings and sorption by HDTMA-bentonite. The greater capacity of the mixed iron filing/HDTMA-bentonite compared HDTMA-bentonite was due to an enhanced chromate reduction in addition to chromate sorption. The presence of chromate caused greater inhibition of TCE removal in the column with iron filings, while the presence of TCE caused less inhibition of TCE. Also, nitrate caused the decrease in TCE removal relative to chloride. Nitrate ions may also significantly affect TCE reduction rates by competing for electrons with the chlorinated compounds. The anion and co-existed contaminants competing effects should be considered when designed permeable reactive barriers (PRBs) composed of zero valent iron for field applications to remediate TCE and chromate.

• Journal of Soil and Groundwater Environment
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• v.6 no.4
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• pp.41-50
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• 2001

The use of clay has been the favored method of reducing or eliminating hazardous contaminants in the leachate from landfills. But, neither natural clays nor organoclays modified with surfactants are able to effectively sorb both heavy metals and organic contaminants. Therefore, the objective of this study is to determine the optimal amount of surfactant added on the clay mineral to effectively remove both of them. For this purpose, Na-Bentonite as the natural clay, and hexadecyltrimethylammonium (HDTMA) as the cationic surfactant were used, Chlorobenzene and lead ($Pb^{2-}$) were selected as representative contaminants. Experimental result showed that chlorobenzene sorption increased with increasing HDTMA to bentonite, ratios. On the contrary, the removal rate of lead decreased as the amount of HDTMA increased. The removal of chlorobenzene was influenced by the amount of HDTMA added to the bentonites rather than initial concentration of chlorobenzene, but the removal of lead was much more influenced by the initial concentration of lead. The adsorption of lead was not affected by chlorobenzene, and vice versa. The competitive sorption between the heavy metal and the organic contaminant was not present.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2001.04a
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• pp.15-18
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• 2001

Sorption/desorption studies were conducted to determine sorption/desorption characteristics of phenolic compounds (phenol and 4-chlorophenol) in organically modified natural bentonite. The cationic exchange capacity (CEC) of bentonite was exchanged with a cationic surfactant, hexadecyltrimethylammonium (HDTMA), to enhance the removal capacity of organic phenol contaminants dissolved in aqueous solution. This modification produces a change of the surface property of bentonite from hydrophilic to organophilic. The single-solute and bi-solute competitive adsorptions were performed In batch mode to investigate the removal of two toxic organic Phenols, chlorophenol and 4-chlorophenol on the HDTMA-bentonite. The adsorption affinity of the 4-chlorophenol was higher than phenol due to higher octanol:water partition coefficient (Kow). The single-solute and bi-solute competitive desorptions were also performed investigate the competitive desorption of the phenolic compounds from HDTMA-bentonite. Freundlich model was used to analyze the single-solute adsorption/desorption results, while the IAST model predicted the hi-solute adsorption/desorption equilibria. The IAST model well predicted hi-solute competitive adsorption/desorption behaviors.

• Journal of the Mineralogical Society of Korea
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• v.15 no.4
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• pp.243-257
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• 2002

Ca-type and Na-type bentonites show the great difference of some physicochemical properties. Na exchanged bentonite is mainly used for the foundry and construction materials in domestic utilization. This study tries to identify in detail the differences of some physicochemical properties and thermal properties between Ca-type and Na-type bentonites. Also the adsorption behavior and interlayer expansion for the HDTMA (Hexadecyltrimethylammonium) exchanged and CP (Cetylprydinium) exchanged Ca-type and Na-type bentonites were compared. Na-type bentonite shows the strong alkaline property, high viscosity and swelling compared to Ca-type bentonite. However, two types are very similar for the cation exchange capacity and MB (Methylene Blue) adsorption. The decomposition of adsorbed and interlayer water of Na-type bentonite is caused in the lower temperature than Ca-type bentonite. And Ca-type bentonite shows the decomposition of structural water in the lower temperature than Na-type bentonite. The interlayer expansion of montmorillonite resulted to the intercalation of HDTMA and CP into bentonite is so strongly caused from 12～15 $\AA$ to $40\AA$ (basal spacing). HDTMA-bentonite is almost expanded to $37～38\AA$ when 200% CEC equivalent amount of HDTMA is added, and CP-bentonite is fullly expanded to 40 $\AA$ in the 140% CEC equivalent amount of CP It means that CP causes the stronger interlayer expansion of montmorillonite and easier adsorption than HDTMA. Adsorption behaviors of CP into bentonite is so stable and continuously sorbed in the proportion to the treatment of amount until 200% of the CEC equivalents. CP-bentonite shows the same adsorption behavior regardless of Ca-type or Na-type montmorillonite.

• Journal of the Mineralogical Society of Korea
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• v.15 no.4
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• pp.305-314
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• 2002

The dehydration of hexadecyltrimethylammonium (HDTMA)-exchanged montmorillonite has been studied using X-ray diffractometry (XRD) and differential scanning calorimetry (DSC). The dehydration in HDTMA-montmorillonite seems to influence the swelling behavior of the organo-clay during heating. The basal d(001) spacing vs temperature curve of the HDTMA-montmorillonite has one broad swelling edge with a shoulder on the low-temperature side. We believe that the shoulder at $100^{\circ}C$ for the HDTMA-montmorillonite is due to interlayer swelling induced by the initial rearrangement of surfactants, and the second edge at $200^{\circ}C$ is caused by interlayer swelling resulting from the secondary vertical reorientation of alkyl chains. It seems that the dehydration of organo-clay induces a reorientation of the alkyl chains by transition to more vertical position relative to the silicate sheets, allowing instantly greater d-spacing.

• Journal of Korean Society on Water Environment
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• v.20 no.5
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• pp.512-519
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• 2004

Hybrid barriers using reduction and immobilization were tested to remediate the groundwater contaminated with multi-pollutants in this study. Iron filings and HDTMA(hexadecyltrimethylammonium)-bentonite were simulated in columns to assess the performance of hybrid barriers for remediation of trichloroethylene(TCE)-contaminated water. TCE reduction rate for the mixture of iron filings and HDTMA-bentonite was about 7 times higher than that for iron filings, only suggesting the reduction of TCE was accelerated when HDTMA-bentonite was mixed with iron filings. TCE reduction rate for the two layers of iron and HDTMA-bentonite was nearly similar to that for iron filings alone, but the partition coefficient($K_d$) for the two layers was 4.5 times higher than for that iron filings only. TCE was immobilized in the first layer with HDTMA-bentonite, and then dechlorinated in the second layer with iron filings. HDTMA-bentonite may contribute to the increase in TCE concentration on iron surface so that more TCE can be reduced. Also, TCE removal in the hybrid barriers was not affected by chromate and naphthalene while the reduction rate of TCE with the co-existing contaminants by iron filings was significantly decreased. Significant TCE removal in this research indicates that the proposed hybrid barrier system has the potential to become the effective remediation alternative during the occurrence of oil shock. Also, if subsurface environments are contaminated with multi-pollutants that contain non-reducible compounds as well as reducible compounds such as TCE, the conventional reactive barriers cannot be applied to this subsurface environment, while the proposed hybrid system can be applied successfully.

• Journal of the Mineralogical Society of Korea
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• v.16 no.4
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• pp.295-305
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• 2003

This study aims to provide the physicochemical properties of three kinds of organo­smectites which can be diversely used in industries. Some properties of them were compared with Na­smectite. Three kinds of organo­smectites such as Hexadecyltrimethylammonium(HDTMA), Benzyldimethyltetradecylammonium(BDTDA), and Cetylpyridinium(CP) exchanged smectites were manufactured for this study. Three types of organo­smectites showed the alkaline character(pH 9), very low swelling property and viscosity, and a fast flocculation behavior because of strong hydrophobic property in contrast to hydrophilic Na­smectite. Three organo­smectites showed the strong interlayer expansion with basal spacing from $19\AA$ to $23\AA$ compared with the Na­smectite of about 12 $\AA$. Organic cations such as HDTMA, BDTDA, and CP exchanged into smectite were completely decomposed in the temperature range from $250^{\circ}C$ to $400^{\circ}C$. Generally, three organo­smectites showed the similar mineralogical, physicochemical and thermal properties. But their properties are quite different from Na­smectite. Considering economically, CP exchanged smectite would be used for the diverse utilization field in the future time.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2004.09a
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• pp.68-71
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• 2004

Effects of surfactants and natural organic matter (NOM) on the sorption and reduction of tetrachloroethylene (PCE) and chromate with iron were examined in this study. PCE and chromate reduction by iron depended on the ionic type of the surfactants in this study. The apparent reaction rate constants of PCE with Triton X-100 and hexadecyltrimethyl ammonium (HDTMA) at one half and two times of the critical micelle concentration (CMC) were relatively higher than without surfactants because of the enhanced PCE partitioning and surface concentration. In the presence of sodium dodecyl benzene sulfonate (SDDBS) at 2000 mg/L and NOM at 50 mg/L, the apparent reaction rate constants of PCE increased, but TCE production decreased. The enhanced removal rate of PCE was not due to the dechlorination, and the sorption was dominant iron with SDDBS and NOM. The apparent reaction rate constants of chromate by iron with Triton X-100 and NOM were 1.4-3.1 times lower than without surfactants while that with HDTMA was two times higher than without HDTMA, When the sorbed HDTMA molecules form admicelles, negatively-charged chromate has an affinity for the positively-charged HDTMA head group.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2001.09a
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• pp.19-22
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• 2001

The effects of pH on the sequential sorption/desorption of chlorinated phenols (2-chlorophenol, 2.4-dichlorophenol and 2,4,5-trichlorophenol) in HDTMA-montmorillonite were investigated by maintaining pH 4.85 or 9.15 in the sequential batch sorption and desorption experiments. The chlorinated phenols are hydrophobic ionizable orginic compounds; they can exist as either neutral (pH << pKa) or anionic (pH >> pKa) forms. Among the tested chlorinated phenols, 2,4,5-trichlorophenol showed the highest sorption affinity at pH 4.85 as expected by the $K_{ow}$ . Neutral speciation at pH 4.85 exhibited higher sorption affinity than anionic speciation at pH 9.15. Our results indicates that desorption of chlorinated phenols is strongly dependent on pH of the aqueous phase. Freundlich model was used to analyze the single-solute sorption/desorption results. The ideal adsorbed solution theory(IAST) was employed to predict the hi-solute sorption/desorption equilibria.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2003.04a
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• pp.434-437
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• 2003

The fate and the behavior of polycyclic aromatic hydrocarbons (PAHs) and heavy metals in the environment are mainly controlled by their interactions with various components of soils and sediments. Due to their large surface area and abundance in many soils, smectites may greatly influence the fate and transport of the contaminants in the environment. In our experiment, PAH sorption by hexadecyltrimethylammonium (HDTMA)-modified smectite linearly increased in proportion to the amount of HDTMA added on the clay. However, trimethylammonium (TMA)-modified smectite did not show superiority in its sorption of PAH compared with the HDTMA-smectite or dodecyltrimethylammonium (DTMA)-smectite. Meanwhile, the smectites modified with the same cationic surfactants adsorbed Cd$^{2+}$ (heavy metal) significantly from water at low surfactant loading level, but the Cd$^{2+}$ adsorption linearly decreased as the loading of surfactant increased. The result shows that the sorption tendency of organoclays for organic or inorganic contaminants was significantly influenced by the amount and size of the surfactants added on the clay. It means that the stabilization and configuration of cationic surfactant formed on the clay interlayer according to the loading amount of each surfactant of different sizes may be an important factor in effectively sorbing environmental pollutants.nts.