• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2000.11a
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• pp.171-176
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• 2000

Bioremediation of hazardous hydrophobic organic compounds, such as polycyclic aromatic hydrocarbons (PAHs), is a major environmental concern due to their toxic and carcinogenic properties. Due to their hydrophobicity, the hydrophobic organic compounds are mainly associated with the soil organic matter or nonaqueous-phase liquids. A major question concerns the relationships between biodegradation and sorption. This work develops and utilizes a non- steady state model for evaluating the interactions between sorption and biodegradation of phenanthrene, a 3-ring PAH compound, in soil-slurry systems. The model includes sorption/desorption of a target compound, its utilization by microorganisms as a primary substrate existing in the dissolved phase and/or the sorbed phase in biomass and soil, oxygen transfer, and oxygen utilization as an electron acceptor. Biodegradation tests with phenanthrene were conducted in liquid and soil-slurry systems. The soil-slurry tests were performed with very different mass transfer rate: fast mass transfer in a flask test at 150 rpm, and slow mass transfer in a roller-bottle test at 2 rpm. In the slurry tests, phenanthrene was degraded more rapidly than in liquid tests, but with a similar rate in both slurry systems. Modeling analyses with several hypotheses indicate that a model without biodegradation of compound sorbed to the soil was not able to account for the rapid degradation of phenanthrene, particularly in the roller bottle slurry test. Reduced mass-transfer resistance to bacteria attached to the soil is the most likely phenomenon accounting for rapid sorbed-phase biodegradation.

• Journal of Environmental Science International
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• v.19 no.5
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• pp.549-563
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• 2010

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 ($k_1$) was in the order of silica > kaolin > natural soil, whereas the slow sorbing fraction ($k_2$) was in the reverse order. Sorption isotherms of naphthalene were linear with organic carbon content ($f_{oc}$) 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 ($K_D$) 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 ($K_D$) of naphthalene increased with surfactant concentration. However, the $K_D$ 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 ($K_{mic}$) 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.

• Journal of Korea Soil Environment Society
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• v.4 no.2
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• pp.77-86
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• 1999

Partitioning of two hydrophobic organic compounds (HOCs), phenanthrene and naphthalene, to kaolinite and sorbed surfactants was studied to evaluate the feasibility of surfactant-enhanced remediation (SER) of contaminated subsurface systems. Sorbed surfactant partition coefficients. $K_ss$, showed a strong dependence on the surfactant sorption isotherms at low sorbed surfactant levels $K_ss$ values were at their highest and then decreased with increasing surfactant sorption densities. $K_ss$ values for SDS were always larger than corresponding $K_mic$values. For Tween 80, however. $K_ss$ values $K_mic$ were higher than $K_mic$ values only at the lower sorbed surfactant densities. HOC distribution between immobile and mobile phases varied with surfactant dose distribution coefficients increased initially with increasing surfactant concentrations and then decreased at higher doses. This observation shows directly the competition between sorbed and micellar surfactants for HOC partitioning. Overall results of this study demonstrate that surfactant sorption to the solid phase can lead to increases in HOC retardation in some SER applications. Therefore, before an SER process is selected, appropriate consideration of surfactant sorption and HOC partitioning to immobile versus mobile phases pertinent to a specific subsurface system must be contemplated.

• Journal of Soil and Groundwater Environment
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• v.8 no.2
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• pp.44-54
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• 2003

A kinetic model for evaluating effects of surfactant on the biodegradation of HOC(hazardous organic chemicals) in soil-slurry systems was developed. The model includes the partition of HOC and surfactant, the dissolved-, micellar-, and sorbed-phase biodegradation, the enhanced solubilization of HOC by surfactant addition, and the mass transfer of HOC. Phenanthrene as HOC and Trition X-100, Tergitol NP-10, Igepal CA-720, and Brij 30 were used in the model simulations. The biodegradation rate was increased even with a small micellera-phase bioavailability. The biodegradation was not greatly enhanced due to decreased aqueous HOC concentration by increasing surfactant dose in both cases with and without micellar-phase bioavailability. The effect of sorbed-phase biodegradation on total biodegradation rate was not highly important compared to aqueous- and micellar-phase biodegradation. The model can be applied for surfactant screening and optimal design of surfactant-based soil bioremediation process.

• KSCE Journal of Civil and Environmental Engineering Research
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• v.29 no.2B
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• pp.207-212
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• 2009

Surfactants were used as representative anionic and non ionic surfactants to investigate the effect of mass transfer on the mineral-catalyzed Fenton-like oxidation of sorbed phenanthrene. Mass transfer of phenanthrene on the oxide surface or interlayer between aqueous and solid phases was generated by surfactant addition. Apparent solubility of phenanthrene was increased as surfactant concentration increasesd. In tests using Tween 80, oxidation of phenanthrene decreased as apparent solubility increased. High apparent solubility was not responsible for oxidation of sorbed phenanthrene in the sand due to the surfactant acted as a scavenger of degradation. In tests with SDS, $H_{2}O_{2}$ decomposition rate in Fenton-like oxidation was decreased by complexation between goethite and SDS. However, in tests using 32 mM of SDS, efficiency of phenanthrene treatment increased compared to the test without SDS addition. Therefore, suitable amount of SDS addition could provide optimum condition for phenanthrene oxidation on the oxide surface or interlayer between aqueous and solid phase, and decrease $H_{2}O_{2}$ decomposition, and as a result, phenanthrene removal efficiency can be improved.

• Proceedings of the Membrane Society of Korea Conference
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• 1995.04a
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• pp.34-35
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• 1995

The unique feature of pervaporation is the mass transfer from a liquid phase to a vapor phase through a non-porous polymeric membrane. When a liquid mixture is brought into contact with a membrane at one side, it is sorbed into the membrane. Due to a driving force applied across the membrane, the sotbed liquid molecules permeate through the membrane and evaporate at the downstream side of the membrane. In pervaporation the permeated species are usually removed from the downstream side under a relatively low vapor pressure, for example by evacuation with a vacuum pump. As far as this condition is fulfilled, the evaporation step can be considered to be much faster than sorption or diffusion. Hence evaporation does not contribute to permselectivity. Therefore the separation by pervaporation results from the differences in the preferential sorption of the individual components of a mixture into the membrane together with the diffusion rates through the membrane. This postulation implies that both sorption and diffusion phenomena have to be accounted for to understand the physico-chemical nature of the pervaporation separation process.

• Environmental Engineering Research
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• v.10 no.3
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• pp.138-143
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• 2005

Laboratory batch experiments were conducted to evaluate the Fenton degradation rates of phenanthrene. Fenton reactions for the degradation of phenanthrene were carried out with aqueous and slurry phase, to investigate the effects of sorption of phenanthrene onto solid phase. Various types of surfactants and electrolyte solutions were used to evaluate the effects on the phenanthrene degradation rates by Fenton's reaction. A maximum 90% removal of phenanthrene was achieved in aqueous phase with 0.9% of $H_2O_2$ and 300 mg/L of $Fe^{2+}$ at pH 3. In aqueous phase reaction, inhibitory effects of synthetic surfactants on the removal of phenanthrene were observed, implying that surfactant molecules acted as strong scavenger of hydroxyl radicals. However, use of $carboxymethyl-{\beta}-cyclodextrin$ (CMCD), natural surfactant, showed a slight enhancement in the degradation of phenanthrene. It was considered that reactive radicals formed at ternary complex were located in close proximity to phenanthrene partitioned into CMCD cavities. It was also show that Fenton degradation of phenanthrene were greatly enhanced by addition of NaCl, indicating that potent radical ion ($OCI^-$) played an important role in the phenanthrene degradation, although chloride ion might be acted as scavenger of radicals at low concentrations. Phenanthrene in slurry phase was resistant to Fenton degradation. It might be due to the fact that free radicals were mostly reacting with dissolved species rather than with sorbed phenanthrene. Even though synthetic surfactants were added to increase the phenanthrene concentration in dissolved phase, low degradation efficiency was obtained because of the scavenging of radicals by surfactants molecules. However, use of CMCD in slurry phase, showed a slight enhancement in the phenanthrene degradation. As an alternative, use of Fenton reaction with CMCD could be considered to increase the degradation rates of phenanthrene desorbed from solid phase.

• Journal of Korean Society of Environmental Engineers
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• v.29 no.7
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• pp.778-782
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• 2007

This study investigated the dechlorination mechanisms of TCE by Fe(II) associated with cement. Batch slurry experiments were peformed to investigate the behaviors of selected ions; Fe(II), Fe(III), $Ca^{2+}$, $SO_4^{2-}$ in cement/Fe(II) system. The kinetic experiments of TCE in cement/Fe(II) systems showed that injected Fe(II) was mostly sorbed on cement within 0.5 day and 90% of injected 200 mM sulfate was sorbed on cement within 0.5 day when $[TCE]_0$ = 0.25 mM and $[Fe(II)]_0$ = 200 mM. The kinetic experiments of TCE in hematite/CaO/Fe((II) systems were conducted for simulation of cement/Fe(II) system. Calcium oxide that is one of the major components in cement hydration reactions or has a reactivity in limited conditions. Hematite assumed the ferric iron oxide component of cement. The reactivities observed in hematite/CaO/Fe(II) system were comparable to those reported for cement/Fe(II) systems containing similar molar amounts of Fe(II). The behavior of Fe(II) and $SO_4^{2-}$ sorbed on solid phase at an early stage of reaction in hematite/CaO/Fe(II) system was similar to that of cement/Fe(II) system. Ferric ion was released from hematite at an early period of reaction at low pH. The experimental evidence of kinetic test using hematite/CaO/Fe(II) system implies that the reactive reductant is a mixed-valent Fe(II)-Fe(III) mineral, which may be similar to green rust. Fe(II) sorbed on cement can be converted to new mineral phase having a reactivity such as Fe(II)-Fe(III) (hydr)oxides in cement/Fe(II) systems.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 1998.11a
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• pp.64-68
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• 1998

본 연구는 오염토양/지하수의 정화를 위하여 사용되는 계면활성제 교정기술의 보다 현실적인 평가를 위하여 토양에 흡착된 계면활성제에 대한 소수성 유기오염물인 Naphthalene과 Phenanthrene의 흡수현상에 대한 연구결과를 나타내었다. 음이온 계면활성제인 Sodium Dodecyl Sulfate (SDS)와 중성 계면활성제인 Tween 80의 흡착곡선은 소수성 꼬리 (hydrophobic tails)간의 상호작용에 의하여 S-형 모양을 보이며 이들 흡착된 계면활성제는 Micelle로 존재하는 계면활성제에 비하여 유기오염물에 대한 보다 강한 흡수능력을 나타내었다. 결과에 나타난 흡수능력의 차이는 계면활성제가 흡착되어있거나 Micelle상태로 존재할 경우 다른 구조를 형성하기 때문이라 사료된다. 흡수된 계면활성제와 Micelle의 상호경쟁에 의하여 유기오염물의 부동성(immobility)을 나타내는 분배계수(distribution coefficient)는 계면활성제의 농도에 반비례하였다. 결론적으로 토양/지하수의 오염물 정화를 위하여 계면활성제 교정기술의 적용 시 고정상 (solid phase)에 있는 흡착 계면활성제에 의한 유기오염물의 지체현상 (retardation)을 고려하여야 한다.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2002.09a
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• pp.183-186
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• 2002

Experiments in the batch soil/aqueous systems were conducted to compare the sorption onto soil and extraction efficiency of sorbed phenanthrene in the presence of the micelle-forming anionic surfactant(SDS) or the micelle-like amphiphilic nano-sized polyurethane particles. Micelle-like amphiphilic nano-sized polyurethane(APU) particles synthesized from amphiphilic urethane acrylate anionomers(UAA) could solubilize phenanthrene within their hydrophobic interiors as the same way that surfactants micelles did in aqueous phase.