• Title/Summary/Keyword: Nonlinear sorption

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Single and Binary Competitive Sorption of Phenanthrene and Pyrene in Natural and Synthetic Sorbents

  • Masud, Md Abdullah Al;Shin, Won Sik
    • Journal of Soil and Groundwater Environment
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    • v.27 no.6
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    • pp.11-21
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    • 2022
  • Sorption of phenanthrene (PHE) and pyrene (PYR) in several sorbents, i.e., natural soil, BionSoil®, Pahokee peat, vermicompost and Devonian Ohio Shale and a surfactant (hexadecyltrimethyl ammonium chloride)-modified montmorillonite (HDTMA-M) were investigated. Pyrene exhibited higher sorption tendency than phenanthrene, as predicted by its higher octanol to water partition coefficient (Kow). Several sorption models: linear, Freundlich, solubility-normalized Freundlich model, and Polanyi-Manes model (PMM) were used to analyze sorption isotherms. Linear isotherms were observed for natural soil, BionSoil®, Pahokee peat, vermicompost, while nonlinear Freundlich isotherms fitted for Ohio shale and HDTMA-M. The relationship between sorption model parameters, organic carbon content (foc), and elemental C/N ratio was studied. In the binary competitive sorption of phenanthrene and pyrene in natural soil, competition between the solutes caused reduction in the sorption of each solute compared with that in the single-solute system. The ideal adsorbed solution theory (IAST) coupled with the single-solute Freundlich model was not successful in describing the binary competitive sorption equilibria. This was due to the inherent nature of linear sorption of phenanthrene and pyrene in natural soil. The result indicates that the applicability of IAST for the prediction of binary competitive sorption is limited when the sorption isotherms are inherently linear.

Sorption Isotherms and KocS Estimation of Pyrethroids in Sediments

  • Lee, Sang-Jin;Shin, Hyun-Moo
    • Journal of Environmental Science International
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    • v.12 no.11
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    • pp.1173-1179
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    • 2003
  • Laboratory sorption isotherm batch studies have been attempted to elucidate interaction of synthetic pyrethroids (bifenthrin and permethrin) with sediments and their fractions. As a nonlinear isothermal model, the Freundlich equation was applied to sorption results obtained from sediments to investigate the relationship between synthetic pyrethroids and sediments containing different amounts of organic carbon. Results demonstrated that the sorption capabilities of bifenthrin and cis- and trans-permethrin was in the order of bifenthrin, cis-permethrin and trans-permethrin, respectively, indicating that adsorbed bifenthrin was the most stable followed by cis- and trans-permethrin in all sediments. Their sorption capability was closely related to organic carbon contents in sediments. Higher sorption was observed in sediments containing higher organic carbon contents. Sorption study extended into the fractions, clay and humic acids, extracted from a sediment, indicated that higher sorption capacity in humic acids occurred than in the clay of both examined bifenthrin and permethrin. This study demonstrates the sorption of synthetic pyrethroids with sediments, and will help in the understanding of the transport and fate of synthetic pyrethroids existing in field sediments.

The Relationship between $^{129}Xe$ NMR Chemical Shifts and Nanostructure of Polymers

  • Yoshimizu, Hiroaki;Suzuki, Tomoyuki;Asano, Tomoko;Tsujita, Yoshiharu
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.339-339
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    • 2006
  • In this study, the microvoids in glassy polymers were investigated by Xe sorption and $^{129}Xe$ NMR measurements. Xe sorption isotherms of glassy polymers have been successfully interpreted by the dual-mode sorption model. $^{129}Xe$ NMR chemical shift of the $^{129}Xe$ in the samples show nonlinear low-field shift with increasing sorption amount of Xe because of a fast exchange of Xe atoms between Henry and Langmuir sites, whereas it has showed linear shift against sorption amount of Xe into the Langmuir site. From this Xe-density dependence of the $^{129}Xe$ NMR chemical shift, it has been able to estimate mean size of the microvoids in glassy polymer. It is confirmed that there is correlation between ${C_H}'$ and volume or number of microvoids. From these findings, it is demonstrated that $^{129}Xe$ NMR spectroscopy is a powerful technique to determine the mean size and number of microvoids in glassy polymers.

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Evaluation of Moisture Sorption Characteristics in Polymer Material (고분자 소재에서 흡습 특성의 평가)

  • Park, Hee-Jin
    • Transactions of the Korean Society of Mechanical Engineers A
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    • v.36 no.11
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    • pp.1297-1303
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    • 2012
  • In this paper, the standard procedures for measuring the moisture sorption properties of thin polymeric materials such as polyethylene terephthalate (PET) by using the thermo-gravimetric method to characterize the moisture diffusion in the polymer are presented, and the sorption properties are quantified. The moisture diffusivity and solubility are characterized to investigate the effect of temperature and humidity on the moisture sorption properties according to the Arrhenius equation. The validation of the obtained sorption properties using thermogravimetry is discussed with the measured permeability based on Fickian diffusion. The nonlinear behavior of the concentration dependent moisture diffusion is investigated experimentally, and the nonlinearity is characterized numerically for the case of having an interface with an inorganic material such as a metal. The Fickian/Non-Fickian model based on the obtained moisture sorption properties is compared and discussed.

Solubility of Methane in Poly(n-Butyl Methacrylate) at Elevated Pressures (Poly(n-Butyl Methacrylate)에 의한 메탄가스의 용해도)

  • ;;;Stern, S. A.
    • Membrane Journal
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    • v.2 no.2
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    • pp.129-134
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    • 1992
  • The solubility of methane in poly(n-butyl methacrylate)(PnBMA) was determined at pressures up to 35 atm. These measurements were made by volumetric technique in the temperature range from -10 to 30$^{\circ}$C. The solubility was found to be a nonlinear function of the applied pressure and could be satisfactorily described by dual-mode sorption model at temperatures below the glass txansition temperature($T_g$) of the polymer. The Langmuir capacity constant decreased with increasing temperature and vanished near the glass transition temperature of PnBMA. The solubility isotherm became linear at temperatures above the glass transition temperature of PnBMA. The temperature dependence of the dual-mode sorption parameters was also discussed.

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A Study on the Correlations between Molecular Structures of Soil Humins and Sorption Properties of Phenanthrene (토양 휴민(Humin)의 분자구조 특성과 Phenanthrene 흡착상수와의 상관관계에 대한 연구)

  • Lee, Doo-Hee;Eom, Won-Suk;Shin, Hyun-Sang
    • Journal of Korean Society of Environmental Engineers
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    • v.35 no.12
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    • pp.897-905
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    • 2013
  • In this study, sorption coefficients (${\log}K_{OC}$, n) for the binding of phenanthrene (PHE) to soil humins, insoluble fraction of soil humc substances (HS), were determined and relationship between the sorption coefficients and structural characteristics of the soil humins were investigated. The soil humins used in the present study were isolated from 7 different soils including 5 domestic soils, an IHSS standard and a peat soil, and characterized by elemental analysis and CPMAS $^{13}C$ NMR method. $^{13}C$ NMR spectral features indicate that the soil humins are mainly made up of aliphatic carbons (57.1~72.3% in total carbon) with high alkyl-C moiety, and the alkyl-C contents ($C_{Al-H,C}$, %) was in order of granite soil Hu (26~42%) > volcanic ash soil, HL Hu (23.9%) > Peat Hu (14.0%). The results of correlation study show that a positive relationship ($r^2$ = 0.77, p < 0.05) between organic carbon normalized-sorption coefficients ($K_{OC}$, mL/g) and alkyl-C contents($C_{Al-H,C}$, %), while negative relationship ($r^2$ = (-)0.74, p < 0.05) between Freundlich sorption parameter (n) and H,C-substituted aromatic carbon contents ($C_{Ar-H,C}$, %). The magnitude of $K_{OC}$ values are also negatively well correlated with polarity index (e.g., PI, N + O)/C) ($r^2$ = (-)0.74, p < 0.1). These results suggest that the binding capacity (e.g., $K_{OC}$) for PHE is increased in soil humin molecules having high contents of alkyl-C or lower polarity, and nonlinear sorption for PHE increased as the H,C-substituted aromatic carbon contents ($C_{Ar-H,C}$, %) in the soil humins increased. The PHE sorption characteristics on soil humins are discussed based on the dual reactive mode of sorption model.

Non-Fickian Diffusion of Organic Solvents in Fluoropolymeys (불소고분자내 유기용매의 비-픽 확산)

  • 이상화
    • Polymer(Korea)
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    • v.28 no.1
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    • pp.24-34
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    • 2004
  • Transient sorption experiments were conducted among several combinations of fluoropolymers and various organic solvents. Fully fluorinated polymer tended to exhibit ideal sorption behavior, while partially fluorinated polymers showed anomalous sorption behaviors with a drastic acceleration at the final stage of uptake. Minimization of least-squares of the measured and predicted fractional uptake, which indicated the increasing degree of deviation from Fickian diffusion, gave values of 3.0${\times}$10$\^$-4/, 1.75${\times}$10$\^$-3/, 8.68${\times}$10/sup-3/, 1.75${\times}$10$\^$-2/, respectively, for perfluoroalkoxy copolymer, poly(ethylene-co-tetrafluoroethylene), poly(vinylidene fluoride), poly(ethylene-co-chlorotrifluoroethylene). From stress-strain tests, it was confirmed that non-Fickian diffusion is closely related to the significant variation of mechanical properties (such as modulus and tensile strength) of swollen polymer. Anomalous sorption behavior stemmed from non-Fickian diffusion caused by nonlinear disruption of polar inter-segmental bonds due to solvent-induced plasticization. Thus, it is imperative to investigate the diffusion behavior of swelling solvents in partially fluorinated polymers, especially for the application to barrier materials or perm-selective membranes.

Removal of Sorbed Naphthalene from Soils Using Nonionic Surfactant (비이온성 계면활성제를 이용한 토양내 수착된 나프탈렌의 제거)

  • Ha, Dong-Hyun;Shin, Won-Sik;Oh, Sang-Hwa;Song, Dong-Ik;Ko, Seok-Oh
    • 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.

INFLUENCE OF HUMIC SUBSTANCE (HS) ADSORPTIVE FRACTIONATION ON PYRENE PARTITIONING TO DISSOLVED AND MINERAL-ASSOCIATED HS

  • Hur, Jin;Schlautman, Mark A.
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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    • 2003.09a
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    • pp.123-127
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    • 2003
  • Changes in pyrene partitioning due to mineral surface adsorptive fractionation processes of humic substances (HS) were examined in model environmental systems. For purified Aldrich humic acid(PAHA), carbon-normalized pyrene binding coefficients ( $K_{oc}$ ) for the residual (i.e., nonadsorbed and dissolved) PAHA components were different from the original dissolved PAHA $K_{oc}$ , value prior to contact with mineral suspensions. A positive correlation between the extent of pyrene binding and weight-average molecular weight (M $W_{w}$) of residual PAHA components was observed, which appeared to be unaffected by the specific mineral adsorbents use and fractionation mechanisms. A similar positive correlation was not observed with the adsorbed PAHA components, suggesting that conformational changes occurred for the mineral-associated components upon adsorption. Nonlinear pyrene sorption to mineral-associated PAHA was observed, and the degree of nonlinearity is hypothesized to be dependent on adsorptive fractionation effects and/or structural rearrangement of the adsorbed PAHA components.s.

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