• Journal of the Korean GEO-environmental Society
• /
• v.2 no.1
• /
• pp.103-114
• /
• 2001

Sorption studies were conducted to determine if slow sorption fraction is observed in recent1y deposited organic matter by studying wetland soils explicitly. Sorption characteristics of hydrophobic organic compounds (chlorobenzene and phenanthrene) in recently deposited freshwater marsh soils were determined using a batch sorption procedure. Relative indicators of organic matter age were assessed using several techniques including the ratio of elemental oxygen to carbon in the organic matter. Slow sorption characteristics for both surface marsh soil (top 0-2 cm, <5 years old) and deeper marsh soil (below 10-cm, >20 years old) were compared against relatively older PPI (Petro Processors, Inc. Superfund site) and BM (Bayou Manchac) soils to investigate whether soil age can cause differences in sorption of organic compounds in wetland soils. Increases in sorption non-linearity of slow sorption model parameters (increase in KF and decrease in N) explain the existence of slow sorption fraction. The results of slow sorption model indicates the presence of a sizable slow sorption fraction; 25.4 - 26.3% (chlorobenzene) and 1.4 - 1.9% (phenanthrene) of the sorbed mass in wetland soils and 40.0 - 55.93% (chlorobenzene) and 2.9 - 3.19% (phenanthrene) of the sorbed mass in PPI and BM soils, respectively. The slow sorption fraction increased in the order of surface < deeper < PPI < BM soil indicating that size of the slow sorption fraction increases with soil organic matter age.

• Korean Journal of Ecology and Environment
• /
• v.36 no.3 s.104
• /
• pp.295-303
• /
• 2003

Sorption kinetics of hydrophobic organic compounds (chlorobenzene and phenanthrene) in natural wetland soils was investigated using laboratory batch adsorbers. One -site mass transfer model (OSMTM) and two compartment first-order kinetic model (TCFOKM) were used to analyze sorption kinetics. Analysis of OSMTM reveals that apparent sorption equilibria were obtained within 10 to 75 hours for chlorobenzene and 2 hours for phenanthrene, respectively. For chlorobenzene, the sorption equilibrium time for surface soil was longer than that of deeper soil presumably due to physico-chemical differences between the soils. For phenanthrene, however, no difference in sorption equilibrium time was observed between the soils. As expected from the number of model parameters involved, the three-parameter TCFOKM was better than the two-parameter OSMTM in describing sorption kinetics, The fraction of fast sorption ($f_1$) and the first-order sorption rate constants for fast ($k_1$)and slow ($k_2$) compartments were determined by fitting experimental data to the TCFOKM. The results of TCFOKM analysis indicate that the sorption rate constant in the fast compartment($k_1$) was much greater than that of slow fraction($k_2$) . The fraction of the fast sorption ($f_1$) and the sorption rate constant in the fast compartment($k_1$) were increasing in the order of increasing $k_{ow}$, phenanthrene > chlorobenzene. The first-order sorption rate constants in the fast ($k_1$) and slow ($k_2$) compartments were found to vary from $10^{-0.1}\;to\;-10^{1.0}$ and from $10^{-4}\;to-10^{-2}$, respectively.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
• /
• 2004.04a
• /
• pp.186-191
• /
• 2004

Sorption kinetics of 2-chlorophenol(2-ChP), 2,4-dichlorophenol(2,4-DChP) and 2,4,5-trichlorophenol (2,4,5-TChP), onto montmorillonite modified with hexadecyltrimethyl ammonium cations(HDTMA-mont) were investigated. One-site mass transfer model(OSMTM) and two compartment first-order kinetic model(TCFOKM) were used to analyze kinetics. As expected from the number of model parameters involved, the three-parameter TCFOKM was better than the two-parameter OSMTM in describing sorption and desorption kinetics of chlorophenols in HDTMA-mont. For all chlorophenols, the results of OSMTM analysis indicate that the predominant deprotonated speciation(at pH 9.15) exhibited higher mass transfer coefficient( $k_{s}$ ) than the protonated speciation(at pH 4.85). This is because the deprotonated speciation has stronger hydrophobic interaction than protonated speciation. Most sorption completes in three hours. The fraction of the fast sorption and the first-order sorption rate constants for the fast and slow compartments in TCFOKM were determined by fitting experimental data to the TCFOKM. The results of kinetics reveal that the fraction of the fast sorption( $f_1$) and the sorption rate constants in the fast compartments( $k_1$) were in the order 2,4,5-TChP > 2,4-DChP > 2-ChP, which agrees with the magnitude of the $K_{ow}$ . The first-order sorption rate constants in the fast compartment(10$^{0.8}$ - 10$^{1.22}$ h $r^{-1}$ ) were much larger than those in the slow compartment(10$^{-1}$.74/ - 10$^{-2}$.622/ h $r^{-1}$ ).> ).).

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
• /
• 2000.11a
• /
• pp.107-118
• /
• 2000

For the last several decades, the fate of organic pollutants has been extensively studied in natural environments with emphasis on sorption and desorption phenomena. Although the mechanisms involved are not clear yet there is a consensus about the existence of hysteresis in the sorption and desorption of organic pollutants. Furthermore, it is found that hysteresis is the outcome of slow nonequilibrium sorption of organic pollutants, which results in the formation of desorption-resistant fractions of the pollutants. Desorption-resistant fractions may increase as a function of the residence time of the pollutants in the environments. Field monitoring data show a slow but continuous decline of chemicals applied to soil, followed by little or no subsequent disappearance. One plausible explanation for such resistance to biodegradation, desorption, or extraction can be attributed the gradual movement of organic pollutants to less accessible remote sites inside the matrix with time. This phenomenon has been termed sequestration or aging. The fact that some pollutants are sequestered in soil with time may have a great impact on bioremediation and risk assessment, Some portion of the resistant pollutants may still be present in the environments after bioremediation. It requires vigorous means to completely remove the aged portion that may not be further bioavailable. However, precaution should be taken since aging is not always evident. Aging seems to be soil and chemical specific.

• Journal of Soil and Groundwater Environment
• /
• v.16 no.6
• /
• pp.79-94
• /
• 2011

Black carbon (BC), a kind of high surface area carbonaceous material (HSACM), was isolated from Andong lake sediment. Sorption and desorption kinetics of naphthalene (Naph) and phenanthrene (Phen) in organic carbon (OC) and BC in the Andong lake sediment were investigated. Several kinetic models such as one-site mass transfer model (OSMTM), two-compartment first-order kinetic model (TCFOKM), and a newly proposed modified two-compartment first-order kinetic model (MTCFOKM) were used to describe the sorption and desorption kinetics. The MTCFOKM was the best fitting model. The MTCFOKM for sorption kinetics showed that i) the sorbed amounts of PAHs onto BC were higher than those onto OC, consistent with BET surface area; ii) the equilibration time for sorption onto BC was longer than those onto OC due to smaller size of micropore ($11.67{\AA}$) of BC than OC ($38.18{\AA}$); iii) initial sorption velocity of BC was higher than OC; and iv) the slow sorption velocity in BC caused the later equilibrium time than OC even though the fast sorption velocity was early completed in both BC and OC. The MTCFOKM also described the desorption of PAHs from the OC and BC well. After desorption, the remaining fractions of PAHs in BC were higher than those in OC due to stronger PAHs-BC binding. The remaining fractions increased with aging for both BC and OC.

• Korean Journal of Ecology and Environment
• /
• v.39 no.4 s.118
• /
• pp.450-461
• /
• 2006

In this study, sorption kinetics of lead (Pb) and cadmium (Cd) onto coastal sediments were investigated at pH 5.5 using laboratory batch adsorbers. Four different models: one-site mass transfer model (OSMTM), pseudo-first-order kinetic model (PFOKM) ,pseudo-second-order kinetic model (PSOKM) and two compartment first-order kinetic model (TCFOKM) were used to analyze the sorption kinetics. As expected from the number of model parameters involved, the three-parameter TCFOKM was better than the two-parameter OSMTM, PFOKM and PSOKM in describing sorption kinetics of Pb and Cd onto sediments. Most sorption of Pb and Cd was rapidly completed within the first three hours, followed by slow sorption in the subsequent period of sorption. All models predicted that the sorbed amount at the apparent sorption ($q_{e,s}$) equilibria increased as the CEC and surface area of the sediments increased, regardless of initial spiking concentration ($C_0$) and heavy metal and the sediment type. The sorption rate constant ($k_s,\;hr^{-1}$) in OSMTM also increased as the CEC and BET surface area increased. The rate constant of pseudo-first-order sorption ($k_{p1,s},\;hr^{-1}$) in PFOKM were not correlated with sediment characteristics. The results of PSOKM analysis showed that the rate constant of pseudo-second-order sorption ($k_{p2,s},\;g\;mmol^{-1}\;hr^{-1}$) and the initial sorption rate ($v_{o,s},\;mg\;g^{-1}\;hr^{-1}$) were not correlated with sediment characteristics. The fast sorption fraction ($f_{1,s}$) in TCFOKM increased as CEC and BET surface increased regardless of initial aqueous phase concentrations. The sorption rate constant of fast fraction ($k_{1,s}=10^{0.1}-10^{1.0}\;hr^{-1}$) was much greater than that of slow sorption fraction ($k_{2,s}=10^{-2}-10^{-4}\;hr^{-1}$) respectively.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
• /
• 2000.11a
• /
• pp.171-176
• /
• 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 Korean Society of Water and Wastewater
• /
• v.22 no.4
• /
• pp.467-473
• /
• 2008

Natural organic matter (NOM) removal by physico-chemical adsorption and biological oxidation was investigated in five slow sand filters with different media depths. Non-purgeable dissolved organic carbon(NPDOC) and $UV_{254}$ absorbance were measured to evaluate the characteristics of NOM removal at different filter depths. Removal efficiency of NOM was in the range of 10-40% throughout the operation time. At start-up of the filters packed with clean sand media, NOM was probably removed by physico-chemical adsorption on the surface of sand through the overall layer of filter bed. However, when Schumutzdecke layer was built up after 30 days operation, the major portion of NPDOC was removed by biological oxidation and/or bio-sorption in lower depth above 50 mm. NOM removal rate in the upper 50 mm filter bed was $0.82hr^{-1}$. It was about 20 times of the rate($0.04hr^{-1}$) in the deeper filter bed. Small portion of NPDOC could be removed in the deeper filter bed by both bio-sorption and biodegradation. SEM analysis and VSS measurement clearly showed the growth of biofilm in the deeper filter bed below 500 mm, which possibly played an important role in the NOM removal by biological activity besides the physco-chemical adsorption mechanism

• Journal of Korean Society of Environmental Engineers
• /
• v.30 no.9
• /
• pp.907-912
• /
• 2008

In order to reduce the availability of dissolved inorganic phosphorus in surface water, lakes, and estuaries, black shale and zero valent iron can be used as reacitve materials. Sorption of phosphate to sampled sediment, black shale, and zero valent iron was quantitatively evaluated in this research. Effect of coexistence of calcium was also tested, since coexisting ions can enhance the precipitation of phosphate. An empirical kinetic model with fast sorption(k$_t$), slow sorption(k$_s$), and precipitation(k$_p$) was well fitted to experiment data from this research. Langmuir and Freundlich sorption isotherms were also used to evaluated phosphate maximum sorption capacity. Calcium ions at 0, 1 and 5 mM affected the precipitation kinetic coefficient in empirical kinetic model but did not have impact on the maximum sorbed concentration.

• Journal of the Mineralogical Society of Korea
• /
• v.15 no.2
• /
• pp.104-113
• /
• 2002

The sorption of Cd$^{2+}$ on calcite was studied in aqueous solutions of several electrolytes. The Cd$^{2+}$ concentration, 10$^{-8}$ M, was kept well below saturation with respect to CdCO$_3$(s). Sorption behavior of Cd$^{2+}$ in different ionic strengths of NaClO$_4$solutions shows that sorption is independent of ionic strength. This result suggests that Cd$^{2+}$ sorption on calcite surface is of a specific nature, and adsorption is controlled by an inner-sphere type of surface complex. Two stages in the sorption behavior could be identified: an initial rapid uptake, followed by slower uptake reaching a maximum steady state by 145 hrs. No evidence was observed for surface precipitation, although it can not be entirely ruled out. Desorption of Cd$^{2+}$ from the calcite surface after resuspension into Cd-free solution is initially very rapid, but depends partly on the previous sorption history. Desorption behavior of Cd$^{2+}$ show that an initial rapid desorption followed either by slow uptake reaching a maximum, as in the adsorption experiments, or slowing desorption to reach a steady state minimum. This irreversible behavior of Cd$^{2+}$ sorption and desorption may act as one of the controls for regulating the mobility of dissolved Cd$^{2+}$ natural aqueous systems. Calculated adsorption partition coefficients suggest that overall sorption and desorption process in the concentration range are controlled by d single mechanism.ingle mechanism.