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ABSTRACT: An allophanic soil (AS) catalyzed the formation of dark-colored polymers via polycondensation reactions between catechol and glycine. The organic carbon content of the AS was increased from 0.16% to 1.3%, indicating that some of the dark-colored polymers had been adsorbed to the AS. The characteristics of the dark-colored polymers adsorbed on the AS were similar to those of a humin that is not extractable with an aqueous alkaline solution. Such a humin-like substance (HuLS) was separated from the AS by treatment with a mixture of HF and HCl. The HuLS and humic acid-like substance (HaLS), comprising the acid-insoluble fraction in the reaction mixture, were characterized by elemental analysis, size exclusion chromatography, pyrolysis-GC/MS and (13)C NMR. However, the structural features of HaLS and HuLS had many points in common. These results suggest that HuLS-AS can be regarded as an organo-clay complex formed by the strong adsorption of HaLS to the AS. The adsorption of pentachlorophenol (PCP) to AS and HuLS-AS was examined at pH 5.5. At this pH, the zeta potential of the HuLS-AS showed a negative value. It would, therefore, be expected that pentachlorophenolate anions would adsorb with difficulty to HuLS-AS because of electrostatic repulsion. Nevertheless, the adsorption coefficient for PCP to HuLS-AS, as estimated by the Freundlich isotherm, was seven times larger than that for AS. These results show that HuLS, when adsorbed on the AS surface, has the capability to enhance the adsorption of PCP.
Chemosphere 02/2011; 83(11):1502-6. · 3.21 Impact Factor
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ABSTRACT: To suppress the coagulation of humic acid (HA) in aqueous solutions, HA was modified with hydrophilic amines, such as glucosamine or taurine. These amines were attached to carboxyl groups in HA via amide bond formation. The degree of modification (R(m)) was estimated to be 21-38%. Infrared spectra of the modified HAs were also consistent with the presence of amide bonds. Acid-base titration showed that the average acid-dissociation constant (pK(app)) of the HA samples was increased by the modification. The Ca(2+) binding capacity of HA decreased with an increase in R(m) value. Critical pH or Ca(2+) concentration, at which HA coagulation occurs, was increased as the result of the modification. These critical points for taurine-HA were higher than those for glucosamine-HA. This is mainly due to electrostatic repulsion by sulfonate groups in taurine. These results indicate that the coagulation of HA is suppressed by modifying the molecules with glucosamine or taurine.
Chemosphere 10/2007; 69(2):240-6. · 3.21 Impact Factor
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ABSTRACT: Solubilizing abilities of aggregates of humic acid (HA) to chlorinated benzenes (CBs) were investigated by means of the apparent water solubility enhancement. Both the water solubilities of 1,4-dichlorobenzene (DCB) and 1,2,4,5-tetrachlorobenzene (TeCB) linearly increased with increasing concentration of HA above the critical micelle concentration (CMC). Such solubilization behavior of CBs for HA was compatible with those for sodium dodecyl sulfate (SDS). These results indicate that the solubilization of CBs in the aqueous solution of HA above the CMC can be interpreted on the basis of the phase-separation model. Thus, the partition coefficients (K(mic)) of CBs between water and HA aggregate phases were calculated by assuming this model. The fact that the K(mic) value increased with increasing K(ow) of CBs supported the partition into the HA aggregate phase by hydrophobic interaction. The estimated K(mic) values of DCB were not dependent on the solution pH. Both K(mic) values of DCB and TeCB for the HA aggregate were found to be 4-5-fold lower than those of SDS.
Chemosphere 12/2004; 57(6):439-45. · 3.21 Impact Factor
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ABSTRACT: The photo-Fenton reactions, which could yield hydroxyl radicals via the catalytic degradation of H2O2 by Fe(II), were focused as one of the abiotic degradation processes of bisphenol A (BPA) in surface waters. At pH 6, in the presence of H2O2 only, 32% of BPA was degraded after 120 min of irradiation. However, 97% of BPA was degraded in the presence of both H2O2 and Fe(II). Without light irradiation, no BPA degradation was observed even in the presence of Fe(II) and H2O2. These results show that photo-Fenton processes are effective in the natural attenuation of BPA in surface water. In addition, the presence of humic acids (HAs), which were of more aliphatic nature, resulted in enhancing BPA degradation via the photo-Fenton processes. Therefore, HAs can be one of the important factors in enhancing the degradation of BPA in surface water via the photo-Fenton processes.
Toxicol. and Environ. Chem. 07/2003; 85(4-6):95-102.
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ABSTRACT: The distribution behavior of pyrene on humic acid (HA)-kaolin complexes, prepared by adsorbing HA on kaolin, was investigated by batch experiments. The distribution coefficient (Kd) of pyrene on the HA-kaolin complex increased with the fraction (f(oc)) of organic carbon adsorbed to the surface of the kaolin. This can be attributed to hydrophobic interactions between pyrene and the adsorbed HAs. The effects of adsorbed HAs were quantitatively evaluated by calculating the distribution coefficient (K(oc)) and affinity constant (K(oc)ads) for pyrene to the adsorbed HAs. A fluorescence quenching method was employed to determine the affinity constant (K(oc)aq) of pyrene to HAs dissolved in an aqueous solution. When the K(oc) values were compared with the K(oc)aq values, the K(oc) values were found to be 4 to 11 times larger than the K(oc)aq values. On the other hand, the K(oc)ads values were 4 to 9 times larger than the K(oc)aq values. These indicate that the affinity for pyrene is enhanced by the adsorption of HAs to kaolin. In addition, the K(oc) values increased with increasing average molecular weights of the HAs. These results demonstrate that HAs, when they are adsorbed to clay minerals, play an important role in the deposition of polycyclic aromatic hydrocarbons (PAHs) in a soil environment.
Journal of Environmental Quality 32(2):591-8. · 2.32 Impact Factor