[Interactions between Goethite and Humic Acid and the Stability of Goethite-Humic Acid Complex].

Goethite-humic acid complex was prepared in a suspension containing goethite and humic acid. X-ray diffraction (XRD) results showed that the crystal structure of this complex had no obvious changes compared to pure goethite, but the peak intensity of the complex was slightly reduced. Transmission electron microscopy (TEM) images indicated that the surface of the goethite was coated by particles of humic acid. Compared to the infra-red (IR) spectra of goethite and humic acid, the anti-vibrational frequencies of COO- and the vibrational frequencies of ≡Fe-OH decreased by 20 cm-1 and 9 cm-1, respectively, while the vibrational frequencies of the associated hydroxyls increased by 10 cm-1 and the absorption band of carboxylic C-O and free hydroxyls almost disappeared. This indicates that the interactional mechanisms between goethite and humic acid include the monodentate coordination of Fe(Ⅲ) -carboxylate and hydrogen-bonds. Thermogravimetry/differential thermogravimetry (TG/DTG) analysis showed that the temperature of the weight loss peak for ≡Fe-OH in goethite and the complex were 258℃ and 276℃, respectively. This indicates that the coating of humic acid enhances the heat stability of ≡Fe-OH in goethite. Compared with humic acid, the temperature of the weight loss peak for aliphatic organics and aromatic organics in complex decreased by 60℃ and 26℃, respectively and the ratio of weight loss from aliphatic organics to aromatic organics in complex increased. This indicates that organics with a lower heat stability may be more easily adsorbed onto goethite and the affinity to goethite was higher for the aliphatic organics than for aromatic organics. After ultrasonic dispersion, the content of large particles (≥ 2 µm) decreased significantly for both goethite and humic acid, but the content and the size of large particles in the complex changed only slightly.

[Adsorption Properties of Fluorine onto Fulvic Acid-Bentonite Complex].

Fulvic Acid-Bentonite (FA-BENT) complex was prepared using coprecipitation method, and basic properties of the complex and sorption properties of fluorine at different environmental conditions were studied. XRD results showed that the d001 spacing of FA- BENT complex had no obvious change compared with the raw bentonite, although the diffraction peak intensity of smectite in FA-BENT complex reduced, and indicated that FA mainly existed as a coating on the external surface of bentonite. Some functional groups (such as C==O, −OH, etc. ) of FA were observed in FA-BENT FTIR spectra, thus suggesting ligand exchange-surface complexation between FA and bentonite. Higher initial pH values of the reaction system were in favor of the adsorption of fluorine onto FA-BENT, while the equilibrium capacity decreased with the increase of pH at initial pH ≥ 4.50. The adsorption of fluorine onto FA-BENT was also affected by ionic strength, and the main reason might be the "polarity" effect. The adsorption of fluorine onto FA-BENT followed pseudo-second-order kinetic model and was controlled by chemical process ( R² = 0.999 2). Compared with the Freundlich model, Langmuir model was apparently of a higher goodness of fit (R² > 0.994 9) for absorption of fluorine onto FA-BENT. Thermodynamic parameters indicated that the adsorption process of fluorine was an spontaneously endothermic reaction, and was an entropy-driven process (ΔH 32.57 kJ · mol⁻¹, ΔS 112.31 J · (mol · K)⁻¹, ΔG −0.65- −1.76 kJ · mol⁻¹).

[Adsorption Characteristics for Humic Acid by Binary Systems Containing Kaolinite and Goethite].

In this study, the binary systems of kaolinite-goethite mixture (KGM) and kaolinite-goethite complex (KGC) were prepared by different methods, and the surface properties and humic acid adsorption of the samples were investigated. Results showed that the specific surface area (SSA) of the samples followed the order of goethite> KGC> KGM> kaolinite, and the SSAs increased significantly for KGC while slightly for KGM when compared to the average value of kaolinite and goethite. The isoelectric point (IEP) of kaolinite, goethite, KGM and KGC appeared around 3.2, 7.9, 6.1 and 6.7, and the Zeta potential at pH 5.0 was -13.9, 38.2, 14.3 and 19.7 mV, respectively. The adsorption kinetic data for humic acid were well fitted using the pseudo-second-order kinetic models, suggesting that chemisorption was important in the adsorption process. Both one-site and two-site Langmuir models were suitable to describe the isotherm adsorption data (R² 0.962-0.993), and the correlation coefficients of two-site model for the binary systems were relatively higher (R2>0.989). The R2 values of Freundlich model fiting the adsorption data were low for the four samples, especially for the two pure samples. This indicated that the adsorption with various sites and mono-layer model was important in adsorbing humic acid onto the binary systems. At the initial pH of 5.0, the adsorption capacity (qmax) of kaolinite, goethite, KGM and KGC was 6.02, 61.83, 35.13 and 42.10 mg·g^-1, respectively. The qmax values of KGC and KGM increased to different extents when compared to the average of kaolinite and goethite. Thermodynamic parameters indicated that the adsorption of humic acid were endothermic for the four samples and non-spontaneous for kaolinite while spontaneous for the other samples.

[Surface properties and adsorption characteristics for fluoride of goethite, kaolinite and their association].

The basic properties of goethite, kaolinite and their association were characterized using X-ray diffraction (XRD) , scanning electron microscopes (SEM), Fourier transform infrared spectroscopy (FT-IR), potentiometric titrations, specific surface area (SSA) and micropore analysis. Moreover, the adsorption capacity and adsorption models of fluoride by the investigated samples were studied. Results show that when kaolinite and goethite presented simultaneously in the same suspension system, goethite was apt to coat the surface of kaolinite and the interactions between them could occur rapidly. As a result, the binary association containing kaolinite and goethite was formed. The binary association possessed the pore diameter of 0.42 nm and 0.61 nm, specific surface area of 34.08 m2/g, surface fractal dimension of D = 2.726 and the pH(PZNPC) (pH of point of zero net proton charge) in the range of 5.50-6.50. At the initial pH 6. 00, the maximum adsorption capacity (q(max) of goethite, kaolinite and association was 4.506, 0.608 and 3.520 mg/g respectively. The adsorption of fluoride by the single kaolinite or goethite could be attributed to monolayer adsorption and the data of isotherm adsorption could be well fitted by Langmuir model (R2 = 0.991 and R2 = 0.964 respectively). The Freundlich model was suitable for describing the adsorption of fluoride by the binary association (R2 = 0.995), which indicated that the surface of the binary association is heterogeneous and is probably provided with multilayer adsorption sites. The adsorption mechanisms for fluoride by the investigated samples include anion ligand exchange, surface coordination and electrostatic attraction. In addition, F acting as a bond bridge between the surfaces of kaolinite and goethite contributed to the adsorption of fluoride too. Compared to the single goethite or kaolinite, the binary association exhibited the higher specific surface area, surface fractal dimension and adsorption capacity for fluoride as well as the lower amount of hydroxyls and net proton charges on it's surface, although no significant variation was found in the porosity structure of the association.