Migration of l-Selenomethionine in the Water-Soil Interface Dominated by Iron Oxides.

Organic selenium (Se) accounts for up to 10-80% of total Se in soils, and l-selenomethionine (SeMet) is a typical organic Se species. However, the migration of SeMet in soils remains elusive. This study investigated the solid-liquid distribution, adsorption, desorption by phosphate, and self-oxidization of SeMet in solution under the influence of ferrihydrite, goethite, and hematite through batch experiments. Iron oxides could adsorb a much larger amount of SeMet than inorganic Se. At the initial Se element concentrations of 0-200 mg/L, the solid/liquid partition coefficient of SeMet was constant, which was 0.41, 0.43, and 0.50 on ferrihydrite, goethite, and hematite, respectively. In addition, the adsorption process of SeMet on the three iron oxides could be well described by the linear driving force model. Accordingly, the intraparticle diffusion coefficient of SeMet in ferrihydrite, goethite, and hematite was 1.4 × 103, 7.9 × 104, and 1.2 × 105 nm2/min, respectively. The adsorption of SeMet on the three iron oxides was slightly influenced by the pH and the coexisting ions, such as Cl-, NO3-, SO42-, and H2PO4-. The desorption ratio of SeMet on the three iron oxides by phosphate was lower than 2.5%. SeMet would aggregate the nanoparticles of iron oxides, resulting in a synergistic effect on the adsorption of phosphate. The oxidization ratio of SeMet was 23.9% in the solution, while it decreased to 17.1-17.5% in iron oxide suspensions. For this oxidization process, the three iron oxides exhibited varying effects to decelerate SeMet oxidation, as represented by the equivalent reaction. The findings of this study reveal the migration of SeMet in the water-soil interface under the influence of iron oxides, which can improve the understanding of Se cycling in the environment as well as provide some guidance for the better utilization of Se in soils and environmental remediation of Se pollution.

Microbial metabolic limitation of rhizosphere under heavy metal stress: Evidence from soil ecoenzymatic stoichiometry.

Slow nutrient turnover and destructed soil function were the main factors causing low efficiency in phytoremediation of heavy metal (HM)-contaminated soil. Soil ecoenzymatic stoichiometry can reflect the ability of soil microorganisms to acquire energy and nutrients, and drive nutrient cycling and carbon (C) decomposition in HM-contaminated soil. Therefore, for the first time, we used the enzymatic stoichiometry modeling to examine the microbial nutrient limitation in rhizospheric and bulk soil of different plants (Medicago sativa, Halogeton arachnoideus and Agropyron cristatum) near the Baiyin Copper Mine. Results showed that the main pollutants in this area were Cu, Zn, Cd, and Pb, while Cd and Zn have the greatest contribution according to the analysis of pollution load index (PLI). The activities of soil C-, nitrogen (N)-, and phosphorus (P)-acquiring enzymes in the rhizosphere of plants were significantly greater than that in bulk soil. Moreover, microbial C and P limitations were observed in all plant treatments, while the lower limitation was generally in the rhizosphere compared to bulk soil. The HM stress significantly increased microbial C limitation and decreased microbial P limitation, especially in the rhizospheric soil. The partial least squares path modeling (PLS-PM) further indicated that HM concentration has the greatest effects on microbial P limitation (-0.64). In addition, the highest enzyme activities and the lowest P limitation were observed in the rhizospheric and bulk soil of M. sativa, thereby implying that soil microbial communities under the remediation of M. sativa were steadier and more efficient in terms of their metabolism. These findings are important for the elucidation of the nutrient cycling and microbial metabolism of rhizosphere under phytoremediation, and provide guidance for the restoration of HM-contaminated soil.

Facile fabrication of MOF(Fe)@alginate aerogel and its application for a high-performance slow-release N-fertilizer.

In this work, a novel MOF(Fe)@NaAlg aerogels composite were fabricated by a facile method of ion cross-linking, and characterized via Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TG), X-ray photoelectron spectroscopy (XPS) and BET surface area analysis. The MOF(Fe)@NaAlg aerogels loaded by ammonium (NH4+) was prepare to the slow-release fertilizer (SRF). The adsorption capacity and swelling of MOF(Fe)@NaAlg(2:10) were 29.4 mg/g and 73 g/g, respectively. The swelling behaviors of MOF(Fe)@NaAlg(2:10) in different saline solutions were investigated. The release assessments confirmed the effective role of MOF(Fe) in slow-release property of the prepared formulation. Also, the prepared fertilizer formulation exhibited excellent water-retention capacity in soil. Therefore, they will have a great potential application in the field of agriculture.

Impact of low-molecular weight organic acids on selenite immobilization by goethite: Understanding a competitive-synergistic coupling effect and speciation transformation.

The interactions between low-molecular weight organic acids (LMWOAs) and selenium (Se) on mineral/water interfaces affect the release, immobilization and bioavailability of Se in nature. Herein, the effects of three environmentally relevant LMWOAs (i.e., oxalic (Oxa), succinic (Suc) and citric (Cit) acids) on Se(IV) adsorption to goethite under oxic conditions were investigated using batch experiments, speciation fractionation, and ATR-FTIR and XPS analyses. The LMWOAs exhibited a competitive-synergistic coupling effect on Se(IV) adsorption to goethite, which inhibited the adsorption rate of Se(IV) by 14.1, 13.3 and 8.0 times. However, immobilization of Se(IV) was simultaneously enhanced by 39.1%, 34.6% and 14.1% in the following order Oxa > Suc > Cit. The results obtained by fractionation of the adsorbed Se(IV) revealed that the enhancement was due to surface binding as well as speciation transformation from ligand-exchangeable Se(IV) into residual fractions, which increased by approximately 18% in the presence of the LMWOAs. The dissolution of goethite significantly improved due to the LMWOAs and decreased to different degrees as the concentration of Se(IV) increased. The monodentate mononuclear complexes (58.2%) and Lewis base sites bonded Se (41.8%) were the predominant surface species of Se(IV) in goethite-Se(IV) system. The ATR-FTIR and high-resolution XPS analyses demonstrated that the formation of ≡FeO(SeO)O-CO surface complexes (22.8-27.0%) occurred in the presence of LMWOAs, which could be closely correlated with the interface-mediated reduction of Se(IV). In addition, the predominant mechanism for the formation of residual Se is LMWOA specific, in which ferric selenite-like precipitation was dominant for Suc (10.6%) and Cit (11.6%) and reduction was dominant for Oxa (17.5%). Overall, LMWOAs play an important role in Se(IV) immobilization and speciation transformation and may facilitate understanding the Se bioavailability in rhizosphere soils under oxic conditions.

High-quality Al@Fe-MOF prepared using Fe-MOF as a micro-reactor to improve adsorption performance for selenite.

High-quality Al@Fe-MOF was prepared by in situ modification of Fe-MOF with Al3+ to improve the adsorption performance for selenite (Se(Ⅳ)). The structures and properties of Al@Fe-MOF were characterized by powder X-ray diffraction, high resolution transmission electron microscope, X-ray photoelectron spectroscopy (XPS), nitrogen isothermal adsorption-desorption measurement and zeta potential. The adsorption performance of Al@Fe-MOF for Se(Ⅳ) was studied by batch adsorption experiments. A large number of pores in Al@Fe-MOF were filled by AlOOH and some bayerite formed on the surfaces. Compared with those of Fe-MOF, the specific surface area (SSA) and microporosity of Al@Fe-MOF decreased to 1368 m2/g and 38.5%, respectively. Hydrolysis occurred at pH > 5.0 for Fe-MOF, but did not for Al@Fe-MOF at the pH range of 3.0-7.0. Compared with in Fe-MOF, the adsorption capacity and efficiency of SSA for Se(Ⅳ) were increased by 77% and 112%, and the average free energy of adsorption was increased to 11.62 kJ/mol in Al@Fe-MOF. Besides, the Se(Ⅳ) adsorption amount of Al@Fe-MOF was almost not influenced by the pH from 3.0 to 7.0. The high resolution XPS (HR-XPS) and pH analysis indicated that Al species in Al@Fe-MOF could significantly increase the density of adsorption sites to improve its adsorption capacity for Se(Ⅳ).

[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.