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.

Amino acid promoted oxidation of atrazine by Fe3O4/persulfate.

In the present study, we demonstrated that the presence of cysteine could remarkably enhance the degradation of atrazine by Fe3O4/persulfate system. The results of electron paramagnetic resonance (EPR) spectra confirmed the combination of cysteine and Fe3O4 exhibited much higher activity on activation of persulfate to generate more SO4•- and •OH than Fe3O4 alone. At pH of 3.0, SO4•- and •OH contributed to about 58.2 % and 41.8 % of atrazine removal respectively, while •OH gradually dominated the oxidation of atrazine from neutral condition to alkaline condition. The co-existing Cl- and HCO3- could quench SO4•-, resulting in the inhibition of atrazine degradation. The presence of low natural organic matters (NOM) concentration (0-2 mg L-1) could enhance the atrazine removal, and high concentration (>5 mg L-1) of NOM restrained the atrazine degradation. During the Cysteine/Fe3O4/Persulfate process, cysteine served as a complexing reagent and reductant. Through acidolysis and complexation, Fe3O4 could release dissolved and surface bound Fe2+, both of which contributed to the activation of persulfate together. Meanwhile, cysteine was not rapidly consumed due to a regeneration process, which was beneficial for maintaining Fe2+/Fe3+ cycle and constantly accelerating the activation of persulfate for atrazine degradation. The reused Fe3O4 and cysteine in the Cysteine/Fe3O4/Persulfate process exhibited high stability for the atrazine degradation after three cycles. The degradation pathway of atrazine included alkylic-oxidation, dealkylation, dechlorination-hydroxylation processes. The present study indicates the novel Cysteine/Fe3O4/Persulfate process might be a high potential for treatment of organic polluted water.

Transcriptomics and iTRAQ-proteomics analyses provide novel insights into the defense mechanism of black shank disease in tobacco.

Black shank disease caused by Phytophthora nicotianae is one of the most important diseases in tobacco worldwide and can result in a devastating loss in tobacco cultivation. Many efforts have been carried out to identify the chromosome segment from Nicotiana plumbaginifolia containing a resistance locus carrying a gene named Php; however, the Php gene has not been cloned, and knowledge of the potential mechanism of the Php gene in the resistant lines is limited. To further characterize the resistance mechanism of the Php gene, we first used the resistant line "RBST" and the susceptible cultivar "Honghuadajinyuan" (HD) to obtain the near-isogenic line RBS89 containing the Php gene from RBST. RBS89 showed high resistance to black shank disease. Transcriptomic and iTRAQ analyses were applied to explore the potential defense mechanisms in RBS89 plants in comparison with HD plants with or without inoculation. Many differentially expressed genes (DEGs) and proteins were identified, and some pathogenesis-related (PR) proteins were extensively abundant in the RBS89 plants when compared with the HD plants in response to black shank disease. Importantly, overexpression of the PR gene NtPR-1B in HD plants improved the resistance of tobacco plants to black shank disease, indicating that NtPR-1B and Php genes might have similar roles in protecting tobacco from black shank disease. However, the relationship between NtPR-1B and Php genes requires further analysis. Therefore, our study provides valuable information for breeding tobacco cultivars with black shank disease resistance and sheds light on the defense mechanism of black shank disease in tobacco for enhancing Phytophthora resistance in other Solanaceae crops.

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.

Transcriptomic profile of tobacco in response to Phytophthora nicotianae infection.

Black shank, caused by Phytophthora nicotianae (P. nicotianae), is a serious disease of cultivated tobacco (Nicotiana tabacum) worldwide. The interactions between tobacco and P. nicotianae are complex and the outcomes of the interactions depend on the tobacco genotype, P. nicotianae strain, and environmental conditions. In this study, we used RNA-sequencing (RNA-Seq) to investigate and compare transcriptional changes in the stems of tobacco upon inoculation with P. nicotianae strain race 0. We used two tobacco varieties: RBST (named from resistance to black shank and tobacco mosaic virus), which was resistant to the P. nicotianae strain race 0, and Honghuadajinyuan (HD), which was susceptible to P. nicotianae race 0. Samples were collected 12 and 72-hour post inoculation (hpi). Analysis of differentially expressed genes (DEGs) and significantly enriched GO terms indicated that several basic defense mechanisms were suppressed in both varieties, which included response to wounding (GO: 0009611), and defense response to fungus (GO: 0050832). We also found some genes that may especially be related to mechanisms of resistance in RBST, such as the one encoding a chitinase. These results will provide a valuable resource for understanding the interactions between P. nicotianae and tobacco plants.

[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.

Isolation and characterisation of rhizosphere bacteria active against Meloidogyne incognita, Phytophthora nicotianae and the root knot-black shank complex in tobacco.

BACKGROUND: The use of dually antagonistic bacteria (DAB) as alternatives to chemicals for biological control of disease complexes has received little attention. In this study targeting the Meloidogyne incognita-Phytophthora nicotianae complex, DAB from the tobacco rhizosphere were identified and screened against the diseases caused by one or both pathogens in tobacco. RESULTS: From 450 soil tobacco rhizosphere samples, 26 DAB were identified and had in vitro nematicidal and antifungal efficacies of 37.2-100% and 32.9-73.4% respectively. These DAB were classified into 19 species of 11 genera. In pot experiments, Streptomyces flavofungini SNA26, Pseudomonas putida SNB53 and Serratia marcescens subsp. sakuensis SNB54 effectively suppressed black shank (control effect 72.0-80.2%), root knot (70.0-81.7) and the disease complex (58.7-68.5%) caused by P. nicotianae, M. incognita and both pathogens in tobacco respectively. CONCLUSION: Nineteen DAB species were demonstrated to be antagonists against the M. incognita-P. nicotianae complex. Because S. flavofungini SNA26, P. putida SNB53 and S. marcescens subsp. sakuensis SNB54 significantly suppressed the infection of M. incognita and P. nicotianae in tobacco, these species have potential for development as biocontrol agents against the diseases and complex caused by these two pathogens.