Transforming Plain LaMnO3 Perovskite into a Powerful Ozonation Catalyst: Elucidating the Mechanisms of Simultaneous A and B Sites Modulation for Enhanced Toluene Degradation.

Herein, we propose preferential dissolution paired with Cu-doping as an effective method for synergistically modulating the A- and B-sites of LaMnO3 perovskite. Through Cu-doping into the B-sites of LaMnO3, specifically modifying the B-sites, the double perovskite La2CuMnO6 was created. Subsequently, partial La from the A-sites of La2CuMnO6 was etched using HNO3, forming novel La2CuMnO6/MnO2 (LCMO/MnO2) catalysts. The optimized catalyst, featuring an ideal Mn:Cu ratio of 4.5:1 (LCMO/MnO2-4.5), exhibited exceptional catalytic ozonation performance. It achieved approximately 90% toluene degradation with 56% selectivity toward CO2, even under ambient temperature (35 °C) and a relatively humid environment (45%). Modulation of A-sites induced the elongation of Mn-O bonds and decrease in the coordination number of Mn-O (from 6 to 4.3) in LCMO/MnO2-4.5, resulting in the creation of abundant multivalent Mn and oxygen vacancies. Doping Cu into B-sites led to the preferential chemisorption of toluene on multivalent Cu (Cu(I)/Cu(II)), consistent with theoretical predictions. Effective electronic supplementary interactions enabled the cycling of multiple oxidation states of Mn for ozone decomposition, facilitating the production of reactive oxygen species and the regeneration of oxygen vacancies. This study establishes high-performance perovskites for the synergistic regulation of O3 and toluene, contributing to cleaner and safer industrial activities.

Kinetics of Thallium(I) Oxidation by Free Chlorine in Bromide-Containing Waters: Insights into the Reactivity with Bromine Species.

The oxidation of thallium [Tl(I)] to Tl(III) by chlorine (HOCl) is an important process changing its removal performance in water treatment. However, the role of bromide (Br-), a common constituent in natural water, in the oxidation behavior of Tl(I) during chlorination remains unknown. Our results demonstrated that Br- was cycled and acted as a catalyst to enhance the kinetics of Tl(I) oxidation by HOCl over the pH range of 5.0-9.5. Different Tl(I) species (i.e., Tl+ and TlOH(aq)) and reactive bromine species (i.e., HOBr/BrO-, BrCl, Br2O, and BrOCl) were kinetically relevant to the enhanced oxidation of Tl(I). The oxidation by free bromine species became the dominant pathway even at a low Br- level of 50 µg/L for a chlorine dose of 2 mg of Cl2/L. It was found that the reactions of Tl+/BrCl, Tl+/BrOCl, and TlOH(aq)/HOBr dominated the kinetics of Tl(I) oxidation at pH < 6.0, pH 6.0-8.0, and pH > 8.0, respectively. The species-specific rate constants for Tl+ reacting with individual bromine species were determined and decreased in the order: BrCl > Br2 > BrOCl > Br2O > HOBr. Overall, the presented results refine our knowledge regarding the species-specific reactivity of TI(I) with bromine species and will be useful for further prediction of thallium mobility in chlorinated waters containing bromide.

UVA-LED-Assisted Activation of the Ferrate(VI) Process for Enhanced Micropollutant Degradation: Important Role of Ferrate(IV) and Ferrate(V).

This paper investigated ultraviolet A light-emitting diode (UVA-LED) irradiation to activate Fe(VI) for the degradation of micropollutants (e.g., sulfamethoxazole (SMX), enrofloxacin, and trimethoprim). UVA-LED/Fe(VI) could significantly promote the degradation of micropollutants, with rates that were 2.6-7.2-fold faster than for Fe(VI) alone. Comparatively, UVA-LED alone hardly degraded selected micropollutants. The degradation performance was further evaluated in SMX degradation via different wavelengths (365-405 nm), light intensity, and pH. Increased wavelengths led to linearly decreased SMX degradation rates because Fe(VI) has a lower molar absorption coefficient at higher wavelengths. Higher light intensity caused faster SMX degradation, owing to the enhanced level of reactive species by stronger photolysis of Fe(VI). Significantly, SMX degradation was gradually suppressed from pH 7.0 to 9.0 due to the changing speciation of Fe(VI). Scavenging and probing experiments for identifying oxidative species indicated that high-valent iron species (Fe(V)/Fe(IV)) were responsible for the enhanced degradation. A kinetic model involving target compound (TC) degradation by Fe(VI), Fe(V), and Fe(IV) was employed to fit the TC degradation kinetics by UVA-LED/Fe(VI). The fitted results revealed that Fe(IV) and Fe(V) primarily contributed to TC degradation in this system. In addition, transformation products of SMX degradation by Fe(VI) and UVA-LED/Fe(VI) were identified and the possible pathways included hydroxylation, self-coupling, bond cleavage, and oxidation reactions. Removal of SMX in real water also showed remarkable promotion by UVA-LED/Fe(VI). Overall, these findings could shed light on the understanding and application of UVA-LED/Fe(VI) for eliminating micropollutants in water treatments.

Efficient Degradation of Organoarsenic by UV/Chlorine Treatment: Kinetics, Mechanism, Enhanced Arsenic Removal, and Cytotoxicity.

Roxarsone (ROX) has been widely used as an organoarsenic additive in animal feeding operations and poses a risk to the environment. Here, we first report the efficient degradation of ROX by UV/chlorine, where the kinetics, removal of total arsenic (As), and cytotoxicity were investigated. The kinetics study presented that reactive chlorine species (RCS) and HO• were the dominant species to react with ROX. Furthermore, the degradation rate of ROX can reach the maximum value at pH 7.5 due to the formation of more RCS. The degradation of ROX was affected by the amount of chlorine, pH, and water matrix. Through product analysis and Gauss theoretical calculation, two possible ROX degradation pathways were proposed. The free radicals attacked the As-C bond of ROX and resulted in releasing arsenate (As(V)). It was the reason that for an enhancement of the removal of total As by ferrous appeared after UV/chlorine, and over 98% of the total As was removed. In addition, cytotoxicity studies indicated that the cytotoxicity significantly enhanced during the degradation of ROX by UV/chlorine. However, by combination of UV/chlorine and adsorption, cytotoxicity can be greatly eliminated, probably due to the removal of As(V) and chlorinated products. These results further demonstrated that UV/chlorine treatment could be an effective method for the control of the potential environmental risks posed by organoarsenic.

Thallium(I) Oxidation by Permanganate and Chlorine: Kinetics and Manganese Dioxide Catalysis.

The oxidation of the toxic heavy metal thallium(I) (Tl(I)) is an efficient way to enhance Tl removal from water and wastewater. However, few studies have focused on the kinetics of Tl(I) oxidation in water, especially at environmentally relevant pH values. Therefore, the kinetics and mechanisms of Tl(I) oxidation by the common agents KMnO4 and HOCl under environmentally relevant pH condition were explored in the present study. The results indicated that the pH-dependent oxidation of Tl(I) by KMnO4 exhibited second-order kinetics under alkaline conditions (pH 8-10) with the main active species being TlOH, while the reaction could be characterized by autocatalysis at pH 4-6, and Mn(III) might also play an essential role in the MnO2 catalysis. Furthermore, a two-electron transfer mechanism under alkaline conditions was preliminarily proposed by using linear free energy relationships and X-ray photoelectron spectroscopy (XPS) analysis. Distinctively, the reaction rate of Tl(I) oxidation by HOCl decreased with increasing pH, and protonated chlorine might be the main active species. Moreover, the Tl(I)-HOCl reaction could be regarded as first order with respect to Tl(I), but the order with respect to HOCl was variable. Significant catalysis by MnO2 could also be observed in the oxidation of Tl(I) by HOCl, mainly due to the vacancies on MnO2 as active sites for sorbing Tl. This study elucidates the oxidation characteristics of thallium and establishes a theoretical foundation for the oxidation processes in thallium removal.

Removal of Organoarsenic with Ferrate and Ferrate Resultant Nanoparticles: Oxidation and Adsorption.

Many investigations focused on the capacity of ferrate for the oxidation of organic pollutant or adsorption of hazardous species, while little attention has been paid on the effect of ferrate resultant nanoparticles for the removal of organics. Removing organics could improve microbiological stability of treated water and control the formation of disinfection byproducts in following treatment procedures. Herein, we studied ferrate oxidation of p-arsanilic acid ( p-ASA), an extensively used organoarsenic feed additive. p-ASA was oxidized into As(V), p-aminophenol ( p-AP), and nitarsone in the reaction process. The released As(V) could be eliminated by in situ formed ferric (oxyhydr) oxides through surface adsorption, while p-AP can be further oxidized into 4,4'-(diazene-1,2-diyl) diphenol, p-nitrophenol, and NO3-. Nitarsone is resistant to ferrate oxidation, but mostly adsorbed (>85%) by ferrate resultant ferric (oxyhydr) oxides. Ferrate oxidation (ferrate/ p-ASA = 20:1) eliminated 18% of total organic carbon (TOC), while ferrate resultant particles removed 40% of TOC in the system. TOC removal efficiency is 1.6 to 38 times higher in ferrate treatment group than those in O3, HClO, and permanganate treatment groups. Besides ferrate oxidation, adsorption of organic pollutants with ferrate resultant nanoparticles could also be an effective method for water treatment and environmental remediation.

Thermal decomposition characteristics of BHT and its peroxide (BHTOOH).

2,6-Di-tert-butyl-4-methylphenol (BHT) is an excellent antioxidant that is easily oxidized to 2,6-di-tert-butyl-4-hydroperoxyl-4-methyl-2,5-cyclohexadienone (BHTOOH). For the safety of BHT production and usage, it is meaningful to study the thermal stability and decomposition properties of BHT and BHTOOH. In this paper, the thermal decomposition properties of BHT and BHTOOH were compared by the mini closed pressure vessel test (MCPVT) and differential scanning calorimetry (DSC). Their kinetics of thermal decomposition were studied using thermogravimetric analysis (TGA). The thermal decomposition products of BHT and BHTOOH were analyzed by gas chromatography-mass spectrometry (GC-MS). The results show that there was no significant change in temperature pressure when BHT was warmed up under a nitrogen atmosphere, indicating that BHT was stable within 400 K. The thermal decomposition reaction of BHTOOH was rapid with an initial reaction temperature of 375.2 K. The initial exothermic temperature (Ti) and heat release (QDSC) of DSC were 384.9 K and 865.0 J g-1, respectively. The apparent activation energies (Ea) for the thermal decomposition reactions of BHT and BHTOOH calculated by the Kissinger method were 151.8 kJ mol-1 and 66.07 kJ mol-1, respectively. The main decomposition products of BHT were isobutene and 2-tert-butyl-4-methylphenol. The thermal decomposition products of BHTOOH included BHT, 2,6-di-tert-butyl-4-ethylphenol, 3,5-di-tert-butyl-4-hydroxybenzaldehyde, 4,4'-(1,2-ethanediyl) bis [2,6-bis (1,1-dimethylethyl) phenol, etc. Based on the thermal decomposition behavior and products, the reaction pathway has been described. These results indicate that BHT is a potential thermal hazard during production, storage and application. For the safety of the chemical industry, the oxidation of BHT should be avoided.

Oxidation characteristic and thermal runaway of isoprene.

In this study, the oxidation characteristics of isoprene were investigated using a custom-designed mini closed pressure vessel test (MCPVT). The results show that isoprene is unstable and polymerization occurs under a nitrogen atmosphere. Under an oxygen atmosphere, the oxidation process of isoprene was divided into three stages: (1) isoprene reacts with oxygen to produce peroxide; (2) Peroxides produce free radicals through thermal decomposition; (3) Free radicals cause complex oxidation and thermal runaway reactions. The oxidation of isoprene conforms to the second-order reaction kinetics, and the activation energy was 86.88 kJ·mol-1. The thermal decomposition characteristics of the total oxidation product and purified peroxide mixture were determined by differential scanning calorimetry (DSC). The initial exothermic temperatures Ton were 371.17 K and 365.84 K, respectively. And the decomposition heat QDSC were 816.66 J·g-1 and 991.08 J·g-1, respectively. It indicates that high concentration of isoprene peroxide has a high risk of thermal runaway. The results of thermal runaway experiment showed that the temperature and pressure of isoprene oxidation were prone to rise rapidly, which indicates that the oxidation reaction was dangerous. The reaction products of isoprene were analyzed by gas chromatography-mass spectrometry (GC-MS). The main oxidation products were methyl vinyl ketone, methacrolein, 3-methylfuran, etc. The main thermal runaway products were dimethoxymethane, 2,3-pentanedione, naphthalene, etc. Based on the reaction products, the possible reaction pathway of isoprene was proposed.

Constructed electron-dense Mn sites in nitrogen-doped Mn3O4 for efficient catalytic ozonation of pyrazines: Degradation and odor elimination.

In this study, N-doped Mn3O4 catalysts (Mn-nN) with electron-dense Mn sites were synthesized and employed in heterogeneous catalytic ozonation (HCO). These catalysts demonstrated excellent performance in pyrazines degradation and odor elimination. The synthesis of Mn-nN was achieved through a facile urea-assisted heat treatment method. Experimental characterization and theoretical analyses revealed that the MnN structures in Mn-nN, played a crucial role in facilitating the formation of electron-dense Mn sites that served as the primary active sites for ozone activation. In particular, Mn-1N exhibited excellent performance in the HCO system, demonstrating the highest 2,5-dimethylpyrazine (2,5-DMP) degradation efficiency. •OH was confirmed as the primary reactive oxygen species involved in the HCO process. The second-order rate constants for 2,5-DMP degradation with O3 and •OH, were determined to be (3.75 ± 0.018) × 10-1 and (6.29 ± 0.844) × 109 M-1 s-1, respectively. Seventeen intermediates were identified through GC-MS analysis during the degradation of 2,5-DMP via HCO process with Mn-1N. The degradation pathways were subsequently proposed by considering these identified intermediates. This study introduces a novel approach to synthesize N-doped Mn3O4 catalysts and demonstrates their efficacy in HCO for the degradation of pyrazines and the elimination of associated odors. The results show that the catalysts are promising for addressing odor-related environmental issues and provide valuable insights about the broader significance of catalytic ozonation processes.

Mn(II) oxidation by the UV/chlorine system under near-neutral pH conditions: The important role of ClO· and ClO2.

The oxidation kinetics of Mn(II) by free chlorine is relatively low under near-neutral pH conditions which limits the Mn removal efficiency in drinking water treatment. Therefore, this study investigated the oxidation efficiency of Mn(II) by the UV-enhanced chlorination (UV/chlorine) system and identified the responsible reactive radical species. The results show that the oxidation kinetic of Mn(II) was greatly enhanced by the UV/chlorine system under near-neutral pH or even acidic conditions. The pseudo-first-order reaction rate of Mn(II) at pH 8.0 (within the first 20 min) increased from 2.60 × 10-5 s-1 to 3.41 × 10-4 s-1. Based on the scavenging experiments and the steady-state kinetic modeling, ClO· and ClO2, whose steady-state concentration (∼10-10 M and ∼10-9 M, respectively at pH 8.0) was at least 4 orders of magnitude higher than that of HO· and Cl·, were recognized as the dominant reactive species contributing to the oxidation of Mn(II). Kinetic model calculations indicate that the contribution of ClO· to the oxidation of Mn(II) was consistently maintained above 70 %, and ClO2 also played an important role in the oxidation of Mn(II) especially under acidic and alkaline conditions. In addition, the background components of HCO3- and Cl- had negligible influence on the oxidation efficiency because they barely changed the concentration of the ClO· and ClO2. This study first demonstrates the important role of ClO2 in the oxidation of Mn(II) in the UV/chlorine system, and the possible role of ClO2 in the degradation of some organic pollutants needs to be carefully evaluated in the future.

CuAPO-5 as a Multiphase Catalyst for Synthesis of Verbenone from α-Pinene.

Copper(II)-containing aluminum phosphate material (CuAPO-5) was synthesized hydrothermally and used as a multiphase catalyst for the oxidation of α-pinene to verbenone. The catalysts were analyzed using X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) surface area techniques, X-ray photoelectron spectroscopy (XPS), and ammonia temperature programmed reduction (NH3-TPD). Scanning electron microscopy (SEM), X-ray energy spectrometry (EDS), inductively coupled plasma emission spectroscopy (ICP-OES), Fourier infrared spectroscopy (FT-IR), and ultraviolet-visible spectroscopy (UV-vis) were performed to characterize the material. The effects of reaction temperature, reaction time, n(α-pinene)/n(TBHP), and solvent on the catalytic performance of CuAPO-5 were investigated. The results show that all the prepared catalysts have AFI topology and a large specific surface area. Copper is evenly distributed in the skeleton in a bivalent form. The introduction of copper increases the acid content of the catalyst. Under the optimized reaction conditions, 96.8% conversion of α-pinene and 46.4% selectivity to verbenone were achieved by CuAPO-5(0.06) molecular sieve within a reaction time of 12 h. CuAPO-5(0.06) can be recycled for five cycles without losing the conversion of α-pinene and the selectivity to verbenone.

Reactivity and kinetics of 1,3-butadiene under ultraviolet irradiation at 254 nm.

The reaction process of gaseous 1,3-butadiene following ultraviolet irradiation at the temperature range from 298 to 323 K under nitrogen atmosphere was monitored by UV-vis spectrophotometry. A gaseous mini-reactor was used as a reaction vessel and could be directly monitored in a UV-vis spectrophotometer. We investigated the reactivity and kinetics of 1,3-butadiene under non-UV and UV irradiation to evaluate its photochemical stability. A second-order kinetic model with 50.48 kJ·mol-1 activation energy fitted the reaction data for non-UV irradiation, whereas a first-order kinetic model was appropriate in the case of UV irradiation with activation energies of 19.92-43.65 kJ mol-1. This indicates that ultraviolet light could accelerate the photolysis reaction rate of 1,3-butadiene. In addition, the reaction products were determined using gas chromatography-mass spectrometry (GC-MS), and the reaction pathways were identified. The photolysis of 1,3-butadiene gave rise to various volatile products by cleavage and rearrangement of single C-C bonds. The differences between dimerization and dissociation of 1,3-butadiene under ultraviolet irradiation were elucidated by combining experimental and theoretical methods. The present findings provide fundamental insight into the photochemistry of 1,3-butadiene compounds.

Macrolactonization of methyl 15-hydroxypentadecanoate to cyclopentadecanolide using KF-La/γ-Al2O3 catalyst.

It has been a challenge to synthesize macrolide musk in excellent yields with high purity. KF-La/γ-Al2O3 catalyst was prepared from a highly basic mesoporous framework using a mild method. The prepared KF-La/γ-Al2O3 catalyst was employed for the synthesis of cyclopentadecanolide from methyl 15-hydroxypentadecanoate. The morphology and structure of prepared catalysts were characterized using XRD, TG-DTG, SEM, EDX, TEM, BET and CO2-TPD. The results revealed that the K3AlF6 and LaOF are produced on the surface of KF-La/γ-Al2O3, and LaO can promote the dispersion of KF on the surface of Al2O3. Catalysts pore size main distribution ranges between 10 and 30 nm, the maximum CO2 desorption temperature is 715°C when the La loading is 25%. Because F- ion has a higher electronegativity than O2- ion, the KF-promoted metal oxide (Al2O3 or/and La2O3) contained more strong basic sites, compared with that of the corresponding metal oxide. The yield of cyclopentadecanolide obtained at 0.5 g KF-25La/γ-Al2O3 catalyst and a reaction temperature of 190°C for 7 h were 58.50%, and the content after reactive distillation is 98.8%. The KF-La/γ-Al2O3 catalyst has a larger pore size and basic strength, which is more conducive to the macrolactonization of long-chain hydroxy ester.

Calcium Glycerolate Catalyst Derived from Eggshell Waste for Cyclopentadecanolide Synthesis.

The synthesis costs of macrolide musks are higher than those of other commercial musks. To make this process less expensive, eggshell waste was calcined at a low temperature to obtain a catalyst for the cyclopentadecanolide production via reactive distillation using a glycerol entrainer. X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy analyses of the original and recovered catalysts revealed that the main catalytic ingredient was calcium glycerolate (CaG) and not calcium diglyceroxide (CaDG). The basic strengths of CaG and CaDG obtained by Hammett indicators were 7.2 < H_≤ 15.0 and 9.8 < H_≤15.0, while the corresponding base amounts were 1.9 and 7.3 mmol/ g, respectively. Because CaG was soluble in glycerine, the catalyst was efficiently reused. The reaction product containing over 95.0% cyclopentadecanolide with a yield of 49.8% was obtained at a temperature of 190°C and catalyst amount of 12 wt% after 7 h of reaction. Thus, eggshell waste may be directly placed into the reaction mixture after calcination at 600°C to synthesise a large amount of cyclopentadecanolide within a relatively short time. The results of this work indicate that eggshell waste can serve as a potential eco-friendly and affordable catalyst source for the production of macrolide musks.

Thermal stability and pathways for the oxidation of four 3-phenyl-2-propene compounds.

Cinnamaldehyde, cinnamyl alcohol, ß-methylstyrene and cinnamic acid are four important biomass 3-phenyl-2-propene compounds. In the field of perfume and organic synthesis, their thermal stability and oxidation pathways deserve attention. This paper reports a new attempt to investigate the thermal stability and reactivity by a custom-designed mini closed pressure vessel test (MCPVT). The pressure and temperature behaviors were measured by MCPVT under nitrogen and oxygen atmosphere. The temperature of initial oxygen absorption (T a) and rapid oxidation (T R) were calculated. The results showed that four 3-phenyl-2-propene compounds were stable under nitrogen atmosphere. The T a of cinnamaldehyde, cinnamyl alcohol, ß-methylstyrene, and cinnamic acid was 271.25 K, 292.375 K, 323.125 K, and 363.875 K, and their T R was 301.125 K, 332.75 K, 357.91 K, and 385.375 K, respectively. The oxidation reactivity order was derived to be cinnamaldehyde > cinnamyl alcohol > ß-methylstyrene > cinnamic acid. The oxidation kinetics were determined using n versus time (n-t) plots, which showed a second-order reaction. Peroxide was determined by iodimetry, and the oxidation products were analyzed by gas chromatography-mass spectrometry (GC-MS). The results showed that the peroxide value of cinnamaldehyde, cinnamyl alcohol, ß-methylstyrene, and cinnamic acid reached 18.88, 15.07, 9.62, and 4.24 mmol kg-1 at 373 K for 6 h, respectively. The common oxidation products of four 3-phenyl-2-propene compounds were benzaldehyde, benzoic acid, and epoxide, which resulted from the carbon-carbon double bond oxidation. The substituents' oxidation products were obtained from the oxidation of cinnamaldehyde, cinnamyl alcohol, and ß-methylstyrene. In particular, the difference is that no oxidation products of the carboxyl group of cinnamic acid were detected. The common oxidation products of the four 3-phenyl-2-propene compounds were benzaldehyde, benzoic acid, and epoxide, which resulted from the carbon-carbon double bond oxidation. The substituents' oxidation products were caught in the oxidation of cinnamaldehyde, cinnamyl alcohol, and ß-methylstyrene. In particular, the difference is that no oxidation products of the carboxyl group of cinnamic acid were detected. According to the complex oxidation products, important insights into the oxidation pathways were provided.

Phytofabrication of Silver Nanoparticles Using Three Flower Extracts and Their Antibacterial Activities Against Pathogen Ralstonia solanacearum Strain YY06 of Bacterial Wilt.

Bacterial wilt caused by the phytopathogen Ralstonia solanacearum (R. solanacearum) is a devastating plant disease worldwide. The use of bactericides and antibiotics for controlling bacterial wilt has shown low efficiency and posed environmental risks. This study was to phytofabricate silver nanoparticles (AgNPs) mediated by canna lily flower (Canna indica L.), Cosmos flower (Cosmos bipinnata Cav.), and Lantana flower (Lantana camara L.). The biosynthesized AgNPs were confirmed and characterized by UV-visible spectroscopy, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), transmission electron microscope (TEM), and scanning electron microscopy (SEM). UV-visible spectra showed absorption peak bands at 448, 440, and 428 nm of AgNPs synthesized by C. indica L., C. bipinnata Cav., and L. camara L. flowers, respectively. FTIR spectra confirmed that biofunctional groups of flower extract were involved in the synthesis of AgNPs as capping and stabilizing agents. The spherical AgNPs synthesized by C. indica L., C. bipinnata Cav., and L. camara L. flowers had average diameters of 43.1, 36.1, and 24.5 nm, respectively. The AgNPs (10.0 µg/ml) synthesized by L. camara L. flower had a maximum suppression zone of 18 mm against R. solanacearum strain YY06 compared with AgNPs synthesized by C. indica L. and C. bipinnata Cav. flowers. Bacterial growth, biofilm formation, swimming motility, efflux of nucleic acid, cell death, cell membrane damage, and reactive oxygen species (ROS) generation of R. solanacearum were also negatively affected by AgNPs with high concentration and small size. In summary, the biosynthesized AgNPs can be used as an efficient and environmentally friendly antibacterial agent to reasonably inhibit R. solanacearum.

The aggregation kinetics of manganese oxides nanoparticles in Al(III) electrolyte solutions: Roles of distinct Al(III) species and natural organic matters.

This study explored the aggregation kinetics of manganese oxides (MnOx) nanoparticles in Al(III) electrolyte solutions. This is a common process in both water treatments and the natural environment. The results show that aggregation kinetics are Al(III) species-dependent. Without natural organic matters (NOM), ferron Ala (monomeric Al(III)) and ferron Alb (polymeric Al(III)) are the main species controlling the Derjaguin-Landau-Verwey-Overbeek (DLVO) type aggregation behavior of MnOx at pH 5.0 and 7.2, respectively. Ala and Alb can neutralize and reverse the negative charge of MnOx. Correspondingly, the attachment efficiency as a function of Al(III) concentrations contains three stages: destabilization, diffusion-limited, and re-stabilization stage. Interestingly, due to the tiny size of Alb nanoclusters, they behave similar to free ions and do not induce heteroaggregation at pH 7.2. The influence of some model NOM (i.e., bovine serum albumin (BSA), Sigma humic acid (HA), and alginate) was also studied. At pH 5.0, alginate polymers, while Sigma HA and BSA cannot be, are linked by Al(III) to form alginate gel clusters which bridge MnOx nanoparticles, and thus induce bridging flocculation. At pH 7.2, NOM induce the aggregation of Alb nanoclusters to form NOM-Al(III) aggregates through charge neutralization effects. Consequently, highly enhanced aggregation rate, due to the heteroaggregation between these aggregates and MnOx, was observed.

Mn2+ effect on manganese oxides (MnOx) nanoparticles aggregation in solution: Chemical adsorption and cation bridging.

Manganese oxides (MnOx) and Mn2+ usually co-exist in the natural environment, as well as in water treatments for Mn2+ removal. Therefore, it is necessary to investigate the influence of Mn2+ on the stability of MnOx nanoparticles, as it is vital to their fate and reactivity. In this study, we used the time-resolved dynamic light scattering technique to study the influence of Mn2+ on the initial aggregation kinetics of MnOx nanoparticles. The results show that Mn2+ was highly efficient in destabilizing MnOx nanoparticles. The critical coagulation concentration ratio of Mn2+ (0.3 mM) to Na+ (30 mM) was 2-6.64, which is beyond the ratio range indicated by the Schulze-Hardy rule. This is due to the coordination bond formed between Mn2+ and the surface O of MnOx, which could efficiently decrease the negative surface charge of MnOx. As a result, in the co-presence of Mn2+ and Na+, a small amount of Mn2+ (5 µM) could efficiently neutralize the negative charge of MnOx, thereby decreasing the amount of Na+, which mainly destabilized nanoparticles through electric double-layer compression, required to initiate aggregation. Further, Mn2+ behaved as a cation bridge linking both the negatively charged MnOx and humic acid, thereby increasing the stability of the MnOx nanoparticles as a result of the steric repulsion of the adsorbed humic acid. The results of this study enhance the understanding of the stability of the MnOx nanoparticles in the natural environment, as well as in water treatments.

Highly efficient removal of p-arsanilic acid with Fe(II)/peroxydisulfate under near-neutral conditions.

As a common animal feed additive, p-arsanilic acid (p-AsA) is thought to be excreted with little uptake and unchanged chemical structure, threatening the environment by potentially releasing more toxic inorganic arsenic. We herein investigated the removal of arsenic by in situ formed ferric (oxyhydr)oxides with the promotion of p-AsA degradation in Fe(II)/peroxydisulfate (PDS) system. Results showed that under acid conditions, p-AsA degraded very quickly and over 99% of p-AsA (5 µM) was degraded within 10 min at the optimal dosage of Fe(II) (100 µM) and PDS (150 µM) at pH 3, while less than 66.4% of arsenic was removed at pH 3-5. Higher pH (3-7) would inhibit the degradation of p-AsA but promote the arsenic removal. At pH 6-7, over 98.5% of total arsenic was removed, while the degradation efficiency of p-AsA was lower than 52.4%. HPLC-ICP-MS results indicated that the arsenic group was cleaved from p-AsA in the form of As(III) and then rapidly oxidized to As(V). FTIR and XPS analysis indicated that both As(V) products and residual p-AsA were bonded to ferric (oxyhydr)oxides via hydroxyl groups. Common cations (e.g., Na+, Ca2+, Mg2+) and anions such as Cl-, SO42-, CO32- had no significant influence on arsenic removal, while SiO32-, PO43- and HA inhibited the removal of total arsenic, mainly by affecting the zeta potential of iron particles. In summary, the Fe(II)/PDS process, as an efficient method for partial oxidation and simultaneous adsorption of p-AsA under near-neutral conditions, is expected to control the potential environmental risks of p-AsA.

Aggregation Kinetics of Manganese Oxides Formed from permanganate activated by (Bi)sulfite: Dual Role of Ca2+ and MnII/III.

Aqueous aggregation kinetics of manganese oxides, the solid products formed during water treatment and subsurface remediation with permanganate, are crucial for its application. In this study, manganese oxides nanoparticles were in situ formed in a permanganate/(bi)sulfite system, which was found to have excellent oxidation ability. Aggregation kinetics of such manganese oxides (i.e., MnOx-1.5, MnOx-2.5 and MnOx-5; the number represents the molar ratio of (bi)sulfite to permanganate) were evaluated by employing time-resolved dynamic light scattering under various aquatic conditions. In NaNO3 solution, the stability of manganese oxides decreased in the order of MnOx-1.5 > MnOx-2.5 > MnOx-5, indicated by their critical coagulation concentrations (CCCs). X-ray photoelectron spectroscopy (XPS) and zeta potential measurements indicated that MnII/III were responsible for the decreased stability due to their charge neutralization effects. However, in Ca(NO3)2 solution, three manganese oxides had similar CCCs, probably due to the relatively great charge neutralization ability of Ca2+. Suwannee River fulvic acid (SRFA), through electrosteric interaction, suppressed the aggregation of MnOx-1.5 in Ca(NO3)2 solution, but had no such effect in NaNO3 solution. Comparatively, the stability of MnOx-5 was markedly enhanced with SRFA in NaNO3 solutions. It was proposed that Ca2+ and MnII/III could increase the adsorption of SRFA through charge neutralization and cation bridging. This study highlights the dual role, dependent on either presence or absence of SRFA, of Ca2+ and MnII/III in controlling the aggregation of manganese oxides nanoparticles.