Changes in the Glucose Concentration Affect the Formation of Humic-like Substances in Polyphenol-Maillard Reactions Involving Gibbsite.

The polyphenol-Maillard reaction is considered one of the important pathways in the formation of humic-like substances (HLSs). Glucose serves as a microbial energy source that drives the humification process. However, the effects of changes in glucose, particularly its concentration, on abiotic pathways remain unclear. Given that the polyphenol-Maillard reaction requires high precursor concentrations and elevated temperatures (which are not present in soil), gibbsite was used as a catalyst to overcome energetic barriers. Catechol and glycine were introduced in fixed concentrations into a phosphate-buffered solution containing gibbsite using the liquid shake-flask incubation method, while the concentration of glucose was controlled in a sterile incubation system. The supernatant fluid and HLS components were dynamically extracted over a period of 360 h for analysis, thus revealing the influence of different glucose concentrations on abiotic humification pathways. The results showed the following: (1) The addition of glucose led to a higher degree of aromatic condensation in the supernatant fluid. In contrast, the supernatant fluid without glucose (Glu0) and the control group without any Maillard precursor (CK control group) exhibited lower degrees of aromatic condensation. Although the total organic C (TOC) content in the supernatant fluid decreased in all treatments during the incubation period, the addition of Maillard precursors effectively mitigated the decreasing trend of TOC content. (2) While the C content of humic-like acid (CHLA) and the CHLA/CFLA ratio (the ratio of humic-like acid to fulvic-like acid) showed varying increases after incubation, the addition of Maillard precursors resulted in a more noticeable increase in CHLA content and the CHLA/CFLA ratio compared to the CK control group. This indicated that more FLA was converted into HLA, which exhibited a higher degree of condensation and humification, thus improving the quality of HLS. The addition of glycine and catechol without glucose or with a glucose concentration of 0.06 mol/L was particularly beneficial in enhancing the degree of HLA humification. Furthermore, the presence of glycine and catechol, as well as higher concentrations of glucose, promoted the production of N-containing compounds in HLA. (3) The presence of Maillard precursors enhanced the stretching vibration of the hydroxyl group (-OH) of HLA. After the polyphenol-Maillard reaction of glycine and catechol with glucose concentrations of 0, 0.03, 0.06, 0.12, or 0.24 mol/L, the aromatic C structure in HLA products increased, while the carboxyl group decreased. The presence of Maillard precursors facilitated the accumulation of polysaccharides in HLA with higher glucose concentrations, ultimately promoting the formation of Al-O bonds. However, the quantities of phenolic groups and phenols in HLA decreased to varying extents.

Treatment of shale gas produced water by magnetic CuFe2O4/TNTs hybrid heterogeneous catalyzed ozone: Efficiency and mechanisms.

Magnetic spinel ferrite (CuFe2O4) has been applied to catalyze ozone for treating the practical shale gas produced water (PW) in our previous study. In this work, CuFe2O4/titanium nanotubes (TNTs) catalyst was successfully prepared by an impregnation-calcination method. Characterization results revealed that the crystal form of CuFe2O4 was bound to the surface of TNTs, the particle size is much smaller than the pure CuFe2O4 crystal particle, which could weaken the influence of the internal diffusion process on its catalytic efficiency. The experimental results showed that the removal ratio of CODCr in the CuFe2O4/TNTs/O3 system was approximately 14% higher than that of the CuFe2O4/O3 system. The dissolution of metal elements decreased to one-third that of the CuFe2O4/O3 system. The inhibition ratio of PW on the growth of E. coli K12 decreased 68% after the CuFe2O4/TNTs catalytic oxidation process. Experimental results of complete capture experiments illustrated that the yield of HO• of the CuFe2O4/TNTs/O3 system was 10-19% higher than that of the CuFe2O4/O3 system. The elemental valence analysis revealed that the transition of Cu(II)-Cu(III) and Fe(II)-Fe(III) coexisted in the catalytic system. Besides, the surface hydroxyl groups promoted the electron transfer process and enhanced the ozone adsorption affinity. The proposed catalytic mechanisms of the CuFe2O4/TNTs/O3 system were proposed via the above analysis.

Two different states conversion mechanism of the imprinting sites.

Bisphenol A molecular imprinted adsorbent (BMIA) was successfully synthesized by a sol-gel process and showed a good specific binding performance in the water. The further studies showed that the mass transfer process was controlled by in-diffusion, and the synthesis conditions would effect on the amount of imprinting sites. Scatchard model analysis evidenced that the high binding affinity sites and the low binding affinity sites were both on BMIA, and the high binding affinity sites played a key role in the specific binding process. Scatchard model analysis of temperature effect experiments and dosage effect experiments proved that the specific binding sites with high binding affinity and the unexpressed specific binding sites with low binding affinity were the two different states of the imprinting binding sites. The conversion between the two different states depended on the reaction driving force, and the increasing reaction driving force would increase the number of specific binding sites. Especially, the temperature showed a linear positive correlation with the amount of specific binding sites. Finally, a possible model was put forward to explain the two different states conversion mechanism of the imprinting sites.

Electrochemical activation of persulfates at BDD anode: Radical or nonradical oxidation?

The combination of persulfates (peroxydisulfate (PDS) and peroxymonosulfate (PMS)) and electrolysis using boron-doped diamond (BDD) anode is a promising green advanced oxidation process. In comparison with electrolysis alone, electrochemical activation of persulfates at BDD anode considerably enhanced the degradation of carbamazepine (CBZ). The experimental results indicate that the surface-adsorbed hydroxyl radical (HO) played the dominant role. The generally proposed nonradical oxidation mechanism ignored hydroxyl radical (HO) oxidation because low concentration of radical scavenger (<10 M methanol or 5 M tertbutanol) could not effectively scavenge the surface-adsorbed HO. The quasi steady-state concentration of HO was estimated to be about 5.0-9.1 × 10-12 M for electrolysis with BDD anode, and it was increased to 1.1-1.6 × 10-11 M and 3.2-5.0 × 10-11 M for addition of 5 mM PDS and PMS, respectively. The results of cyclic voltammetry (CV) and chronoamperometry as well as evolution of dissolved oxygen (DO) reveal that the electrochemically activated persulfates molecule (PDS∗/PMS∗) promoted the production of HO via water dissociation at BDD anode and enhanced the direct electron transfer (DET) reaction, which otherwise inhibited the oxygen evolution side reaction. Therefore, higher current efficiency was achieved in electrochemical activation of persulfates process compared with electrolysis process. Additionally, the transformation products of CBZ were also investigated and their formation pathways were proposed.

Study on enhanced degradation of atrazine by ozonation in the presence of hydroxylamine.

Degradation of atrazine (ATZ) by ozonation in the presence of hydroxylamine (HA) was experimentally investigated in this study. The results showed approximately 80% of ATZ was degraded by ozonation in the presence of HA, while only 20% was degraded by ozonation alone. The obvious inhibition of the ATZ degradation by tert-butanol suggested the enhanced ATZ degradation by ozone/HA was primarily attributed to OH. The OH yield was determined to be 25.8%. Additionally, the optimum HA dosage for the ATZ degradation was 4µM, when the ozone dosage was 20µM. The effects of pH, bicarbonate and temperature on ATZ degradation by ozone/HA were investigated in details. Most importantly, the enhanced ATZ degradation by ozonation in the presence of HA was still observed in real water especially at acidic pHs. Furthermore, the potential mechanism of OH formation during the reaction of ozone with HA was proposed herein. Nine products were identified by UPLC/Q-TOF-MS system. The ATZ degradation involved dealkylation, dechlorination-hydroxylation and olefination. The evolutions of the concentrations of three available transformation products including deethylatrazine, deisopropylatrazine and deethyldeisopropylatrazine in ozone/HA were evaluated and compared with that in ozonation alone.

Magnetic CoFe2O4 nanoparticles supported on titanate nanotubes (CoFe2O4/TNTs) as a novel heterogeneous catalyst for peroxymonosulfate activation and degradation of organic pollutants.

Magnetic spinel ferrites, as heterogeneous catalysts to generate powerful radicals from peroxymonosulfate (PMS) for the degradation of organic pollutants, have received much attention in recent years due to the characteristic of environmental benefits. In this study, with titanate nanotubes (TNTs) as catalyst support, a novel CoFe2O4/TNTs hybrid was constructed by an impregnation-calcination method. Characterization results revealed that TNTs support could promise small size and good dispersion of CoFe2O4 nanoparticles. Compared to the pure CoFe2O4, the as-prepared CoFe2O4/TNTs not only exhibited better performance in catalytic decomposition of Rhodamine B, but also realized higher total organic carbon removal and less cobalt leaching, which could be attributed to the enhanced catalytic ability from smaller CoFe2O4 nanoparticles and the unique ion-exchange ability from TNTs support. Some influential factors, including reaction temperature, dosages of PMS and CoFe2O4/TNTs, and pH values were investigated and analyzed. Moreover, CoFe2O4/TNTs maintained its catalytic efficiency during the repeated batch experiments and also displayed functional advantages in the catalytic degradation of phenol. We believe the CoFe2O4/TNTs hybrid can be an efficient and green heterogeneous catalyst for the degradation of organic pollutants, and this study provides insights into the rational design and development of alternative catalysts for wastewater treatment.

Preparation of zirconium oxy ion-imprinted particle for the selective separation of trace zirconium ion from water.

Zr(IV) oxy ion-imprinted particle (Zr-IIP) was prepared using the metal ion imprinting technique in a sol-gel process on the surface of amino-silica. The dosages of zirconium ions as imprinted target, (3-aminopropyl) triethoxysilane (APTES) as a functional monomer and teraethyl orthosilicate (TEOS) as a cross-linker were optimized. The prepared Zr-IIP and Zr(IV) oxy ion non-imprinted particle (Zr-NIP) were characterized. pH effect, binding ability and the selectivity were investigated in detail. The results showed that the Zr-IIP had an excellent binding capacity and selectivity in the water. The equilibrium data fitted well to the pseudo-second-order kinetic and the Langmuir model for Zr(IV) binding onto Zr-IIP, respectively. The saturate binding capacity of Zr-IIP was found to be 196.08 µmol g(-1), which was 18 times higher than that of Zr-NIP. The sequence of binding efficiency of Zr-IIP for various ions was Zr(IV)>Cu(II)>Sb(III)>Eu(III). The coordination number has an important effect on the dimensional binding capacity. The equilibrium binding capacity of Zr-IIP for Zr(IV) decreased little under various concentrations of Pb(II) ions. The analysis of relative selectivity coefficient (Kr) indicated that the Zr-IIP had an appreciable binding specificity towards Zr(IV) although the competitive ions coexisted in the water. The Zr-IIP could serve as an efficient selective material for recovering or removing zirconium from the water environment.