Xu X, Liu Y, Wang T, Ji H, Chen L, Li S, Liu W. Co-adsorption of ciprofloxacin and Cu(II) onto titanate nanotubes: Speciation variation and metal-organic complexation. Journal of Molecular Liquids [Internet]. 2019;292:111375. 访问链接Abstract
Titanate nanotubes (TNTs) have been reported to show good adsorption performance for heavy metals, but researches on organic contaminants adsorption by TNTs are limited. In this study, co-adsorption of a heavy metal (Cu) and an emerging organic contaminant (ciprofloxacin, CIP) by TNTs was investigated in binary systems. TNTs could simultaneously remove the two contaminants, with a high adsorption capacity of 234.5 μmol/g for Cu(II) and 237.0 μmol/g for CIP at pH 4 in the binary system. pH greatly affected adsorption due to speciation variation of the contaminants and surface charge change of TNTs. Cu(II)-CIP complexes dominated adsorption capacity and mechanism. Adsorption of CIP was promoted by high concentration of Cu(II) at pH 3–8 due to formation of abundant Cu(CIP±)2+, while inhibited by low concentration of Cu(II) because of competitive adsorption. The adsorption affinity of CIP species to TNTs was ranked as: Cu(CIP±)2+ > CIP+ > CIP± > Cu(CIP±)2+ > Cu(CIP−·CIP±)+ > CIP−. In comparison, the co-existence of CIP slightly affected Cu(II) adsorption considering the strong affinity of Cu2+ to TNTs. X-ray photoelectron spectrometer (XPS) and Fourier transform infrared spectroscopy (FTIR) results further confirmed the formation of Cu(II)-CIP complexes through –NH2Cu/–COOCu linkages. This work not only proposed a feasible technology for co-removal of heavy metals and organics from water, but also presented insight into interaction mechanisms of different contaminants with nanomaterials during adsorption.
Cai Z, Hao X, Sun X, Du P, Liu W, Fu J. Highly active WO3@anatase-SiO2 aerogel for solar-light-driven phenanthrene degradation: Mechanism insight and toxicity assessment. Water Research [Internet]. 2019;162:369 - 382. 访问链接Abstract
The global energy crisis and water pollution drive the researchers to develop highly effective and less energy intensive water purification technologies. In this study, a highly active WO3@TiO2–SiO2 nanocomposite was synthesized and used for photocatalytic degradation of persistent organic pollutants under simulated solar light. The optimum WO3@TiO2–SiO2 prepared with 2 wt% WO3 loading and calcination at 800 °C exhibited higher photocatalytic activity, as the rate constant (k1) for phenanthrene degradation was ∼7.1 times of that for the commercial TiO2 (P25). The extremely large specific surface area (>400 m2/g) of WO3@TiO2–SiO2 afforded it with enlarged pollutants adsorption performance and abundant active surface sites. The heterojunction of anatase with SiO2 as well as loading of WO3 decreased the band gap energy (Eg) of TiO2, which extended the utilization spectrum of TiO2 to visible region. Formation of Ti–O–Si band indicated the excess charges can cause Brønsted acidity due to the absorption of protons to compensate the charges. Moreover, the migration of photo-excited electrons from the conduction band of anatase to WO3 and holes in the opposite direction restrained the electron-hole recombination. The photocatalytic degradation mechanism and pathway for phenanthrene degradation were proposed based on experimental analysis and density functional theory (DFT) calculation, and the toxicities of the degradation intermediates were evaluated by quantitative structure–activity relationship (QSAR) analysis. WO3@TiO2–SiO2 also showed good separation (settling) performance and high stability. Our work is expected to offer new insight into the photocatalytic mechanism for WO3, TiO2 and SiO2 based heterojunctions, and rational design and synthesis of highly efficient photocatalysts for environmental application.
Zhou N, Zhao Z, Wang H, Chen X, Wang M, He S, Liu W, Zheng M. The effects of graphene oxide on nitrification and N2O emission: Dose and exposure time dependent. Environmental Pollution [Internet]. 2019;252:960 - 966. 访问链接Abstract
With the extensive application of graphene oxide (GO), its leakage and release into wastewater treatment plants become inevitable. However, the toxicity of graphene oxide (GO) on nitrification process and the underlying mechanisms still remain unclear. In this study, the toxic effects of GO at concentration of 10 and 100 mg/L in 4 h and 10 days were evaluated with sealed reactors operated in sequencing batch mode. In the initial 4 h, both GO concentrations showed no negative effect on nitrogen conversion. However, the exposure to 100 mg/L GO significantly weakened the NH+ 4-N and NO- 2-N conversion capabilities and intensified the nitrous oxide (N2O) generation after 10 days. Extracellular polymeric substance (EPS) analysis suggested that 100 mg/L GO decreased the protein content of the nitrifying activated sludge. Moreover, reactive oxygen species (ROS) level was promoted by 100 mg/L GO owing to the impaired endogenous antioxidant enzymes including superoxide dismutase (SOD) and catalase (CAT), which caused oxidative stress to bacteria. Finally, quantitative PCR results confirmed that nitrite-oxidizing bacteria (NOB) and complete ammonia oxidizing bacteria (CAOB) were more sensitive to GO, which was the primary cause for the significant promotion of N2O generation in the high GO concentration. This study offered new insights in the toxicity of GO on nitrification and N2O generation in the terms of dose and exposure time.
Chen Q, Chen L, Qi J, Tong Y, Lv Y, Xu C, Ni J, Liu W. Photocatalytic degradation of amoxicillin by carbon quantum dots modified K2Ti6O13 nanotubes: Effect of light wavelength. Chinese Chemical Letters [Internet]. 2019;30:1214 - 1218. 访问链接Abstract
A novel carbon quantum dots modified potassium titanate nanotubes (CQDs/K2Ti6O13) composite photocatalyst was synthesized by hydrothermal treatment combined with calcination. X-ray diffraction (XRD) pattern and transmission electron microscopy (TEM) indicated formation of potassium titanate nanotubes and successful deposition of CQDs onto K2Ti6O13. The photocatalytic performance of CQDs/K2Ti6O13 composite was evaluated by degradation of amoxicillin (AMX) under the irradiation of visible light and lights with the wavelengths of 365, 385, 420, 450, 485, 520, 595 and 630 nm. The results showed that the photocatalytic activity of CQDs/K2Ti6O13 hybrid material was greatly enhanced compared with the neat K2Ti6O13 calcined at 300 °C. The narrowed band gap energy (Eg) and transfer of photo-excited electron by CQDs inhibited the immediate combination of electron-hole pairs, thus promoting photocatalytic activity. Moreover, CQDs/K2Ti6O13 exhibited a broad spectrum of photocatalytic ability and it was interesting that the photocatalytic activity decreased with the increase of the irradiation wavelength. Reactive oxygen species (ROS) quenching tests suggested the hole (h+) and hydroxyl radical (OH) played the primary roles in photocatalytic degradation of AMX. Moreover, CQDs/K2Ti6O13 showed good reusability for AMX photocatalytic degradation after five successive runs. This study proposed an available method for titanate nanomaterials modification, and the developed novel CQDs/K2Ti6O13 hybrid material is promising for potential application on antibiotics removal from water and wastewater.
Liu X, Ji H, Li S, Liu W. Graphene modified anatase/titanate nanosheets with enhanced photocatalytic activity for efficient degradation of sulfamethazine under simulated solar light. Chemosphere [Internet]. 2019;233:198 - 206. 访问链接Abstract
Graphene modified anatase/titanate nanosheets (G/A/TNS) synthesized through hydrothermal treatment were used for solar-light-driven photocatalytic degradation of a typical pharmaceutically active compound, sulfamethazine (SMT). The optimal material was synthesized with 0.5 wt% of graphene loading (G/A/TNS-0.5), which could efficiently degrade 96.1% of SMT at 4 h. G/A/TNS-0.5 showed enhanced photocatalytic activity compared with the neat anatase and unmodified anatase/titanate nanosheets (A/TNS). UV–vis diffuse reflection spectra indicated that G/A/TNS-0.5 had a lower energy band gap (Eg) of 2.8 eV than A/TNS (3.1 eV). The grafted graphene acted as an electron transfer mediator after photoexcitation, resulting in inhibition on rapid recombination of electron-hole pairs. More importantly, architecture of graphene and titanate nanosheets both with two-dimensional structures greatly facilitated the photoexcited electron transfer. •OH and 1O2 were the primary reactive oxygen species (ROS) to SMT degradation. Fukui index (f -) derived from density functional theory (DFT) calculation predicted the active sites on SMT molecule, and then SMT degradation pathway was proposed by means of intermediates identification and theoretical calculation. Furthermore, G/A/TNS-0.5 could be well reused and 90.5% of SMT was also degraded after five runs. The developed new photocatalysts show great potential for degradation of emerging organic contaminants through photocatalysis under solar light.
Li M, Liu F, Ma Z, Liu W, Liang J, Tong M. Different mechanisms for E. coli disinfection and BPA degradation by CeO2-AgI under visible light irradiation. Chemical Engineering Journal [Internet]. 2019;371:750 - 758. 访问链接Abstract
CeO2-AgI, synthesized via depositing AgI nanoparticles onto CeO2 nanorods, was utilized for bacterial disinfection and organic contaminant degradation. Escherichia coli (E. coli) and Bisphenol A (BPA) were used as the model bacteria and emerging organic contaminant to test the photocatalytic activity of CeO2-AgI, respectively. Results showed that CeO2-AgI with the optimal AgI content exhibited superior photocatalytic activity over pure CeO2 or AgI for both inactivation of E. coli cells and BPA removal. However, the photocatalytic mechanisms for E. coli inactivation and BPA degradation were different. Specifically, the photo-generated holes (h+), photo-generated electrons (e−) and superoxide radicals (O2−) were the dominated active species for E. coli inactivation, whereas, BPA degradation relied on the generation of O2− and e−. Cell membrane disruption was found to be the main disinfection mechanism. The decomposition of BPA was clarified by detecting the degradation intermediates by LC–MS and DFT calculation. The facile synthesized CeO2-AgI exhibited good photocatalytic stability in four reused cycles and thus could be potentially applied to purify water.
Wang X, Liu W, Fu H, Yi X-H, Wang P, Zhao C, Wang C-C, Zheng W. Simultaneous Cr(VI) reduction and Cr(III) removal of bifunctional MOF/Titanate nanotube composites. Environmental Pollution [Internet]. 2019;249:502 - 511. 访问链接Abstract
Abstract: In this study, a series of BUC-21/titanate nanotube (BT-X) composites were facilely fabricated via ball-milling of 2-dimensional (2D) metal-organic framework (MOF) BUC-21 and titanate nanotubes (TNTs). The BT-X composites were characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), UV–visible diffuse-reflectance spectroscopy (UV–vis DRS), X-ray photoelectron spectrometer (XPS) and high resolution transmission electron microscopy (HRTEM). Both the photocatalytic reduction from Cr(VI) to Cr(III) and adsorptive removal of formed Cr(III) of BT-X composites were systematically investigated under different conditions including pH values and co-existing inorganic ions. It was found that BUC-21 (100 mg)/TNTs (100 mg) (BT-1) composites demonstrate remarkable ability of photocatalytic Cr(VI) reduction and adsorptive Cr(III) removal, as well as good reusability and stability. It is believed that the introduction of TNTs could capture the formed Cr(III) from the surface of BUC-21, which provided more active sites exposed to enhance the Cr(VI) reduction.
Chen X, You M, Wei J, Ke Y, Liu W, Sun W. Carbon nanotubes affect the formation of trihalomethanes during chlorination of bisphenol A. Chemical Engineering Journal [Internet]. 2019;370:337 - 345. 访问链接Abstract
Carbon nanotubes (CNTs) and trace contaminants often co-occur in natural waters and wastewaters, and they may become the precursors of disinfection byproducts (DBPs). However, the effects of CNTs on the formation of DBPs during chlorination of co-existed organic pollutants are unknown. This study compared the effects of three types of CNTs on the formation of DBPs during chlorination of bisphenol A (BPA). The results showed that, compared with the single system of BPA, CNTs significantly decreased the initial rate (Ri) and the second-order rate constant (k) of trihalomethanes (THMs) formation in the binary systems of CNTs and BPA. For example, Ri for the binary system (38.7–49.6 µg/(L·h)) was much lower than that for the single system of BPA (63.1 µg/(L·h)). Furthermore, the suppression effects depended not only on the type but also on the concentration of CNTs: the suppression of Ri and k by CNTs followed the order of pristine CNTs > hydroxyl CNTs > carboxylic CNTs, and increased with rising concentration of CNTs. The adsorption experiments and density functional theory (DFT) calculation further revealed that higher adsorption and stronger binding of BPA to CNTs resulted in greater suppression degree of Ri and k by CNTs.
Wu Q, Du Y, Huang Z, Gu J, Leung JYS, Mai B, Xiao T, Liu W, Fu J. Vertical profile of soil/sediment pollution and microbial community change by e-waste recycling operation. Science of The Total Environment [Internet]. 2019;669:1001 - 1010. 访问链接Abstract
The present study aims to assess the effect of electronic waste (e-waste) recycling on microbial community and the underlying modulation mechanism. Core soil/sediment samples were collected from an abandoned e-waste burning site and neighboring farmland/stream sites in Guiyu, China. High concentrations and health risks of toxic heavy metals, particularly, Sb and Sn, and halogenated flame retardants (HFRs), including decabromodiphenyl ether (BDE 209) and decabromodiphenyl ethane (DBDPE) were mostly retained at the top surface layers of soils/sediments (0–30 cm) after more than one year of natural vertical diffusion and microbe-facilitated biodegradation. Heavy metals, such as Ag, Cd, Cu, Pb, Sb, and Sn, played a critical role for the reduction of microbial diversity. This is the first study reporting the open burning of e-waste caused an obvious heat effect and enriched thermophilic/mesophilic microbes in local area. The acid washing during e-waste recycling process may result in the enrichment of acidophilic microbes. This investigation showed that e-waste processing operation resulted in not only severe pollution of the soils/sediments by various pollutants, but also reduction of microbial diversity that was difficult to self-store by the local ecosystem.
Zheng M, Zhou N, Liu S, Dang C, Liu Y, He S, Zhao Y, Liu W, Wang X. N2O and NO emission from a biological aerated filter treating coking wastewater: Main source and microbial community. Journal of Cleaner Production [Internet]. 2019;213:365 - 374. 访问链接Abstract
Nitrous oxide (N2O) and nitric oxide (NO) emissions from domestic wastewater treatment had been widely investigated due to their severe greenhouse effect and stratospheric ozone depletion. Researches concerning N2O and NO emissions from industrial wastewater treatment which usually contain high concentrations of nitrogen and refractory organics were still limited. In this study, N2O and NO emissions from a biological aerated filter (BAF) for coking wastewater treatment were investigated that achieved efficient nitrogen and chemical oxygen demand (COD) removal efficiency through short-cut nitrification and denitrification. Notably, emission factor of N2O and NO reached 23.58% and 0.09% respectively, much higher than those emitted from most domestic wastewater treatment plants. Moreover, batch experiments revealed that nitrifier denitrification contributed as high as 97.17% and 93.89% of the total generated N2O and NO, which was supposed to be the main source of green-house gases (GHGs) during coking wastewater treatment. The inhibition of denitrifying reductase by the toxic components in coking wastewater and the severe nitrite accumulations were key factors promoting the high emission of N2O and NO. Microbial community analysis based on high throughput sequencing of 16S rRNA gene revealed that ammonia-oxidizing bacteria and denitrifying bacteria distributed abundantly in the BAF reactor, while nitrite-oxidizing bacteria was almost absent. The huge imbalance between NO and N2O reductase was an underlying explanation for the high N2O emission in the present coking wastewater treatment according to Phylogenetic Investigation of Communities by Reconstruction of Unobserved States (PICRUSt) result. This study is of great significance to understanding the high N2O and NO emission and developing the control strategy when treating industrial wastewater with high-strength nitrogen and refractory organics.
Duan J, Ji H, Liu W, Zhao X, Han B, Tian S, Zhao D. Enhanced immobilization of U(VI) using a new type of FeS-modified Fe0 core-shell particles. Chemical Engineering Journal [Internet]. 2019;359:1617 - 1628. 访问链接Abstract
Sulfur-modified zero valent iron (S-ZVI) particles have been reported to show improved reactivity and selectivity than conventional ZVI. However, current methods for ZVI sulfidation do not fully utilize the advantages of the material, and S-ZVI has not been tested for U(VI) immobilization. In this work, we synthesized a new type of FeS-modified ZVI core-shell particles (FeS@Fe0) through a facile two-step reaction approach, and then tested for reductive sequestration of U(VI) in water. X-ray diffraction, Scanning transmission electron microscopy, and physical property analyses confirmed the formation of the core-shell structure, surface compositions and magnetic properties. Batch kinetic tests showed that FeS@Fe0 with an Fe0/FeS molar ratio of 1:1 offered the highest U(VI) reduction rate, prolonged reactive life than pristine ZVI, and the reduced uranium was most resistant to re-oxidation when exposed to oxygen. The retarded first-order kinetic model was able to adequately interpret the experimental rate data. FeS@Fe0 performed well over the pH range 5.5–9.0, with higher pH more favoring the reaction. High concentrations (5–10 mg/L) of humic acid, bicarbonate (1–5 mM) and Ca2+ (1 mM) showed only modest inhibition to the U(VI) reduction. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and extraction studies indicated that U(VI) was immobilized via both direct adsorption and reductive precipitation, where Fe0 was the main electron source, with Fe0, sorbed Fe(II) and structural Fe(II) acting as the electron donors. FeS@Fe0 may serve as an improved material for efficient immobilization of U(VI) and other redox-active contaminants in water.
Liu W, Li Y, Liu F, Jiang W, Zhang D, Liang J. Visible-light-driven photocatalytic degradation of diclofenac by carbon quantum dots modified porous g-C3N4: Mechanisms, degradation pathway and DFT calculation. Water Research [Internet]. 2019;150:431 - 441. 访问链接Abstract
Metal-free photocatalysts have attracted growing concern in recent years. In this work, a new class of carbon quantum dots (CQDs) modified porous graphitic carbon nitride (g-C3N4) is synthesized via a facile polymerization method. With the optimal CQDs loading, the CQDs modified g-C3N4 exhibits ∼15 times higher degradation kinetic towards diclofenac (DCF) than that of pure g-C3N4. The enhanced photocatalytic activity can be ascribed to the improved separation of charge carriers as well as the tuned band structure. Moreover, a photosensitation-like mechanism is proposed to elucidate the photo-generated electrons transfer and reactive radicals formation. CQDs are anchored to g-C3N4 surface via CO bond, which provide channels for the preferential transfer of photo-excited electrons on DCF molecule to the conduction band of g-C3N4. Superoxide radical (·O2−) dominates the degradation of DCF, while holes (h+) show a negligible contribution. Density functional theory (DFT) calculation successfully predicts that the sites on DCF molecule with high Fukui index (f0) are preferable to be attacked by radicals. DCF degradation pathway mainly includes ring hydroxylation, ring closure and CN bond cleavage processes. Acute toxicity estimation indicates the formation of less toxic intermediates/products compared to DCF after photocatalysis. Moreover, the hybrid photocatalysts exhibit good reusability in five consecutive cycles. This work not only proposes a deep insight into photosensitation-like mechanism in the photocatalysis system by using C3N4-based materials, but also develops new photocatalysts for potential application on removal of emerging organic pollutants from waters and wastewaters.
Liu F, Liang J, Chen L, Tong M, Liu W. Photocatalytic removal of diclofenac by Ti doped BiOI microspheres under visible light irradiation: Kinetics, mechanism, and pathways. Journal of Molecular Liquids [Internet]. 2019;275:807 - 814. 访问链接Abstract
BiOI microspheres doped with different amounts of Ti were fabricated and used to remove diclofenac (DCF) from water under visible light irradiation. The fabricated photocatalysts were well characterized. Ti doped BiOI microspheres were found to exhibit higher photocatalytic activity towards DCF under visible light compared with BiOI. Ti doping broadened the band gap of BiOI, which leads to a more negative conduction band edge and a higher reducing activity of photo-generated electrons, thus facilitates ·O2− production during photocatalysis. Among all the fabricated Ti doped BiOI microspheres, TB450 exhibited the highest DCF photocatalytic removal efficiency. Specifically, 99.2% of DCF (C0 = 10 mg L−1) was removed by TB450 (250 mg L−1) at pH 5 within 90 min under visible light irradiation. Scavenger experiments indicated that active species including h+, ·O2− and H2O2 played important roles in the photocatalytic process. The degradation pathway of DCF was elucidated by theoretical density functional theory (DFT) and by-products identification through liquid chromatograph mass spectrometer (LC-MS) analysis. DCF degradation pathway mainly included hydroxylation and the cleavage of CN bond. DFT calculation can well interpret the degradation mechanism and the sites of DCF molecule with high radical-attack Fukui index (f0) exhibit high reactivity. Acidic condition was found to facilitate the DCF photocatalytic removal. Due to strong photo-stability, Ti doped BiOI microspheres contained good visible-light-driven (VLD) photocatalytic removal efficiency for DCF in the fourth consecutive reused cycle. Ti doped BiOI microspheres can be employed as a cost-effective and high-efficient material to efficiently degrade emerging contaminants (e.g., pharmaceutical) from wastewaters under visible light conditions.
Ji H, Zhu Y, Liu W, Bozack MJ, Qian T, Zhao D. Sequestration of pertechnetate using carboxymethyl cellulose stabilized FeS nanoparticles: Effectiveness and mechanisms. Colloids and Surfaces A: Physicochemical and Engineering Aspects [Internet]. 2019;561:373 - 380. 访问链接Abstract
Technetium (99Tc) typically exists as pertechnetate (TcO4−) and hydrated oxide (TcO2·nH2O) in soil and groundwater. While the former, Tc(VII), is very soluble and mobile in the environment, the latter is considered sparingly soluble and immobile. Consequently, immobilization of Tc(VII) can be achieved through conversion of Tc(VII) into Tc(IV). In this study, carboxymethyl cellulose (CMC) stabilized FeS nanoparticles (CMC-FeS) were prepared and tested for reductive immobilization of Tc(VII). Effects of nanoparticle dosage and water chemistry, including pH, humic acid and Ca2+ ions, were examined. At a dosage of 100 mg/L of CMC-FeS as Fe, CMC-FeS rapidly removed >96% of 1.2 μM of Tc(VII) within 1 h, with a retarded first-order rate constant (ka) of 150.32 h-1. Higher pH in the range of 5.0–9.0 favored the reaction, with an optimal pH range of 8.0–9.0. While Ca2+ (up to 2 mM) only modestly affected the Tc(VII) removal, high concentrations of humic acid (up to 10 mg/L as TOC) showed increased inhibition on the Tc(VII) removal rate. FTIR and XPS analyses indicated that CMC-FeS immobilized TcO4− through reductive conversion of TcO4− into TcO2(s) and formation of Tc2S7 precipitate. The immobilized Tc remained insoluble when aged for 100 days under anoxic conditions, whereas up to 22.9% of the immobilized Tc was remobilized when it was exposed to air for 100 days.
Cheng K, Cai Z, Fu J, Sun X, Sun W, Chen L, Zhang D, Liu W. Synergistic adsorption of Cu(II) and photocatalytic degradation of phenanthrene by a jaboticaba-like TiO2/titanate nanotube composite: An experimental and theoretical study. Chemical Engineering Journal [Internet]. 2019;358:1155 - 1165. 访问链接Abstract
Combined water pollution with the coexistence of heavy metals and organic contaminants is of great concern for practical wastewater treatment. In this study, a jaboticaba-like nanocomposite, titanate nanotubes supported TiO2 (TiO2/TiNTs), was synthesized by a two-step hydrothermal treatment. TiO2/TiNTs had large surface area, abundant of –ONa/H groups and fine crystal anatase phase, thus exhibited both good adsorptive performance for Cu(II) and high photocatalytic activity for phenanthrene degradation. The maximum Cu(II) adsorption capacity on TiO2/TiNTs was 115.0 mg/g at pH 5 according to Langmuir isotherm model, and >95% of phenanthrene was degraded within 4 h under UV light. TiO2/TiNTs showed about 10 times higher observed rate constant (kobs) for phenanthrene degradation compared to the unmodified TiNTs. More importantly, the coexistence of Cu(II) promoted photocatalytic degradation of phenanthrene, because the incorporated Cu(II) in the lattice of TiNTs could trap photo-excited electron and thus inhibited the electron-hole recombination. Density functional theory (DFT) calculation indicated that the sites of phenanthrene with high Fukui index (f0) preferred to be attacked by OH radicals. The quantitative structure–activity relationship (QSAR) analysis revealed that the degradation intermediates had lower acute toxicity and mutagenicity than phenanthrene. TiO2/TiNTs also owned high stability, as only slight loss of Cu(II) and phenanthrene removal efficiency was observed even after four reuse cycles. The developed material in this study is of great application potential for water or wastewater treatment with multi-contaminants, and this work can help us to better understand the mechanisms on reaction between Ti-based nanomaterials and different kinds of contaminants.
Zheng T, Wang T, Ma R, Liu W, Cui F, Sun W. Influences of isolated fractions of natural organic matter on adsorption of Cu(II) by titanate nanotubes. Science of The Total Environment [Internet]. 2019;650:1412 - 1418. 访问链接Abstract
With different functional groups and hydrophobic/hydrophilic properties, natural organic matters (NOMs) displayed different combining capacities with metal ions. By using XAD-4 and DAX-8 resins, NOMs in natural lake were isolated into three fractions, i.e., HoB (hydrophobic base), HoA (hydrophobic acid) and HiM (hydrophilic matter). Afterwards, influences on Cu(II) adsorption onto titanate nanotubes (TNTs) were compared with varying NOMs and initial pH. As results, HoB can significantly control Cu(II) adsorption at pH 5, with the adsorption capacity increased 15% for 0.5 mg L−1 of HoB (ca. 120 mg g−1), which could be attributed to the formation of HoB-Cu complexation and electrostatic bridge effect of HoB with optimal concentration. Due to the easier ionization and complexation with Cu(II) at lower pH, HoA showed more obvious impaction on Cu(II) adsorption at pH 2. While HiM can influence Cu(II) adsorption at all pH ranges due to its hydrophilic groups and weak affinity to both TNTs and Cu(II). Furthermore, HoB dramatically changed the Langmuir model, with sharp increase of adsorption capacity as equilibrium Cu(II) increased, suggesting its significant involvement in Cu(II) adsorption. X-ray photoelectron spectroscopy (XPS) analysis revealed the absorbed Cu(II) existed in the form of TNTs‑OCu, TNTs‑COOCu and Cu(OH)2, proving Cu(II) adsorption mechanism including both direct adsorption by TNTs and bridging connection with NOMs. Moreover, the CO and OCO groups content ranked as HiM > HoB > HoA, while TNTs‑COOCu content ranked as HoA > HoB > HiM, suggesting HoB had the moderate connection with both TNTs and Cu(II), thus the impact on Cu(II) adsorption was remarkable.
Dang C, Liu W, Lin Y, Zheng M, Jiang H, Chen Q, Ni J. Dominant role of ammonia-oxidizing bacteria in nitrification due to ammonia accumulation in sediments of Danjiangkou reservoir, China. Applied Microbiology and Biotechnology [Internet]. 2018;102:3399–3410. 访问链接Abstract
Surface sediments are the inner source of contaminations in aquatic systems and usually maintain aerobic conditions. As the key participators of nitrification process, little is known about the activities and contributions of ammonia-oxidizing archaea (AOA) and bacteria (AOB) in the surface sediments. In this study, we determined the net and potential nitrification rates and used 1-octyne as an AOB specific inhibitor to detect the contributions of AOA and AOB to nitrification in surface sediments of Danjiangkou reservoir, which is the water source area of the middle route of South-to-North Water Diversion Project in China. Quantitative PCR and Illumina high-throughput sequencing were used to evaluate the abundance and diversity of the amoA gene. The net and potential nitrification rates ranged from 0.42 to 1.93 and 2.06 to 8.79 mg N kg−1 dry sediments d−1, respectively. AOB dominated in both net and potential nitrification, whose contribution accounted for 52.7–78.6% and 59.9–88.1%, respectively. The cell-specific ammonia oxidation rate calculation also revealed the cell-specific rates of AOB were higher than that of AOA. The Spearman's rank correlation analysis suggested that ammonia accumulation led to the AOB predominant role in net nitrification activity, and AOB abundance played the key role in potential nitrification activity. Furthermore, phylogenetic analysis suggested AOB were predominantly characterized by the Nitrosospira cluster, while AOA by the Nitrososphaera and Nitrososphaera sister clusters. This study will help us to better understand the contributions and characteristics of AOA and AOB in aquatic sediments and provide improved strategies for nitrogen control in large reservoirs.
Du P, Liu W, Cao H, Zhao H, Huang C-H. Oxidation of amino acids by peracetic acid: Reaction kinetics, pathways and theoretical calculations. Water Research X [Internet]. 2018;1:100002. 访问链接Abstract
Peracetic acid (PAA) is a sanitizer with increasing use in food, medical and water treatment industries. Amino acids are important components in targeted foods for PAA treatment and ubiquitous in natural waterbodies and wastewater effluents as the primary form of dissolved organic nitrogen. To better understand the possible reactions, this work investigated the reaction kinetics and transformation pathways of selected amino acids towards PAA. Experimental results demonstrated that most amino acids showed sluggish reactivity to PAA except cysteine (CYS), methionine (MET), and histidine (HIS). CYS showed the highest reactivity with a very rapid reaction rate. Reactions of MET and HIS with PAA followed second-order kinetics with rate constants of 4.6 ± 0.2, and 1.8 ± 0.1 M−1⋅s−1 at pH 7, respectively. The reactions were faster at pH 5 and 7 than at pH 9 due to PAA speciation. Low concentrations of H2O2 coexistent with PAA contributed little to the oxidation of amino acids. The primary oxidation products of amino acids with PAA were [O] addition compounds on the reactive sites at thiol, thioether and imidazole groups. Theoretical calculations were applied to predict the reactivity and regioselectivity of PAA electrophilic attacks on amino acids and improved mechanistic understanding. As an oxidative disinfectant, the reaction of PAA with organics to form byproducts is inevitable; however, this study shows that PAA exhibits lower and more selective reactivity towards biomolecules such as amino acids than other common disinfectants, causing less concern of toxic disinfection byproducts. This attribute may allow greater stability and more targeted actions of PAA in various applications.
Wang M, Huang G, Zhao Z, Dang C, Liu W, Zheng M. Newly designed primer pair revealed dominant and diverse comammox amoA gene in full-scale wastewater treatment plants. Bioresource Technology [Internet]. 2018;270:580 - 587. 访问链接Abstract
The discovery of complete ammonia oxidizing bacteria (CAOB) capable of performing the two-step nitrification process on their own has fundamentally upended our traditional perception. However, their environmental distribution and ecological significance in driving ammonia oxidation are still urgently awaited to be assessed. In this study, the diversity and abundance of CAOB amoA gene in wastewater treatment plants (WWTPs) were presented taking advantage of a newly designed primer pair specifically targeting CAOB amoA gene. Phylogenetic results demonstrated the novel amoA gene formed a clearly distinct cluster from the canonical amoA and pmoA genes. Among the five well-supported sub-clusters, Nitrospira nitrosa cluster accounted for 94.34% of all the currently retrieved sequences from WWTPs. More importantly, qPCR results demonstrated a remarkably high abundance of CAOB amoA gene, which were up to 182.7-fold more abundant than AOB amoA gene. This study provided new dimension and fundamental basis for future researches towards biogeochemical nitrogen cycle.
Zhao D, Liu W.; 2018. Material for removing contaminants from water. United States of America patent US US20180214851A1. 访问链接Abstract
A composite comprises a carbonaceous and a metallic nanotube conjugated with a carbonaceous support. The composite may be used to remove contaminants from water.