Preparation of novel N-doped biochar and its high adsorption capacity for atrazine based on π-π electron donor-acceptor interaction.

Novel nitrogen (N)-doped cellulose biochar (NC1000-10) with large adsorption capacity (103.59 mg g-1) for atrazine (ATZ) was synthesized through the one-pot method. It has the best adsorption efficiency than N-doped biochars prepared from hemicellulose and lignin. The adsorption behaviors of ATZ by N-doped biochars with different N doping ratios (NC1000-5, NC1000-10, NC1000-20 and NC1000-30) were significantly different, which was attributed to the difference of sp2 conjugate C (ID/IG = 0.99-1.18) and doped heteroatom N (pyridinic N, pyrrolic N and graphitic N). Adsorption performance of ATZ on NC1000-10 conformed to the pseudo-second-order kinetic and Langmuir adsorption isotherm model. Thermodynamic calculations showed that adsorption performance was favorable. Besides, wide pH adaptability (pH = 2-10), good resistance to ionic strength and excellent recycling efficiency make it have extensive practical application potential. Further material characterizations and the density functional theory (DFT) calculations indicated that good adsorption performance of NC1000-10 for ATZ mainly depended on chemisorption, and π-π electron donor-acceptor (EDA) interaction contributed the most due to high graphitization degree. Specifically, pyridinic N and graphitic N further promoted adsorption performance by hydrophobic effect and π-π EDA interaction between ATZ and NC1000-10, respectively. Pyrrolic N and other surface functional groups (-COOH, -OH) facilitated the hydrogen bond effect.

N-nitrosodimethylamine formation during oxidation of N,N-dimethylhydrazine compounds by peroxymonosulfate: Kinetics, reactive species, mechanism and influencing factors.

This study found that peroxymonosulfate (PMS) oxidation without activation has the potential to generate a suspected human carcinogen, N-nitrosodimethylamine (NDMA), in water containing N,N-dimethylhydrazine compounds. Considerable amounts of NDMA formed from three compounds by PMS oxidation were observed. 1,1,1',1'-Tetramethyl-4,4'-(methylene-di-p-phenylene) disemicarbazide (TMDS), which is an industrial antiyellowing agent and light stabilizer, was used as a representative to elucidate the kinetics, transformation products, mechanism and NDMA formation pathways of PMS oxidation. TMDS degradation and NDMA formation involved direct PMS oxidation and singlet oxygen (1O2) oxidation. The oxidation by PMS/1O2 was pH-dependent, which was related to the pH-dependent characteristics of the reactive oxygen species and intermediates. The degradation mechanism of TMDS mainly included the side chain cleavage, dealkylation, and O-addition. NDMA was generated from TMDS mainly via O-addition and 1,1-dimethylhydrazine (UDMH) generation. The cleavage of amide nitrogen in O-addition products and primary amine nitrogen in UDMH are likely the key steps in NDMA generation. The results emphasized that the formation of harmful by-products should be taken into account when assessing the feasibility of PMS oxidation.

Enhanced degradation of iohexol in water by CuFe2O4 activated peroxymonosulfate: Efficiency, mechanism and degradation pathway.

Iohexol as an iodinated X-ray contrast agent is widely used, and it is the potential precursor for toxic iodinated disinfection by-products in the disinfection process. In this study, a series of CuFe2O4 catalysts were prepared by sol-gel method with different molar ratios of total metal cations to citric acid ([Men+]T/CA) and employed as heterogeneous catalysts to activate peroxymonosulfate (PMS) for the removal of iohexol. The catalysts were characterized by various technologies, and the effect of [Men+]T/CA molar ratio on the catalysts' properties was explored. The CuFe2O4 synthesized with [Men+]T/CA molar ratio of 1:1 showed the best catalytic activity to PMS, and 95.0% of 1.0 mg/L iohexol was removed within 15 min by using 50 mg/L CuFe2O4 and 20 mg/L PMS. The quenching experiment and electron spin resonance (ESR) spectra indicated the generation of SO4- and OH in the CuFe2O4/PMS system, and the quantity experiments revealed that the generation concentration of SO4- was ten times higher than that of OH. The generation mechanism of SO4- and ·OH were investigated by ATR-FTIR and X-ray photoelectron spectroscopy (XPS) spectra. The effects of catalyst dosage, PMS and iohexol concentration on the removal of iohexol were studied, and various water matrix factors including solution pH, natural organic matter (NOM) concentration and inorganic ions were also considered. Based on the twelve intermediate products of iohexol detected by UPLC-QTOF/MS, the degradation pathway was proposed. The high catalytic activity and reusability of CuFe2O4 indicated that CuFe2O4 activating PMS is an effective and sustainable way for the treatment of iohexol.

Adsorption property and mechanism of polyacrylate-divinylbenzene microspheres for removal of trace organic micropollutants from water.

In this study, polyacrylate-divinylbenzene (PADVB) microspheres were facilely prepared via the precipitation polymerization method, and the microspheres were used as an efficient adsorbent for the removal of trace level organic micropollutants (OMPs) from environmental waters. Preparation conditions of PADVB microspheres were optimized, and the characterizations of the microspheres were performed using a scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT-IR), and N2 adsorption/desorption isotherms. The microspheres had broad-spectrum adsorption ability for various organic micropollutants containing hydroxy, amidogen, aromatic or heteroaromatic ring in their chemical structure, such as atrazine, 2,4 dichlorophenol, 2,4 dibromophenol, 2,6 dichlorophenol, sulfamethoxazole, estradiol, and bisphenol A. Besides, the effects of initial concentration, initial pH value, adsorption time, and the type of adsorbates on the adsorption performance were investigated systematically. PADVB microspheres could be used for removing trace OMPs from environmental water. Monolayer and homogeneous sorption process occurred on the surface of PADVB microspheres through chemisorption mechanisms. The X-ray photoelectron spectroscopy (XPS) and FT-IR spectrum of PADVB microspheres before and after adsorption proved that the OMPs adsorption onto PADVB microspheres was mainly due to the formation of the hydrogen bond and π-π electron-donor-acceptor (EDA) interactions. Besides, PADVB microspheres can be recovered for reuse via (low-pressure) microfiltration and could be regenerated sufficiently by using 80% (v/v) ethanol.

Variations of disinfection byproduct precursors through conventional drinking water treatment processes and a real-time monitoring method.

In this investigation, raw water (RW), settled water (SW), and filtered water (FW) collected from a drinking water treatment plant were fractionated into 24 natural organic matter (NOM) fractions with varying molecular weights and hydrophobicity. The yields of disinfection byproducts (DBPs) obtained during the chlorination of the NOM fractions were explored. Results revealed that the 0-1 kDa, 5-10 kDa, and hydrophobic DBP precursors dominated RW. Hydrophobic fractions cannot be effectively removed, which contributed to the high DBP precursors remaining in the FW. The optional optical parameters, including UVA (UV340, UV360, and UV380), UVB (UV280, UV300, and UV310), and UVC (UV254, UV260, and UV272), were analyzed to determine the DBP yields during chlorination of different NOM fractions. Results revealed that UVC could be applied to indicate the regulated DBP yields of the humified precursors. Contrary to the generally accepted view, for biologically derived precursors, their regulated DBPs and dichloroacetonitrile correlated better with UVA (e.g. UV340). Moreover, PARAFAC analysis was applied to decompose an array of 24 EEM spectra. Good linear correlations were found between the PARAFAC components and most DBP yields. Furthermore, four fluorescence parameters were proposed via a modified fluorescence picking method, which can serve as excellent surrogates of PARAFAC components. These fluorescence parameters were found to be effective in indicating most DBP yields. Finally, the fluorescence intensity at excitation wavelength/emission wavelength = 310/416 nm was found to be a promising built-in parameter for the real-time monitoring of DBP precursors, regardless of the humification degree of the precursors.

Selective adsorption and enhanced photodegradation of diclofenac in water by molecularly imprinted TiO2.

In the paper, molecularly imprinted TiO2 was prepared by surface molecularly imprinted technology and liquid phase deposition method for preferential removal of persistent toxic pollutants from complex environmental water. Diclofenac was selected as the template molecule and target for photodegradation study. The characterization results of SEM, TEM, FTIR and XRD showed that the TiO2 film with imprinted diclofenac was successfully synthesized on the surface of TiO2 particles. Meanwhile, the adsorption and photodegradation experiments also indicated that the molecularly imprinted TiO2 had larger adsorption capacity, better selectivity and higher photodegradation performance for diclofenac than non-imprinted TiO2. The primary active species and degradation pathways during photodegradation process were also elucidated according to radical capture experiments and UPLC-MS-TOF technology. The prepared molecularly imprinted TiO2 has the advantages of efficient removal ability, high stability and environmental protection, so it has a wide application value in water treatment and water environmental restoration, especially when involved persistent toxic pollutants.