Molecularly Imprinted Heterostructure-Based Electrochemosensor for Ultratrace and Precise Detection of 2-Methylisoborneol in Water.

Ultratrace 2-methylisoborneol (2-MIB, ∼ng/L) in source water is the main odorant in the algae-derived odor episodes, whose accurate on-site detection will have a promising application potential. Due to the chemical inertness of 2-MIB, sensitive and selective detection of 2-MIB remains much challenging. Herein, molecularly imprinted polymer cavities were polymerized on the heterostructure Ti3C2Tx@CuFc-metal-organic framework to selectively capture 2-MIB, where the heterostructure could catalyze the probe redox reaction of [Fe(CN)63-/4-] and amplify the corresponding current signals. The prepared electrochemical sensor showed higher sensitivity on 2-MIB detection than the reported ones. Excellent stability, reusability, and selectivity for 2-MIB detection were also verified. The linear range and limit of detection of our sensor for 2-MIB were optimized to 0.0001-100 µg/L and 30 pg/L, respectively, performing much better than the reported sensors. Comparable performance to gas chromatography-mass spectrometry was achieved when the sensor was applied to real water samples with or without 2-MIB standards. Overall, our research has made great progress in the application of an on-site sensor in 2-MIB detection and well advances the development of molecularly imprinted polymer-based electrochemical sensors.

Pre-oxidation coupled with charged covalent organic framework membranes for highly efficient removal of organic chloramines precursors in algae-containing water treatment.

Organic chloramines in water would pose both chemical and microbiological risks. It is essential to remove the precursors of organic chloramine (amino acids and decomposed peptides/proteins) to limit its formation in disinfection. In our work, nanofiltration was chosen to remove organic chloramines precursors. To solve the "trade-off" effect and low rejection of small molecules in algae organic matter, we synthesized a thin film composite (TFC) nanofiltration (NF) membrane with a crumpled polyamide (PA) layer via interfacial polymerization on polyacrylonitrile (PAN) composite support loaded with covalent organic framework (COF) nanoparticles (TpPa-SO3H). The obtained NF membrane (PA-TpPa-SO3H/PAN) increased the permeance from 10.2 to 28.2 L m-2 h-1 bar-1 and the amino acid rejection from 24% to 69% compared to the control NF membrane. The addition of TpPa-SO3H nanoparticles decreased the thickness of PA layers, increased the hydrophilicity of the membrane, and increased the transition energy barrier for amino acids transferring through the membrane, which was identified by scanning electron microscope, contact angle test, and density functional theory computations, respectively. Finally, pre-oxidation coupled with PA-TpPa-SO3H/PAN membrane nanofiltration on the limitation of organic chloramines formation was evaluated. We found that the combined application of KMnO4 pre-oxidation and PA-TpPa-SO3H/PAN membranes nanofiltration in algae-containing water treatment could minimize the formation of organic chloramines in subsequent chlorination and maintain a high flux during filtration. Our work provides an effective way for algae-containing water treatment and organic chloramines control.

Effects of UV/Fe(II)/sulfite pre-treatment on NOM-enhanced Ca2+ scaling during nanofiltration treatment: Fouling mitigation, mechanisms, and correlation analysis of membrane resistance.

This study was aimed to evaluate the effects of a pre-treatment involving sulfite (S(IV)) synergistically activated by ultraviolet (UV)/Fe(II) on natural organic matter (NOM)-enhanced Ca2+ scaling during nanofiltration treatment. Based on the variations in the physicochemical properties and correlation analyses of irreversible resistance, the intrinsic fouling mechanisms were revealed from two aspects: bulk crystallization (interaction between NOM and inorganic ions) and surface crystallization (morphology of surface crystallization and a change in the Ca2+ concentration in the scaling layer). Furthermore, the degradation contribution rates of different free radicals during the UV/Fe(II)/S(IV) (UFS) treatment process were evaluated. During the reactions in the UFS, three free radicals (SO·-4, OH·- and e- aq) were generated, and in-situ Fe(III) was formed in-situ. The carboxyl groups of the NOM were attacked by the free radicals, resulting in decreased of carboxyl concentration and density. In addition, the bond between Ca2+ and NOM weakened, and hydrophobic (HPO) substances were mineralized. However, the Fe(III) formed in-situ was active and electropositive, competing with Ca2+ for the complexation active sites on the NOM. The synergy effect of bulk crystallization and surface crystallization led to a significant decrease in the particle size of feed solution. The crystal size and roughness of membrane surface also decreased, which was conducive to reducing the membrane irreversible resistance. Correlation analysis revealed that the HPO ratio, carboxyl density and particle size (> 100 nm) ratio were effective characterization parameters for predicting irreversible resistance. This study not only provides guidance for alleviating membrane fouling caused by NOM-enhanced Ca2+ scaling during the nanofiltration process, but also presents the rationality of irreversible resistance during nanofiltration process and various indicators with strong linear correlation.

Ultrafiltration pre-oxidation by boron-doped diamond anode for algae-laden water treatment: membrane fouling mitigation, interface characteristics and cake layer organic release.

In this study, ultrafiltration (UF) pre-oxidation with a boron-doped diamond (BDD) electrode was employed aiming to mitigate membrane fouling during algae-laden water treatment. It was found that BDD anodizing can efficiently alleviate membrane fouling regardless of the filtration membrane material when the oxidation time was over 30 min. This was because that the cake layer fouling resistance was highly mitigated by the pre-oxidation process. The generated small molecular organics after anodic oxidation might increase the potential of pore blockage. The anodizing preferentially oxidized hydrophobic organic and fluorescent substances, which is conducive to reducing membrane fouling and improving production efficiency. Besides, disinfection byproduct precursors and harmful algae derived substances of UF filtrated solution were contained. The algae bodies tend to agglomeration and the zeta potential obviously declined after the pretreatment, which is instrumental in forming a loose cake layer structure. In addition, the interaction force between membrane and foulants also converted to a repulsion force after pre-oxidation, which implies that BDD pre-oxidation was an effective way to mitigate cake layer fouling by reducing foulant-membrane interactions. At last, the secondary organic release of a dynamic formed cake layer was proved to be limited especially for living algae cells.

Characterization of algal organic matters of Microcystis aeruginosa: biodegradability, DBP formation and membrane fouling potential.

Algal organic matters (AOM), including extracellular organic matters (EOM) and intracellular organic matters (IOM), were comprehensively studied in terms of their biodegradability, disinfection byproduct (DBP) formation potentials and membrane fouling. EOM and IOM were fractionated into hydrophobic (HP), transphilic (TP) and hydrophilic (HL) constituents. The HP, TP and HL fractions of EOM and IOM were highly biodegradable with BDOC/DOC ranging from 52.5% to 67.4% and the DBP formation potentials followed the order of HP > TP > HL, except of IOM-HL. Biodegradable process proved very effective in removing the DBP formation potentials. Moreover, the AOM characteristics were also evaluated during ultrafiltration (UF) treatment. Results demonstrated that UF favourably remove DOC and DBP formation potential of IOM than those of EOM. And the HL constituents played a more important role in membrane fouling than HP and TP. The UF foulants exhibited higher BDOC/DOC than AOM, suggesting EOM and IOM might enhance biofouling because more biodegradable proteins and polysaccharides were found in membrane foulants. Therefore, appropriate biological treatment, ultrafiltration, or combination of the both are potential options to address these algae-caused water quality issues.

Influence of hydrophobic/hydrophilic fractions of extracellular organic matters of Microcystis aeruginosa on ultrafiltration membrane fouling.

Fouling is a major obstacle to maintain the efficiency of ultrafiltration-based drinking water treatment process. Algal extracellular organic matters (EOMs) are currently considered as one of the major sources of membrane fouling. The objective of this study was to investigate the influence of different hydrophobic/hydrophilic fractions of EOM extracted from Microcystis aeruginosa on ultrafiltration membrane fouling at lab scale. The experimental data indicated that EOM exhibited similar flux decline trends on polyethersulfone (PES) and regenerated cellulose (RC) membranes but caused greater irreversible fouling on PES membrane than RC membrane due to its hydrophobic property. It was also observed that charged hydrophilic (CHPI) and neutral hydrophilic (NHPI) fractions caused greater flux decline over hydrophobic (HPO) and transphilic (TPI) fractions. For PES membrane, the order of the irreversible fouling potentials for the four fractions was HPO>TPI>CHPI>NHPI, while the irreversible fouling potentials of RC membrane were tiny and could be ignored. Fluorescence excitation-emission matrix (EEM) spectra and Fourier transform infrared (FTIR) spectra suggested that protein-like, polysaccharide-like and humic-like substances were the major components responsible for membrane fouling. The results also indicated that the irreversible fouling increased as the pH decreased. The addition of calcium to feed solutions led to more severe flux decline and irreversible fouling.