Efficient and sustainable photocatalytic inactivation of E. coli by an innovative immobilized Ag/TiO2 photocatalyst with peroxymonosulfate (PMS) under visible light.

A novel catalytic system for effective photocatalytic inactivation of Escherichia coli (E. coli) was constructed by anchoring Ag nanoparticles (AgNPs) on silane coupling agent (SCA) pretreated TiO2 nano-tube arrays (Ag/SCA/TiO2NTAs). Morphology and structural analyses revealed that SCA could disperse AgNPs evenly on TiO2NTAs, thus inducing a superior surface plasmon resonance (SPR) effect. Ag/SCA/TiO2NTAs catalyst exhibited excellent inactivation performance when in the presence of peroxymonosulfate (PMS) and visible light (VL), with 6-log E. coli was completely inactivated within 60 min, which was 5.3, 12.5 and 13.2 times higher than that of Ag/SCA/TiO2NTAs/VL, PMS/VL and Ag/SCA/TiO2NTAs/PMS/dark systems, respectively. Additionally, the photocatalyst exhibited a highly reusable property, with the inactivation performance almost unchanged after ten cycles of uses with minimal Ag leaching. The inactivation mechanism analysis demonstrated that both radical (SO4•-, OH) and non-radical (h+, 1O2) pathways involved in E. coli inactivation, and SCA played a pivotal role in the production of reactive species. Chloride ions (Cl-) greatly enhanced the inactivation efficiency, while bicarbonate (HCO3-) and phosphate (H2PO4-) showed an inhibitory effect. Humic acid (HA) displayed a dual effect on inactivation performance, where the low concentration of HA facilitated the bacteria inactivation, while the higher dose suppressed bacteria inactivation. Moreover, the system exhibited excellent inactivation performance in tap water. This work first used SCA as the binder to fix AgNPs on TiO2NTAs for VL photocatalytic inactivation of bacteria with the assistance of PMS, which was expected to provide some insights into the practical treatment of drinking water.

Degradation of cyanobacterial neurotoxin ß-N-methylamino-L-alanine (BMAA) using ozone process: influencing factors and mechanism.

ß-N-methylamino-L-alanine (BMAA), which has been considered as an environmental factor that caused amyotrophic lateral sclerosis/parkinsonism-dementia complex (ALS/PDC) or Alzheimer's disease, could be produced by a variety of genera cyanobacteria. BMAA is widely present in water sources contaminated by cyanobacteria and may threaten human health through drinking water. Although oxidants commonly used in drinking water plants such as chlorine, ozone, hydrogen peroxide, and hydroxyl radicals have been shown to effectively degrade BMAA, there are limited studies on the mechanism of BMAA degradation by different oxidants, especially ozone. This work systematically explored the effectiveness of BMAA ozonation degradation, investigated the effect of the operating parameters on the effectiveness of degradation, and speculated on the pathways of BMAA decomposition. The results showed that BMAA could be quickly eliminated by ozone, and the removal rates of BMAA were nearly 100% in pure water, but the removal rates were reduced in actual water. BMAA was primarily degraded by direct oxidation of ozone molecules in acidic and near-neutral conditions, and indirect oxidation of •OH accounted for the main part under strong alkaline conditions. The pH value had a significant effect on the decomposition of BMAA, and the degradation rate of BMAA was fastest at near-neutral pH value. The degradation rates of TOC were significantly lower than that of BMAA, indicating that by-products were generated during the degradation process. Three by-products ([M-H]+ = 105, 90, and 88) were identified by UPLC-MS/MS, and the degradation pathways of BMAA were proposed. The production of by-products was attributed to the fracture of the C-N bonds. This work is helpful for the in-depth understanding on the mechanism and demonstration of the feasibility of the oxidation of BMAA by the ozone process. HIGHLIGHTS: • The reaction of ozonation BMAA was easy to occur. • The degradation rate was fast under near-neutral conditions. • Direct oxidation under neural conditions was the main pathway for ozone degradation of BMAA. • Three products were detected, and the reaction path was inferred.

Degradation mechanisms of cyanobacteria neurotoxin ß-N-methylamino-l-alanine (BMAA) during UV254/H2O2 process: Kinetics and pathways.

In this work, the UV254/H2O2 process was utilized to remove ß-N-methylamino-l-alanine (BMAA), a kind of cyanobacteria neurotoxin, and the influence of reaction parameters and environmental factors on the degradation of BMAA has been systematically investigated. The results showed that BMAA could be effectively removed in the UV254/H2O2 system compared to UV or H2O2 alone and OH was confirmed as the main ROS to degrade BMAA. The degradation rate of BMAA increased first and then decreased with the increase of pH and the maximum kobs was 0.1545 min-1 obtained at pH 9. The removal of BMAA in the UV254/H2O2 system was inhibited in actual water, while the degradation rate of BMAA in actual water could still exceed 90% by appropriately extending the reaction time. The decrease in the degradation efficiency of BMAA in actual water was primarily due to the ultraviolet light absorption and competition effects of NOM, and anions (Cl- and HCO3-) would also inhibit the degradation of BMAA. Five by-products ([M - H]- = 118, 103, 88, 87 and 59) were identified in this study and the degradation pathways of BMAA were proposed. The production of by-products was attributed to the fracture of the C-N bond and hydroxylation reaction. This study is worthwhile to deepen the understanding of the degradation mechanism of BMAA in the UV254/H2O2 system.

Impact factors on the production of ß-methylamino-L-alanine (BMAA) by cyanobacteria.

Cyanobacteria produce a series of secondary metabolites, one of which is beta-N-methylamino-l-alanine (BMAA). BMAA is considered to be the cause of human neurodegeneration. Compared with other cyanotoxins, the role of BMAA in cyanobacteria remains unclear. To investigate this question, six strains of cyanobacteria were cultured and tested in this experiment with an optimized and validated BMAA determination method. The results show that four strains can produce BMAA. The effects of nutrient levels on the production of BMAA by Anabaena sp. FACHB-418 were studied by changing the initial concentrations of nitrate (NaNO3) and phosphate (K2HPO4) in mediums. Bound BMAA was detected in all samples and the concentrations were within 50-100 ng/g. Free BMAA was presence when the concentration of nitrogen was lower than 1.7 mg/L (121.43 µM). Free BMAA was released from the dead and ruptured cells during the cell decline period, so dissolved BMAA cannot be detectable in the adaptation and logarithmic periods, but could be abundant in the decline periods. Statistical analyses show that free BMAA concentrations were negatively correlated with nitrogen strongly (p = 2.334 × 10-10 and r = -0.842), but positively correlated with phosphorus weakly (p = 0.016 and r = 0.405). Moreover, the results of culture experiments indicated that exogenous BMAA could inhibit the growth of cyanobacteria that cannot produce BMAA, and the effect was enhanced as the concentration of exogenous BMAA increased. This phenomenon implies that the production of BMAA may be the stress response by some cyanobacteria to low nitrogen conditions to kill other cyanobacteria, i.e., their competitors.

Effects and mechanism on the removal of neurotoxin ß-N-methylamino-l-alanine (BMAA) by chlorination.

ß-N-Methylamino-l-alanine (BMAA), a new cyanobacterial toxin, is found in different aquatic ecosystems worldwide and is to threaten the human nervous system. Therefore, it is important for water plants to develop feasible methods to counter the effects of BMAA. In this study, the removal of BMAA by chlorine, as well as its intermediate products, at different pH values and the mechanism of pH on the removal BMAA were investigated. The results showed that the chlorination of BMAA is in accordance with the second-order kinetics model. The reaction rate of chlorinated BMAA increased with the increase in the concentration of chlorine. The pH of the solution significantly affected the reaction rate. The apparent kinetic constant (kapp) decreased from 6.00 × 103 M-1·min-1 to 35.5 M-1·min-1 when the pH increased from 4.5 to 9 in the chlorine concentration of 32.23 µM. It is probable that the species distribution and proportion of BMAA and chlorine at different pH values were the main causes of this phenomenon. Additionally, the chlorination reaction consisted of four elementary reactions and hydrogen ions were beneficial to the reaction. The temperature also affected the reaction rate and the activation energy of the reaction was 16.6 ± 1.99 kJ·M-1. A variety of degradation products were detected and the path of degradation was speculated. Chlorination, dechlorination, and decarboxylation were the main processes of oxidative degradation. Furthermore, the composition of the degradation products was the same at different pH values.

Formation kinetics of disinfection byproducts in algal-laden water during chlorination: A new insight into evaluating disinfection formation risk.

It is necessary and important to investigate the formation of disinfection byproducts (DBPs) in water treatment systems for the management of disinfection formation risk. In the present study, the formation potential of trichloromethane (TCM) and haloacetic acids in different algal metabolites were compared, and the formation kinetics of these DBPs were investigated. The results indicated that DBP formation potential, the traditional index widely used to evaluate the disinfection formation risk, can represent neither the total precursors of DBPs nor the possible generated amounts of DBPs in drinking water systems. Kinetic analyses showed that the formation of DBPs could be well described by a classical second-order reaction kinetic model and that the actual concentrations of DBPs during chlorination were predictable with the model. The formation of DBPs in drinking water treatment systems was highly dependent on the total precursors of DBPs in water and the formation rate of DBPs with chlorine; the latter is usually underestimated in previous studies. Because of their high reactivity, TCM in hydrophilic extracellular organic matter and trichloroacetic acid in all algal metabolites should be serious considerations in the management of disinfection formation risk.

Optimization of the Determination Method for Dissolved Cyanobacterial Toxin BMAA in Natural Water.

There is a serious dispute on the existence of ß-N-methylamino-l-alanine (BMAA) in water, which is a neurotoxin that may cause amyotrophic lateral sclerosis/Parkinson's disease (ALS/PDC) and Alzheimer' disease. It is believed that a reliable and sensitive analytical method for the determination of BMAA is urgently required to resolve this dispute. In the present study, the solid phase extraction (SPE) procedure and the analytical method for dissolved BMAA in water were investigated and optimized. The results showed both derivatized and underivatized methods were qualified for the measurement of BMAA and its isomer in natural water, and the limit of detection and the precision of the two methods were comparable. Cartridge characteristics and SPE conditions could greatly affect the SPE performance, and the competition of natural organic matter is the primary factor causing the low recovery of BMAA, which was reduced from approximately 90% in pure water to 38.11% in natural water. The optimized SPE method for BMAA was a combination of rinsed SPE cartridges, controlled loading/elution rates and elution solution, evaporation at 55 °C, reconstitution of a solution mixture, and filtration by polyvinylidene fluoride membrane. This optimized method achieved > 88% recovery of BMAA in both algal solution and river water. The developed method can provide an efficient way to evaluate the actual concentration levels of BMAA in actual water environments and drinking water systems.