MXene-supported MIL-88A(Fe) as persulfate activator for removal of tetracycline.

The poor conductivity, poor stability, and agglomeration of iron-based metal organic framework MIL-88A(Fe) limit its application as persulfate (PS) activator in water purification. Herein, MXene-supported MIL-88A(Fe) composites (M88A/MX) were synthesized to enhance its adsorption and catalytic capability for tetracycline (TC) removal. Scanning electron microscope (SEM), X-ray diffractometer (XRD), Fourier transform infrared spectrometer (FT-IR), and X-ray photoelectron spectroscopy (XPS) were used to characterize prepared materials, confirming the successful attachment of MIL-88A(Fe) to the surface of MXene. M88A/MX-0.2 composites, prepared with 0.2 g MXene addition, exhibit optimal degradation efficiency, reaching 98% under conditions of 0.2 g/L M88A/MX-0.2, 1.0 mM PS, 20 ppm TC, and pH 5. The degradation rate constants of M88A/MX-0.2 were 0.03217 min-1, which was much higher than that of MIL-88A(Fe) (0.00159 min-1) and MXene (0.00626 min-1). The removal effects of reaction parameters, such as dosage of M88A/MX-0.2 and PS; initial solution pH; and the presence of the common co-existing constituents (humic acid and the inorganic anions) were investigated in detail. Additionally, the reuse of M88A/MX-0.2 showed that the composites had good cycling stability by recurrent experiments. The results of electron paramagnetic resonance (EPR) and quenching experiments indicated that ·OH, ·SO4-, and ·O2- were involved in the M88A/MX-0.2/PS system where persulfate oxidation process was activated with prepared M88A/MX-0.2. In addition, the intermediates of photocatalytic degradation were determined by HPLC-MS, and the possible degradation pathways of the target molecules were inferred. This study offered a new avenue for sulfate-based degradation of Fe-based metal organic framework.

Degradation of Butylated Hydroxyanisole by the Combined Use of Peroxymonosulfate and Ferrate(VI): Reaction Kinetics, Mechanism and Toxicity Evaluation.

Butylated hydroxyanisole (BHA), a synthetic phenolic antioxidant (SPA), is now widely present in natural waters. To improve the degradation efficiency of BHA and reduce product toxicity, a combination of peroxymonosulfate (PMS) and Ferrate(VI) (Fe(VI)) was used in this study. We systematically investigated the reaction kinetics, mechanism and product toxicity in the degradation of BHA through the combined use of PMS and Fe(VI). The results showed that PMS and Fe(VI) have synergistic effects on the degradation of BHA. The effects of operational factors, including PMS dosage, pH and coexisting ions (Cl-, SO42-, HCO3-, K+, NH4+ and Mg2+), and different water matrices were investigated through a series of kinetic experiments. When T = 25 °C, the initial pH was 8.0, the initial BHA concentration was 100 µM, the initial concentration ratio of [PMS]0:[Fe(VI)]0:[BHA]0 was 100:1:1 and the degradation rate could reach 92.4% within 30 min. Through liquid chromatography time-of-flight mass spectrometry (LC-TOF-MS) identification, it was determined that the oxidation pathway of BHA caused by PMS/Fe(VI) mainly includes hydroxylation, ring-opening and coupling reactions. Density functional theory (DFT) calculations indicated that •OH was most likely to attack BHA and generate hydroxylated products. The comprehensive comparison of product toxicity results showed that the PMS/Fe(VI) system can effectively reduce the environmental risk of a reaction. This study contributes to the development of PMS/Fe(VI) for water treatment applications.

Assessment of the UV/DCCNa and UV/NaClO oxidation process for the removal of diethyl phthalate (DEP) in the aqueous system.

In this work, the removal and transformation process of diethyl phthalate (DEP) in UV/dichloroisocyanurate (UV/DCCNa) and UV/sodium hypochlorite (UV/NaClO) systems were compared to evaluate the application potential of UV/DCCNa technology. Compared with UV/NaClO, UV/DCCNa process has the advantage of DEP removal and caused a higher degradation efficiency (93.8%) within 45 min of oxidation in ultrapure water due to the sustained release of hypochloric acid (HOCl). Fourteen intermediate products were found by high-resolution mass spectrometry, and the transformation patterns including hydroxylation, hydrolysis, chlorination, cross-coupling, and nitrosation were proposed. The oxidation processes were also performed under quasi-realistic environmental conditions, and it was found that DEP could be effectively removed in both systems, with yields of disinfection byproduct meeting the drinking water disinfection standard (<60.0 µg/L). Comparing the single system, the removal of DEP decreased in the mixed system containing five kinds of PAEs, which could be attributed to the regeneration of DEP and the competitive effect of •OH occurred among the Dimethyl phthalate (DMP), DEP, Dipropyl phthalate (DPrP), Diallyl phthalate (DAP) and Diisobutyl phthalate (DiBP). However, a greater removal performance presented in UV/DCCNa system compared with UV/NaClO system (69.4% > 62.1%). Further, assessment of mutagenicity and developmental toxicity by Toxicity Estimation Software Tool (T.E.S.T) software indicated that UV/DCCNa process has fewer adverse effects on the environment and is a more environmentally friendly chlorination method. This study may provide some guidance for selecting the suitable disinfection technology for drinking water treatment.

Simultaneous determination of three strong polarity herbicides in tea by ion chromatography-triple quadrupole mass spectrometry.

Due to lack of chromogenic groups and fluorescence groups, high boiling point, high polarity, low volatility, and small molecular weight of glyphosate, glufosinate and bentazone, the detection of three analyses were limited in all kinds of food. Herein, a method for the simultaneous determination of glyphosate, glufosinate and bentazone in tea by ion chromatography tandem triple quadrupole mass spectrometry (IC-MS) was developed, which is without organic solvent and complex derivatization. The recoveries of three compounds in different teas (black tea, green tea, white tea) ranged from 80.40 % to 107.00 %, and the intraday precision (n = 6) ranged from 0.57 % to 9.90 %, the daytime precision ranged from 1.00 % to 5.30 %, the quantitative limit (LOQ) ranged from 0.36 to 1.30 µg/L, and the detection limit (LOD) ranged from 0.11 to 0.39 µg/L. Furthermore, the detection limit and quantitative limit of glyphosate, glufosinate and bentazone by this method are lower than other methods in real samples. Meanwhile, the established method was successfully applied to determine the terminal residues of the three analytes in twelve tea samples from commercial market. Therefore, this method can provide reliable technical support for the study of residue status in vegetables and fruits.

Oxidative degradation and possible interactions of coexisting decabromodiphenyl ether (BDE-209) on polystyrene microplastics in UV/chlorine process.

This work was to investigate the transformation of coexisting decabromodiphenyl ether (BDE-209) on microplastics and their possible interactions in UV/chlorine process. Compared with pristine microplastics, the highly aged polystyrene (PS) showed an inhibitory effect on degradation of BDE-209. Increasing initial concentration of BDE-209 on PS inhibited degradation, while the chlorine concentration and pH did not affect the final degradation efficiency. Moreover, the presence of NO3-, SO42-, HCO3- and HA in water was unfavorable for BDE-209 degradation. According to the experimental and calculation results, the contribution to the degradation of BDE-209 was ranked as direct photolysis > HO• > •Cl in the UV/ chlorine system. Chlorination products released by PS during UV/chlorination were detected. Four possible reaction pathways of BDE-209 were proposed, which mainly involved debromination, hydroxylation, chlorine substitution, cleavage of ether bond, and intramolecular elimination of HBr. It was worth noting that PS microplastics not only inhibited the degradation of BDE-209, but also affected the type and abundance of its transformation products. Meanwhile, interaction products of PS and BDE-209 were determined, which was attributed to reactions of PS-derived radicals with •Br/•C6Br5 and •Cl. Results of toxicity evaluation showed that the introduction of carbon-halogen bonds, especially C-Br bond, increased the toxicity of chain scission products of PS. This work provides some new insights into transformation, interaction, and associated ecological risks of coexisting microplastics and surface adsorbed contaminants in the UV/chlorine process of drinking water treatment plants (DWTPs) and wastewater treatment plants (WWTPs).

Urinary antibiotic concentrations in preschool children from eastern China and health risk assessment.

Despite limited biomonitoring studies suggesting extensive antibiotic exposure in general population, the body burden of antibiotics in young children and their potential health risks remain unclear. To assess the antibiotic exposure levels in young children, 508 preschoolers aged 3-6 years were recruited from eastern China in 2022, and a total of 50 representative antibiotics from 8 categories, including 17 human antibiotics (HAs), 4 antibiotics preferred as HAs (PHAs), 16 veterinary antibiotics (VAs), and 13 antibiotics preferred as VAs (PVAs), were analyzed by UPLC-MS/MS. Hazard quotient (HQ) and hazard index (HI) were calculated to evaluate the health risks, and multivariate logistic regression was applied to examine diet with antibiotic exposure. Our results showed that there were 41 antibiotics detected in children's urine, and the overall detection frequency was as high as 100%. Sulfonamides, macrolides, ß-lactams, quinolones, and azoles were the predominant categories of antibiotic detected. Among the studied children, 6.5% had a sum of estimated daily intake (EDI) of all VAs and PVAs larger than 1 µg/kg/day. Notably, 10.0% of the children had a microbiological HI value exceeding 1, primarily contributed by ciprofloxacin. Children with higher consumption of seafood had a relatively increased exposure to multiple categories of antibiotics, including HAs, VAs, quinolones, azoles, and others. Principal component analysis suggested that "Aquatic products and viscera preferred dietary pattern" scores were positively correlated with the exposure levels of ciprofloxacin (OR: 1.23; 95% CI: 1.02-1.47) and carbadox (OR: 1.32; 95% CI: 1.10-1.59), and a relatively increased exposure of PHAs was realized in children with higher "Meat-egg preferred dietary pattern" scores (OR: 1.24; 95% CI: 1.03-1.50). In conclusion, there was a widespread exposure to antibiotics among preschool children from eastern China, and children who consumed more animal-derived foods may had an increased exposure to antibiotics.

Preparation of amine-modified amphiphilic resins for the extraction of trace pharmaceuticals and personal care products in environmental waters.

Herein, four amine-modified amphiphilic resins were synthesized and utilized as solid-phase extraction (SPE) materials to enrich pharmaceuticals and personal care products (PPCPs) from environmental water. The obtained materials (Strong anion-exchange amphiphilic materials, SAAMs; Weak anion-exchange amphiphilic materials, WAAMs) possessed large specific surface area (473-626 m2/g), high ion exchange capacity (0.89-1.97 mmol/g), and small contact angle (74.41-79.74°), indicating good hydrophilicity. The main factors affecting the efficiency of the extraction process were studied, including column volume, column flow rate, sample salinity and sample pH. Notably, the trend observed in absolute recovery was significantly correlated with the Zeta potential of the employed adsorbents. Furthermore, based on the obtained materials, a method of SPE coupled with ultra-performance liquid chromatography and tandem mass spectrometry (SPE/LC-MS/MS) was developed, and then utilized to determine PPCPs in the samples collected from the Yangtze River Delta. The Method detection limit (MDL) and Method quantification limit (MQL) ranged from 0.05 to 0.60 ng/L and 0.17 to 2.00 ng/L, respectively, with a relative standard deviation (RSD) below 6.3%, demonstrating good accuracy and sensitivity. As evidenced by comparison with previous literature, the developed method exhibited satisfactory performance, showing great potential for further commercial application in the extraction of trace PPCPs from environmental water samples.

The effect of FeS on the fate of Cr(VI) in the presence of organic matters under dynamic anoxic/oxic conditions.

The reduction of Cr(VI) by FeS under anoxic conditions has been studied extensively. However, when the redox environments alternate from anoxic to oxic, the effect of FeS on the fate of Cr(VI) in the presence of organic matters still remains unknown. Therefore, this study investigated the effect of FeS coupled with humic acids (HA) and alga on the transformation of Cr(VI) under dynamic anoxic/oxic conditions. HA could promote the reduction of Cr(VI) from 86.6% to 100% under anoxic conditions due to the enhancement of the dissolution and dispersibility of FeS particles by HA. However, the strong complexing and oxidizing properties of alga inhibited the reduction of FeS. Reactive oxygen species (ROS) generated from FeS oxidation under oxic conditions could oxidize 3.80 µM of Cr(III) to aqueous Cr(VI) at pH 5.0, while aqueous Cr(VI) reached to 4.83 µM in the presence of HA, which was ascribed to the increasing amount of free radicals. In addition, acidic conditions and excess FeS would increase strong reducing Fe(II) and S(-II) species, and improve the efficiency of Fenton reaction. The findings provided new insights into the fate of Cr(VI) in aquatic systems containing FeS and organic matters under dynamic anoxic/oxic conditions.

Biochar assists phosphate solubilizing bacteria to resist combined Pb and Cd stress by promoting acid secretion and extracellular electron transfer.

Microorganisms have difficulty surviving and performing remediation functions in mixed systems with high concentrations of Pb and Cd. Biochar has the potential to assist microorganism remediation as an excellent adsorbent for heavy metals. In this study, pig manure biochar (PMB) was used to assist phosphorus solubilizing bacteria (PSB) to explore the mineralization protection and biofeedback mechanism of biochar on PSB under mixed stress of 1000 mg/L Pb2+ and 500 mg/L Cd2+. The adsorption results showed that the removal of Pb2+ and Cd2+ by PMB+PSB was 148.77% and 72.27% higher than that by PSB. Meanwhile, the non-bioavailable fraction of Cd2+ and acid-soluble fraction of Pb2+ in PMB+PSB were increased by 9% and 3%, respectively. Mineralogical and microbial secretion results confirm that showed that the acidic soluble fraction and non-bioavailable fraction were mostly Pb/Cd-carbonate and Pb/Cd-phosphate. The pore adsorption and precipitation (carbonate) of biochar were able to reduce the exposure of PSB to Pb/Cd and the background stress concentration, thus stimulating the biological positive feedback effect of PSB and forming a microenvironment in the cell periphery. The vesicle detoxification and extracellular polymeric substance protection mechanism of PSB were improved under biochar protection, and the individual size and activity of PSB cells were enhanced. Besides, citric acid release from PSB (28.85% increase) accelerated the dissolution of unstable Cd-carbonate, thereby releasing a large amount of Cd2+ to compete with Pb2+ for PO43-. Thus, the protection of biochar and the positive feedback effect of PSB could reduce the biotoxicity of Cd2+ in the stress system by preferentially forming a stable Cd-phosphate. In addition, the excellent electrical conductivity and organic material adsorption of biochar increased the extracellular electron transport rate of microorganisms, which further accelerated the mineralization and immobilization of Pb2+ and Cd2+, so as to ensure the repair effect of PSB on heavy metals.

An analytical method for the determination of glyphosate and aminomethylphosphoric acid using an anionic polar pesticide column and the application in urine and serum from glyphosate poisoning patients.

An analytical method for the determination of glyphosate (GLY) and aminomethylphosphoric acid (AMPA) in biological fluid samples (serum and urine) from poisoning patients using liquid chromatography-tandem mass spectrometry (LC-MS/MS) is established. After the sample pretreatment, including protein precipitation and a modified liquid-liquid extraction method, the chromatographic separation was conducted on a trifunctional modified hydrophilic column. The mobile phases in the gradient program were 2.5% formic acid aqueous solution and acetonitrile. The multiple reaction monitoring (MRM) models and the isotope-labeled internal standards were used in the acquisition process. Good linearities and satisfying recovery rates were obtained in two sample matrices with good RSDs. The detection limits of GLY and AMPA were <2 µg L-1, which were close to those obtained in our previous research. The established method was applied to biological samples from five patients with glyphosate intoxication. The analysis of the trend for the concentration of GLY and AMPA in two biological samples was investigated, and the difference in the downward trend of AMPA in urine was found in patients with a relatively higher concentration of GLY in serum.

Isolation and screening of phosphorus solubilizing bacteria from saline alkali soil and their potential for Pb pollution remediation.

The high pH and salinity of saline alkali soil not only seriously restrict the growth of crops, but also aggravate the pollution of heavy metals. The fixation of heavy metals and the regulation of pH by phosphorus solubilizing microorganisms may become a new way to repair heavy mental and improve saline alkali soil. In this study, a saline-alkali resistant bacteria (CZ-B1, CGMCC No: 1.19458) was screened from saline-alkali soil, and its tolerance to salt/alkali/lead stress was investigated by shaking flask experiment. The strain was identified as Bacillus amyloliquefaciens by morphology and 16S rRNA gene sequence analysis. The optimum growth temperature of CZ-B1 is about 35°C-40℃. The maximum salt stress and pH that it can tolerance are 100 g/L and 9 respectively, and its tolerance to Pb2+ can reach 2000 mg/L. The phosphorus release amount of CZ-B1 to Ca3(PO4)2 within 72 h is 91.00-102.73 mg/L. The phosphate solubilizing index in PVK agar medium and NBRIP agar medium are more than 2, which can be defined as phosphate solubilizing bacteria. Moreover, the dissolution of CZ-B1 to phosphorus is mainly attributed to tartaric acid, citric acid and succinic acid in inorganic medium. In addition, the removal rate of Pb2+ by CZ-B1 can reach 90.38% for 500 mg/L. This study found that CZ-B1 can immobilize Pb through three biological mechanisms (organic acid, extracellular polymers and mineralization reaction). The release of succinic acid (10.97 g/L) and citric acid (5.26 g/L) may be the main mechanism to promote the mineralization reaction of CZ-B1 (phosphate and oxalate) and resistance to Pb stress. In addition, the high enrichment of Pb2+ by EPS can increase the rate of extracellular electron transfer and accelerate the mineralization of CZ-B1. The screening and domestication of saline-tolerant phosphorus-solubilizing bacteria not only help to remediate Pb contamination in saline soils, but also can provide P element for plant growth in saline soil.

Human serum lipidomics analysis revealed glyphosate may lead to lipid metabolism disorders and health risks.

Glyphosate-based herbicides (GBH) are one of the most widely used pesticides worldwide. Industrial workers in glyphosate-based herbicides manufacture are the populations who experience long-term exposure to high glyphosate levels. The impacts of glyphosate on human health are the important public health problem of great concern. Up to date, the potential adverse effects of glyphosate on humans or other mammals have been reported in multiple studies. However, limited research is available on lipid alternations related to human exposure to glyphosate. In fact, the perturbations in some lipid metabolisms have been found in industrial workers in previous work. This study aims to explore the serum lipidomic characterization and to understand the underlying mechanisms of health risks associated with glyphosate exposure. A nontargeted lipidomics study was conducted to investigate the 391 serum samples from the general population and chemical factory workers. It was demonstrated that glyphosate caused significant perturbations of 115 differentially expressed lipids. The main manifestations were the elevation of circulating diacylglycerols (DG), cholesteryl esters (CE), ceramides (Cer), sphingomyelins (SM), lysophosphatidylethanolamines (LPE) and phosphatidylcholines (PC), and the decrease of ysophosphatidylcholines (LPC), triacylglycerols (TG), fatty acids (FA) and phosphatidylethanolamines (PE). A total of 88 lipids were further screened as potential lipid biomarkers associated closely with glyphosate using partial correlation analysis, and five of which (including PC 16:0/18:2; O, PC 18:0/18:2; O, PC 18:0/20:4; O, PC O-40:9 and CE 18:3) showed excellent superior performance (AUC = 1) to evaluate and monitor health risks due to glyphosate exposure. The present work discovered glyphosate-induced potential health risks, including chronic hepatic and renal dysfunction, atherosclerosis, cardiovascular disease and neurodegenerative diseases from a lipidomic perspective, and could inform the identification of early indicators and interpretation of biological mechanisms to detect health risks of the glyphosate-exposed populations as early as possible.

Insight into the photodegradation and universal interactive products of 2,2',4,4'-tetrabromodiphenyl ether on three microplastics.

The transformation process of contaminants on microplastics (MPs) exposed to sunlight has attracted increasing attention. However, the interactions between them are typically disregarded; therefore, this work investigated the photodegradation of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) on three MPs (polystyrene (PS), polypropylene (PP) and polyethylene (PE)) and the interactions between these two. The inhibition of aged PS on the elimination of BDE-47 was due to light shielding, while aged PP and PE increased the degradation rate. More hydroxyl radicals (HO•) was detected in the PS system, which resulted in the higher degradation rate of BDE-47 on PS. A total of 33 different products were identified and four reaction pathways were presented, and the reaction mechanisms mainly included debromination, hydroxylation, carbon-oxygen-bond breaking and interactive reactions. The Ecological Structure Activity Relationship (ECOSAR) and Toxicity Estimation Software Tool (TEST) programs were used to evaluate the toxicity of reaction products, and the results indicated that even though BDE-47 was the most toxic, the interaction products were still toxic or harmful to aquatic organisms. This study provides significant information on the photodegradation of contaminants on common microplastics and their interaction, which cannot be ignored.

A Comprehensive Strategy Based on UPLC-Q/TOF-MS for the Identification of Compounds in a Chinese Patent Medicine, Xiao'er Chiqiao Qingre Granules.

The aim of this study was to establish a comprehensive strategy based on liquid chromatography coupled with mass spectrometry to potently identify as many compounds of Chinese patent medicine as possible. Ultrahigh performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UPLC-Q/TOF-MS) was used to qualitatively analyze the Chinese patent medicine Xiao'er Chiqiao Qingre Granules (XCQG), which is recorded in the Chinese Pharmacopoeia. A novel strategy, including targeted, semi-targeted and non-targeted identification, was built to explore the compounds based on accurate mass, characteristic fragments, retention time of standard substances, databases or literature. Based on the integrated identification, 250 compounds were identified in total, including 7 alcohols, 3 aldehydes, 17 alkaloids, 9 amino acids, 10 coumarins, 30 flavonoids, 29 glycosides, 12 ketones, 7 lignans, 20 organic acids, 12 phenols, 11 phenylpropanoids, 9 quinones, 3 steroids, 26 terpenes, 14 volatile oils and 31 other compounds. A novel strategy for the identification of compounds in traditional Chinese medicine (TCM) was developed with Ultrahigh performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UPLC-Q/TOF-MS). It is also the first systematic study of compounds in XCQG, laying a foundation for further mechanism research of XCQG. More importantly, the strategy shows good application prospect in identifying compounds of TCM.

The study of human serum metabolome on the health effects of glyphosate and early warning of potential damage.

Glyphosate is one of the most widely used herbicide with high efficiency, low toxicity and broad-spectrum. In recent decades, increasing evidence suggests that glyphosate may cause adverse health effects on human beings. However, until now, there is little data on the human metabolic changes. Since occupational workers are under greater health risks than ordinary people, the understanding regarding the health effects of glyphosate on occupational workers is very important for the early warning of potential damage. In this study, serum metabolic alterations in workers from three chemical factories were analyzed by gas chromatography-mass spectrometry (GC-MS) to assess the potential health risks caused by glyphosate at the molecular level. It was found that the levels of 27 metabolites changed significantly in the exposed group compared to the controls. The altered metabolic pathways, including amino acid metabolism, energy metabolism (glycolysis and TCA cycle) and glutathione metabolism (oxidative stress), etc., indicated a series of changes occur in health profile of the human body after glyphosate exposure, and the suboptimal health status of human may further evolve into various diseases, such as Parkinson's disease, renal and liver dysfunction, hepatocellular carcinoma, and colorectal cancer. Subsequently, 4 biomarkers (i.e., benzoic acid, 2-ketoisocaproic acid, alpha-ketoglutarate, and monoolein) were identified as potential biomarkers related to glyphosate exposure based on the partial correlation analyses, linear regression analyses, and FDR correction. Receiver-operating curve (ROC) analyses manifested that these potential biomarkers and their combinational pattern had good performance and potential clinical value to assess the potential health risk associated with glyphosate exposure while retaining high accuracy. Our findings provided new insights on mechanisms of health effects probably induced by glyphosate, and may be valuable for the health risk assessment of glyphosate exposure.

Photochemical transformation of hexachlorobenzene (HCB) in solid-water system: Kinetics, mechanism and toxicity evaluation.

As one of the first batch of persistent organic pollutants (POPs) included in Stockholm Convention, hexachlorobenzene (HCB) has attracted great attention because of its wide occurrence and great environmental risks. Considering the easy adsorption of HCB on solids and the complexity of natural particles, we systematically investigated the photodegradation of HCB on the surface of silica gel (SG) in aqueous solution in this work to reveal its fate in natural waters. Under mercury lamp irradiation, more than 90% of HCB loaded on SG could be removed after 240 min. Moreover, the effects of solution pH and water constituents were examined, and results showed that the presence of NO2-, NO3-, Fe3+ and humic acid (HA) significantly inhibited the reaction due to the scavenging of ROS and/or competitive absorption of light. According to radical quenching experiments and electron paramagnetic resonance (EPR) spectra, hydroxyl radicals and singlet oxygen generated on the surface of SG could participate in the transformation of HCB, but •OH played a dominant role. Based on products identified by high performance liquid chromatography-mass spectrometry (HPLC-MS) and gas chromatography-mass spectrometry (GC-MS), two main pathways were proposed for the removal of HCB, including dechlorination and hydroxylation which represent direct and indirect photodegradation, respectively, and the occurrence of these two reactions was further supported by density functional theory (DFT) calculations. From the quantitative analysis of penta-chlorobenzene, it was estimated that dechlorination and hydroxylation contributed to approximately 44.4% and 55.6% of initial HCB degradation, respectively. Furthermore, toxicity predictions by the ecological structure-activity relationship model (ECOSAR) suggested that the toxicity of HCB was decreased in the photodegradation process. This study would provide important information for understanding the photochemical transformation mechanism of HCB at the solid/water interface.

Ultraviolet photolysis of monochloro-p-benzoquinone (MCBQ) in aqueous solution: Theoretical investigation into the dechlorination.

In this work, the UV-induced transformation of monochloro-p-benzoquinone (MCBQ) in aqueous solution has been systematically investigated through quantum chemical calculations. During the UV irradiation at 253.7 nm, the first triplet state of MCBQ (3MCBQ*) was from the intersystem crossing of its first excited singlet state (1MCBQ*). In aqueous solution, the nucleophilic attack of OH- on carbon atoms in 3MCBQ* was the central reaction. The addition of OH- to olefinic carbon atoms was much more kinetically feasible than that to carbonyl carbon atoms, even though the carbonyl carbon atoms were more positively charged. Moreover, OH- preferred to add to the ortho-position of C-Cl bond, where the unchlorinated atom was more negatively charged than the chlorinated one. The UV photolysis of the primary intermediate (HO-CBQ) was not the same as that of MCBQ. The attack of OH- on the para-position of C-Cl bond was the most efficient pathway. The addition of OH- to the chlorinated atom of 3HO-CBQ* was much more efficient than that in the case of 3MCBQ*, which reveals that more UV irradiation may promote the dechlorination. The findings in the present study may be helpful to enrich the understanding of the halobenzoquinones transformation in aqueous solution.

Experimental and theoretical study on the degradation of Benzophenone-1 by Ferrate(VI): New insights into the oxidation mechanism.

The oxidation of Benzophenone-1 (BP-1) by ferrate (Fe(VI)) was systemically investigated in this study. Neutral pH and high oxidant dose were favorable for the reaction, and the second order rate constant was 1.03 × 103 M-1·s-1 at pH = 7.0 and [Fe(VI)]0:[BP-1]0 = 10:1. The removal efficiency of BP-1 was enhanced by cations (K+, Ca2+, Mg2+, Cu2+, and Fe3+), while inhibited by high concentrations of anions (Cl- and HCO3-) and low concentrations of humic acid. Moreover, intermediates were identified by LC-MS, and five dominating reaction pathways were predicted, involving single hydroxylation, dioxygen transfer, bond breaking, polymerization and carboxylation. Theoretical calculations showed the dioxygen transfer could occur by Fe(VI) attacking the CC double-bond in benzene ring of BP-1 to form a five-membered ring intermediate, which was hydrolyzed twice followed by H-abstraction to generate the dihydroxy-added product directly from the parent compound. Dissolved CO2 or HCO3- might be fixed to produce carboxylated products, and Cl- led to the formation of two chlorinated products. In addition, the toxicity assessments showed the reaction reduced the environmental risk of BP-1. This work illustrates Fe(VI) could remove BP-1 in water environments efficiently, and the newly proposed dioxygen transfer mechanism herein may contribute to the development of Fe(VI) chemistry.

Transformation of bisphenol AF by chlorination: kinetic study and product identification.

Bisphenol AF (BPAF), commonly used as a substitute for bisphenol A (BPA), is also an endocrine disruptor with cytotoxicity, neurotoxicity, genotoxicity, and biotoxicity. In this study, we found that BPAF could be effectively degraded by free chlorine. The second order rate constant of the reaction ranged from 1.67 to 126.67 M-1·s-1 in the pH range of 5.0-11.0. Nineteen products were detected by LC-Q-TOF-MS analysis, including chlorinated BPAF (i.e., mono/di/tri/tetrachloro-BPAF), 8 dimers, and 6 trimers. According to the identified products, two transformation pathways of electrophilic substitution and electron transfer are proposed. Humic acid (HA) could inhibit the degradation rate of BPAF due to its ability to reduce the reactive BPAF radical intermediates to the parent compound. The addition of low concentrations of Br- and I- accelerates the reaction rate of BPAF, due to the formation of HOBr and HOI with a higher oxidizing capacity. In seawater, BPAF degraded rapidly, and 16 new halogenated products were formed. Theoretical calculation shows that electrophilic substitution is more prone to occur at the ortho position of the hydroxyl group to form chlorinated products, while electron transfer tends to occur at the hydroxyl oxygen, resulting in the formation of BPAF radical and its subsequent coupling products.

A New Group of Heterocyclic Nitrogenous Disinfection Byproducts (DBPs) in Drinking Water: Role of Extraction pH in Unknown DBP Exploration.

pH adjustment prior to extraction is an important step in water sample pretreatment processes for exploration of new/unknown disinfection byproducts (DBPs) in drinking water. To achieve a better extraction efficiency, the pH of a water sample is usually adjusted to a low level (e.g., < 0.5) to ensure that target DBPs are in their neutral forms. However, such a practice may elude some amphoteric DBPs (especially those nitrogenous DBPs with multiple functional groups), which can accept protons at a low pH and lose protons at a high pH. In this study, with careful extraction pH selection and optimization, we first report the detection and identification of a new group of heterocyclic nitrogenous DBPs, halogenated pyridinols, in simulated drinking water using ultra performance liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry and time-of-flight mass spectrometry, including 5-chloro-3-pyridinol, 2-bromo-3-pyridinol, 2,6-dichloro-4-pyridinol, 2,6-dibromo-3-pyridinol, 3-bromo-2-chloro-5-pyridinol, 5-bromo-2-chloro-3-pyridinol, 3,5,6-trichloro-2-pyridinol, and 2,4,6-tribromo-3-pyridinol. On the basis of the speciation of dissociated chemical species and recovery tests at different extraction pH values, it was found that, only at a pH of 3.0, all the eight new DBPs could achieve recoveries of >50%. With subsequent instrumental parameter optimization, the method detection and quantitation limits of the eight new DBPs were determined to be 0.04-1.58 and 0.15-4.11 ng/L, respectively. The optimized method enabled an accurate detection of the eight new DBPs in two real drinking water samples. Further aided with in vivo developmental and acute toxicity assays using zebrafish embryos, the developmental and acute toxicity of the new DBPs were found to be slightly lower than those of halogenated benzoquinones but dozens of times higher than those of commonly known DBPs such as tribromomethane and iodoacetic acid.