[Application of chromatographic retention time correction in untargeted screening].

OBJECTIVE: Chromatographic retention time correction is one of the important steps to effectively improve the accuracy of identification. This article proposed a strategy for untargeted screening of biological samples based on retention time correction. METHODS: A pre-treatment method for biological samples was established. The conditions of liquid chromatography and mass spectrometry were optimized. Fourteen compounds were selected as calibration agents. The retention time correction of different samples, different injection time, different brands of instruments, changing chromatographic column and changing mobile phase were investigated. RESULTS: Calibration agents had a wide coverage, good stability and no interference with sample determination. They could be uniformly distributed in the chromatogram in both positive and negative ion modes. The chromatogram was divided into several time intervals. Calibration agents in each time period were used for retention time linear correction, and the correction effects were good. CONCLUSION: The retention time correction method could eliminate the retention time drift caused by experimental conditions, improve the accuracy of qualitative analysis, and help to solve the problem of high false positive result based on mass spectrum information.

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.

Fe-Activated Peroxymonosulfate Enhances the Degradation of Dibutyl Phthalate on Ground Quartz Sand.

Soil contamination by organic compounds has received worldwide concern for decades. Here, we found that dibutyl phthalate (DBP) could be degraded on moist quartz sand (QS, crystal, a typical soil constituent) during stirring, and the removal rate reached 57.2 ± 3.1% after 8 h of reaction. The introduction of peroxymonosulfate (PMS) and zerovalent iron (Fe0) substantially improved the decomposition of DBP to 94.2 ± 1.6% in 8 h, suggesting they have great contributions. DBP decomposition was caused by multiple reactive species, such as surface silicon-based radicals (like ≡SiO•) and other reactive species like superoxide radical (O2•-), hydroxyl radical (•OH), and sulfate radical (SO4•-). In the QS/ultrapure water system, DBP was mainly attacked by O2•- or ≡SiO•, with the formation of hydrolysis products. In the iron@QS/PMS system, due to the activation of PMS by Fe0, SO4•- and •OH were produced while the latter led to DBP degradation, and thus hydroxyl substitution products of DBP were ubiquitous. DBP was hardly removed on amorphous supporters like silica gel, alumina, and red soil even with the presence of PMS and Fe0, indicating the indispensable role of surface radicals on crystals like QS. This work presents a new remediation technology for polluted soil, especially aquifer.

[Determination of 1, 4-dioxane in aerosol cosmetic by new isotope dilution-headspace gas chromatography-mass spectrometry].

OBJECTIVE: To develop a simple, fast and sensitive analytical method based on isotope dilution-headspace gas chromatography-mass spectrometry for the determination of 1, 4-dioxane residue in the aerosol cosmetics. METHODS: Sample was successive weighed and dissolved in 1, 3-dimehyl-2-imidazolidinone(DMI)solvent and isotope internal standard was added. Then transfered to a 20 mL headspace vial. The headspace vial was sealed and extracted 15 min by ultrasonic-assisted extraction. After separated by HP-5 MS fused silica capillary column(30 m×25 mm, 0. 25 µm), the compound was analyzed by gas chromatography-mass spectrometry in selected ion monitoring mode(GC-MS-SIM) and quantified by internal standard method. RESULTS: There were good linear correlations with R~2 no less than 0. 999 in the range of 1. 0-100 mg/kg. The limit of detection(LOD) of this method was 0. 3 mg/kg. At 0. 3, 1. 0, 5. 0 and 30 mg/kg four added concentration, recovery for five kinds of aerosol cosmetic were all between 91. 4% and 104. 2%. The relative standard deviations(RSDs) were 1. 5%-6. 3% and 1. 7%-6. 4%(n=6), respectively. CONCLUSION: The developed method has proved convenient, time-saving, accurate and sensitive and suited for determination 1, 4-dioxane in aerosol cosmetic.

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.

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.

Efficient degradation of benzalkonium chloride (BAC) by zero-valent iron activated persulfate: Kinetics, reaction mechanisms, theoretical calculations and toxicity evolution.

The present study systematically investigated the elimination of benzalkonium chloride (BAC) in the zero valent iron activated persulfate (Fe0/PS) system. The influence of operational parameters, including PS concentration, Fe0 dosage and pH, were investigated through a series of kinetic experiments. When the Fe0 dosage was 5.0 mM, the initial ratio of [PS]: [BAC] was 10:1, the degradation efficiency could achieve 91.7% at pH 7.0 within 60 min. Common inorganic anions and humic acid did not significantly affect BAC degradation, implying that Fe0/PS system had a potential application prospect in the actual wastewater remediation. Based on the electron paramagnetic resonance test and quenching experiments, the BAC degradation was found to be contributed by •OH, SO4•- and Fe(IV). A total of 23 intermediates were identified by the liquid chromatography-mass spectrometry, and the degradation pathways were proposed accordingly, including dealkylation and demethylation, hydroxylation, sulfate substitution and benzyl C-N cleavage reactions. Density functional theory based calculations were conducted to realize the rationality of the proposed reaction mechanisms. The toxicity of transformation products was predicted by ECOSAR program. This work demonstrated the possibility of BAC removal in hospital and municipal wastewater by Fe0/PS treatment, and also provides a safe choice for deep treatment of quaternary ammonium salt wastewater.

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.

[Determination of glyphosate in air of workplaces by ion chromatography].

OBJECTIVE: To establish a method for determining glyphosate in the air of workplaces by ion chromatography. METHODS: Ultra-fine glass fiber filter paper was used to collect glyphosate from the workplace air. After being ultrasonically eluted with deionized water, samples were determined by ion chromatography using a conductivity detector. RESULTS: Within the range of 0.05-1.00 mg/L, a linear relationship was found with a limit of detection of 0.003 mg/m(3). The minimum detectable concentration was 0.000 41 mg/m(3) (calculated by sampling 75 L of air). For three different concentrations of glyphosate, the intra-batch relative standard deviations (RSDs) were 1.8%, 1.6%, and 0.8%, respectively, and the inter-batch RSDs were 1.9%, 2.1%, and 2.2%, respectively. The recovery rate ranged from 94.8% to 97.4%. The elution efficiency ranged from 94.5% to 96.7%. The sampling efficiency was 100%. Samples could be stored at room temperature for at least 7 days. CONCLUSION: This presented method meets the requirements of Guide for establishing occupational health standards-Part 4: Determination methods of air chemicals in workplace and is feasible for determination of glyphosate in the air of workplaces.

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.

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).

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.

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.

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.

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.

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.

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.

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.

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.