Biomonitoring urinary pesticide metabolites in preschool children by supported liquid extraction and ultra-high performance liquid chromatography-tandem mass spectrometry and their association with oxidative stress.

Investigating pesticide exposure and oxidative stress in preschool children is essential for elucidating the determinants of environmental health in early life, with human biomonitoring of urinary pesticide metabolites serving as a critical strategy for achieving this objective. This study demonstrated biomonitoring of 2 phenoxyacetic acid herbicides, 2 organophosphorus pesticide metabolites, and 4 pyrethroid pesticide metabolites in 159 preschool children and evaluated their association with oxidative stress biomarker 8-hydroxydeoxyguanosine. An enzymatic deconjugation process was used to release urinary pesticide metabolites, which were then extracted and enriched by supported liquid extraction, and quantified by ultra-high performance liquid chromatography-tandem mass spectrometry with internal standard calibration. Dichloromethane: methyl tert­butyl ether (1:1, v/v) was optimized as the solvent for supported liquid extraction, and we validated the method for linear range, recovery, matrix effect and method detection limit. Method detection limit of the pesticide metabolites ranged from 0.01 µg/L to 0.04 µg/L, with satisfactory recoveries ranging from 70.5 % to 95.5 %. 2,4,5-Trichlorophenoxyacetic acid was not detected, whereas the other seven pesticide metabolites were detected with frequencies ranging from 10.1 % to 100 %. The concentration of urinary pesticide metabolites did not significantly differ between boys and girls, with the median concentrations being 9.39 µg/L for boys and 4.90 µg/L for girls, respectively. Spearman correlation analysis indicated that significant positive correlations among urinary metabolites. Bayesian kernel machine regression revealed a significant positive association between urinary pesticide metabolites and 8-hydroxydeoxyguanosine. Para-nitrophenol was the pesticide metabolite that contributed significantly to the elevated level of oxidative stress.

Association of co-exposure to polycyclic aromatic hydrocarbons and phthalates with oxidative stress and inflammation.

Exposure to multiple environmental pollutants is ubiquitous and inevitable, but studies investigating their exposure effects on oxidative stress or inflammation have mainly been restricted to single-pollutant models. This study investigated the association of co-exposure to polycyclic aromatic hydrocarbons and phthalates with oxidative stress and inflammation. Using a cross-sectional study in adults, we measured urinary concentrations of metabolites of polycyclic aromatic hydrocarbons (OH-PAHs) and phthalates (mPAEs), urinary oxidative stress biomarker 8-hydroxy-2'-deoxyguanosine, and 9 inflammatory biomarkers in paired blood samples. The associations of urinary OH-PAHs and mPAEs with oxidative stress and inflammation biomarkers were evaluated by different statistical models. The Bayesian kernel machine regression and quantile g-computation was used to examine the joint effects, and increased levels of urinary concentrations of OH-PAHs and mPAEs were associated with elevated 8-hydroxy-2'-deoxyguanosine level and white blood cell counts. Exposure to polycyclic aromatic hydrocarbons contributed more significantly to inflammation, while exposure to phthalates contributed more to oxidative stress. Monoisobutyl phthalate was identified as the most significant metabolite contributing to elevated oxidative stress levels. 1-Hydroxypyrene was negatively associated with platelet, and monomethyl phthalate was significantly positively associated with interleukin 6 in multivariate linear regression. The restricted cubic spline analysis revealed non-linear patterns of 3-hydroxyfluorene with white blood cell, lymphocyte, neutrophil, and C-reactive protein. The results indicated significant associations between increased co-exposure to polycyclic aromatic hydrocarbons and phthalates with elevated oxidative stress and inflammation. Further investigation is needed to elucidate the underlying biological mechanisms and to determine the potential public health implications.

Association between polycyclic aromatic hydrocarbon exposure and blood lipid levels: the indirect effects of inflammation and oxidative stress.

Although previous studies have indicated polycyclic aromatic hydrocarbons (PAHs) as cardiovascular health risk factors, evidence linking exposure to PAHs and blood lipids is still lacking, and the mechanism remains largely unknown. In this study, we evaluated the association between human internal exposure to PAHs and blood lipid levels in adults, as well as the indirect effects of inflammation and oxidative stress. The internal exposure of PAHs was assessed by determining serum PAHs and their hydroxylated metabolites (OH-PAHs) in the paired urine samples. Multivariable linear regression results demonstrated significant positive associations of individual PAHs and OH-PAHs with blood lipid biomarkers. The Bayesian kernel machine regression model revealed positive joint effects of PAH internal exposure on the fasting blood glucose, low-density lipoprotein cholesterol, total cholesterol, and total triglyceride, as well as an increased ratio of apolipoprotein B to apolipoprotein A1. In evaluating individual effects, serum phenanthrene played the most significant role in the association of increased PAH exposure with elevated fasting blood glucose. Quantile g-computation demonstrated the significant change in the levels of apolipoprotein B, ratio of apolipoprotein B to apolipoprotein A1, low-density lipoprotein cholesterol, and total cholesterol per quartile increase in PAH internal exposure. The restricted cubic spline analysis demonstrated the non-linear relationship between individual PAHs and OH-PAHs on blood lipid biomarkers. The mediation analysis indicated that PAH exposure may affect blood lipids not directly, but rather indirectly through intermediate inflammation and oxidative stress. The results demonstrated a significant association between increased PAH exposure levels and elevated blood lipids, highlighting the indirect effects of inflammation and oxidative stress.

Preparation of cationic hierarchical porous covalent organic frameworks for rapid and effective enrichment of perfluorinated substances in dairy products.

Perfluorinated substances (PFASs) are harmful pollutants that have environmental persistence and high bioaccumulation. Effective sample pretreatment must be performed to detect trace or even ultra-trace PFASs in actual samples because of their extremely low contents in complex samples. In this study, a cationic hierarchical porous covalent organic frameworks (C-H-COF) were customized via a template-assisted strategy using polystyrene spheres (PS) as sacrificial materials and a post-synthetic modification method. C-H-COF showed good adsorption selectivity for PFASs owing to the dual effects of the full utilization of the internal adsorption sites and electrostatic interaction. The key role of electrostatic attraction in the extraction of PFASs using C-H-COF was further proven by density functional theory (DFT) calculations. The maximum adsorption capacity of the C-H-COF for perfluorooctanoic acid (PFOA) was 400 mg·g⁻1, which was superior to that of microporous COFs (M-COF) and hierarchical porous COFs without cationic functionalization (H-COF). Accordingly, an analytical method for sensitively detecting five PFASs was established by employing C-H-COF as a dispersive solid phase extraction (DSPE) adsorbent combined with ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), and the limits of detection were 0.011‒0.29 ng·L⁻1. Moreover, the hierarchical porous structure of the C-H-COF accelerated the mass transfer of analytes so that the extraction process could be completed within 10 min. This method was employed to analyze PFASs in dairy products, in which the ultra-trace levels of analytes were quickly determined with spiked recoveries of 80.1‒112.6%. This work not only provides a rational synthetic strategy for novel ionic hierarchical porous COFs but also helps to expand the application of COFs in sample pretreatment.

Community evidence of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) transmission through air.

BACKGROUND: Nine COVID-19 (Corona Virus Disease, 2019) cases were observed in one community in Guangzhou. All the cases lived in three vertically aligned units of one building sharing the same piping system, which provided one unique opportunity to examine the transmission mode of SARS-CoV-2. METHODS: We interviewed the cases on the history of travelling and close contact with the index patients. Respiratory samples from all the cases were collected for viral phylogenetic analyses. A simulation experiment in the building and a parallel control experiment in a similar building were then conducted to investigate the possibility of transmission through air. RESULTS: Index patients living in Apartment 15-b had a travelling history in Wuhan, and four cases who lived in Apartment 25-b and 27-b were subsequently diagnosed. Phylogenetic analyses showed that virus of all the patients were from the same strain of the virus. No close contacts between the index cases and other families indicated that the transmission might not occur through droplet and close contacts. Airflow detection and simulation experiment revealed that flushing the toilets could increase the speed of airflow in the pipes and transmitted the airflow from Apartment 15-b to 25-b and 27-b. Reduced exhaust flow rates in the infected building might have contributed to the outbreak. CONCLUSIONS: The outbreak of COVID-19 in this community could be largely explained by the transmission through air, and future efforts to prevent the infection should take the possibility of transmission through air into consideration. A disconnected drain pipe and exhaust pipe for toilet should be considered in the architectural design to help prevent possible virus spreading through the air.

Ultra-high performance liquid chromatography tandem mass spectrometry for the determination of five glycopeptide antibiotics in food and biological samples using solid-phase extraction.

This paper demonstrated the development and validation of an ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) method for simultaneous determination of five glycopeptide antibiotics in food and biological samples. The target glycopeptide antibiotics were isolated from the samples by solvent extraction, and the extracts were cleaned with a tandem solid-phase extraction step using mixed strong cation exchange and hydrophilic/lipophilic balance cartridges. Subsequently, the analytes were eluted with different solvents, and then quantified by UHPLC-MS/MS in the positive ionization mode with multiple reaction monitoring. Under optimal conditions, good linear correlations were obtained for the five glycopeptide antibiotics in the concentration range of 1.0 µg/L to 20.0 µg/L, and with linear correlation coefficients >0.998. Employing this method, the target glycopeptide antibiotics in food and biological samples were identified with a recovery of 83.0-102%, and a low quantitation limit of 1.0 µg/kg in food and 2.0 µg/L in biological samples with low matrix effects.

Determination of 19 sulfonamides residues in pork samples by combining QuEChERS with dispersive liquid-liquid microextraction followed by UHPLC-MS/MS.

A new simple and rapid pretreatment method for simultaneous determination of 19 sulfonamides in pork samples was developed through combining the QuEChERS method with dispersive liquid-liquid microextraction followed by ultra-high performance liquid chromatography with tandem mass spectrometry. The sample preparation involves extraction/partitioning with QuEChERS method followed by dispersive liquid-liquid microextraction using tetrachloroethane as extractive solvent and the acetonitrile extract as dispersive solvent that obtained by QuEChERS. The enriched tetrachloroethane organic phase by dispersive liquid-liquid microextraction was evaporated, reconstituted with 100 µL acetonitrile/water (1:9 v/v) and injected into an ultra-high performance liquid chromatography with a mobile phase composed of acetonitrile and 0.1% v/v formic acid under gradient elution and separated using a BHE C18 column. Various parameters affecting the extraction efficiency were investigated. Matrix-matched calibration curves were established. Good linear relationships were obtained for all analytes in a range of 2.0-100 µg/kg and the limits of detection were 0.04-0.49 µg/kg. Average recoveries at three spiking levels were in the range of 78.3-106.1% with relative standard deviations less than 12.7% (n = 6). The developed method was successfully applied to determine sulfonamide residues in pork samples.

Antibody-free ultra-high performance liquid chromatography/tandem mass spectrometry measurement of angiotensin I and II using magnetic epitope-imprinted polymers.

The major challenges in measuring plasma renin activity (PRA) stem from the complexity of biological matrix, as well as from the instability and low circulating concentration of angiotensin. In this study, an ultra-high performance liquid chromatography/tandem mass spectrometry (UPLC-MS/MS) based technique has been developed for the measurement of angiotensin using magnetically imprinted polymers for simultaneous enrichment of the precursor peptide angiotensin II (Ang II) and the upstream peptide precursor angiotensin I (Ang I). This technique involved surface graft imprinting in aqueous solutions using vinyl-modified nano-iron oxide as solid supports, the specificity determinant of Ang I and Ang II as the epitope, and methacrylic acid and N-t-butylacrylamide as functional monomers. The vinyl-modified nano-iron oxide acted as a magnetic separation media, and the molecularly imprinted shell provided analyte selectivity for the recognition of Ang I and Ang II. Selective enrichment of Ang I and Ang II was accomplished by the magnetically imprinted polymers, followed by a magnetic separation procedure and subsequent quantification by UPLC-MS/MS in the positive ionization mode with multiple reaction monitoring. Through the latter protocol, a low limit of detection could be realized, viz. 0.07ng/mL and 0.06ng/mL for Ang I and II, respectively, which was thoroughly validated for accuracy and reproducibility through analyzing Ang I and Ang II in human plasma samples.

Development of hybrid organic-inorganic surface imprinted Mn-doped ZnS QDs and their application as a sensing material for target proteins.

Applying molecular imprinting techniques to the surface of functionalized quantum dots (QDs) allows the preparation of molecularly imprinted polymers (MIPs) with accessible, surface exposed binding sites and excellent optical properties. This paper demonstrates a new strategy for producing such hybrid organic-inorganic imprinted Mn-doped ZnS QDs for specific recognition of bovine hemoglobin. The technique provides surface grafting imprinting in aqueous solutions using amino modified Mn-doped ZnS QDs as supports, acrylamide and methacrylic acid as functional monomers, γ-methacryloxypropyl trimethoxy silane as the grafting agent, and bovine hemoglobin as a template. The amino propyl functional monomer layer directs the selective occurrence of imprinting polymerization at the QDs surface through copolymerization of grafting agents with functional monomers, but also acts as an assistive monomer to drive the template into the formed polymer shells to create effective recognition sites. Using MIP-QDs composites as a fluorescence sensing material, trace amounts of bovine hemoglobin are signaled with high selectivity by emission intensity changes of Mn-doped ZnS QDs, which is embedded into the imprinted polymers.

Determination of 23 organophosphorous pesticides in surface water using SPME followed by GC-MS.

Determination of 23 organophosphorous pesticides (sulfotep, phorate, demeton, diazinon, disulfoton, kitazzin.P, chlorpyrifos-methyl, methyl-parathion, ronnel, fenitrothion, malathion, chlorpyrifos, fenthion, parathion, bromophos, isofenphos-methyl, phenthoate, quinalphos, ethion, triazophos, carbophenothion, pirimiphos-methyl, and pirimiphos-ethyl) in water using solid-phase microextraction (SPME) with gas chromatography-mass spectrometry detection (GC-MS) was investigated. The influence of various parameters on pesticides extraction efficiency by SPME was thoroughly studied. For quantitation in the selective ion monitoring (SIM) mode, the linear range of most compounds was found to be between 0.05-10 microg/L, and the detection limits were between 0.7-50 ng/L. To validate matrix effects for surface water, the recoveries were calculated between 71-104%. SPME in combination with GC-MS is a sensitive and effective method for the determination of organophosphorous pesticides (OPPs) in water samples.

[Lead levels in children after 10-year use of unleaded gasoline in Guangzhou municipality].

OBJECTIVE: To investigate the blood lead levels (BLLs) in children after 10-year use of unleaded gasoline in Guangzhou and evaluate the effect of this measure. METHODS: Through stratified random sampling method, 4 kindergartens and 4 elementary schools were selected from each of three districts among 12 districts of Guangzhou. Totally 2373 children were recruited into this survey and 1-2 ml blood was sampled from each child through vein. The lead concentration in blood samples was determined with Inductively Coupled Plasma Mass Spectrometry (ICP-MS) after diluted with 0.1% Triton X-100 and 0.1% HNO(3) in the ratio of 1:20. RESULTS: Among 2373 children, the highest BLL was 330 microg/L, while the lowest was 10 microg/L. Geometric mean (GM) of BLL was 58.28 microg/L with 61.11 microg/L of male and 55.37 microg/L of female (t=8.671, P=0.000). Sixty (2.51%) children were identified as elevated BLLs (>or=100 microg/L), including 36 (2.90%) male and 24 (2.09%) female (chi2=1.594, P=0.207). Compared to the surveys conducted in China 10-year ago, the children with elevated BLLs decreased 96.28% and the GM of BLLs reduced 58.37%. BLLs in suburb children (60.33 microg/L) were higher than those in downtown (58.09 microg/L) or in countryside (56.72 microg/L). CONCLUSION: The BLLs in children and the ratio for children with elevated BLLs, had declined dramatically after 10-year implement of unleaded gasoline in Guangzhou.

[Application of AOTF in spectral analysis. 4. Enhancing spectral resolution of AOTF atomic emission spectrometer with FSD].

Using Fourier self-deconvolution (FSD) to enhance spectral resolution of AOTF atomic emission spectrometer is described. Choosing the appropriate deconvolution parameters: full width at half maximum (FWHM) and breaking point, the FWHM of the simulated overlapping peaks could be decreased by a factor of 3.5, and the peak height by a factor of 5, but retaining the peak position. Practical samples of La and Ca-Al mixture were scanned by AOTF-ICP-AES respectively, the overlapping spectra of La 407.735 nm and La 408.672 nm as well as Ca 393.366 nm and Al 394.401 nm were well resolved into their respective lines after FSD; as to sample of Eu-Sr mixture and Sc-Sr mixture, after FSD treatment, the overlapping spectra of Eu 420.505 nm and Sr 421.552 nm as well as Sc 424.693 nm and Sr 421.552 nm at various concentration of Eu and Sc respectively were also well resolved into their respective lines. The slopes of their corresponding calibration curves were increased by a factor of 2 to 3.

[Application of AOTF in spectral analysis. 3. Application of AOTF in atomic emission spectral analysis].

An atomic emission spectrometer based on acousto-optic tunable filter (AOTF) was self-constructed and was used to evaluate its practical use in atomic emission analysis. The AOTF used was of model TEAF5-0.36-0.52-S (Brimrose, USA) and the frequency of the direct digital RF synthesizer ranges from 100 MHz to 200 MHz. ICP and PMT were used as light source and detector respectively. The software, written in Visual C++ and running on the Windows 98 platform, is of an utility program system having two data banks and multiwindows. The wavelength calibration was performed with 14 emission lines of Ca, Y, Li, Eu, Sr and Ba using a tenth-order polynomial for line fitting method. The absolute error of the peak position was less than 0.1 nm, and the peak deviation was only 0.04 nm as the PMT varied from 337.5 V to 412.5 V. The scanning emission spectra and the calibration curves of Ba, Y, Eu, Sc and Sr are presented. Their average correlation coefficient was 0.9991 and their detection limits were in the range of 0.051 to 0.97 micrograms.mL-1 respectively. The detection limit can be improved under optimized operating conditions. However, the spectral resolution is only 2.1 nm at the wavelength of 488 nm. Evidently, this poor spectral resolution would restrict the application of AOTF in atomic emission spectral analysis, unless an enhancing techniques is integrated in it.

[Application of AOTF in spectral analysis. 1. Hardware and software designs for the self-constructed visible AOTF spectrophotometer].

A self-constructed visible spectrophotometer using an acousto-optic tunable filter(AOTF) as a dispersing element is described. Two different AOTFs (one from The Institute for Silicate (Shanghai, China) and the other from Brimrose(USA)) are tested. The software written with visual C++ and operated on a Window98 platform is an applied program with dual database and multi-windows. Four independent windows, namely scanning, quantitative, calibration and result are incorporated. The Fourier self-deconvolution algorithm is also incorporated to improve the spectral resolution. The wavelengths are calibrated using the polynomial curve fitting method. The spectra and calibration curves of soluble aniline blue and phenol red are presented to show the feasibility of the constructed spectrophotometer.

[Application of AOTF in spectral analysis. 2. Application of self-constructed visible AOTF spectrophotometer].

The performances of a self-constructed visible AOTF spectrophotometer are presented. The wavelength calibration of AOTF1 and AOTF2 are performed with a didymium glass using a fourth-order polynomial curve fitting method. The absolute error of the peak position is usually less than 0.7 nm. Compared with the commercial UV1100 spectrophotometer, the scanning speed of the AOTF spectrophotometer is much more faster, but the resolution depends on the quality of AOTF. The absorption spectra and the calibration curves of copper sulfate and alizarin red obtained with AOTF1(Institute for Silicate, Shanghai China) and AOTF2 (Brimrose U.S.A) respectively are presented. Their corresponding correlation coefficients of the calibration curves are 0.9991 and 0.9990 respectively. Preliminary results show that the self-constructed AOTF spectrophotometer is feasible.