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.

Probabilistic risk assessment of dietary exposure to lead in residents of Guangzhou, China.

Lead and its compounds can have cumulative harmful effects on the nervous, cardiovascular, and other systems, and especially affect the brain development of children. We collected 4918 samples from 15 food categories in 11 districts of Guangzhou, China, from 2017 to 2022, to investigate the extent of lead contamination in commercial foods and assess the health risk from dietary lead intake of the residents. Lead was measured in the samples using inductively coupled plasma mass spectrometry. Dietary exposure to lead was calculated based on the food consumption survey of Guangzhou residents in 2011, and the health risk of the population was evaluated using the margin of exposure (MOE) method. Lead was detected in 76.5% of the overall samples, with an average lead content of 29.4 µg kg-1. The highest lead level was found in bivalves. The mean daily dietary lead intakes were as follows: 0.44, 0.34, 0.25, and 0.28 µg kg-1 body weight (bw) day-1 for groups aged 3-6, 7-17, 18-59, and ≥ 60 years, respectively. Rice and rice products, leafy vegetables, and wheat flour and wheat products were identified as the primary sources of dietary lead exposure, accounting for 73.1%. The MOE values demonstrated the following tendency: younger age groups had lower MOEs, and 95% confidence ranges for the groups aged 3-6 and 7-17 began at 0.6 and 0.7, respectively, indicating the potential health risk of children, while those for other age groups were all above 1.0. Continued efforts are needed to reduce dietary lead exposure in Guangzhou.

Humoral immunosuppression of exposure to polycyclic aromatic hydrocarbons and the roles of oxidative stress and inflammation.

Previous studies have indicated adverse health effects of exposure to polycyclic aromatic hydrocarbons (PAHs), but evidence on the association between PAH exposure and immunity is scarce and its underlying mechanism is largely unknown. This study assessed human exposure to PAHs by determining the concentrations of PAHs in serum and their metabolites in paired urine. The oxidative stress and inflammation levels were evaluated by urinary DNA damage biomarker 8-hydroxydeoxyguanosine, white blood cell counts and C-reaction protein. We investigated the relationship between PAH exposure and seven immunological components, and explored the indirect roles of oxidative stress and inflammation by mediation and moderation analysis. Multivariate regression analysis revealed that 1-hydroxynaphthalene and 2-hydroxyfluorene were negatively associated with immunoglobulin A, and 3-hydroxyphenanthrene was negatively correlated with complement component 3. Restricted cubic spline analysis demonstrated nonlinear relationships between some individual PAHs or their metabolites with immunological components. Bayesian kernel machine regression and quantile g-computation revealed significant associations of higher PAH exposure with decreased immunoglobulin G and kappa light chain levels. Phenanthrene was the compound that contributed the most to reduced immunoglobulin G. Mediation analysis demonstrated significant indirect effects of 8-hydroxydeoxyguanosine and white blood cell counts on the association between higher PAH exposure and decreased immunological components. Moderation analysis revealed that PAH exposure and decreased immunological components are significantly associated with higher levels of C-reaction protein and white blood cell counts. The results demonstrated significant immunosuppression of PAH exposure and highlighted the indirect roles of oxidative stress and inflammation. Interventions to reduce systemic inflammation may mitigate the adverse immune effects of PAH exposure.

Association between polycyclic aromatic hydrocarbon exposure and liver function: The mediating roles of inflammation and oxidative stress.

Polycyclic aromatic hydrocarbon (PAH) exposure has been associated with adverse health effects, and accumulating evidence suggests that PAH exposure may impair liver function. However, the underlying mechanisms linking PAH exposure and liver function impairment remain unclear. This study aimed to explore the association between PAH exposure and liver function biomarkers, and the mediating effects of inflammation and oxidative stress. The cross-sectional study included 155 adults and their urinary PAH metabolites (OH-PAHs) were determined, and eight liver function biomarkers were measured in paired serum samples. A comprehensive statistical analysis investigated the linear, non-linear, individual, and joint effects of the association between urinary OH-PAHs and liver function biomarkers. The results indicated significant positive associations between urinary OH-PAH concentrations and liver function biomarker levels, suggesting that PAH exposure may adversely affect liver function. 2-hydroxyfluorene was identified as the individual metabolite contributing significantly to elevated gamma-glutamyl transferase levels. Further stratification by gender revealed that this association is more pronounced in males. Moreover, we observed significant mediation effects of the oxidative stress biomarker 8-hydroxy-2'-deoxyguanosine and the inflammatory biomarkers C-reactive protein and white blood cell count on this association. The physiological responses triggered by PAH exposure are mediated by inflammation, which serves as a link between oxidative stress, cellular injury, and elevated liver enzyme levels. The results demonstrated that increased inflammation and oxidative stress mediated the association between increased urinary OH-PAHs and elevated liver function biomarkers. The results contribute to a better understanding of the potential mechanisms underlying PAH exposure's hepatotoxic effects.

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.

METTL3-mediated m6A mRNA modification was involved in cadmium-induced liver injury.

Cadmium is an environmental pollutant that has extensive deleterious effects. However, the mechanisms underlying the hepatotoxicity induced by long-term exposure to cadmium remained undefined. In the present study, we explored the role of m6A methylation in the development of cadmium-induced liver disease. We showed a dynamic change of RNA methylation in liver tissue from mice administrated with cadmium chloride (CdCl2) for 3, 6 and 9 months, respectively. Particularly, the METTL3 expression was declined in a time-dependent manner, associated with the degree of liver injury, indicating the involvement of METTL3 in hepatotoxicity induced by CdCl2. Moreover, we established a mouse model with liver-specific over-expression of Mettl3 and administrated these mice with CdCl2 for 6 months. Notably, METTL3 highly expressed in hepatocytes attenuated CdCl2-induced steatosis and liver fibrosis in mice. In vitro assay also showed METTL3 overexpression ameliorated the CdCl2-induced cytotoxicity and activation of primary hepatic stellate cells. Furthermore, transcriptome analysis identified 268 differentially expressed genes both in mice liver tissue treated with CdCl2 for 3 months and 9 months. Among them, 115 genes were predicted to be regulated by METTL3 determined by m6A2Target database. Further analysis revealed the perturbation of metabolic pathway, glycerophospholipid metabolism, ErbB signaling pathway, Hippo signaling pathway, and choline metabolism in cancer, and circadian rhythm, led to hepatotoxicity induced by CdCl2. Collectively, our findings reveal new insight into the crucial role of epigenetic modifications in hepatic diseases caused by long-term exposure to cadmium.

Association of polycyclic aromatic hydrocarbon internal exposure and urinary iodine concentration with thyroid volume in children.

Thyroid volume was proposed as a factor for malignancy in evaluating thyroid nodules. Previous studies have demonstrated the endocrine disrupting effect of polycyclic aromatic hydrocarbons (PAHs), but studies on the association between internal exposure of PAHs and thyroid volume are still scarce. In this work, we evaluated the association of polycyclic aromatic hydrocarbon internal exposure and urinary iodine concentration with thyroid volume in 590 school-age children without thyroid disease in Guangzhou, China. Urinary hydroxylated polycyclic aromatic hydrocarbons (OH-PAHs), urinary iodine concentrations, and thyroid volumes were measured. The mean concentrations of urinary iodine and ΣOH-PAHs were 271.1 µg/L and 3.27 µg/L, respectively, and the mean thyroid volume was 2.4 mL. The associations of urinary iodine and OH-PAH concentrations with thyroid volume were investigated by multivariable linear regression and the Bayesian kernel machine regression models. Urinary ΣOH-PAHs were observed to be significantly positively associated with thyroid volume in multivariable linear regression models. The increase in each unit in the log-transformed concentration of ΣOH-PAHs caused 3.88% change in thyroid volume. The Bayesian kernel machine regression model demonstrated a positive joint effect of increased urinary ΣOH-PAHs on thyroid volume. Moreover, urinary ΣOH-PAHs were statistically significant linked to urinary iodine, and iodine mediated the relationship between urinary OH-PAHs and thyroid volume with the mediated proportions of 15.2.

Probabilistic risk assessment of dietary exposure to pentachlorophenol in Guangzhou, China.

Pentachlorophenol (PCP) is a ubiquitous environmental contaminant commonly existing as its sodium salt (NaPCP), which enters the human body primarily through long term but low-level dietary exposure. PCP contributes to chemical carcinogenesis and teratogenesis. In this study, the probabilistic risk of dietary exposure to PCP in Guangzhou citizens was investigated. In total, 923 food samples in the categories of pork, livestock (beef and lamb), poultry, offal, eggs, and freshwater fish (considered to be relatively susceptible to PCP contamination) were collected from various markets in Guangzhou and tested for PCP. Probabilistic risk assessment model calculations for PCP dietary exposure and margin of exposure (MOE) values were performed using @RISK software, based on a Monte Carlo simulation with 10,000 iterations. The overall detection rate of PCP (above 1 µg kg-1, the detection limit) was 19.9% (184/923), with an average of 7.9 µg kg-1. The highest rate of PCP detection, 28.2%, was in livestock (beef and lamb). The MOE value for dietary PCP exposure in general Guangzhou residents averaged 400, which was far below 5,000 (the borderline for judging a health risk). The lowest MOE value, 190, was observed in the 3- to-6-year old population and indicates a significant risk. In conclusion, this study suggests that PCP exposure in Guangzhou residents is of considerable health risk, especially for the pre-school young children.

Supported liquid extraction and ultra-high performance liquid chromatography-tandem mass spectrometry for the determination of urinary polycyclic aromatic hydrocarbon metabolites and their application for human biomonitoring.

Polycyclic aromatic hydrocarbons (PAHs) are a class of highly lipophilic and ubiquitous, persistent organic pollutants with carcinogenic and mutagenic toxicities. They are a great public health concern, and avoiding exposure to them is a high priority. Human biomonitoring is critical for the evaluation of exposure levels to PAHs by the general population. In this work, we demonstrated the biomonitoring of eleven hydroxylated PAHs (OHPAHs) in urine samples from 226 volunteers from Guangzhou, and evaluated the health risks. The urinary PAH metabolites were released by enzymatic deconjugation, separated, and enriched by supported liquid extraction, and then quantified by ultra-high performance liquid chromatography-tandem mass spectrometry. The limit of quantification of the individual OHPAHs ranged from 10 ng/L to 40 ng/L, and satisfactory recoveries were obtained, ranging from 92.6% to 97.6%. The detection frequencies of the OHPAHs were 100%, and naphthalene metabolites were found at the highest concentrations with a geometric mean of 8.61 µg/L. The mean total OHPAH level in the urine samples of males (13.2 µg/L) was significantly higher than that of females (5.84 µg/L). Pearson correlation analyses indicated significant and positive correlations among urinary OHPAHs. The total estimated daily intake of PAHs was calculated, and a low health risk was obtained by evaluating their hazard quotients and hazard indexes.

One Health responses to prevent the occurrence of rabies due to attacks by a rabid stray dog.

BACKGROUND: The number of human rabies cases caused by pet dogs in Guangzhou has been decreasing after years of comprehensive interventions. Consequently, attacks by stray dogs become a major issue in rabies control. OBJECTIVES: To share our experience of successfully dealing with rabies to provide some inspiration for prevention and control in countries and regions affected by it. METHODS: A multidisciplinary One Health response was initiated to control this outbreak. Rabies virus was detected by PCR in the brain tissue of the associated stray dog. The sequences were aligned with reference sequences downloaded from GenBank using ClustalX. The maximum likelihood method implemented in MEGA 5.0 software package was used in a phylogenetic analysis of the aligned sequences. RESULTS: Twelve patients with exposure to the stray dog were identified in the field investigation. Rabies vaccines and immunoglobulin were administered to all patients within 48 h. After 1 year of follow-up, no exposed patients showed symptoms. Maximum likelihood analysis of the nucleotide sequences obtained from the PCR products indicated that the rabies virus in the dog was closely related to isolates from neighbouring provinces of Guangdong as well as those from surrounding countries of China. CONCLUSIONS: Multidisciplinary One Health intervention is effective not only in the control of rabies but also in rapid emergency responses to attacks by rabid stray dogs.

Dietary risk assessment of neonicotinoid pesticide in 21 kinds of market-sold vegetables in Guangzhou City / 预防医学

Objective@#To evaluate the dietary risk of neonicotinoid insecticides in market-sold vegetables in Guangzhou City, so as to provide insights into ensuring food safety for residents.@*Methods@#Forty-five samples of 21 kinds of vegetables were collected from supermarkets and farmer's markets in Guangzhou City from June to September in 2022, and 10 kinds of neonicotinoid insecticides were determined using liquid chromatography-mass spectrometry (LC-MS). The vegetable consumption was obtained through the survey of food consumption and nutrients intake of residents in Guangzhou City. The dietary risk was evaluated by calculating daily exposure and non-carcinogenic risk quotients of neonicotinoid insecticides. @*Results@#A total of 27 samples of vegetables were detected with neonicotinoid insecticides, and the detection rate was 60.00%. Among 10 kinds of neonicotinoid insecticides, 6 kinds were identified, including clothianidin, thiamethoxam, imidacloprid, acetamiprid, dinotefuranand and nitenpyram. The detection rates of clothianidin, thiamethoxam and imidacloprid were relatively high (26.67%, 11.11% and 6.67%), and some samples exceeded the standard, with the rate of 4.44%, 2.22% and 2.22%, respectively. The total exposure of neonicotinoid pesticides (IMIRPF) was 3 053.00 ng/g, and the contents and IMIRPF of imidacloprid were the highest in roots and tubers. The daily exposure of imidacloprid, acetamiprid, dinotefuran, clothianidin, thiamethoxam and nitenpyram was 34.58, 3.85, 1.20, 6.87, 7.19 and 0.86 ng/(kg·d). Non-carcinogenic risk quotients of imidacloprid, acetamiprid, dinotefuran, clothianidin, thiamethoxam and nitenpyram was 5.76×10-4, 0.55×10-4, 0.06×10-4, 0.69×10-4, 0.90×10-4 and 0.02×10-4, respectively, which was lower than 1; and the sum of non-carcinogenic risk quotients was 7.98×10-4, which was lower than 1. @*Conclusions@#The dietary risk of neonicotinoid pesticides is low in 21 kinds of market-sold vegetables in Guangzhou City; however, the contents of neonicotinoid insecticides in some vegetable samples exceed the standard. The supervision of vegetable markets should be strengthened.

Probabilistic Risk Assessment of Dietary Exposure to Cadmium in Residents of Guangzhou, China-Young Children Potentially at a Health Risk.

Cadmium (Cd) and its compounds are hazardous environmental pollutants with renal toxicity and human carcinogenicity, with ingestion of contaminated foods representing the major mode of exposure. There have been a number of reports evaluating the Cd content in various foods; however, regarding the actual risk posed by dietary cadmium exposure, only a few reports are available in which single point evaluation (less accurate than multiple point evaluation) was employed. In this study, we used a margin of exposure (MOE) model and @RISK software (for multiple evaluation) to evaluate Cd-related health risk in the local Guangzhou residents at varying ages, through a comparison between the estimated monthly exposures and the provisional tolerable monthly intake (0.025 mg/kg body weight (b.w.)), based on the Cd contents in various food categories available locally (a total of 3964 food samples were collected from each of the 13 districts of Guangzhou between 2015 and 2019), which were determined by using inductively coupled plasma mass spectrometry. In this study, Cd was detected in 69.6% of the samples (averaged 0.120 mg/kg), and rice and its products, leafy vegetables, bivalves, and shrimp and crabs contributed most to Cd exposure (8.63, 3.18, 2.79, and 1.48 ng/kg b.w./day, respectively). The MOE values demonstrated the following tendency: the younger age group, the lower MOE, and its 95% confidence range for the (youngest) 3~6 year old group started from 0.92, indicating a health risk of young children, while that for the other age groups were all above 1.0. Our preliminary findings warrant further clarification using biomarker assays in the relevant population.

Identification of miRNAs involved in liver injury induced by chronic exposure to cadmium.

To elaborate the molecular mechanism underlying the hepatotoxicity induced by chronic exposure to cadmium (Cd), a mouse model with hepatocyte-specific deletion of Ppp2r1a (encoding protein phosphatase 2 A Aα subunit, PP2A Aα) gene was used to investigate the effect of cadmium exposure on liver injury. The wild type littermates (WT) and PP2A Aα-/- mice (KO) were treated with cadmium chloride (CdCl2) at concentrations of 0 mg/L, 10 mg/L, 100 mg/L in drinking water for 3, 6 and 9 months (KO mice only for 9 months), respectively. The pathological findings were characterized by progressive inflammation, steatosis, and liver fibrosis upon treatment of CdCl2 in a dose-response and time-dependent manner. Notably, PP2A Aα depletion leads to a more profound liver injury induced by CdCl2 treatment. The transcriptome analysis in livers of KO mice revealed 20 differentially expressed microRNAs (miRNAs) appeared in both 3- and 9-month. Particularly, the alterations of miR-34a-5p, miR-345-5p, and miR-30e-5p expressions were implicated in the development of liver disease and correlated with the degree of liver injury induced by cadmium treatment. Further analysis indicated that miR-34a-5p, miR-345-5p, and miR-30e-5p might be involved in CdCl2-induced liver injury, in part by dysregulation of lipid metabolism and inflammation. The in vitro studies showed that miR-34a-5p was involved in regulation of CdCl2-induced cytotoxicity through directly targeted adiponectin receptor 2 (AdipoR2) mRNA. Taken together, we identified that specific miRNAs were implicated in hepatotoxicity induced by chronic exposure to CdCl2. These findings also provide new insight into the role of PP2A in regulation of miRNAs-mediated liver injury.

Tissue-specific accumulation, transformation, and depuration of fipronil in adult crucian carp (Carassius auratus).

Accumulation and biotransformation of pesticides in fish tissues are essential to assess their toxicity and associated human exposure risk. The mechanisms on time-dependent and tissue-specific accumulation and transformation of fipronil in adult fish are limited. An experiment consisting of 25-d uptake of fipronil at two levels (10 and 50 µg/L) and 25-d depuration in adult crucian carp (Carassius auratus) was conducted. Fipronil concentration at 25-d exposure was tissue-specific with the order of liver > kidney > blood > muscle. The uptake rate constant of fipronil in the liver (low exposure group: 2.38 ± 0.27 L/kg/d; high exposure group: 1.10 ± 0.11 L/kg/d) was significantly higher than that in other tissues (p < 0.05), and the lowest in muscle (low exposure group: 0.10 ± 0.01 L/kg/d; high exposure group: 0.16 ± 0.11 L/kg/d). The bioconcentration factors of fipronil in different tissues were 1.04-12.7 L/kg wet weight and 177-4268 L/kg lipid. The tissue-blood distribution coefficients of the liver and kidney were lower than 1 based on lipid normalized concentration but higher than 1 based on wet weight concentration, suggesting fipronil was dispersed into other tissues mainly via blood in the lipid-combination pattern. Fipronil sulfone had 1.2-32 times higher concentration and longer depuration time than fipronil, implying fipronil sulfone was more retender in fish bodies. The estimated daily intake of fipronil via fish muscle consumption at 25-d exposure was 8.5-101 and 27-320 ng/kg bw/d for adults and children, respectively. Overall, the human health risk of fipronil and its metabolites with consumption of the polluted fish cannot be negligible.

Glycosyl imprinted mesoporous microspheres for the determination of glycopeptide antibiotics using ultra-high performance liquid chromatography coupled with tandem mass spectrometry.

Glycopeptide antibiotics are critical weapons against serious Gram-positive resistant bacteria, and therefore the development of analytical methods for their determination is essential. In this work, with the aim of extending the scope of molecularly imprinted mesoporous materials to the recognition of large molecules such as proteins and peptides, we selected the glycosyl moiety of glycopeptide antibiotics as a template and synthesised a boronic acid functional monomer by click chemistry reaction to prepare glycosyl imprinted mesoporous microspheres. On the basis of boronate affinity, the template and the functional monomer formed a self-assembly structure that was incorporated into the silica framework during polymerisation. The removal of the glycosyl moiety created cavities with boronic acid groups covalently anchored to the pore walls of the glycosyl imprinted mesoporous microspheres. The resultant microspheres showed regular spherical shape, narrow size distribution and porous structure and exhibited high adsorption capability and fast adsorption kinetics. The size exclusion effect of the mesoporous structure prevents large molecules from entering the cavities, while the glycosyl imprinted cavities provide selectivity for glycopeptide antibiotics. The glycosyl imprinted mesoporous microspheres were employed to separate six glycopeptide antibiotics in serum samples, which were then determined using ultra-high performance liquid chromatography tandem mass spectrometry. The proposed method exhibited satisfactory linearity in the range of 0.1 to 20.0 µg/L, demonstrating great potential for the determination of glycopeptide antibiotics in serum samples.

Probabilistic Risk Assessment of Dietary Exposure to Chloramphenicol in Guangzhou, China.

Chloramphenicol has been used in veterinary medicine, where its residues can remain in food of animal origin, thus potentially causing adverse health effects. This facilitated the ban for its use in food-producing animals globally, but its residues have remained ubiquitous. In this study, food commodities possibly contaminated with chloramphenicol, including livestock meat, poultry, edible viscera, fish, shrimp and crab, molluscs, milk, and eggs, were collected from domestic retail shops in all the 11 districts of Guangzhou and tested for its residue. Probabilistic risk assessment model calculations for its dietary exposure, and the margin of exposure (displayed as mean values and 5th percentile to 95th percentile ranges) were performed by using @RISK software based on a Monte Carlo simulation with 10,000 iterations. The results indicated the detection of chloramphenicol in 248 out of 1454 samples (17.1%), which averaged to a level of 29.1 µg/kg. The highest average value was observed in molluscs (148.2 µg/kg, with the top value as 8196 µg/kg); meanwhile, based on the dietary structure of a typical Cantonese, pond fish, pork, and poultry meat contributed most (about 80%) to the residents' dietary exposure to chloramphenicol. The margin of exposure for dietary chloramphenicol exposure in Guangzhou residents was 2489, which was apparently below 5000 (the borderline for judging a health risk), particularly low in preschool children (2094, suggesting an increased risk). In conclusion, the study suggests that chloramphenicol exposure in Guangzhou residents is considerable, and its relevant health hazard, especially for preschool children, is worthy of further investigation.

Highly sensitive determination of amanita toxins in biological samples using ß-cyclodextrin collaborated molecularly imprinted polymers coupled with ultra-high performance liquid chromatography tandem mass spectrometry.

In this work, a ß-cyclodextrin functional vinyl monomer was synthesized and the common moiety of five amanita toxins was used as the template for preparing molecularly imprinted polymers (MIPs). Chemical calculation was used to evaluate and describe the binding interactions between the template and the functional monomer. The preparation conditions were optimized and the resultant MIPs were characterized and employed as solid-phase extraction (SPE) sorbents. The SPE conditions including the amount of sorbent, extraction solution, and eluting solution were also optimized for the enrichment of the five toxins. Using an ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS), detection limits ranging from 0.34-0.42 µg/L, 0.16-0.33 µg/L, and 0.035-0.056 µg/kg were achieved for the five toxins in serum, urine and liver samples, respectively. The proposed method was further applied to the determination of the amanita toxins in suspected samples and showed great potential in the diagnosis of mushroom poisoning.

Boronate affinity glycosyl molecularly imprinted polymer microspheres for the determination of teicoplanin using ultra-high performance liquid chromatography coupled with tandem mass spectrometry.

Inspired by the fact that antibody recognizes antigen's epitope rather than its whole structure, we selected the glycosyl moiety of teicoplanin as the template, 4-vinylphenylboronic acid and methyl methacrylate as the functional monomers, and divinylbenzene as the cross-linker to synthesis molecularly imprinted polymer microspheres via precipitation co-polymerization. The glycosyl-imprinted microspheres can selectively capture the target glycopeptide antibiotic in aqueous solutions when the pH of surrounding environment is 9.0, and the captured antibiotic can be reversibly released when the pH falls below 4.0 again. This pH-controlled catch-and-release mechanism permits entrapping of glycopeptide antibiotics in slightly basic environments and keeping them entrapped under neutral conditions, and eluting in acidic media. Five teicoplanin components were selectively captured by using the prepared glycosyl-imprinted microspheres as solid-phase extraction adsorbents, and then detected using ultra-high performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS). Finally, the method was thoroughly validated for accuracy and reproducibility by determining teicoplanin in food and biological samples, and achieving quantification limits of 0.1 µg/kg, 0.5 µg/L and 1.0 µg/L for milk, urine and plasma samples, respectively.

Microbiological Contamination of Strawberries from U-Pick Farms in Guangzhou, China.

This study quantified the association of rodent fruit damage and the microbiological quality of irrigation water on the risk of microbiological contamination of strawberries collected from 18 U-pick farms across five different districts in the Guangzhou metropolitan region of southern China. Fifty-four composite strawberries samples, with or without evidence of rodent or avian foraging damage (i.e., bitten), along with 16 irrigation water samples, were collected during the spring of 2014 and winter of 2015 from our cohort of 18 farms. Composite strawberry samples and irrigation water were analyzed for total coliforms, E. coli, Salmonella, E. coli O157, Giardia, and Cryptosporidium. Total coliforms and E. coli were detected in 100% and ~90% of irrigation water samples, respectively. In contrast, Cryptosporidium was detected in only two water samples, while Salmonella, E. coli O157, and Giardia were not detected in any water samples. Strawberries with signs of being bitten by wildlife had significantly higher concentrations of total coliforms and E. coli, compared to strawberries with no physical evidence of rodent damage (p < 0.001). Similarly, Cryptosporidium was detected in 7/18 (39%) of bitten, 4/18 (22%) of edge, and 5/18 (28%) of central strawberry samples, respectively. Concentration of E. coli on strawberries (p < 0.001), air temperature (p = 0.025), and presence of Cryptosporidium in irrigation water (p < 0.001) were all associated with the risk of Cryptosporidium contamination on strawberries. Salmonella and Giardia were detected in <4% strawberry samples and E. coli O157 was not detected in any samples. These results indicate the potential food safety and public health risks of consuming unwashed strawberries from U-pick farms, and the need for improved rodent biosecurity of U-pick strawberry fields and enhanced microbiological quality of irrigation water used at these facilities.

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.