Human exposure to a mixture of endocrine disruptors and serum levels of thyroid hormones: A cross-sectional study.

Exposure to endocrine disruptors (EDCs) could disrupt thyroid hormone homeostasis. However, human epidemiological studies reported inconsistent observations, and scarce information on the effect of a mixture of chemicals. The aim of the present study was to examine the associations of multiple chemicals with thyroid hormones among adults from China. We measured serum levels of thyroid hormones and urinary levels of 11 EDCs, including six phthalate metabolites, bisphenol A (BPA), bisphenol F (BPF), bisphenol S (BPS), perchlorate, and thiocyanate among 177 healthy adults without occupational exposure. Associations of multiple urinary analytes with serum thyroid hormones were examined by performing general linear regression analysis and bayesian kernal machine regression analysis. These EDCs were detected in almost all samples. After adjusting for various covariates, we observed only BPF significantly associated with total thyroxin (TT4) (ß=-0.27, 95% confidence interval (CI) [-0.41, -0.14]), total triiodothyronine (TT3) (ß=-0.02 95% CI [-0.03, -0.01]), free T4 (fT4) (ß=-0.02, 95% CI [-0.03, -0.01]), and free T3 (fT3) (ß=-0.04, 95% CI [-0.07, -0.01]), and mono-(2-ethyl-5-oxohexyl) phthalate (MEOHP) and monoethyl phthalate (MEP) positively associated with TT4 (ß=0.24, 95% CI [0.01, 0.48]) and fT4 (ß=0.02, 95% CI [0.01, 0.04]), respectively. Moreover, we observed significant dose-response relationships between TT4 and the mixture of 11 EDCs, and BPF was the main contributor to the mixture effect, suggesting the priority of potential effect of BPF on disrupting thyroid function under a real scenario of human exposure to multiple EDCs. Our findings supported the hypothesis that human exposure to low levels of EDCs could alter thyroid hormones homeostasis among non-occupational healthy adults.

[Determination of 17 plasticizers in dairy food].

OBJECTIVE: A method was established for determination of 17 kinds of plasticizers in infant formula by solid-phase extraction coupled with UPLC-MS/MS. METHODS: The plasticizers were extracted from the infant formula with acetonitrile, and purified by solid phase extraction column named OASIS Prime HLB. The analytes were then separated by the chromatographic column (BEH Phenyl, 2.1 mm x 100 mm x 1.7 microm). The ion fragment information analytes were obtained using ultra high performance liquid chromatography-tandem mass spectrometry under multiple reaction monitoring mode and the isotope internal standards were used to quantify by calibration curves. RESULTS: The method showed a good linearity (R2 > 0.9990) in the range of 0.5-500 microg/L for 17 plasticizers analytes with average recovery rates of 89.8%-119.0% (n = 6) and the relative standard deviation (RSD) within 3.62%-12.60%. The limits of quantification (LOQ) were between 1 microg/kg and 14 microg/kg. CONCLUSION: The method is simple, sensitive and accurate, and the sample pretreatment is very convenient especially, is suitable for the determination of 17 plasticizers in infant formula and dairy products.

[Determination phthalates in Chinese spirits].

OBJECTIVE: An isotope internal standard analytical process has been developed for the determination of phthalates (PAEs) in Chinese spirits by gas chromatography-mass spectrometry (GC-MS). METHODS: The samples alcoholicity were pre-adjusted after D4-internal standard adjunction, then were extracted with toluene. The supernatant were determined by GC-MS. RESULTS: The calibration curves of 16 phthalates obtained were linear with correlation coefficients greater than 0.997. The calibration curves range from 0.05 - 2 microg/ml. It was effective in the determination of phthalates in Chinese spirits with recoveries of 81.8% - 120% and RSD of 0.711% - 6.63%. The limit of quantification were 0.005 - 0.05 microg/ml. CONCLUSION: The pre-treatment of the process was simple and fast meanwhile the determination was precise. The method has a highly sensitivity. It's suitable for all kinds of phthalates chinese spirits detection.

Ultrasonic synthesis of magnetic covalent organic frameworks and application magnetic solid phase extraction for rapid adsorption of trace bisphenols in food samples.

A simple ultrasonic synthesis strategy was developed for a novel magnetic covalent organic framework. Firstly, the Fe3O4 nanoparticles were encapsulated by imine-type COF, which generated by the Schiff reaction of 4,4',4''-(1,3,5-Triazine-2,4,6-triyl)-trianiline (TAPT) and tris(4-formylphenyl)-amine (TFPA) using ultrasonic synthesis method within 2 h. The synthesised nanocomposites showed a sizeable specific surface area, and high adsorption capacity. A fast, sensitive MSPE method with Fe3O4@TAPT-TFPA-COF as adsorbent for analysing bisphenol compounds was developed. This method's advantages were simple operation, short extraction time, and avoidance of the use of centrifugal equipment. The method validation indicate that this method exhibited superior linearity, and detection limits range between 0.33 and 0.60 µg L-1. The recoveries of BPs ranged from 74.7 % to 107.0 %, with relative standard deviations of less than 3.8 % in water, milk, vinegar, and soy sauce samples. The proposed method was successfully applied for extracting BPs in food samples.

Visualized analysis of microplastics in residents' diets and regional investigation of China.

Microplastics are widely distributed in ecosystems and are increasingly found in food. This poses a potential threat to human health. However, current detections of microplastic in food primarily focused on the simple matrices, such as water, milk, and beverages, with relatively few methods available for complex matrices. Due to the strong matrix interference, non-destructive detection of microplastics in food has always been challenging. Thus, in this study, infrared spectral imaging approach was employed in tandem with chemometrics to perform nondestructive and in-situ characterization of microplastics in twelve diverse Chinese diets including meat and seafood stuffs. Results demonstrate that the proposed method can efficiently characterize common microplastics, such as polypropylene (PP), polyethylene terephthalate (PET), and polyethylene (PE), etc., in various complex matrices. The IR spectral imaging was subsequently applied to the detection of microplastics in seafood samples collected from 24 provinces across China. Results revealed the widespread presence of microplastics in seafood diets with significant regional variations. Overall, this study offers an innovative and applicable means for detecting microplastics in complex foods and provides a reference for the rapid detection of microplastics in various materials.

Potential safety concerns of volatile constituents released from coffee-ground-blended single-use biodegradable drinking straws: A chemical space perspective.

Incorporating spent coffee grounds into single-use drinking straws for enhanced biodegradability also raises safety concerns due to increased chemical complexity. Here, volatile organic compounds (VOCs) present in coffee ground straws (CGS), polylactic acid straws (PLAS), and polypropylene straws (PPS) were characterized using headspace - solid-phase microextraction and migration assays, by which 430 and 153 VOCs of 10 chemical categories were identified by gas chromatography - mass spectrometry, respectively. Further, the VOCs were assessed for potential genetic toxicity by quantitative structure-activity relationship profiling and estimated daily intake (EDI) calculation, revealing that the VOCs identified in the CGS generally triggered the most structural alerts of genetic toxicity, and the EDIs of 37.9% of which exceeded the threshold of 0.15 µg person-1 d-1, also outnumbering that of the PLAS and PPS. Finally, 14 VOCs were prioritized due to their definite hazards, and generally higher EDIs or detection frequencies in the CGS. Meanwhile, the probability of producing safer CGS was also illustrated. Moreover, it was uncovered by chemical space that the VOCs with higher risk potentials tended to gather in the region defined by the molecular descriptor related to electronegativity or octanol/water partition coefficient. Our results provided valuable references to improve the chemical safety of the CGS, to promote consumer health, and to advance the sustainable development of food contact materials.

Characterization, hazard identification, and risk assessment of volatile organic compounds in Poly(butylene adipate-co-terephthalate)-based food contact articles.

The chemical safety of poly (butylene adipate-co-terephthalate) (PBAT) based food contact articles (FCAs) has aroused increasing toxicological concerns in recent years, but the chemical characterization and associated risk assessment still remain inadequate as it fails to elucidate the distribution pattern and discern the potential genotoxic and carcinogenic hazards of the identified substances. Herein, the volatile organic compounds (VOCs) in 50 batches of PBAT-based FCAs of representative categories and 10 batches of PLA and PBAT pellets were characterized, by which 237 VOCs of 10 chemical categories were identified and exhibited characteristic distribution patterns in the chemical spaces derived from their molecular descriptors. Chemical hazards associated with the identified VOCs were discerned by a hazard-driven classification scheme integrating hazard-related knowledge from multiple publicly available sources, and 34 VOCs were found to bear genotoxic or carcinogenic hazards and to feature higher average molecular weight than the other VOCs. Finally, the Risk and hazard quotient (HQ) calculated as the metrics of risk suggested that all identified VOCs posed acceptable risks (Risk<10-4 or HQ < 1), whereas oxolane, butyrolactone, N,N-dimethylacetamide, 2-butoxyethanol, benzyl alcohol, and 1,2,3-trichloropropane posed non-negligible (Risk>10-6) genotoxic or carcinogenic risk and thus should be of prioritized concern to promote the chemical safety of PBAT-based FCAs.

An Insight into the Exploration of Antibiotic Resistance Genes in Calorie Restricted Diet Fed Mice.

Antibiotic resistance genes (ARGs) threaten the success of modern drugs against multidrug resistant infections. ARGs can be transferred to opportunistic pathogens by horizontal gene transfer (HGT). Many studies have investigated the characteristics of ARGs in various chemical stressors. Studies on the effects of dietary nutrition and dietary patterns on ARGs are rare. The study first demonstrated the effect of calorie restricted (CR) diet on the ARGs and mobile genetic elements (MGEs) in mouse feces and explored their relationship with gut microbiota and their functions. The results showed that the abundance of the total ARGs in mouse feces of the CR group increased, especially tetracycline ARGs (tetW-01). The abundance of the MLSB ARGs (ermB) decreased evidently in mouse feces of the CR group. In addition, the total abundance of MGEs decreased evidently in the CR group, especially tnpA-03. In the meantime, the abundance of Lactobacillus and Bifidobacterium in mouse feces of the CR group increased remarkably. The Spearman correlation analysis between gut microbiota and ARGs showed that several probiotics were significantly positively correlated with ARGs (tetW-01), which might be the main contribution to the increase in ARGs of the CR group.

A Nationwide Survey and Risk Assessment of Ethyl Carbamate Exposure Due to Daily Intake of Alcoholic Beverages in the Chinese General Population.

Ethyl carbamate (EC) is carcinogenic, and, in China, oral intake of EC mainly occurs as a result of the consumption of alcoholic beverages. To obtain the latest EC intake and risk analysis results for the general population in China, the China National Center for Food Safety Risk Assessment (CFSA) conducted the sixth total diet study (TDS) as a platform to analyze EC contents and exposure due to the intake of alcoholic beverages. A total of 100 sites in 24 provinces were involved in the collection and preparation of alcohol mixture samples for the sixth TDS. There were 261 different types of alcohol collected across the country, based on local dietary menus and consumption survey results. Ultimately, each province prepared a mixed sample by mixing their respective samples according to the percentage of local consumption. The EC levels of these twenty-four mixed samples were determined using our well-validated gas chromatography-mass spectrometry (GC-MS) method. The values ranged from 1.0 µg/kg to 33.8 µg/kg, with 10.1 µg/kg being the mean. China's EC daily intake ranged from 0.001 ng/kg bw/d to 24.56 ng/kg bw/d, with a mean of 3.23 ng/kg bw/d. According to the margin of exposure (MOE), virtually safe dose (VSD), and T25 risk assessments of the carcinogenicity of EC, the mean lifetime cancer risk for the Chinese population was 9.8 × 104, 1.5 × 10-7, and 8.6 × 10-8, respectively. These data show that the carcinogenicity of EC in the general Chinese population due to alcoholic intake is essentially minimal.

Monosodium Glutamate Intake and Risk Assessment in China Nationwide, and a Comparative Analysis Worldwide.

The sixth Total Diet Study (TDS) of China included a countrywide study to assess the health effects of MSG (monosodium glutamate). MSG detection, consumption analysis, and risk assessment were conducted on 168 samples from seven food categories of the most typical Chinese daily diet. The highest value of MSG in the daily diet of the Chinese population was 8.63 g/kg. An MSG intake of 17.63 mg/kg bw/d for the general population of China was obtained from content measurements combined with food consumption, while the data from the apparent consumption survey alone gave 40.20 mg/kg bw/d. The apparent consumption did not consider the loss of MSG during food cooking, resulting in an overestimate. To offer a global perspective, MSG content, food category contributions, and ingestion levels across nations were summarized and thoroughly investigated. A realistic, logical, and precise risk assessment protocol for MSG daily intake was developed in this article.

Heavy element contents of vegetables and health-risk assessment in China.

This study analyzed five heavy elements (HEs), including cadmium (Cd), chromium (Cr), mercury (Hg), lead (Pb), and arsenic (As), in fresh vegetables (i.e., legume, rhizome and potato, gourd, bulb, solanaceous fruit, leafy, and brassica; total: 7214) collected from 31 provinces in China from 2016 to the first half of 2017. By analyzing the concentration level of the five HEs in seven regions (the Northeast, North China, East China, South China, Central China, the Northwest, and the Southwest), except for As, average HEs concentrations were higher in the Southwest than that in the other six regions. According to the maximum permissible limit (MPL), the highest rate of HEs concentration above the MPL was found in the Southwest (11.038%). Analysis of variance (ANOVA) showed varying degrees of variability between regions and categories. By using principal component analysis (PCA), it was found that two principal components account for 73.79% of the total variance in the data. Together with hierarchical cluster analysis (HCA), concluded that Tibet was significantly different from the other 30 provinces. By calculating estimated daily intake (EDI) and the target hazard quotient (THQ), the EDI of Cr in the Southwest was the highest, with results of 1.2119 µg/kg/day for children and 0.8073 µg/kg/day for adults. North China had the highest total target hazard quotient (TTHQ) for HEs in vegetables ingested by children, with a result of 0.933.

Associations of urinary phthalate metabolites with risk of papillary thyroid cancer.

Some studies have revealed thyrotoxicity of phthalates; however, associations of phthalate exposure with papillary thyroid cancer (PTC) remain unclear. We conducted a pair-matching case-control study of 111 PTC cases and 111 age- and sex-matched non-PTC controls to examine associations between urinary concentrations of phthalate metabolites and PTC. Phthalate metabolites were determined in fasting urine specimens by ultra-performance liquid chromatography - tandem mass spectrometry (UPLC-MS/MS). After adjusting for potential confounders and other phthalate metabolites, the concentrations of the sum of di (2-ethylhexly) phthalate (DEHP) metabolites in urine were positively associated with PTC [odds ratio (OR) = 5.35; 95% confidence interval (CI): 1.61-17.83], suggesting the effect of phthalates exposure on PTC development. The findings require confirmation.

Ultra-High-Performance Liquid Chromatography-Isotope Dilution Tandem Mass Spectrometry for the Determination of Phthalate Secondary Metabolites in Human Serum Based on Solid-Phase Extraction.

>Background: A multitude of biomonitoring analytical methods are applied in urinary detection, but few are applicable to phthalate metabolites in human serum, and those that are invariably involve complex operation. Objective: To develop a novel method for the determination of phthalate monoesters in human serum using solid-phase extraction (SPE) and ultra-HPLC (UHPLC)-tandem mass spectrometry for multiple human serum sample determination. Method: Analytes in serum samples were extracted and purified with a novel SPE cartridge named Prime HLB and then directly injected and analyzed without eluent redissolution. After sample extraction and cleanup, 11 phthalate monoesters were separated on a C18 chromatographic column in UHPLC. Among them, mono-isobutyl phthalate and mono-n-butyl phthalate, a pair of isomers, were successfully separated. Results: Lower LODs of the 11 monoesters in 0.5 mL human serum were in the range of 0.03-3 ng/mL, and lower LOQs accordingly ranged from 0.1 to 10.0 ng/mL. Recoveries from spiked bovine serum samples were in the range of 95.3-109.9%, and RSDs were 8.0-12.0%. Intra- and inter-day recoveries were in the range of 94.1-115.7%, with RSDs <13.7%. Conclusions: The proposed method has been proved to be rapid, simple, accurate, and sensitive, so that it may potentially be used for high-throughput biological monitoring with high efficiency and precision. Highlights: Sample pretreatment does not require eluent drying and redissolution. Mass losses of analytes are avoided. Operational procedures are easy and rapid. The method has proved applicable for 11 phthalate metabolites in multiple human serum sample determinations.

Synthesis and fungicidal activity of aryl carbamic acid-5-aryl-2-furanmethyl ester.

Chitin, a major structural component of insect cuticle and fungus cell wall but absent in plants and vertebrates, is regarded as a safe and selective target for pest control agents. Chitin synthesis inhibitors (CSIs) have been well-known as insect growth regulators (IGRs) but rarely found as fungicides in agriculture. To find novel CSIs with good activity, benzoylphenylurea, a typical kind of CSIs, was chosen as the lead compound and 26 novel aryl carbamic acid-5-aryl-2-furanmethyl esters were designed by converting the urea linkages of benzoylphenylureas to carbamic acid esters and changing the aniline parts into furanmethyl groups. The title compounds were synthesized and their structures confirmed by IR, (1)H NMR, and elemental analysis. Preliminary insecticidal and fungicidal bioassays were carried out. The results indicated that the title compounds had no insecticidal effect on Culex pipiens pallens and Plutella xylostella Linnaeus , but most compounds exhibited good fungicidal activities against Corynespora cassiicola , Thanatephorus cucumeris , Botrytis cinerea , and Fusarium oxysporum . In particular, compounds V-4, V-6, V-7, and V-8 showed better activities against the four strains than those of the commercialized fungicides. The morphologic result suggested that compound V-21 had disturbed the cell wall formation of C. cassiicola. The results indicated that modification on the urea linkage of benzoylphenylurea was an effective way to discover new candidates for fungicides.