Exploring the formation pathway and antioxidant properties of the sugar-smoking pigment 5-GGMF.

The present study aimed to elucidate the pathway of pigment formation and identify the source of antioxidant activity during sugar smoking. Building upon previous research, this investigation replicated the sucrose cleavage process involved in sugar-smoking through model reactions to obtain distinct model reaction products. The products were analyzed using various techniques such as ultraviolet-visible spectrometry, Fourier-transform infrared spectroscopy, high-performance liquid chromatography, and high-performance liquid chromatography-tandem mass spectrometry. The findings revealed that the pyrolysis of sucrose at 330 °C yielded glucose and fructose, with fructose pyrolysis producing significantly more 5-HMF than glucose. Moreover, the antioxidant capacity of 5-HMF was found to make a substantial contribution. The primary source of 5-HMF was identified as fructose resulting from the cleavage of sucrose at 330 °C, while the primary pathway for the formation of the sugar-smoking pigment 5-GGMF was attributed to the intermolecular dehydration of 5-HMF and glucose at 150 °C.

A SILAC-based accurate quantification of shrimp allergen tropomyosin in complex food matrices using UPLC-MS/MS.

The carryover of trace allergens in complex food matrices poses challenges for detection techniques. Here, we demonstrate an accurate UPLC-MS/MS quantification assay for the shrimp allergen tropomyosin with a full-length isotope-labelled recombinant tropomyosin (TM-I) internal standard in complex food matrices. The TM-I, expressed based on the SILAC technique, exhibited a high isotope labelling ratio (>99%), purity, and alignment with the natural sequence. This method determined the tropomyosin ranging from 0.2 to 100 ng/mL. Mean recoveries ranged from 89 to 116%, with intra- and inter-day RSDs below 12%, for three signature peptides across three types of commercially processed food matrices. The limits of quantitation were 1 µg/g in pop food and sauce, and 10 µg/g in surimi product, respectively. This study supports the use of recombinant full-length isotope-labelled proteins rather than stable-isotope labelling peptides as internal standards to achieve more accurate quantitation of food allergens as the digestion error is corrected.

Characterizing the cumulative health risks of 19 kinds of pesticides in Chinese food from the cancer and non-cancer perspective.

Food safety is an important issue of most concern for health, while pesticides are one of the main threats to food safety. In view of the potential health hazard of pesticides in food, the cancer and non-cancer risks were assessed for 19 kinds of pesticides in Chinese food in this study. Furthermore, the health risks of different types of pesticides were compared to uncover the most polluted pesticide types in this study. Results show that methyl parathion, dichlorvos and 2,4-D residues in some food groups exceed the Chinese food standards. The cumulative disease burden of six carcinogenic pesticides for people older than 40 years ranges from 1.03 × 10-6 to 2.27 × 10-6, which exceeds the WHO recommended limit of 10-6. The non-cancer risks of 13 kinds of pesticides are all lower than 1 and will not pose appreciable health risk to the consumers. Livestock and poultry (contribution rate = 38.93%) and Milk and dairy products (contribution rate = 22.38%) are the dominate risk exposure sources for carcinogenic pesticides while staple foods (contribution rate = 31.62%) and vegetables (contribution rate = 21.5%) are the main risk exposure sources for non-carcinogenic pesticides. Comparing the risks of different pesticide types, insecticide is the most harmful category in this study, followed by herbicide and acaricide. This study characterized the health risks of pesticides in Chinese food and provided a scientific basis for pesticide management.

Fluorinated liquid-crystal monomers in paired breast milk and indoor dust: A pilot prospective study.

Fluorinated liquid-crystal monomers (FLCMs), one class of emerging persistent, bioaccumulative and toxic (PBT) compounds, are widely used in liquid-crystal displays (LCDs). As a result, they have been found in the environment and serum from occupational workers. However, little is known about their occurrence in non-occupational exposing populations. Herein, we provided an evaluation of the health risks of FLCMs for infants based on breastfeeding exposure and dust ingestion. The detection frequencies (DF) of FLCMs in indoor dust and breast milk was 100 %, with median concentrations of 12.00 ng/g dry weight (dw) and 133.40 ng/g lipid weight (lw), respectively. 1-butoxy-2,3-difluoro-4-(trans-4-propylcyclohexyl)benzene (BDPrB) was the predominant pollutant in indoor dust and human breast milk. Significant positive correlations were observed between the dust concentrations of seven FLCMs including BDPrB, and their breast milk concentrations (r = 0.275-0.660, P < 0.05). Further, associations were also found in some demographic and behavioral factors and concentrations of some FLCMs (P < 0.05). The highest EDI of ∑FLCMs was observed for infants who were < 1 month of age, with a median breast milk intake of 700.35 ng/kg bw/day, in which 1-ethoxy-2,3-difluoro-4-(trans-4-propylcyclohexyl)benzene (EDPrB), BDPrB, and 4'-[(trans, trans)-4'-butyl[1,1'-bicyclohexyl]-4-yl]-3,4-difluoro-1,1'-biphenyl (BBDB) collectively contributed 94.4 % of the total EDIs. Notably, the lactational intake of FLCMs was higher than that of some environmental pollutants (EPs). Overall, our results suggest higher exposure risks for infants and breastfeeding is the predominant exposure route for daily intake of FLCMs for infants.

Occurrence and migration of organophosphite and organophosphate esters into food simulants from single-use food packaging in China.

Organophosphite antioxidants (OPAs) and organophosphate esters (OPEs) are used as additives in food packaging. Because these chemicals have been found in various foods, they have caused increasing concern about potential health risks through food intake. Little information is available about the migration behaviors of OPAs and OPEs from single-use food packaging into food. In the present study, four OPAs and 23 OPEs were analyzed in paper and plastic single-use food packaging (n = 312), which are widely used for take-out food in China. The total concentrations of OPAs and OPEs in the packaging samples were 1966 and 189 ng/g, respectively. Tris (2,4-di-tert-butylphenyl) phosphite (AO168) was the dominant compound. OPAs and OPEs were present at higher concentrations in the plastic packaging than in the paper packaging. In a migration test, four OPAs and 15 OPEs were found in food simulants (4% acetic acid, 10% ethanol, and hexane). Higher levels of individual and total OPAs were found in hexane than the other food simulants, especially for AO168 migration from plastic packaging. The amounts of OPEs in the food simulants increased from the aqueous simulants (4% acetic acid and 10% ethanol) to the fatty food simulant (hexane). The migration efficiencies of the OPAs were higher than those of the OPEs. Preliminary calculations suggest that dietary exposure to OPAs and OPEs because of migration will be low for the population in China.

Multi-immunoaffinity column for the simultaneous analysis of bisphenol A and its analogues in Chinese foods by liquid chromatography tandem mass spectrometry.

Bisphenol A (BPA) and its four analogues have been receiving considerable attention owing to their potential endocrine disrupting effects. The European Food Safety Authority has proposed 0.04 ng/kg·body weight/day of thetemporary tolerable daily intake for BPA. Therefore, a more sensitive analytical method was urgently needed for the necessity of the risk reassessment of bisphenols (BPs). The matrix effect of Chinese foods is a challenge for the analysis of ultra-trace analytes due to the presence of various spices. A multi-immunoaffinity column (mIAC) was prepared for the purification of BPA, BPB, BPF, BPS, and BPAF in Chinese foods following ultra-high-performance liquid chromatography tandem mass spectrometry detection (UHLPC-MS/MS). The recoveries of each of BPs were ranged from 84.6% to 116.7%, and the intra-day precision and inter-day precision were ranged from 1.6% to 12.4%, and from 4.1% to 14.0%, respectively. This is the first report on the mIACs for simultaneous clean-up and analysis of BPs in complex Chinese foods.

Dietary Exposure and Health Risk of the Emerging Contaminant Fluorinated Liquid-Crystal Monomers.

Fluorinated liquid-crystal monomers (FLCMs) widely used in liquid crystal displays are considered to be a new generation of persistent, bioaccumulative, and toxic contaminants. They have been widely detected in the environment. However, little is known about their occurrence in food and human dietary exposure until now. Herein, we provided an evaluation of dietary exposure and health risks of FLCMs in the Chinese adult population based on the fifth and sixth total diet studies (TDSs). The detection frequencies of FLCMs in the two surveys were 90.5 and 99.5%, with concentrations ranging from not detected ∼72.6 µg/kg wet weight (ww) and ND ∼74.7 µg/kg ww, respectively. All TDS samples contained the multiresidue of FLCMs. The mean estimated daily intakes (EDIs) of FLCMs were 172.86 and 163.10 ng/kg bw/day in the fifth and sixth TDS, respectively. Meats, vegetables, and cereals contributed the most to the EDI of FLCMs. According to the threshold of toxicological concern (TTC) method, the EDIs of 1-fluoro-4-[2-(4-propylphenyl)ethynyl]benzene (4.56 and 3.26 ng/kg bw/day) and 2-fluoro-4-[4'-propyl-1,1'-bi(cyclohexyl)-4-yl]phenyl trifluoromethyl ether (3.12 and 3.28 ng/kg bw/day) were above their TTC value (2.5 ng/kg bw/day), suggesting their potential health risk. This is the first comprehensive national dietary exposure assessment of FLCMs.

[Determination of 26 bisphenols in dust by ultra performance liquid chromatography-tandem mass spectrometry].

Bisphenol A (BPA) is one of the most widely produced compounds in the world and was listed as a substance of very high concern by the European Chemicals Agency in 2016. Because of its toxicity, many countries and regions, including China, have banned BPA addition in feeding-bottles. And the European Union (EU) has banned BPA use in other food contact materials and thermal paper. Restrictions on BPA have contributed to the widespread use of alternatives. As the toxicity of BPA alternatives continues to be revealed, the alternatives of BPA alternatives are being developing. As the most extensive alternative for BPA, bisphenol S (BPS) was proven to have estrogen-disrupting effects and developmental toxicity of the neuroendocrine system. Therefore, BPS alternatives are used in thermal paper. In this study, alternatives to both BPA and BPS are collectively referred to as bisphenols (BPs). As a pooling matrix of many indoor chemicals, dust is an important pathway for human exposure to BPs. BPA and its alternatives are routinely detected in dust. As BPS alternatives have been detected in recycled paper and sludge, it is also very important to detected in dust. However, common analytical methods for BPs have low sensitivity and contain few BPS alternatives. Therefore, a high-throughput, high-accuracy, and high-sensitivity method must be established for the determination of BPs in dust; this will lay the foundation for subsequent studies on the environmental behavior and exposure risk of BPs. In this study, an ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method was developed for the simultaneous determination of 26 variations of BPs in dust. UPLC-MS/MS parameters of the variations were optimized to compare the separation effect and response intensity in different columns and mobile phases. The influence of the extraction solvent and solid phase extraction (SPE) on the extraction efficiency and purification effect of target compounds were optimized by using the isotopic internal standard method, and the 26 variations of BPs in dust was quantitatively analyzed. Finally, the dust samples were extracted by using 3 mL of acetonitrile and 3 mL of a 50% methanol aqueous solution in an ultrasound bath. The combined extract was further purified by using an Oasis HLB cartridge (60 mg/3 mL). The cartridge was then washed with a 40% methanol aqueous solution (0.5 mL) and eluted with methanol (2 mL). The target compounds were separated on a CORTECS® UPLC® C18 column (100 mm×2.1 mm, 1.6 µm), with methanol and 1 mmol/L ammonium fluoride solution as mobile phases and a flow rate of 0.3 mL/min. Electrospray ionization (ESI) was applied in the positive, negative, and multiple reaction monitoring (MRM) modes for the mass scan. Under optimized conditions, the linear ranges of the 26 targets behaved well linearly in their respective ranges with correlation coefficients (r2)>0.999. The limits of detection (LODs) and limits of quantification (LOQs) were assessed using signal-to-noise (S/N) ratios of 3 and 10, respectively. The LODs and LOQs of the method were 0.01-0.75 µg/kg and 0.02-2.50 µg/kg, respectively. The accuracy of the method was evaluated by conducting a recovery test at three spiked levels: LOQ, two times the LOQ, and 10 times the LOQ, with the average recoveries ranging from 83.7% to 114.9%. The precision of the method was evaluated by using the relative standard deviation (RSD). The intra-day RSDs and inter-day RSDs were 0.86%-9.79% (n=6) and 5.16%-19.5% (n=6), respectively. The established method was used to determine 11 dust samples. Fifteen BPs were detected at a detection rate of 9.1%-100.0%. The detection rate for BPA, BPS, bisphenol F (BPF), 4-hydroxy-4'-isopropoxydiphenylsulfone (BPSIP), and diphenyl sulfone (DPS) was 100.0%. BPSIP, 4-allyloxy-4'-hydroxydiphenyl sulfone (BPS-MAE), and bis-(3-allyl-4-hydroxyphenyl) sulfone (TGSA) were first detected in Chinese dust, whereas 4-benzyloxy-4'-hydroxydiphenyl sulfone (BPS-MPE), 4-hydroxybenzoic acid benzyl (PHBB), and DPS were first detected in dust samples worldwide. This method is simple, rapid, and sensitive, and is suitable for the qualitative screening and quantitative analysis of the 26 BPs in dust samples.

[Determination of 14 paralytic shellfish toxins in plasma and urine by ultra-high performance liquid chromatography-tandem mass spectrometry].

The detection of paralytic shellfish toxins in human biological matrices is important for the diagnosis and treatment of food poisoning caused by them. An ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method was established for the determination of 14 paralytic shellfish toxins in plasma and urine. The effect of solid phase extraction (SPE) cartridges was also investigated and the pretreatment and chromatographic conditions were optimized. Under these optimal conditions, 0.2 mL water, 0.4 mL methanol, and 0.6 mL acetonitrile were successively added to plasma and urine samples for extraction. The supernatants from plasma extraction were subjected to an UHPLC-MS/MS analysis, whereas the supernatants from urine extraction were further purified using polyamide (PA) SPE cartridges and then analyzed by UHPLC-MS/MS. Chromatographic separation was conducted on a Poroshell 120 HILIC-Z column (100 mm×2.1 mm, 2.7 µm) with a flow rate of 0.5 mL/min. The mobile phase was 0.1% (v/v) formic acid aqueous solution containing 5 mmoL/L ammonium formate and acetonitrile containing 0.1% (v/v) formic acid. The analytes were detected in the multiple reaction monitoring (MRM) mode after being ionized by an electrospray ion (ESI) in positive and negative modes. Quantitation of the target compounds was performed using the external standard method. Under the optimal conditions, the method showed good linearity in the range of 0.24-84.06 µg/L, with correlation coefficients greater than 0.995. The limits of quantification (LOQs) for the plasma and urine samples were 1.68-12.04 ng/mL and 4.80-34.4 ng/mL, respectively. The average recoveries for all the compounds were 70.4%-123.4% at spiked levels of 1, 2, and 10 times the LOQs, the intra-day precisions were 2.3%-19.1% and the inter-day precisions were 5.0%-16.0%. The established method was used to determine the target compounds in the plasma and urine from mice intraperitoneally injected with 14 shellfish toxins. All 14 toxins were detected in the 20 urine and 20 plasma samples, with contents of 19.40-55.60 µg/L and 8.75-13.86 µg/L, respectively. The method is simple, sensitive, and only requires a small amount of sample. Therefore, it is highly suitable for the rapid detection of paralytic shellfish toxins in plasma and urine.

Metabolic profiling of the fluorinated liquid-crystal monomer 1-ethoxy-2,3-difluoro-4-(trans-4-propylcyclohexyl)benzene.

1-Ethoxy-2,3-difluoro-4-(trans-4-propylcyclohexyl)benzene (EDPrB) is a typical fluorinated liquid-crystal monomer (LCM). LCMs contaminants are becoming increasingly concerning due to their potential persistence, bioaccumulation, toxicity, and broad prevalence in environmental and human samples. However, LCM metabolism is poorly understood. Herein, by introducing selected EDPrB into the appropriate liver microsomes in vitro, we examined the metabolic pathways of LCM in humans, rats, pigs, Cyprinus carpio, crucian carp, and Channa argus. A total of 20 species-dependent metabolites were identified and structurally elucidated by gas and liquid chromatography-high resolution mass spectrometry for the first time. Dealkylation, H-abstraction, and hydroxylation reactions are the primary metabolic pathways. Half of these in vitro metabolites were found in the urine, serum, and fecal samples of Sprague-Dawley rats exposed to EDPrB. Toxicity predictions indicate that 17 metabolites can be classified as toxic. According to the Ecological Structure Activity Relationships (ECOSAR), a number of metabolites exhibit equivalent or greater aquatic toxicity to that of EDPrB. Toxicity Estimation Software Tool (T.E.S.T.) predicts that some metabolites exhibit developmental toxicity and mutagenicity in rats. These findings suggest that biotransformation should be particularly emphasized, and more toxicological and monitoring studies should be performed to assess the ecological and human safety of LCMs.

Human dietary exposure to bisphenol-diglycidyl ethers in China: Comprehensive assessment through a total diet study.

Despite the widespread use of bisphenol A diglycidyl ether (BADGE) and bisphenol F diglycidyl ether (BFDGE) in various consumer products as protective plasticizer, studies on human dietary exposure to these compounds are scare. In this study, nine bisphenol diglycidyl ethers (BDGEs) including BADGE, BFDGE, and seven of their derivatives were determined in the Chinese adult population based on composite dietary samples collected from the sixth (2016-2019) China total diet study (TDS). Contamination level of nine BDGEs was determined in 288 composite dietary samples from 24 provinces in China. BADGE·2H2O and BADGE are the most frequently detected and BADGE·2H2O presented the highest mean concentration (2.402 µg/kg). The most contaminated food composite is meats, with a mean ∑9BDGEs of 8.203 µg/kg, followed by aquatic products (4.255 µg/kg), eggs (4.045 µg/kg), and dairy products (3.256 µg/kg). The estimated daily intake (EDI) of ∑9BDGEs based on the mean and 95th percentile concentrations are 121.27 ng/kg bw/day and 249.71 ng/kg bw/day. Meats, eggs, and aquatic products are the main source of dietary exposure. Notably, beverages and water, alcohols were the main contributors of dietary exposure to BADGE and BADGE·2H2O, followed by animal-derived foods. Dietary exposure assessment demonstrated that human dietary BDGEs do not pose risks to general population based on the mean and 95th percentile hazard index with < 1. This is the first comprehensive national dietary exposure assessment of BDGEs in Chinese general population.

Identification of key constituent of sugar-smoking pigment and its photobleaching, antioxidant and antiproliferative properties.

The key constituent(s) of sugar-smoking brown pigments were identified, the chemical and biological properties were subsequently investigated, and the possibility of obtaining it from nature was explored. A pigment was isolated, which was identified as condensation product of 5-hydroxymethyl-2-furfuraldehyde (5-HMF) with glucose: 5-(α-D-glucopyranosyl-(1-6)-α-D-glucopyranosyloxymenthyl)-2-furancarboxaldehyde (5-GGMF). The molecular weight was 450.00. The interaction between pigment with protein on chicken skin was mainly via hydrogen and carbon-hydrogen bonds. It was obtained by caramelization instead of Maillard reaction. Discoloration of sugar-smoking pigments were mainly due to cleavage of chromophores caused by the oxidation reaction followed by photobleaching mechanism. Both radical scavenging and antiproliferative capacity of sugar-smoking pigment were in a dose-dependent manner. However, the IC50 values for HepG2 and PANC-1 cells differed by more than ten times. Since 5-GGMF is also present in plant resources (like Rehmanniae Radix), it can be obtained as natural additive to produce clean label sugar-smoked meat products.

Metabolic profiling of bisphenol A diglycidyl ether in vitro and in vivo.

Bisphenol A diglycidyl ethers (BADGE) is one class of human-made chemicals, and it is one of the most widely used raw materials for epoxy resins. As an active compound, BADGE undergoes biotransformation in vitro and in vivo. However, there is a limited understanding of the biotransformation of BADGE and toxicity studies on transformation products. We conducted comprehensive research on the metabolic transformation of BADGE in vitro and in vivo. The results showed that 12 metabolites and 7 metabolites were identified in vitro and in vivo, respectively. Four biotransformation products, including M1 (hydrolysis), M3 (dehydroxylation), M10 (carboxylation), and M11 (glucose conjugation), can be found in both in vitro and in vivo samples. The main metabolic pathways were hydroxylation, carboxylation, cysteine (Cys) conjugation, and glucose conjugation. Besides, our results suggested the existence of metabolic differences in BADGE between species and gender. Further, we investigated toxicities of BADGE metabolites in-silico. Importantly, some hydrolysis (M1, M2), hydroxylation (M7), and oxidation (M8) products showed similar or even higher potential toxicity than BADGE depending on the endpoint. These results enrich the biotransformation profiles of BADGE and provide useful information for understanding its biotransformation in humans and a reference for the comprehensive assessment for human health risk.

Bisphenol-diglycidyl ethers in paired urine and serum samples from children and adolescents: Partitioning, clearance and exposure assessment.

Bisphenol A diglycidyl ether (BADGE), bisphenol F diglycidyl ether (BFDGE), and their derivatives are frequently used in food packaging materials. Some toxicological studies have shown that the endocrine-disrupting activities of these compounds are similar to or higher than those of bisphenol A (BPA), which may also adversely affect the growth and development of children and adolescents. Here, we investigated nine bisphenol-diglycidyl ethers (BDGEs) in 181 paired urine and serum samples from children and adolescents from Beijing to determine their partitioning, clearance and exposure levels. The results showed that nine BDGEs were detected in 181 urine and serum samples from children and adolescents from Beijing. Bisphenol A bis(2,3-dihydroxypropyl) glycidyl ether (BADGE·2H2O) was the primary pollutant. The daily intake of ∑BDGEs was 15.217 ng/kg bw/day among children and adolescents in Beijing. The ranking of BDGEs in terms of renal clearance rate (CLrenal) in this study population was BADGE > BADGE·2H2O > BFDGE > bisphenol F bis(3-chloro-2-hydroxypropyl) glycidyl ether (BFDGE·2HCl) > bisphenol A (3-chloro-2-hydroxypropyl) (2,3-dihydroxypropyl) glycidyl ether (BADGE·HCl·H2O). In addition, the serum and urine ratios (S/U ratios) of BFDGE·2HCl, BADGE·2H2O, BFDGE, BADGE, and BADGE·HCl·H2O were higher than 1, indicating that these contaminants have a higher enrichment capacity in human blood. To our knowledge, this is the first study on the partitioning and renal clearance rate of BDGEs in paired urine and serum samples from children and adolescents.

Estimation of lactating mothers' daily intakes of bisphenol A using breast milk.

Breast milk is a unique biological sample that reflects the exposure levels of both lactating mothers and infants. The exposure levels of BPA due to breast milk consumption for infants can be estimated easily, but the method to estimate the total daily intake (TDI) of lactating mothers from breast milk has not yet been established. In this study, BPA concentrations were detected in breast milk samples from 149 lactating mothers from Hunan, China. The median concentration of BPA in breast milk was 0.053 µg/L with a range of 0.001-2.535 µg/L, and a temporal decline trend was found for BPA concentrations in breast milk (p < 0.05). The median intake of BPA via breast milk was 26.8 ng/kg bw/day for 0-3-month-old infants and 7.0 ng/kg bw/day for 4-12-month-old infants. Based on the predicted concentrations of BPA in urine and blood via the conversion coefficients from breast milk, the TDIs of lactating mothers were estimated. The TDIs estimated from the simulated urine concentration were 84.0 ± 175.2 ng/kg bw/day for 0-3-month-old infants' mothers and 36.9 ± 80.8 ng/kg bw/day for 4-12-month-old infants' mothers. The dietary daily intakes estimated from the simulated blood concentration were 579.6 ± 370.8 ng/kg bw/day for 0-3-month-old infants' mothers and 280.1 ± 195.2 ng/kg bw/day for 4-12-month-old infants' mothers. When assuming the dietary daily intakes in Hunan of the fifth total diet study (TDS) as the "true" total dietary intake of our population, the contribution of diet was estimated to be 63.7%, which suggested that non-dietary BPA exposure may be underestimated.

Emerging Brominated Flame Retardants 2-Ethylhexyl-2,3,4,5-tetrabromobenzoate (EHTBB) and Bis(2-ethylhexyl)-tetrabromophthalate (BEH-TEBP) in Chinese Food and Their Health Implications.

2-Ethylhexyl-2,3,4,5-tetrabromobenzoate (EHTBB) and bis(2-ethylhexyl) tetrabromophthalate (BEH-TEBP) have been frequently detected in the environment, whereas studies in food are scare. The European Food Safety Authority has requested data for their risk assessment. Herein, dietary exposure and hazard quotient (HQ) were studied based on the 5th (2009-2012) and 6th (2015-2018) Chinese total diet studies (TDSs). EHTBB was found in 61.1 and 75.9% of the two TDS sample sets, respectively. The concentrations of EHTBB in animal-derived food were higher than those in plant-derived food. The estimated daily intakes (EDIs) were 1.33 and 0.97 ng/kg bw/day, and vegetables contributed to 48.5 and 39.2% of the EDIs based on the 5th and 6th TDS, respectively. The dietary exposure to EHTBB was similar to that to hexabromocyclododecane, brominated diphenyl ether-209, and tetrabromobisphenol A (TBBPA). The HQ for EHTBB was similar to that for decabromodiphenyl ethane and surpassed that for TBBPA. Therefore, EHTBB warrants further study in food.

[Simultaneous determination of 12 lipophilic shellfish toxins in plasma and urine by ultra-high performance liquid chromatography-tandem mass spectrometry].

Lipophilic shellfish toxins pose significant threats to the health of seafood consumers and public health. The symptoms of these kinds of toxins include severe diarrhea, abdominal cramps, nausea and gastrointestinal disorders. These symptoms could be hardly distinguished with many other symptoms of food poisoning and diseases. Therefore, a fast and accurate determination method in human biological samples is urgently needed for the accurate judgement of food poisoning incident, which is important for the investigation of public health emergencies and clinical treatment of poisoned patients. However, there were several flaws of the previous studies reported on the analysis of lipophilic shellfish toxins: (1) limited target compounds were covered; (2) the pre-treatment process was complex; (3) the sensitivity of the compound was low. In this study, a simple extraction method coupled with ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was developed for the simultaneous determination of 12 lipophilic shellfish toxins, including azaspir acid 1 (AZA1), azaspir acid 2 (AZA2), azaspir acid 3 (AZA3), dinophysistoxin 1 (DTX1), dinophysistoxin 2 (DTX2), gymnodimine (GYM), hyessotoxin (HYTX), okadaic acid (OA), pinnatoxin (Pntx), pectenotoxins 2 (PTX2), spirolides 1 (SPX1), yessotoxin (YTX), in plasma and urine. Firstly, the instrument conditions were optimized. Different additions in mobile phase were compared and 0.05% (v/v) ammonia solution was selected since it can improve the peak shape of YTX and HYTX, and increase the respondence by four times. Secondly, the volume of acetonitrile (0.2, 0.4, 0.6, 0.8, 1.0 mL) use for the extraction of the target compounds in plasma was optimized. Satisfactory recoveries were obtained when 0.6 mL of acetonitrile was used. At the same time, satisfactory recoveries were obtained when 0.9 mL of acetonitrile was used in urine samples. Finally, under the optimized conditions, the 12 compounds in plasma and urine samples were ultrasonically extracted with acetonitrile. Chromatographic separation was performed on a Phenomenex Kinetex C18 column (50 mm×3 mm, 2.6 µm) with 90% (v/v) acetonitrile aqueous solution and water containing 0.05% (v/v) ammonia as mobile phases. Gradient elution with a flow rate of 0.40 mL/min was employed. The 12 compounds were monitored in the multiple reactions monitoring (MRM) mode with electrospray ionization (ESI) under both positive and negative conditions. The matrix effects of the 12 compounds ranged from 0.8 to 1.1. Therefore, external standard calibration curves were used for the quantification. The 12 shellfish toxins showed good linear relationship in the range of 0.03-36.25 µg/L with the correlation coefficients greater than 0.995. The limits of detection (LODs, S/N=3) were 0.08-0.21 ng/mL for the urine samples and 0.10-0.28 µg/L for the plasma samples, respectively. The limit of quantitations (LOQs, S/N=10) were 0.23-0.63 µg/L for the urine samples and 0.31-0.84 µg/L for the plasma samples, respectively. The recoveries of the 12 compounds were in the range of 72.7%-124.1% at three spiked levels (i. e., LOQ, three times LOQ, and ten times LOQ). The intra-day and inter-day precisions were 2.1%-20.0% and 2.1%-15.3%, respectively. The method was applied in the detection of the 12 lipophilic shellfish toxins in the urine and plasma samples of healthy humans and mice previously injected with the 12 shellfish toxins intraperitoneally. None of the 12 toxins were found in the samples from healthy human, while all of the 12 lipophilic shellfish toxins were found in the urine and plasma samples collected from the poisoned mice in the range of 1.14-2.35 µg/L and 1.01-1.17 µg/L, respectively. The established method has the advantages of sensitive, quick, easy to operate, and of low sample volume. It can be used for the simultaneous determination of 12 lipophilic shellfish toxins in urine and plasma samples.

Bisphenol Analogues and Their Chlorinated Derivatives in Breast Milk in China: Occurrence and Exposure Assessment.

Concentrations of bisphenol A (BPA) and its analogues (together with their chlorinated derivatives are referred to as BPs) were measured in 181 breastmilk samples collected from 9 provinces in China in 2014. Twelve BP types were found. The BP concentrations ranged from not detected to 5.912 µg/L. BPA was the predominant BP, followed by bisphenol F (BPF) and bisphenol S (BPS). The mean BPA, BPF, and BPS levels were 0.444, 0.107, and 0.027 µg/L, respectively. Other BPs were sporadically detected in breastmilk samples. There were no differences (p > 0.05) in BPA, BPF, BPS, or total BP levels in the urban and rural regions or the northern and southern regions. BPA accounted for approximately 70% of the BPs and BPF accounted for more than 20% of the BPs in breast milk samples. The high contribution of BPF indicated that BPA analogues, not only BPA, should receive attention. The upper-bound daily intakes of BPs for infants 0-6 months old were 0.044-1.291 µg/kg bw/day. Despite the absence of tolerable daily intake data, attention should be paid not only on BPA but also BPF.

[Non-targeted screening of triazole fungicides in tomatoes by ultra-high performance liquid chromatography-quadrupole-time of flight mass spectrometry].

In order to cope with the differences in international trade regulations, it is necessary to establish a rapid non-targeted screening method for triazole fungicides in food. Therefore, a non-targeted method based on ultra-high performance liquid chromatography-quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS) was established for the rapid screening of triazole fungicides in tomatoes. Tomato samples were extracted with acetonitrile and then purified by QuEChERS. The purified solution was separated on a BEH C18 column (100 mm×2.1 mm, 1.7 µm) using a gradient mobile phase consisting of acetonitrile and water (both containing 0.1% formic acid). Full information tandem mass spectrometry (MSE) acquisition using electrospray ion source under positive ion mode was performed. The 19 triazole fungicides were divided into eight groups based on their structural differences. The secondary mass fragments of eight typical standards in the eight groups of triazole fungicides were analyzed, and then, the regularities of the characteristic fragment ions and neutral loss fragments produced by collision-induced dissociation of the triazole fungicides were summarized. The fragmentation regularity was further verified by the other 11 triazole fungicides. A total of 16 tomato samples collected from local supermarkets in Beijing were screened using this non-targeted method. Diniconazole was identified and confirmed in one sample, which demonstrated that the method could achieve rapid and accurate non-targeted screening of triazole fungicides in tomatoes. The proposed method is highly efficient, sensitive, and accurate, thus providing a reference for screening triazole fungicide residues in food.

Preliminary test on the distribution, hydrolyzation and excretion of aluminum dialkyl phosphinate flame retardants in rats.

Aluminum dialkyl phosphinates (ADPs) are a promising class of chemicals offering superior flame retardance. However, knowledge on their behavior in vivo is scarce. Hydrolysis has been suggested as one of the major routes of environmental degradation of ADPs. Herein, aluminum methylcyclohexyl phosphinic (AMHP), a kind of ADPs with industrial production in China, and its hydrolysate methyl cyclohexyl phosphinic acid (MHPA) were continuously exposed to Sprague Dawley (SD) rats for 28 days in this study. The same ratio of MHPA in organs to serum and the same daily excretion of MHPA were observed for AMHP exposure group and MHPA exposure group, suggesting the hydrolysis of AMHP in vivo. The hydrolysis of AMHP to MHPA was further confirmed by in vitro simulated human gastric intestinal juice. Therefore, both AMHP and MHPA distributed in liver, kidney and even brain in the form of MHPA. More than 80% of AMHP and MHPA could be excreted by feces and urine. Feces are the main route of excretion of AMHP and MHPA. The denseness of the inflammatory cell in the hepatic portal area and biochemical indexes showed the obvious dose-effect relationship. However, the toxicity of AMHP and MHPA was quite low even with exposure level up to 100 mg/kg dw/day. The low cumulative ability and mild toxicity indicated AMHP as a promising substitute for brominated flame retardant.