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Prenatal perfluoroalkyl substances (PFAS) exposure has been reported to affect offspring neurodevelopment, while epidemiological evidences were limited and inconsistent.We aimed to evaluate the associations between cord serum PFAS concentrations and neurodevelopment in toddlers from 1 to 3 years of age.A total of 716 children from Sheyang Mini Birth Cohort Study (SMBCS) were included in this study. 12 PFAS concentrations were quantified in cord serum. Neurodevelopment was assessed using the Developmental Screen Test for Children Aged 0-6 Years at 1 year and the Gesell Developmental Schedules (GDS) at 2 and 3 years, respectively. Development quotient (DQ) z-score was standardized from DQ to eliminate the difference caused by two methods. We used generalized linear model (GLM) and Bayesian kernel machine regression (BKMR) to explore the associations of single or mixture PFAS exposure with neurodevelopment measurements at each time point. Associations between PFAS exposure and longitudinal changes in DQ z-score were investigated through generalized estimating equation (GEE) and trajectory analysis.In general, prenatal PFAS concentrations showed negative associations with neurodevelopment measurements at specific age. When accounting for longitudinal changes from 1 to 3 years of age, PFOA was negatively associated with DQ z-score (β = -0.212, 95% CI: -0.422, -0.003), the association was only found significant in boys after stratified by gender (β = -0.327, 95% CI: -0.616, -0.038). Meanwhile, increased PFBS (OR = 2.159, 95% CI: 1.177, 3.959) and PFHpA (OR = 1.700, 95% CI: 1.016, 2.846) exposure was associated with elevated odds for the low-score trajectory group. The results of mixture of PFAS further confirmed above findings.Our findings suggested that prenatal PFAS exposure may be associated with adverse neurodevelopment effects in the first 3 years of life. Further studies are warranted to confirm our findings.

Herbal teas have potential health benefits, but they also contain a variety of pesticides and pesticide transformation products (PTPs) that might brings health risks. Our study maps the pesticides and PTPs in two herbal teas (chrysanthemum and Lusterleaf Holly) from two main producing areas in China. Almost all 122 samples contain pesticides, with concentration ranging from 0.0005 to 10.305 mg/kg. Nearly 40% carbendazim and imidacloprid in chrysanthemum teas and λ-cyhalothrin in Lusterleaf Holly have higher concentration levels than the values permitted in EC Regulation No. 396/2005. Distinct distributions of pesticides were found in different teas and production areas. Eight PTPs were identified along with their parents, and were confirmed using a biosynthetic strategy. Acute, chronic and cumulative health risk assessments of pesticides revealed acceptable results. Our study uncovers the profile of pesticides in herbal teas, and provides new insight into discovering the potential environmental pollution and food contaminants.

Computational QSAR models have gradually been preferred for retention time prediction in data mining of emerging environmental contaminants using liquid chromatography coupled with mass spectrometry. Generally, the model performance relies on the components such as machine learning algorithms, chemical features, and example data. In this study, we evaluated the performances of four algorithms on three feature sets, using 321 and 77 pesticides as the training and validation sets, respectively. The results were varied with different combinations of algorithms on distinct feature sets. Two strategies including enhancing the complexity of chemical features and enlarging the size of the training set were proved to improve the results. XGBoost, Random Forest, and lightGBM algorithms exhibited the best results when built on a large-scale chemical descriptors, while the Keras algorithm preferred fingerprints. These four models have comparable prediction accuracies that at least 90% of pesticides in validation set can be successfully predicted with ΔRT1.0 min. Meanwhile, a blended prediction strategy using average results from four models presented a better result than any single model. This strategy was used for assisting identification of pesticides and pesticide transformation products in 120 strawberry samples from a national survey of food contamination. Twenty pesticides and twelve pesticide transformation products were tentatively identified, where all pesticides and two pesticide transformation products (bifenazate diazene and spirotetramat-enol) were confirmed by standard materials. The outcome of this study suggested that retention time prediction is a valuable approach in compound identification when integrated with in silico MS

Polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs), as the secondary environmental pollutants of the widely used brominated flame retardants (BFRs), possess the similar physicochemical and toxic properties as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). However, studies on human body exposure to them are extremely limited. In this study, forty human milk samples collected in Shanghai were measured for 13 PBDD/F congeners using gas chromatography-high resolution mass spectrometry (GC-HRMS), to investigate their exposure level and characteristics, potential source and corresponding health risks to breastfed infants. The results showed no PBDDs but three PBDF congeners including 2,3,7,8-TBDF, 1,2,3,4,6,7,8-HpBDF and OBDF (mean concentration (detection rates) are 3.2 pg/g (72.5%), 9.5 pg/g (100%) and 28 pg/g (67.5%), respectively) were detected. The average toxic equivalent quantity (TEQ, 0.42 pg/g lw) presented the highest concentration level compared to other regions reported. The contribution of PBDFs to the total TEQ of PBDD/Fs and PCDD/Fs is 6.8%. The correlation between PBDD/Fs and age or dietary habits was not observed, which normally existed in their chlorinated analogues-PCDD/Fs. Significant correlations were observed between PBDFs and highly brominated polybrominated diphenyl ethers (PBDEs) (especially for BDE 183 and BDE 209). The correlation between PCDD/Fs and PBDFs was not observed except 2,3,7,8-TBDF. The high PBDFs exposure in Shanghai may originate from the emission of PBDEs and/or non-PBDE BFRs in environment, according to the consistency of the environmental data previously reported. The average estimated dietary intakes (EDI) for breastfed infants is 2.0 pg TEQ/kg·bw/day (0.13-13 pg TEQ/kg·bw/day), within the range of the tolerable daily intake (TDI) for TCDD (1-4 pg TEQ/kg·bw/day) suggested by the World Health Organization (WHO). However, given the high toxicity of PBDD/Fs, the potential health risks of these pollutants for breastfed infants should be of concern.

Bromophenols (BrPs), as the metabolites of PBDEs, would be the potential exposure markers for human biomonitoring (HB) of PBDEs in urine. An analytical method using solid-phrase extraction (SPE) and gas chromatography coupled to tandem mass spectrometer (GC-MS/MS) was developed and validated for simultaneous determination of nineteen BrPs in human urine. The method detection limits (MDLs) were below 23pgmL(-1), with recovery ranged from 63% to 133% and inter-day repeatability ranged from 3% to 11% for the majority of target analytes. This method was applied in a pilot study and 2-Bromophenol (2-BrP), 4-Bromophenol (4-BrP), 2,4-Dibromophenol (2,4-DBP) and 2,4,6-Tribromophenol (2,4,6-TBP) as the predominant analytes were detected in human urine samples collected from the general population. Among the four detected analytes, 2-BrP and 4-BrP as the mono-brominated BrP congeners were firstly reported. To our knowledge, it is the first study covering all BrP congeners (from mono-brominated to penta-brominated, totally 19 congeners) in human urine. Therefore, this study is very useful for profiling urinary BrPs and discovering potential relationship between urinary BrPs and human internal exposure to PBDEs. The mechanism of fragmentation pathway of silanized BrPs was firstly illustrated in this study.

It is of great interest to develop strategic methods to enable chemicals' metabolites to be accurately and rapidly screened and identified. To screen and identify a category of metabolites with distinct isotopic distribution, this study proposed a generic strategy using in silico metabolite prediction plus accurate-mass-based isotopic pattern recognition (AMBIPR) and library identification on the data acquired via the data dependent MS/MS scan of LC-Q Exactive Orbitrap mass spectrometry. The proposed method was evaluated by the analysis of flurochloridone (FLC) metabolites in rat urine sample collected from toxicity tests. Different from the traditional isotopic pattern recognition (IPR) approach, AMBIPR here was performed based on the potential metabolites predicted via in silico metabolite prediction tools. Thus, the AMBIPR treated FLC data was only associated with FLC metabolites, consequently not only avoiding great efforts made to remove FLC-unrelated information and reveal FLC metabolites, but also increasing the percent of positive hits. Among the FLC metabolite peaks screened using AMBIPR, 87% of them (corresponding 97 metabolites and 49 biotransformation) were successfully identified via multiple MS identification techniques packaged in an established FLC's metabolites library based on Mass Frontier. Noteworthy, 34 metabolites (89%) were identified without distinct naturally isotopic distribution. The universal strategic approach based on background subtraction (BS) and mass defect filtering (MDF) was used to evaluate the AMBIPR and no more false positive and negative metabolites were detected. Furthermore, our results revealed that AMBIPR is very effective, inherently sensitive and accurate, and is easily automated for the rapidly screening and profiling chemicals related metabolites.

Human milk samples were collected from 150 mothers in 2011 and 2012 in Shanghai, China and analyzed for 17 polychlorinated dibenzo- p -dioxins/furans (PCDD/Fs) and 12 dioxin-like polychlorinated biphenyls (DL-PCBs). The up-bound Toxic Equivalent Quantity (TEQ) ranged from 0.27 to 16.8 pg TEQ/g lipid (mean 5.4 pg TEQ/g lipid) for ∑PCDD/Fs and from 0.75 to 10.2 pg TEQ/g lipid (mean 2.9 pg TEQ/g lipid) for ∑DL-PCBs. TEQs in our study were lower than those in most countries worldwide, and displayed a notable uptrend, in contrast with those in China’s national survey in 2007. TEQs in mother milks from urban areas were higher than those from rural areas, and an orderly distribution was found in four geographical regions: Eastern China > Central China ≈ Southwestern China > Northwestern China. Levels of analytes in Shanghai native mothers’ milk ranked the first among those from all provinces and cities investigated. Migrant mothers to Shanghai from other inland provinces could potentially represent the population for exposure and risk assessment in their birth and grown-up places. Both the distribution and the uptrend were associated with release of these pollutants due to rapid industrialization and urbanization in China. Fine correlations were observed between TEQs and age of mothers, and weak correlations between TEQs and consumption of meat & meat products. Participants, who preferred both fresh water and marine fish to freshwater fish only, were prone to be exposed to higher level of PCBs. The estimated daily intake (EDI) doses for breastfed neonates entirely exceeded the tolerable intake dose by WHO.

a b s t r a c t A new method was developed to determine polybrominated diphenyl ethers (PBDEs) and polychlori- nated biphenyls (PCBs) in fishery and aquaculture products. Samples were extracted by an accelerated solvent extraction system and cleaned up by sequential solid phase extraction (SPE) including dispersive SPE (D-SPE) and tandem SPE. PBDEs and PCBs were analyzed by a large-volume injection gas chro- matography triple quadrupole mass spectrometry (LVI-GC-QqQ-MS/MS). Good linearity (R 2 ≥ 0.9958) was achieved. Method detection limits (MDLs) were 0.16-3.3 pg g−1 (wet weight, ww) for PBDEs and 0.13-0.97 pg g −1 ww for PCBs. Mean recoveries were 60-140% with relative standard deviations (RSDs) of less than 20% in weever fish, scallop and shrimp samples spiked at a lower level of 13-31 pg g−1 ww and a higher level of 50-125 pg g −1 ww. Certified reference materials were analyzed with acceptable results. The method reduced solvent consumption, analytical time and labor, and is suitable for the routine analysis of PBDEs and PCBs in fishery and aquaculture products. © 2013 Published by Elsevier B.V.

In this study, a method was developed to determine 45 selected pesticides (of different chemical families) in fruit and vegetable (including apple, spinach and cucumber). Samples were extracted using an improved QuEChERS method with salting out and phase separation in two steps. The target pesticides in concentrated extracts were analyzed by an on-line gel permeation chromatography-gas chromatography/mass spectrometer (online-GPC-GC/MS). Online GPC effectively removed matrix interferences and greatly improved the method sensitivity, recoveries and automation. Method limits of quantification were 10 ng/g for uniconazole and metalaxyl, and 5 ng/g for other 43 target analytes. In three fruit and vegetable matrices each spiked with 45 pesticides (0.01 μg/g), mean recoveries ranged from 80 to 118% for most of the tested pesticides except for profenofos (77% in apple) and chlorpyrifos (68% in apple and 75% in cucumber), with relative standard deviations (RSDs) of less than 14%. The results of the proficiency testing showed that the method is very successful in measuring the certified pesticides with less than 1.3 of the absolute value of Z-score. This method has been applied for routinely monitoring pesticides in fresh fruit and vegetable.