Novel biomonitoring method for determining five classes of legacy and alternative flame retardants in human serum samples.

Flame retardants (FRs) are ubiquitous in environment and biota and may pose harm to human health. In recent years, concern regarding legacy and alternative FRs has been intensified due to their widespread production and increasing contamination in environmental and human matrices. In this study, we developed and validated a novel analytical method for simultaneous determination of legacy and alternative FRs, including polychlorinated naphthalenes (PCNs), short- and middle-chain chlorinated paraffins (SCCPs and MCCPs), novel brominated flame retardants (NBFRs), and organophosphate esters (OPEs) in human serum. Serum samples were prepared by liquid-liquid extraction using ethyl acetate, and purified with Oasis® HLB cartridge and Florisil-silica gel columns. Instrumental analyses were carried out using gas chromatography-triple quadrupole mass spectrometry, high-resolution gas chromatography coupled with high-resolution mass spectrometry, and gas chromatography coupled with quadrupole time-of-flight mass spectrometry, respectively. The proposed method was validated for linearity, sensitivity, precision, accuracy, and matrix effects. Method detection limits for NBFRs, OPEs, PCNs, SCCPs, and MCCPs were 4.6 × 10-4-8.6 × 10-2, 4.3 × 10-3-1.3, 1.1 × 10-5-1.0 × 10-4, 1.5, and 9.0 × 10-1 ng/mL, respectively. Matrix spike recoveries ranged from 73%-122%, 71%-124%, 75%-129%, 92%-126%, and 94%-126% for NBFRs, OPEs, PCNs, SCCPs, and MCCPs, respectively. The analytical method was applied for detection of real human serum. CPs were the dominant FRs in serum, indicating CPs were widely presented in human serum and should be pay more attention for their health risk.

Parent and Halogenated Polycyclic Aromatic Hydrocarbons in the Serum of Coal-Fired Power Plant Workers: Levels, Sex Differences, Accumulation Trends, and Risks.

Workers in coal-fired power plants are at a high risk of exposure to polycyclic aromatic hydrocarbons (PAHs) and their halogenated derivatives (HPAHs), yet no studies have investigated such exposure of HPAHs. In this study, 12 PAHs and 8 chlorinated PAHs, but no brominated PAHs, were detected in >80% of serum samples from workers of a coal-fired power plant in eastern China. Serum HPAH concentrations were higher in plant workers (16-273 ng/g lipid) than in people without occupational exposure (12-51 ng/g lipid), and serum PAH and HPAH concentrations both in male and female workers were positively correlated with the occupational exposure duration, with an estimated doubling time of 11-17 years. Correlations were found between concentrations of ∑8HPAHs and ∑12PAHs but not between 7-chlorobenz[a]anthracene (7-ClBaA) and 1-chloropyrene (1-ClPyr) and their respective parent PAHs. In males, total concentrations of PAHs and HPAHs were positively correlated with pulmonary hypofunction and hypertension but not with abnormal electrocardiogram. The benzo[a]pyrene equivalents ratio of ∑8HPAHs/∑12PAHs was 0.3 ± 0.1. Among the HPAHs in the serum, 9-chlorophenanthrene, 7-ClBaA, and 1-ClPyr showed high health risks. This study is the first report on HPAH exposure in coal-fired power plant workers and provides new evidence on the health risks of PAHs and HPAHs in humans.

Photo-Oxidation of Bisphenol A in Aqueous Solutions at Near Neutral pH by a Fe(III)-Carboxylate Complex with Oxalacetic Acid as a Benign Molecule.

The photo-oxidation of organic pollutants as induced by ferric-carboxylate complexes was known to be a photo-Fenton-like process. The use of a carboxylate ligand with higher efficiency and lower toxicity at near neutral pH is of high interest to researchers. In this work, photo-oxidation of bisphenol A (BPA) induced by a ferric-oxalacetic acid complex in aqueous solutions was investigated under 395 nm LED lamps. The results showed that the rate of BPA degradation increased in the order pH 10.0.

Parent and halogenated polycyclic aromatic hydrocarbons exposure in aluminum smelter workers: Serum levels, accumulation trends, and association with health indicators.

Polycyclic aromatic hydrocarbons (PAHs) and their halogenated derivatives (HPAHs) can be unintentionally formed and released during industrial thermal processes. However, information on internal exposure and health risks of PAHs and HPAHs for thermal industry workers is very limited. In this study, serum samples from 220 aluminum smelter workers in East China were analyzed, and the relationship between the levels of these pollutants and various health indicators was also assessed. The workers had markedly higher serum concentrations of PAHs and HPAHs than the controls. The serum concentrations of ∑13PAHs and ∑9HPAHs increased with increasing age and occupational exposure duration in male workers. A positive correlation was observed between the ∑13PAH and ∑9HPAH serum concentrations, and the concentration of ∑13PAHs was approximately 50 times higher than that of ∑9HPAHs. For benzo[a]pyrene equivalent (BaPeq)-based risk assessment, the contribution of PAHs and HPAHs to the risk was 80 % and 20 % in the workers. PAHs and HPAHs showed a positive association with pulmonary hypofunction, hypertension and abnormal electrocardiogram. This study indicates occupational exposure to these toxic pollutants remains a significant issue and provides evidence that elevated serum levels of ∑13PAHs and ∑9HPAHs may be associated with an increased risk of lung and cardiovascular diseases.

Ultrasensitive determination of 39 parent and emerging halogenated polycyclic aromatic hydrocarbons in human serum.

Halogenated polycyclic aromatic hydrocarbons (HPAHs) have attracted extensive attention because of their high toxicity and bioaccumulation. However, there has been no report on the content of HPAHs in human tissues and the corresponding analytical method. In this study, a method for the simultaneous determination of 16 polycyclic aromatic hydrocarbons (PAHs) and 23 HPAHs in human serum was developed and validated. Simple and stable removal of interfering substances in complex serum and the detection of ultra-trace HPAHs are the key difficulties. After 0.5 mL serum was treated with formic acid and 10% isopropanol, samples were prepared by solid phase extraction (SPE) and analyzed by gas chromatography-triple quadrupole mass spectrometry (GC-MS/MS). The recoveries of the method were 65-103%, with low detection limits of 0.001-0.019 ng mL-1. For HPAHs, the precision was in the range of 0.2-10% according to relative standard deviation (RSD). Subsequently, the developed method was validated for serum samples obtained in hospitals, and 8 PAHs and 12 HPAHs were detected. The concentration of ∑HPAHs was 23 ± 12 ng g-1 lipid in females and 21 ± 10 ng g-1 lipid in males, in which phenanthrene and anthracene halogenated derivatives were the main components. The level of HPAHs was correlated with PAHs, which was 23-119 times higher than that of HPAHs. The detected HPAHs contain highly toxic and persistent components, representing an ongoing human health risk, which should receive more attention.