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Polybrominated diphenyl ethers (PBDEs) and their hydroxylated (OH-BDE) analogues are known as contaminants with potential risks to human health. In this work, a HPLC-ICP-MS method was developed for simultaneous determination of four polybrominated diphenyl ethers (BDE-47, −99, −153 and −209) and four hydroxylated analogues (3-OH-BDE-47, 5-OH-BDE-47, 6-OH-BDE-47, 5′-OH-BDE-99) in human serum. Solid-phase extraction (SPE) was employed as the primary extraction and purification procedure. By using mixtures of acetone and hexane with different rations, OH-PBDEs and PBDEs were efficiently recovered during elution procedure. With additional ultrasonic assisted extraction of PBDEs from solid residue after protein precipitation, the recoveries of investigated analytes ranged from 79.1 %to 89.9%. Due to the characteristics of inductively coupled plasma (ICP), organic matrix effects were effectively eliminated. Good sensitivity and precision were also obtained. The limits of quantification ranged from 0.060 to 0.081 ng mL−1 and inter-/intra-day relative standard deviations were all below 4%. In addition, compound-independent calibration (CIC) was investigated and the spray chamber efficiency might be a key factor for CIC application among different kinds of brominated chemicals. Finally, the developed method was successfully applied for analysis of 20 human serum samples collected from the Tianjin city. This work provided an alternative approach for simultaneous determination of halogenated chemicals by quantification of halogen element with one-time pretreatment, especially for human serum samples with limited sample volume.

In situ remediation of groundwater by zerovalent iron (ZVI)-based technology faces the problems of rapid passivation, fast agglomeration, limited range of pollutants and secondary contamination. Here a new concept of Magnesium–Aluminum (Mg–Al) alloys and in situ layered double hydroxides on is proposed for the degradation and removal of a wide variety of inorganic and organic pollutants from groundwater. The Mg–Al alloy provides the electrons for the chemical reduction and/or the degradation of pollutants while released Mg 2+, Al 3+ and OH - ions react to generate in situ LDH precipitates, incorporating other divalent and trivalent metals and oxyanions pollutants and further adsorbing the micropollutants. The Mg–Al alloy outperforms ZVI for treating acidic, synthetic groundwater samples contaminated by complex chemical mixtures of heavy metals (Cd 2+, Cr 6+, Cu 2+, Ni 2+ and Zn 2+), nitrate, AsO 3 3-, methyl blue, trichloroacetic acid and glyphosate. Specifically, the Mg–Al alloy achieves removal efficiency ≥99.7% for these multiple pollutants at concentrations ranging between 10 and 50 mg L −1 without producing any secondary contaminants. In contrast, ZVI removal efficiency did not exceed 90% and secondary contamination up to 220 mg L −1 Fe was observed. Overall, this study provides a new alternative approach to develop efficient, cost-effective and green remediation for water and groundwater.

A simple indirectly competitive ratiometric fluorescent immunoassay was designed based on fluorescein amidite (FAM)-DNA–functionalized CdSe/ZnS quantum dots (QDs) for the sensitive determination of tetrabromobisphenol A (TBBPA). At the detection system, catalase (CAT) was labeled on the secondary antibody (Ab2), which served as a controller of the H2O2 concentration. After the competitive binding step, the emitted red fluorescence (excitation at 490 nm) from FAM-DNA–functionalized CdSe/ZnS QDs could be effectively quenched by the H2O2 added. Under the optimized conditions, the limit of detection (LOD) reached 0.118 μg/L with a linear range of 0.34–45.34 μg/L, which was approximately 1 order of magnitude lower than that by HRP-based traditional ELISA. Furthermore, the combination of the dual-output ratiometric fluorescence assays with ELISA improved the inherent built-in rectification to the environment, which brought about satisfactory accuracy and precision (recoveries, 83.16–112.4%; CV, 2.42–7.28%), indicating great potential for the determination of trace TBBPA from food and environmental samples.

A simple and practical magnetic solid-phase extraction high-performance liquid chromatography-inductively coupled plasma mass spectrometry (MSPE-HPLC-ICP-MS) method for extraction and determination of trace mercury species, including inorganic mercury (IHg), monomethylmercury (MeHg) and ethylmercury (EtHg), was developed. The MSPE adsorbent, urchin-like thiol and thioether-functionalized magnetic covalent organic frameworks (Fe3O4@COF-S-SH), was synthesized by coating covalent organic frameworks (COFs) on the surface of Fe3O4 nanoparticles at room temperature and then easily grafting 1,2-Ethanedithiol on the COFs. The as-prepared Fe3O4@COF-S-SH has strong adsorption capacity for IHg, MeHg and EtHg, with excellent static adsorption capacity: 571, 559 and 564 mg g-1, respectively. The parameters influencing the extraction and enrichment had been optimized, including pH, adsorption and desorption time, composition and amount of the eluent, co-existing ions and dissolved organic materials etc. Under the optimized condition, the limit of detection (3δ) of the proposed method were 0.96, 0.17 and 0.47 ng L-1 for IHg, MeHg and EtHg, and the developed method has high actual enrichment factors of 370, 395, 365-fold for IHg, MeHg and EtHg based on 200 mL samples, respectively. The high accuracy and reproducibility has been proved by the spiked recoveries (96.0‒108 %) in real water samples and determination of the certified reference material. Both the adsorption and desorption process can be completed within 5 min. The proposed method with simple operation, short pre-concentration time and high sensitivity has been successfully applied to mercury speciation at trace levels in the samples with complicated matrices, including underground water, surface water, sea water and fish samples.