PM2.5-bound polyhalogenated carbazoles (PHCZs) in urban Beijing, China: Occurrence and the source implication.

Polyhalogenated carbazoles (PHCZs) are recently raising much attention due to their toxicity and ubiquitous environmental distribution. However, little knowledge is known about their ambient occurrences and the potential source. In this study, we developed an analytical method based on GC-MS/MS to simultaneously determine 11 PHCZs in PM2.5 from urban Beijing, China. The optimized method provided low method limit of quantifications (MLOQs, 1.45-7.39 fg/m3) and satisfied recoveries (73.4%-109.5%). This method was applied to analyze the PHCZs in the outdoor PM2.5 (n = 46) and fly ash (n = 6) collected from 3 kinds of surrounding incinerator plants (steel plant, medical waste incinerator and domestic waste incinerator). The levels of ∑11PHCZs in PM2.5 ranged from 0.117 to 5.54 pg/m3 (median 1.18 pg/m3). 3-chloro-9H-carbazole (3-CCZ), 3-bromo-9H-carbazole (3-BCZ), and 3,6-dichloro-9H-carbazole (36-CCZ) were the dominant compounds, accounting for 93%. 3-CCZ and 3-BCZ were significantly higher in winter due to the high PM2.5 concentration, while 36-CCZ was higher in spring, which may be related to the resuspending of surface soil. Furthermore, the levels of ∑11PHCZs in fly ash ranged from 338 to 6101 pg/g. 3-CCZ, 3-BCZ and 36-CCZ accounted for 86.0%. The congener profiles of PHCZs between fly ash and PM2.5 were highly similar, indicating that combustion process could be an important source of ambient PHCZs. To the best of our knowledge, this is the first research providing the occurrences of PHCZs in outdoor PM2.5.

Kinetics of PCDD/Fs from feed to cow milk and its implications for food safety.

Guideline levels of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) in feed and food have been separately recommended for the official food safety control around the world. However, less is considered about the transfer effect of PCDD/Fs from feed to food, and consequently possible human exposure risk. In this study, different controlled feeding experiments (E1 group: 4.92 pg TEQ/g in feed, E2 group: 0.61 pg TEQ/g in feed) were conducted on dairy cow (Chinese Holstein breed) to evaluate kinetics of PCDD/Fs from feed to milk and blood. Even though the PCDD/F level in feed in E2 was satisfied with the EU Regulation (No 277/2012), the TEQ levels in milk and tissues exceeded the European Union maximum level (EU ML) after approximately one-week exposure. The dynamic variation in milk during the initial 20-day exposure was successfully described by a first-order kinetic model. The levels at the plateau period showed a significant linear relationship (p < 0.01, R2 = 0.98) against the intake amounts from feed. Based on modeling, a maximum content was obtained at approximately 0.33 pg TEQ/g in cow feed with 12 % moisture to ensure the milk and meat safety under the current regulatory requirements of EU for cow-origin food. After the cease of exposure, the PCDD/F levels in milk declined below the EU ML within 40 days, while those in meat were still higher than the EU ML over 160 days. In serum, PCDD/Fs detected in E1 showed a similar dynamic variation during the exposure period. Regarding congener profile, higher-chlorinated congeners tended to transfer from feed to feces, whereas lower ones were preferably transferred into milk, which required specific concern about the metabolic effect of PCDD/Fs in large mammals. This study revealed a necessity for re-evaluation of official regulation on pollutants in cow feed and cow-origin food in terms of biotransfer and bioaccumulation.

Indoor exposure to selected flame retardants and quantifying importance of environmental, human behavioral and physiological parameters.

Indoor exposure to organic flame retardants (FRs) has raised extensive concern due to associated adverse health effects. Indoor-exposure induced daily intakes of six widely used FRs individually ranged 0.002-611 ng/day and 0.02-463 ng/day, respectively, for adults and 2-6-year-old children; and resulting internal exposure levels ranged 0.1-159 and 2.1-4500 ng/g lipid, respectively. A proportion of 0.001-5.9% and 0.006-10.3% of individual FRs emitted into indoor air ultimately entered bodies of adults and children respectively. Tris(2-chloroisopropyl)phosphate dominated in emissions, whilst 2-ethylhexyl-2,3,4,5-tetrabromobenzoate dominated in human bodies. Hand-to-mouth contact was the most important exposure pathway for less volatile FRs including most brominated FRs, whilst inhalation was the predominant intake pathway of tris(2-chloroisopropyl)phosphate. Relative importance of 29 environmental, behavioral and physiological parameters was ranked to explore key drivers influencing exposure and accumulation of FRs in humans. Results suggested that frequent bathing and handwashing can reduce exposure effectively, especially for children. Bodyweight and lipid fraction were only positively related to internal accumulation and body-weight-normalized concentrations of compounds with low metabolic rates (half-lives ≥103 h) in humans. Our findings help control indoor exposure to FRs and are supportive of human exposome studies in the future.

Modeling of Flame Retardants in Typical Urban Indoor Environments in China during 2010-2030: Influence of Policy and Decoration and Implications for Human Exposure.

Novel flame retardants (FRs) are of increasing concern, given growing evidence of health effects and use to replace polybrominated diphenyl ethers (PBDEs). This study modeled combined effects of use policies and decoration on indoor FRs and human exposure for 18 widely used PBDEs, organophosphate esters (OPEs), and novel brominated flame retardants in typical urban indoor environments in China. The current estimated indoor emission rates and average concentrations in air and dust of the 18 FRs were 102-103 ng/h, 561 ng/m3, and 1.5 × 104 ng/g, respectively, with seven OPEs dominant (>69%). Different use patterns exist between China and the US and Europe. Scenarios modeled over 2010-2030 suggested that decoration would affect indoor concentrations of FRs more than use policies, and use policies were mainly responsible for shifts of FR composition. Additional use of hexabromobenzene and 2,3,4,5,6-pentabromotoluene and removal of BDE-209 would make the total human exposure to the modeled FR mixture increase after the restriction of penta- and octa-BDE but decrease after deca-BDE was banned. Better knowledge of the toxicity of substitutes is needed for a complete understanding of the health implications of such changes. Toddlers may be more affected by use changes than adults. Such studies are supportive to the management of FR use.

Preparation and application of magnetic molecular imprinted polymers for extraction of cephalexin from pork and milk samples.

A highly selective and effective method was successfully developed using magnetic molecular imprinted polymers (MMIPs) as solid-phase extraction (SPE) coupled with high performance liquid chromatography-ultraviolet detector (HPLC-UV) to rapidly determine cephalexin (CFX) in complex animal-derived food. MMIPs were creatively synthesized via suspension polymerization using Fe3O4 magnetic nanoparticles as supporter, CFX as template, acrylamide (AM) as functional monomer, and ethylene glycol dimethacrylate (EGDMA) as cross-linker. The MMIPs were characterized using X-ray diffraction (XRD), Fourier transform infrared spectrometry (FT-IR), scanning electron microscopy (SEM), and vibrating sample magnetometry (VSM). The binding process fitted well with pseudo-second-order model with good selectivity. Scatchard plot analysis suggested that MMIPs have two types of binding sites with the Qmax of 24.18 mg g-1 and 40.25 mg g-1, respectively. And Langmuir model proved that the recognition sites were uniformly distributed in a monolayer on the surface of MMIPs. The methodological assessment showed good applicability of MMIPs with excellent recovery (85.5%-94.0%), precision (1.2%-2.4%), and stability (intra-day 1.3%-3.6%; inter-day 2.6%-4.3%) in determining CFX content. In addition, the linearity of the calibration curve was good in the range of 0.02-5.00 mg L-1, with a sensitive detection limit of 5.00 µg kg-1. The results above suggest that the obtained MMIPs exert good performance for separation of CFX in animal-derived food, and the proposed method is suitable for the reliable determination of CFX in complex samples.

Preparation of magnetic molecularly imprinted polymers with double functional monomers for the extraction and detection of chloramphenicol in food.

In this study, an efficient, selective, and simple analytical method for the extraction of chloramphenicol (CAP) from food using magnetic molecularly imprinted polymers (MMIPs) as the solid-phase extraction (SPE) sorbent was successfully developed. MMIPs with varying ratios of methacrylic acid to acrylamide were prepared by suspension polymerization on the surface of double-bond-modified Fe3O4 magnetic nanoparticles. Further, these MMIPs were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy, as well as using a vibrating sample magnetometer. Furthermore, the adsorption capacities of MMIPs and MNIPs were investigated by binding experiments. Methodology evaluation for the detection of CAP from food was carried out using MMIPs as the SPE sorbent. By using an external magnetic field, MMIPs were separated by a simple and rapid method. The diameter of the so-obtained MMIPs, exhibiting good monodispersity, was 400-700 nm. The MMIPs exhibited the maximum apparent adsorption capacity of up to 42.60 mg g-1 with good selectivity. For the detection of food samples, the linear response range was 0.02-10.00 mg L-1, with a detection limit of 10 µg L-1, and intra- and inter-day stabilities ranged from 1.34% to 1.89% and from 1.76% to 2.77%, respectively, with good recoveries (95.31%-106.89%) and satisfactory relative standard deviations (1.21%-2.60%).