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Cocontamination by heavy metals and persistent organic pollutants (POPs) is ubiquitous in the environment. Fate of POPs within soil/water-plant system is a significant concern and an area where much uncertainty still exists when plants suffered cotoxicity from POPs and metals. This study investigated the fate of polybrominated diphenyl ethers (PBDEs) when copper (Cu) was present within the soil/water-plant system using pot and hydroponic experiments. The presence of Cu was found to induce damage to the root cell membranes of corn (Zea mays L. cv. Nongda 108) with increasing concentration in both shoots and roots. The PBDE congeners BDE209 and BDE47 in shoots were also enhanced with the increasing electrolytic leakage from root, attributed to Cu damage, and the highest shoot BDE209 and BDE47 levels were observed under the highest Cu dosage. In addition, positive correlations were observed between the PBDE content of corn shoots and the electrolytic leakage of corn roots. These results indicated that within a defective root system, more PBDEs will penetrate the roots and are acropetally translocated in the shoots. The potential ecological risk associated with the translocation and accumulation of POPs into plant shoots needs careful reconsideration in media cocontaminated with metals and POPs, whereas often ignored or underestimated in environmental risk assessments.

For the first time, we present an analytical method to simultaneously extract, fractionate, and quantify four groups of semi-volatile organic compounds (SVOCs) in silicone wristbands, including 35 polybrominated diphenyl ethers (PBDEs), 10 novel flame retardants (NFRs), 19 organophosphate esters (OPEs), and 13 polycyclic aromatic hydrocarbons (PAHs). Wristbands were extracted using ultrasonication, and cleaned and fractionated on two multi-layer columns: one consisting of neutral alumina, neutral silica and Florisil, and the other consisting of neutral alumina, neutral silica, and acidic silica. Method accuracy and precision were validated using spiked wristband samples (n = 8) and procedural blanks (n = 7). Average matrix spike percent recoveries for all target analytes were within 57 -107% with relative standard errors < 20%, with a few exceptions. This method was applied to analyze thirteen wristbands worn by ten participants for seven days; three participants wore two wristbands to evaluate duplicate samples. Percent recoveries of surrogate standards for all four groups of analytes in these wristbands were all within the 80 -120% range with a few exceptions: recoveries for 13 C 12 BDE-209 and for 13 C 12 -triphenyl phosphate ranged from 35 -62% and 69 -176%, respectively. The majority of target analytes were detected in at least half of worn wristbands. The levels of total PBDEs, NFRs, OPEs and PAHs in deployed wristbands ranged from 28.4 to 412 ng, 40.7 to 625 ng, 2,440 to 9,580 ng, and 76.2 to 1,240 ng, respectively.We developed an efficient method for the determination of a total of 77 analytes, including 35 PBDEs, 10 NFRs, 19 OPEs, and 13 PAHs, in silicone wristbands. This method offers a solution to chromatographic interferences associated with siloxanes from the wristband Romanak et al. Highlights •Silicone wristbands are a novel tool for assessing personal exposures • This is the first method for simultaneous quantitative analysis of 77 SVOCs 35 PBDEs, 9 NFRs, 19 OPEs, and 13 PAHs were simultaneously extracted and analyzed Romanak et al. •

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Rice, one of the most widely cultivated crops, has received great attention in contaminant uptake from soil and air, especially for the special approaches used for its cultivation. The dry−wet alternation method can influence the air−soil partitioning of semivolatile organic compounds (SVOCs) in the paddy ecosystem. Here, we modified a fugacity sampler to investigate the air−surface in situ partitioning of ubiquitous polycyclic aromatic hydrocarbons (PAHs) at different growth stages in a suburban paddy field in South China. The canopy of rice can form a closed space, which acts like a chamber that can force the air under the canopy to equilibrate with the field surface. When we compared the fugacities calculated using a fugacity model of the partition coefficients to the measured fugacities, we observed similar trends in the variation, but significantly different values between different growing stages, especially during the flooding stages. However, the measured and calculated fugacity fractions were comparable when uncertainties in our calculations were considered, with the exception of the high molecular weight (HMW) PAHs. The measured fugacity fractions suggested that the HMW PAHs were also closed to equilibrium between the paddy field and atmosphere. The modified fugacity sampler provided a novel way of accurately determining the in situ air−soil partitioning of SVOCs in a wet paddy field.

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Exposure to flame retardants (FRs) is associated with adverse effects on human health. Focusing on three FR groups, including polybrominated diphenyl ethers (PBDEs), organophosphate FRs (OPFRs), and novel brominated FRs (nBFRs), we determined the levels of these chemicals in indoor air in homes in rural Central Appalachia using passive air samplers and personal exposures in the residents of these homes using silicone wristbands. We also investigated the relationships between the FR levels in wristbands and the thyroid function. The median total concentrations of PBDEs, OPFRs, and nBFRs were 210, 25 000, and 69 pg/m3 in indoor air, and 49, 670, and 110 ng/g in wristbands, respectively. The most abundant chemicals in both air and wristbands were BDE-47 and -99 among PBDEs, tris­[(2R)-1-chloro-2-propyl] phosphate among OPFRs, and 2-ethylhexyl 2,3,4,5-tetrabromobenzoate and bis­(2-ethylhexyl) tetrabromophthalate among nBFRs. In gender-specific regression models that were controlled for age and smoking, significant associations were observed between BDE-99, BDE-197, and 2-ethylhexyldiphenyl phosphate (EHDP) and free thyroxine (FT4), between BDE-100 and free triiodothyronine (FT3), and between anti-Dechlorane Plus (DP) and thyroid-stimulating hormone (TSH). In particular, most penta-BDE congeners were significantly or marginally significantly associated with FT4 and FT3 for both females and males. Our results suggest that wristbands can be used as suitable exposure monitors for evaluating human exposure to FRs.