The relative significance of H-atom transfer versus electron transfer in the dehalogenation of halogenated organic compounds (HOCs) in bimetallic systems has long been debated. In this study, we have investigated this question through the case study of the debromination of 2, 2′, 4, 4’-tetrabromodiphenyl ether (BDE-47). The debromination rates of isomer products of BDE-47 by palladized nano zero-valent iron (n-ZVI/Pd) in the same reactor were compared. The results confirmed a shift in the debromination pathway of BDE-47 when treated with unpalladized nano zero-valent iron (n-ZVI) vs. treatment with n-ZVI/Pd. Study showed that BDEs could be rapidly debrominated in a palladium-H2 system, and the debromination pathway in this system is the same as that in the n-ZVI/Pd system. These results suggest that the H-atom species adsorbed on the surface of palladium are responsible for the enhanced reaction rates and the shift of the debromination pathway in the n-ZVI/Pd system. The Mulliken charges, calculated with density functional theory, on bromine atoms of PBDEs were directly correlated with the susceptibility to the e-transfer pathway in the n-ZVI system and inversely correlated with the susceptibility to the H-transfer pathway in n-ZVI/Pd system. These experimentally verified correlations in BDE-47 permit the prediction of the dominant debromination pathway in other BDEs.

Perfluoroalkyl substances (PFASs) are pollutants that tend to accumulate in the environment and organisms. The animal and human studies to date have focused on thyroid function, but the results are inconsistent.A sample of 118 mother-infant pairs was obtained from the Taiwan Birth Panel Study (TBPS). Cord blood PFASs levels were evaluated using the Waters ACQUITY UPLC system coupled with a Waters Quattro Premier XE triple quadrupole mass spectrometer, and cord blood thyroid hormones were assessed using a Roche Analytics E170 modular analyser (Roche Diagnostics, Mannheim, Germany). PFASs concentrations were analysed in the final models to examine the associations between cord blood PFASs levels and thyroid hormone concentrations.The cord blood perfluorooctane sulfonate (PFOS) concentration was negatively associated with the cord blood thyroxine (T4) concentration [per ln unit: adjusted β (95% confidence interval, CI) = −0.458(−0.916, −0.001)]. Moreover, the level of cord blood thyroid stimulating hormone (TSH) was positively associated with the cord blood PFOS concentration [per ln unit: adjusted β (95% confidence interval, CI) = 0.346(0.101, 0.592)]. The sex stratified effects of PFOS on T4 were suggestive of differential effects in high-exposure groups compared with low-exposure group in boys.We found that cord blood thyroid hormone levels are affected by PFASs, with a negative association between T4 and PFOS and a positive association between TSH and PFOS. The causal associations of thyroid hormones and PFASs require further exploration.

Since the ban of polybrominated diphenyl ethers (PBDEs) excluding deca-BDE in China, new halogenated flame retardants (NHFRs), such as new brominated flame retardants and Dechlorane Plus, have become widely used. In this study, we assessed the atmospheric gaseous and particulate levels of eight NHFRs in nine urban areas in China. We detected high mean atmospheric (vapour plus particle phases) concentrations of tetrabromophthalate (TBPH) (74.8 pg m⁻³) and decabromodiphenyl ethane (DBDPE) (68.8 pg m⁻³), two major NHFRs. Most of the gaseous and particulate NHFR concentrations presented seasonal variations (from summer to autumn), possibly driven by temperature. Spatially, concentrations and patterns of the NHFRs differed among the nine cities. Significantly higher concentrations were detected in cities with higher gross domestic products. The composition, especially the DBDPE/TBPH ratio (S), were clearly different among the cities, which pattern in each city are likely driven by variations in the type of industries operating in each city. Based on the temporal analysis of other researches and our data, PBDE levels have decreased markedly, while NHFRs levels have increased. Since high NHFR levels had detrimental effects on public health, NHFRs research warrants more attention.

Although a large body of literature exists on the use of transplanted mosses for biomonitoring of air pollution, no article has addressed so far the use and the accumulation performance of a cloned moss for this purpose. In this work, a direct comparison of metal accumulation between bags filled with a Sphagnum palustre L. clone or with native Pseudoscleropodium purum Hedw., one of the most used moss species in biomonitoring surveys, was investigated. The test was performed in sites with different atmospheric contamination levels selected in urban, industrial, agricultural and background areas of Italy and Spain. Among the eighteen elements investigated, S. palustre was significantly enriched in 10 elements (Al, Ba, Cr, Cu, Fe, Hg, Pb, Sr, V and Zn), while P. purum was enriched only in 6 elements (Al, Ba, Cu, Hg, Pb and Sr), and had a consistently lower uptake capacity than S. palustre. The clone proved to be more sensitive in terms of metal uptake and showed a better performance as a bioaccumulator, providing a higher accumulation signal and allowing a finer distinction among the different land uses and levels of pollution. The excellent uptake performance of the S. palustre clone compared to the native P. purum and its low and stable baseline elemental content, evidenced in this work, are key features for the improvement of the moss bag approach and its large scale application.

Hazardous Trace elements (HTEs) emitted from coal combustion has raised widespread concern. Studies on the emission characteristics of five HTEs, namely arsenic (As), chromium (Cr), barium (Ba), manganese (Mn), lead (Pb) at three different loads (100%, 83%, 71% output) and different coal types were performed on a 350 MW coal-fired power plant equipped with SCR, ESP + FF, and WFGD. HTEs in the flue gas at the inlet/outlet of each air pollution control device (APCD) were sampled simultaneously based on US EPA Method 29. During flue gas HTEs sampling, coal, bottom ash, fly ash captured by ESP + FF, fresh desulfurization slurry, desulfurization wastewater were also collected. Results show that mass balance rate for the system and each APCD is in an acceptable range. The five studied HTEs mainly distribute in bottom and ESP + FF ash. ESP + FF have high removal efficiency of 99.75–99.95%. WFGD can remove part of HTEs further. Total removal rate across the APCDs ranges from 99.84 to 99.99%. Concentration of HTEs emitted to atmosphere is within the extremely low scope of 0.11–4.93 μg/m3. Emission factor of the five studied HTEs is 0.04–1.54 g/1012J. Content of As, Pb, Ba, Cr in solid samples follows the order of ESP + FF ash > bottom ash > gypsum. More focus should be placed on Mn in desulfuration wastewater, content of which is more than the standard value. This work is meaningful for the prediction and removal of HTEs emitted from coal-fired power plants.

Potential utilities of instrumented lightweight unmanned aerial vehicles (UAVs) to quickly characterize tropospheric ozone pollution and meteorological factors including air temperature and relative humidity at three-dimensional scales are highlighted in this study. Both vertical and horizontal variations of ozone within the 1000 m lower troposphere at a local area of 4 × 4 km² are investigated during summer and autumn times. Results from field measurements show that the UAV platform has a sufficient reliability and precision in capturing spatiotemporal variations of ozone and meteorological factors. The results also reveal that ozone vertical variation is mainly linked to the vertical distribution patterns of air temperature and the horizontal transport of air masses from other regions. In addition, significant horizontal variations of ozone are also observed at different levels. Without major exhaust sources, ozone horizontal variation has a strong correlation with the vertical convection intensity of air masses within the lower troposphere. Higher air temperatures are usually related to lower ozone horizontal variations at the localized area, whereas underlying surface diversity has a week influence. Three-dimensional ozone maps are obtained using an interpolation method based on UAV collected samples, which are capable of clearly demonstrating the diurnal evolution processes of ozone within the 1000 m lower troposphere.

Photo-reduction of Ag+ to silver nanoparticle (AgNPs) by dissolved organic matter (DOM) is a possible source of naturally occurring AgNPs. However, how this photo-reduction process is influenced by ubiquitous metal ions is still not well understood. In addition, in previous studies, the formation of AgNPs in DOM solution was usually monitored by UV-Vis spectroscopy, and there is still lack of quantitative analysis for the formed AgNPs. In the present study, the role of Fe2+/Fe3+ at environmental concentration level on this photochemical process was investigated, and the enhanced formation of AgNPs by Fe2+/Fe3+ was probed and quantified by using UV-Vis spectroscopy, transmission electron microscopy, and liquid chromatography-inductively coupled plasma mass spectrometry. It was demonstrated that while Fe3+ can oxidize AgNPs to release Ag+, Fe2+ can reduce Ag+ into AgNPs. However, the DOM-induced reduction of Fe3+ makes iron an effective electron shuttle between DOM and Ag+, and both Fe2+ and Fe3+ enhanced AgNP formation. The impacts of environmentally relevant factors, including DOM concentration and solution pH, on this process were studied comprehensively, which showed that the catalytic role of iron was more significant at higher DOM concentration and lower pH. This iron-enhanced formation of AgNPs in photo-irradiated Ag+-DOM solution have great environmental implications on the formation of natural AgNPs and the transformation of engineered AgNPs in acidic surface water with high iron content.

Short-chain chlorinated paraffins (SCCPs) are widely used chemicals in household products and might cause adverse human health effects. However, limited information is available on the occurrence of SCCPs in indoor environments and their exposure risks on humans. In this study the concentrations, profiles and human exposure of SCCPs in indoor dust from five different indoor environments, including commercial stores, residential apartments, dormitories, offices and laboratories were characterized. The SCCPs levels ranged from 10.1 to 173.0 μg/g, with the median and mean concentration of 47.2 and 53.6 μg/g, respectively. No significant difference was found on concentrations among the five microenvironments. The most abundant compounds in indoor dust samples were homologues of C13 group, Cl7 group and N20 (N is the total number of C and Cl) group. In the five microenvironments, commercial stores were more frequently exposed to shorter carbon chained and higher chlorinated homologues. Three potential sources for SCCPs were identified by the multiple linear regression of factor score model and correspondence analysis. The major sources of SCCPs in indoor dust were technical mixtures of CP–42 (42% chlorine, w/w) and CP–52 b (52% chlorine, w/w). The total daily exposure doses and hazard quotients (HQ) were calculated by the human exposure models, and they were all below the reference doses and threshold values, respectively. Monte Carlo simulation was applied to predict the human exposure risk of SCCPs. Infants and toddlers were at risk of SCCPs based on predicted HQ values, which were exceeded the threshold for neoplastic effects in the worst case. Our results on the occurrences, sources and human exposures of SCCPs will be useful to provide a better understanding of SCCPs behaviors in indoor environment in China, and to support environmental risk evaluation and regulation of SCCPs in the world.

The potential toxic impacts of different crystal phases of titania nanoparticles (TNPs) on freshwater biofilms, especially under ultraviolet C irradiation (UVC), are unknown. Here, adverse impacts of three phases (anatase, rutile, and P25, 50 mg L−1 respectively) with UVC irradiation (An-UV, Ru-UV, and P25-UV) on freshwater biofilms were conducted. Characterization experiments revealed that rutile TNPs had a higher water environment stability than anatase and P25 TNPs, possessing a stronger photocatalytic activity under UVC irradiation. Phase-dependent inhibition of cell viability and significant decreases of four- and five-fold in algal biomass at 12 h of exposure were observed compared with unexposed biofilms. Moreover, phase-dependent oxidative stress resulted in remarkably significant reductions (P < 0.01) of the photosynthetic yields of the biofilms, to 40.32% (P25-UV), 48.39% (An-UV), and 46.77% (Ru-UV) of the plateau value obtained in the unexposed biofilms. A shift in community composition that manifested as a strong reduction in diatoms, indicating cyanobacteria and green algae were more tolerant than diatoms when exposed to TNPs. In terms of the toxic mechanisms, rutile TNPs resulted in apoptosis by inducing excessive intracellular reactive oxygen species (ROS) production, whereas P25 and anatase TNPs tended to catalyze enormous acellular ROS lead to cell necrosis under UVC irradiation.

The release assessment of multi-walled carbon nanotubes (CNTs) was performed on two types of polymer-CNT nanocomposites: polypropylene (PP) and polyamide 6 (PA6) containing 3 wt% CNT. Nanocomposite films were prepared and then exposed to ethanol as a fatty-food simulant at 40 °C, and the amount of CNT release into ethanol was determined by ultraviolet–visible spectroscopy (UV–Vis) and graphite furnace atomic absorption spectrometry (GFAAS). The CNTs released into ethanol were visualized by transmission electron microscopy (TEM) and verified by Raman spectroscopy. UV–Vis analysis showed a very small amount of CNT release from the nanocomposite films into ethanol over 60 d: maximum CNT concentrations in ethanol were 1.3 mg/L for the PP-CNT film and 1.2 mg/L for the PA6-CNT film. GFAAS results indicated that the amount of CNTs released into ethanol after 12 d was over 20-fold higher than the results obtained by UV–Vis. Overestimation of CNT release by GFAAS suggested aggregation and poor dispersion of CNTs in the solvent. This assumption was verified by TEM images exhibiting the embedded CNTs in the polymer flakes, which could be poorly dispersed in the solvent. In general, CNT release from the nanocomposite films was considered a surface phenomenon, as indicated by detachment of CNT-containing polymer flakes from the film surface.