The presence of PM₂.₅ may affect the photodegradation of benzene in the natural atmosphere. On one hand, the photodegradation of benzene may be promoted with the increase in PM₂.₅ concentrations, owing to adsorption and catalysis effect of PM₂.₅ surface; On the other hand, PM₂.₅ can scatter or block ultraviolet light and lead to weakening the photochemical reactions in the atmospheric system. It is very difficult to prove which process is dominant in the real atmosphere due to the complexity of the atmosphere. Based on coupling detrended fluctuation analysis, the goal of this work is to reveal the role of PM₂.₅ in the photodegradation of benzene in real atmosphere over long time scales. The 9 years regular monitoring data from 2007 to 2016 in Puzi of Taiwan are analyzed. A new nonlinear parameter (PDB) is established to characterize the photodegradation degree of atmospheric benzene. Based on sliding window technique, the correlations between the temporal variation of PDB and PM₂.₅ are analyzed. The results show that there is a positive correlation between PDB and PM₂.₅ in daytime and little correlation between them in nighttime. It indicates that PM₂.₅ mainly plays the promoting effect on the photodegradation of atmospheric benzene. This is the first study to directly determine the role of PM₂.₅ in the photochemical behavior of atmospheric benzene based on long term field observation data. Moreover, the results suggest that the regional transport of PM₂.₅ could seriously affect the geochemistry cycle of some VOCs. This research provides a new analysis method to directly quantify the effect of PM₂.₅ on the photodegradation of VOCs in the real atmosphere. It is helpful for evaluating the role of PM₂.₅ in the complex photochemical system.

Due to the negative health impacts, significant efforts have been directed towards investigating ultrafine particle (UFP) exposure in various indoor environments. As children spend approximately one third of their time in schools, educatory environments deserve particular attention; however, majority of past research has focused on UFP assessment in classrooms. Thus, this work aims to expand the characterization of UFP in primary schools by considering different indoor and outdoor school microenvironments and estimating inhalation doses for the respective students (6–11yrs old). Real-time UFP measurements were daily conducted (9:00–17:30) in 20 primary schools in Oporto (January–April 2014; October–February 2015) in classrooms, canteens, gyms, libraries, and concurrently outdoors. Overall, UFP concentrations showed large temporal and spatial variations. For classrooms (n = 73), median UFP (1.56 × 10³–16.8 × 10³ # cm⁻³) were lower than the corresponding levels in ambient air of schools (1.79 × 10³–24.1 × 10³ # cm⁻³). Outdoor emissions contributed to indoor UFP (indoor-to-outdoor ratios I/O of 0.0.30–0.85), but ventilation, room characteristics and its occupancy were identified as important parameters contributing to overall indoor UFP levels. Considering specific indoor school microenvironments, canteens were the microenvironment with the highest UFP levels (5.47 × 10³–36.4 × 10³ # cm⁻³), cooking conducted directly on school grounds resulted in significantly elevated UFP in the respective classrooms (p < 0.05); the lowest UFP were found in libraries (4.45 × 10³–8.50 × 10³ # cm⁻³) mostly due to the limited occupancies. Although students spend majority of their school time in classrooms (66–71%), classroom exposure was not consistently the predominant contributor to school total UFP inhalation dose (29–75%). Outdoor exposure contributed 23–70% of school dose (depending on UFP levels in ambient levels and/or conducted activities) whereas short periods of lunch break accounted for 8–40%. Therefore, when evaluating UFP exposure in educatory settings other microenvironments beyond classrooms should be an integral part of the study.

Manufactured nanoparticles (MNPs) undergo transformation immediately after they enter wastewater treatment streams and during their partitioning to sewage sludge, which is applied to agricultural soils in form of biosolids. We examined toxicogenomic responses of the model nematode Caenorhabditis elegans to pristine and transformed ZnO-MNPs (phosphatized pZnO- and sulfidized sZnO-MNPs). To account for the toxicity due to dissolved Zn, a ZnSO₄ treatment was included. Transformation of ZnO-MNPs reduced their toxicity by nearly ten-fold, while there was almost no difference in the toxicity of pristine ZnO-MNPs and ZnSO₄. This combined with the fact that far more dissolved Zn was released from ZnO- compared to pZnO- or sZnO-MNPs, suggests that dissolution of pristine ZnO-MNPs is one of the main drivers of their toxicity. Transcriptomic responses at the EC₃₀ for reproduction resulted in a total of 1161 differentially expressed genes. Fifty percent of the genes differentially expressed in the ZnSO₄ treatment, including the three metal responsive genes (mtl-1, mtl-2 and numr-1), were shared among all treatments, suggesting that responses to all forms of Zn could be partially attributed to dissolved Zn. However, the toxicity and transcriptomic responses in all MNP treatments cannot be fully explained by dissolved Zn. Two of the biological pathways identified, one essential for protein biosynthesis (Aminoacyl-tRNA biosynthesis) and another associated with detoxification (ABC transporters), were shared among pristine and one or both transformed ZnO-MNPs, but not ZnSO₄. When comparing pristine and transformed ZnO-MNPs, 66% and 40% of genes were shared between ZnO-MNPs and sZnO-MNPs or pZnO-MNPs, respectively. This suggests greater similarity in transcriptomic responses between ZnO-MNPs and sZnO-MNPs, while toxicity mechanisms are more distinct for pZnO-MNPs, where 13 unique biological pathways were identified. Based on these pathways, the toxicity of pZnO-MNPs is likely to be associated with their adverse effect on digestion and metabolism.

For divalent metals, the Biotic Ligand Model (BLM) has been proven to be an effective tool to predict biological effects by taking into account speciation calculations and competitive interactions. Nonetheless, the BLM has only rarely been validated for trivalent metals (e.g. rare earth elements), and the potential competitive effects of protons has been understudied. In this paper, the short-term biouptake of indium (In), a trivalent metal that is a byproduct of zinc extraction and used in numerous applications including the semiconductor industry, was evaluated under controlled conditions. Short-term (i.e. 60 min) indium biouptake by Chlamydomonas reinhardtii was measured as a function of pH in order to verify the validity of the BLM. At a given pH, In biouptake could be well described by the Michaelis-Menten equation with conditional stability constants of KIn,pH=4.0 = 106.7 M-1, KIn,pH=5.0 = 108.6 M-1, KIn,pH=6.0 = 109.3 M-1 and maximum internalization fluxes of Jmax, pH=4.0 = 0.74 × 10−14 mol cm−2 s−1, Jmax, pH=5.0 = 1.60 × 10−14 mol cm−2 s−1, Jmax, pH=6.0 = 2.22 × 10−14 mol cm−2 s−1. Although several potential mechanisms for the role of pH were examined, the results were best explained by a competitive interaction of H+ with the In uptake sites using overall stability constants of logKIn = 9.76 M-1 and logKH = 15.66 M-1. Based on these results, pH will play a critical role in bioavailability measurements of the trivalent cations in natural waters.

Suffered from serious air pollution, Beijing, the capital of China, has implemented multiple measures to reduce the discharge of PM₂.₅ (particulate matter with aerodynamic diameters of less than 2.5 μm). The average annual PM₂.₅ concentration of Beijing has shown a continued decline in recent years. However, the improvement was not obvious during the heating season, which had heavier pollution than the non-heating season. Analyzing the spatial distribution of PM₂.₅ concentrations during heating and non-heating seasons, as well as their spatial differences, is believed to benefit the study of spatial-temporal variation of air pollution and provide scientific reference for the control of air pollution in Beijing. In this study, land use regression (LUR) model was employed to simulate the spatial distribution of PM₂.₅ concentrations in Beijing during heating and non-heating seasons in 2015. The spatial distribution of the concentration difference between heating and non-heating seasons was analyzed, and the influencing factors were also examined. The results showed that: (1) PM₂.₅ concentrations during heating and non-heating seasons, as well as their differences, were clearly at a maximum in the south and east of Beijing and at a minimum in the north and west; (2) the area with the biggest concentration difference was situated in a suburban area to the south and east, as well as in outer suburbs to the southeast and northwest; and (3) wind speed, area of transport land and industrial-mining-warehouse land were the main influence factors for the PM₂.₅ concentration difference in the central, eastern and southern area. Heating activity was not the only cause for the increased PM₂.₅ concentration during the heating season, vehicle emission, industrial discharge and regional transport of pollutants also played varied roles in PM₂.₅ pollution in different area.

Cigarette smoking (CS) and betel quid (BQ) chewing are two known risk factors that have synergistic potential for the enhancing the development of oral squamous cell carcinoma (OSCC) in Taiwan. Most mutagens and carcinogens are metabolically activated by cytochrome P450 (CYP450) to exert their mutagenicity or carcinogenicity. Previous studies have shown that metabolic activation of the tobacco-specific nitrosamine, 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK), by CYP2A6 activity determines NNK-induced carcinogenesis. In addition, safrole affects cytochrome P450 activity in rodents. However, the effect of BQ safrole on the metabolism of tobacco-specific NNK and its carcinogenicity remains elusive. This study demonstrates that safrole (1 mg/kg/d) induced CYP2A6 activity, reduced urinary 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL) levels, and increased NNK-induced DNA damage, including N7-methylguanine, 8-OH-deoxyguanosine and DNA strand breaks in a Syrian golden hamster model. Furthermore, altered NNK metabolism and increased NNK-induced DNA damage were also observed in healthy subjects with CS and BQ chewing histories compared to healthy subjects with CS histories. In conclusion, BQ containing safrole induced tobacco-specific NNK metabolic activation, resulting in higher NNK-induced genotoxicity. This study provides valuable insight into the synergistic mechanisms of CS- and BQ-induced OSCC.

In this study, a multi-component catalyst, β-cyclodextrin (β-CD) and reduced graphene oxide (rGO) co-modified Fe₃O₄, was fabricated via one-pot solvothermal method and used as a synergistic catalyzer for Bisphenol A (BPA) removal. The study found that catalytic reactions of BPA followed the pseudo-first-order kinetics model, and the correlation rate constants (kₒbₛ) were calculated. Compared with Fe₃O₄@β-CD (0.02173 min⁻¹), Fe₃O₄/rGO (0.09735 min⁻¹) and Fe₃O₄ (0.01666 min⁻¹), the composite (0.15733 min⁻¹) exhibited stronger catalytic ability to remove BPA from aqueous solution under the same conditions, which were attributed to the synergistic enhancement effect among the components. The introduction of rGO in the composites was beneficial to the generation of •OH, and the role of β-CD might enhance the utilization of •OH. A possible three-element catalytic schematic diagram was described. The effects of pH, dosage of the catalyst, initial H₂O₂ and NH₂OH concentrations on the removal efficiency were further investigated. The removal of BPA and TOC retained 78.2 ± 2.4% and 52.9 ± 2.5% after five cycles, indicating its excellent stability and reusability. Furthermore, a probable reaction pathway of BPA removal was suggested by analyzing the intermediate products. All results indicated that the composite had high and stable catalytic performance, which made it have potential application on the industrial treatment of wastewater.

An understanding of the dispersion and level of emissions source of atmospheric pollutants; whether point, area or volume sources, is required to inform policies on air pollution and day-to-day predictions of pollution level. Very few studies have carried out simulations of the dispersion pattern and ground-level concentration of pollutants emitted from real-world gas flares. The limited availability of official data on gas flares from the oil and gas industries makes accurate dispersion calculations difficult. Using ADMS 5 and AERMOD, this study assessed the sensitivity of dispersion and ground-level concentration of pollutants from gas flares in the Niger Delta to prevailing meteorological condition; fuel composition; and flare size. Although, during the non-WAM (West African Monsoon) months (November and March), the simulated ground-level concentrations of pollutants from a single flare are lower, the dispersion of pollutants is towards both the inland and coastal communities. In the WAM months, the ground-level concentrations are higher and are dispersed predominantly over the inland communities. Less buoyant plumes from smaller flares (lower volume flow rates) and/or flaring of fuel with lower heat content results in higher ground-level concentrations in areas closer to the flare. Considering the huge number of flares scattered around the region, a mitigation of the acute local pollution level would be to combine short stacks flaring at lower volume flow rates to enhance the volume flow rate of a single exhaust, and hence, the buoyancy of the plume exiting the stack.

Aluminum dialkyl phosphinates (ADPs) are a class of promising phosphorus-containing flame retardants, but their environmental fate is not well understood. Sorption and transport behaviors of ADPs, and their hydrolysates dialkyl phosphinic acids (DPAs) were studied by batch and column experiments. ADPs are less mobile in soil columns with more than half (>52.6%) of ADPs retained in the soil and residues in the topmost 2-cm layer account for more than 57% of total residues. Dissolution and dispersion of fine grain ADPs were responsible for the transport of ADPs. Sorption DPAs (logKₒc) was significantly related to the lipophilicity of DPAs (logD) (p < 0.05). Soil pH and clay content were the dominant factors governing the sorption and transport of DPAs in soils, indicating the importance of electrostatic interactions. The retardation factors (R) of DPAs derived from leaching experiments were pH-dependent with larger R values in the acidic soil (pH = 4.0) where anionic and neutral species of DPAs coexisted. Both physical and chemical non-equilibrium convection-dispersion equations (CDE) yield appropriate modeling for DPAs transport. In most cases, R values estimated from column tests differed from those derived from the batch experiments, which might be attributed to non-equilibrium sorption processes in dynamic conditions.

Many portable monitors for quantifying mass concentrations of particulate matter air pollution rely on aerosol light scattering as the measurement method; however, the relationship between scattered light (what is measured) and aerosol mass concentration (the metric of interest) is a complex function of the refractive index, size distribution, and shape of the particles. In this study, we compared 33-h personal PM2.5 concentrations measured simultaneously using nephelometry (personal DataRAM pDR-1200) and gravimetric filter sampling for working adults (44 participants, 249 samples). Nephelometer- and filter-derived 33-h average PM2.5 concentrations were correlated (Spearman's ρ = 0.77); however, the nephelometer-derived concentration was within 20% of the filter-derived concentration for only 13% of samples. The nephelometer/filter ratio, which is used to correct light-scattering measurements to a gravimetric sample, had a median value of 0.52 and varied by over a factor of three (10th percentile = 0.35, 90th percentile = 1.1). When 33-h samples with >50% of 10-s average nephelometer readings below the nephelometer limit of detection were removed from the dataset during sensitivity analyses, the fraction of nephelometer-derived concentrations that were within 20% of the filter-derived concentration increased to 25%. We also evaluated how much the accuracy of nephelometer-derived concentrations improved after applying: (1) a median correction factor derived from a subset of 44 gravimetric samples, (2) participant-specific correction factors derived from one same from each subject, and (3) correction factors predicted using linear models based on other variables recorded during the study. Each approach independently increased the fraction of nephelometer-derived concentrations that were within 20% of the filter-derived concentration to approximately 45%. These results illustrate the challenges with using light scattering (without correction to a concurrent gravimetric sample) to estimate personal exposure to PM2.5 mass among mobile adults exposed to low daily average concentrations (median = 8 μg m−3 in this study).