Catalytic pyrolysis is a promising chemical recycling technology to supplement mechanical recycling since plastics can be broken down into monomers or converted to the required fuels and chemicals. In this study, a microwave (MW) -responsive SiC foam@zeoltie core-shell structured catalyst was proposed for the catalytic pyrolysis of polyolefins. Under microwave irradiation, the SiC foam core works as both microwave adsorber and catalyst support, thus concentrating the generated heat energy on the ZSM-5 zeolite shell, where the catalytic reaction takes place. SiC foam with an open cellular structure can also improve the global transport of mass and heat during plastics pyrolysis. In this work, the effects of the SiO₂/Al₂O₃ ratio and alkaline treatment of ZSM-5 zeolite coated SiC foam under MW irradiation on the variations in product distribution from low-density polyethylene (LDPE) pyrolysis were investigated at 450 °C. The results indicated that the appropriate acidity and pore structure were crucial to upgrading gas and liquid products. Particularly, the creation of a mesoporous structure in ZSM-5 zeolite via alkaline treatment could improve the diffusion of large molecules and products, thus significantly increasing the selectivity of high-valued light olefins and aromatics while inhibiting the formation of unwanted alkanes, which are expected in the chemical industry. Concretely, the concentration of olefins in gas increased to 51.0 vol% for ZSM-5(50)-0.25AT, and 65.6 vol% for ZSM-5 (50)-0.50AT, compared with 45.2 vol% for the parent ZSM-5(50). The relative concentration of aromatics in liquid decreased from 96.6% for ZSM-5(50) to 75.9% for ZSM-5(50)-0.25AT, and 71.1% for ZSM-5(50)-0.50AT. Given the respective yield of gas and liquid, the total selectivity of C2–C4 olefins and aromatics for mesoporous ZSM-5 zeolites could reach 58.6–64.9% during LDPE pyrolysis, which were higher than that for the parent ZSM-5 zeolite.

Ground-based Multi-Axis Differential Optical Absorption Spectroscopy (Max-DOAS) measurements of nitrogen dioxide (NO₂) were continuously obtained from January to November 2019 in northeastern China (NEC). Seasonal variations in the mean NO₂ vertical column densities (VCDs) were apparent, with a maximum of 2.9 × 10¹⁶ molecules cm⁻² in the winter due to enhanced NO₂ emissions from coal-fired winter heating, a longer photochemical lifetime and atmospheric transport. Daily maximum and minimum NO₂ VCDs were observed, independent of the season, at around 11:00 and 13:00 local time, respectively, and the most obvious increases and decreases occurred in the winter and autumn, respectively. The mean diurnal NO₂ VCDs at 11:00 increased to at 08:00 by 1.6, 5.8, and 6.7 × 10¹⁵ molecules cm⁻² in the summer, autumn and winter, respectively, due to increased NO₂ emissions, and then decreased by 2.8, 4.2, and 5.1 × 10¹⁵ molecules cm⁻² at 13:00 in the spring, summer, and autumn, respectively. This was due to strong solar radiation and increased planetary boundary layer height. There was no obvious weekend effect, and the NO₂ VCDs only decreased by about 10% on the weekends. We evaluated the contributions of emissions and transport in the different seasons to the NO₂ VCDs using a generalized additive model, where the contributions of local emissions to the total in the spring, summer, autumn, and winter were 89 ± 12%, 92 ± 11%, 86 ± 12%, and 72 ± 16%, respectively. The contribution of regional transport reached 26% in the winter, and this high contribution value was mainly correlated with the northeast wind, which was due to the transport channel of air pollutants along the Changbai Mountains in NEC. The NO₂/SO₂ ratio was used to identify NO₂ from industrial sources and vehicle exhaust. The contribution of industrial NO₂ VCD sources was >66.3 ± 16% in Shenyang due to the large amount of coal combustion from heavy industrial activity, which emitted large amounts of NO₂. Our results suggest that air quality management in Shenyang should consider reductions in local NO₂ emissions from industrial sources along with regional cooperative control.

Nitrated and oxygenated polycyclic aromatic hydrocarbons (NPAHs and OPAHs) are receiving attention because of their high toxicity compared with parent PAHs. However, the experimental data of their physicochemical properties has been limited. This study proposed the gas chromatographic retention time (GC-RT) technique as an effective alternative one to determine octanol-air partition coefficients (KOA) and sub-cooled liquid vapor pressures (PL) for 11 NPAHs, 10 OPAHs, and 19 parent PAHs. The slopes and intercepts of the linear regressions between temperature versus KOA and PL were provided and can be used to estimate KOA and PL for the 40 targeted compounds at any temperature. The internal energies of phase transfer (ΔUOA) and enthalpies of vaporization (ΔHL) for all targeted compounds were also calculated using the GC-RT technique. High-molecular-weight compounds may release or absorb higher heat energy to transform between different phases. NPAHs and OPAHs had a non-ideal solution behavior with activity in octanol (γₒcₜ) in the range of 19–53 and 18–1,078, respectively, which is larger than the unity threshold. A comparison among four groups of PAH derivatives showed that a functional group (nitro-, oxygen-, chloro-, and bromo-) in PAH derivatives increased γₒcₜ for corresponding parent PAHs by tens (mono-group) to hundreds of times (di-group). This study suggests that the GC-RT method is applicable for indirectly measuring the physicochemical properties of various groups of organic compounds.

The health effects of potentially toxic elements (PTEs) in airborne particulate matter (PM) are strongly dependent on their size distribution and dissolution. This study examined PTEs within nine distinct sizes of PM in a Chinese megacity, with a focus on their deposited and dissolved bioaccessibility in the human pulmonary region. A Multiple Path Particle Dosimetry (MPPD) model was used to estimate the deposited bioaccessibility, and an in-vitro experiment with simulated lung fluid was conducted for dissolved bioaccessibility. During the non-heating season, the dissolved bioaccessible fraction (DBF) of As, Cd, Co, Cr, Mn, Pb and V were greater in fine PM (aerodynamics less than 2.1 μm) than in coarse PM (aerodynamics between 2.1 and 10 μm), and vice versa for Ni. With the increased demand of heating, the DBF of Pb and As decreased in fine particle sizes, probably due to the presence of oxide/silicate compounds from coal combustion. Inhalation health risks based on the bioaccessible concentrations of PTEs displayed the peaks in <0.43 μm and 2.1–3.3 μm particulate sizes. The non-cancer risk was at an acceptable level (95th percentiles of hazard index (HI) was 0.49), but the cancer risk exceeded the threshold value (95th percentiles of total incremental lifetime cancer risk (TCR) was 8.91 × 10⁻⁵). Based on the results of uncertainty analysis, except for the exposure frequency, the total concentrations and DBF of As and Cr in <0.43 μm particle size segment have a greater influence on the uncertainty of probabilistic risk.

Sex determination is a complex process that can be influenced by environment in various taxa. Disturbed environments can affect population sex ratios and thus threaten their viability. Emerging evidences support a role of epigenetic mechanisms, notably DNA methylation, in environmental sex determination (ESD). In this work, using zebrafish as model and a transgenerational experiment comprising 4 successive generations, we report a strength link between the promotor methylation level of three genes in female gonads and population sex ratio. One generation of zebrafish was exposed throughout its lifetime to cadmium (Cd), a non-essential metal, at an environmentally relevant concentration. The subsequent generations were not exposed. At the first and the third generation a subset of individuals was exposed to an elevated temperature, a well-known masculinizing factor in zebrafish. While heat was associated to an increase in the methylation level of cyp19a1a gene and population masculinization, foxl2a/dmrt1 methylation levels appeared to be influenced by Cd and fish density leading to offspring feminization. Ancestral Cd exposure indeed led to a progressive feminization of the population over generations and affected the sex plastic response of zebrafish in response to heat. The effect of Cd on the methylation level of foxl2a was observed until the third generation, supporting potential transgenerational inheritance. Our results support (i) a key role of cyp19a1a methylation in SD in zebrafish in response to environmental cues and (ii) the fact that the environment experienced by parents, namely mothers in the present case, can affect their offspring sex ratio via environment-induced DNA methylation changes in gonads.

The presence of microplastics in the various food web raised concerns on human health, but little is known about the target cells and mechanism of toxicity of microplastics. In this study, we evaluated the toxicity of microplastics using relevant cell lines to the oral route of exposure. Approximately 100 μm-sized fragment-type polypropylene (PP) and polystyrene (PS) particles were prepared by sieving after pulverization and further applied the accelerated weathering using ultraviolet and heat. Thus, the panel of microplastics includes fresh PP (f-PP), fresh PS (f-PS), weathered PP (w-PP), and weathered PS (w-PS). The spherical PS with a similar size was used as a reference particle. Treatment of all types of PP and PS did not show any toxic effects to the Caco-2 cells and HepG2 cells. However, the treatment of microplastics to THP-1 macrophages showed significant toxicity in the order of f-PS > f-PP > w-PS > w-PP. The weathering process significantly reduced the reactive oxygen species (ROS) generation potential of both microplastics because the weathered microplastics have an increased affinity to bind serum protein which acts as a ROS scavenger. The intrinsic ROS generation potential of microplastics showed a good correlation with the toxicity endpoints including cytotoxicity and pro-inflammatory cytokines in THP-1 macrophages. In conclusion, the results of this study suggest that the target cell type of microplastics via oral administration can be macrophages and the pathogenic factor to THP-1 macrophages is the intrinsic ROS generation potential of microplastics. Nevertheless, the toxic effect of microplastics tested in this study was much less than that of nano-sized particles.

Antibiotics are commonly used in livestock and poultry breeding along with organic arsenic. Through long-term accumulation, they can enter into the surrounding soil through various pathways and contaminate the soil. In this paper, tetracycline antibiotics (TCs) and roxarsone (ROX) contaminated soil were used as the representatives of the two kinds of veterinary drugs contaminated soil, respectively, to study the thermal desorption behavior and arsenic stabilization process. Different parameters like heating temperatures, heat duration, stabilizer type and dosage were optimized for effective removal of TCs and ROX. Furthermore, TCs and ROX removal path and ROX stabilization mechanism were explored. Results of the study showed that over 98% of tetracycline antibiotics and roxarsone were effectively removed at 300 °C for 60 min. The heat treatment process of TCs contaminated soil was controlled by the first-order kinetics. Based on the detection of degradation products and thermogravimetric analysis, the possible thermal degradation path of TCs and ROX was proposed. Addition of FeSO₄.7H₂O (10% by weight) as stabilizer during the heat treatment process yielded 96.7% stabilization rate. Through the analysis of arsenic fractions, valence and the characterization of soil samples collected after the heat treatment, mechanism of arsenic stabilization in ROX was explored. The results show that thermal treatment combined with chemical stabilization technology can not only degrade TCs and ROX efficiently and completely, but also convert organic arsenic into inorganic state, which is conducive to better stabilization, and finally achieve effective and safe remediation of this kind of contaminated soil.

In this study, municipal solid waste incineration fly ash (MSWIFA) was first washed (pretreatment) with pure water with liquid to solid (L/S) ratio of 2, 3, 6, 10, to understand the removal efficiency of chlorine and sulphate, as well as its consequent ability as alkaline activator for granulated blast furnace slag (GGBFS). Washed MSWIFA was blended with GGBFS at a fixed ratio of 3:7 to examine their impact on mechanical properties, reaction mechanism, microstructure and leaching behavior. The results showed that chlorine in MSWIFA (>70%) can be washed out easily, while the removal of sulphate was largely depended on the L/S. GGBFS can be better activated by a low L/S (e.g. 2) washed-MSWIFA with attaining the compressive strength of 45.2MPa at 28 days. The higher chlorine and sulphate contents retained in the washed-MSWIFA, the higher the total heat release in the activated GGBFS system. Calcium silicate hydrate (C–S–H), ettringite (AFt) and Friedel’s salt were the main hydration products of the activated binders. The rapid formation of AFt was mainly responsible for the 1-day strength development. Large amounts of Friedel’s salts were formed from 1 day to 3 days associated to the inhibition of sulphate, and the presence of C–S–H played the key role in long-term strength development. The leaching test of heavy metals and soluble ions also demonstrated that washed MSWIFA activated GGBFS binders were harmless to the environment.

Indoor air quality is critically important to the human as people spend most time indoors. Indoor PM₂.₅ is related to the outdoor levels, but more directly influenced by internal sources. Severe household air pollution from solid fuel use has been recognized as one major risk for human health especailly in rural area, however, the issue is significantly overlooked in most national air quality controls and intervention policies. Here, by using low-cost sensors, indoor PM₂.₅ in rural homes burning coals was monitored for ~4 months and analyzed for its temporal dynamics, distributions, relationship with outdoor PM₂.₅, and quantitative contributions of internal sources. A bimodal distribution of indoor PM₂.₅ was identified and the bimodal characteristic was more significant at the finer time resolution. The bimodal distribution maxima were corresponding to the emissions from strong internal sources and the influence of outdoor PM₂.₅, respectively. Indoor PM₂.₅ was found to be correlated with the outdoor PM₂.₅, even though indoor coal combustion for heating was thought to be predominant source of indoor PM₂.₅. The indoor-outdoor relationship differed significantly between the heating and non-heating seasons. Impacts of typical indoor sources like cooking, heating associated with coal use, and smoking were quantitatively analyzed based on the highly time-resolved PM₂.₅. Estimated contribution of outdoor PM₂.₅ to the indoor PM₂.₅ was ~48% during the non-heating period, but decreased to about 32% during the heating period. The contribution of indoor heating burning coals comprised up to 47% of the indoor PM₂.₅ during the heating period, while the other indoor sources contributed to ~20%. The study, based on a relatively long-term timely resolved PM₂.₅ data from a large number of rural households, provided informative results on temporal dynamics of indoor PM₂.₅ and quantitative contributions of internal sources, promoting scientific understanding on sources and impacts of household air pollution.

The ability of particulate matter (PM) to induce oxidative stress is frequently estimated by acellular oxidative potential (OP) assays, such as ascorbic acid (AA) and 1,4-dithiothreitol (DTT), used as proxy of reactive oxygen species (ROS) generation in biological systems, and particle-bound ROS measurement, such as 2′,7′-dichlorodihydrofluorescein (DCFH) assay. In this study, we evaluated the spatial and size distribution of OP results obtained by three OP assays (OPᴬᴬ, OPᴰCFᴴ and OPᴰᵀᵀ), to qualitative identify the relative relevance of single source contributions in building up OP values and to map the PM potential to induce oxidative stress in living organisms. To this aim, AA, DCFH and DTT assays were applied to size-segregated PM samples, collected by low-pressure cascade impactors, and to PM₁₀ samples collected at 23 different sampling sites (about 1 km between each other) in Terni, an urban and industrial hot-spot of Central Italy, by using recently developed high spatial resolution samplers of PM, which worked in parallel during three monitoring periods (February, April and December 2017). The sampling sites were chosen for representing the main spatially disaggregated sources of PM (vehicular traffic, rail network, domestic heating, power plant for waste treatment, steel plant) present in the study area. The obtained results clearly showed a very different sensitivity of the three assays toward each local PM source. OPᴬᴬ was particularly sensitive toward coarse particles released from the railway, OPᴰCFᴴ was sensible to fine particles released from the steel plant and domestic biomass heating, and OPᴰᵀᵀ was quite selectively sensitive toward the fine fraction of PM released by industrial and biomass burning sources.