Effect of potential HONO sources on peroxyacetyl nitrate (PAN) formation in eastern China in winter

As an important secondary photochemical pollutant, peroxyacetyl nitrate (PAN) has been studied over decades, yet its simulations usually underestimate the corresponding observations, especially in polluted areas. Recent observations in north China found unusually high concentrations of PAN during wintertime heavy haze events, but the current model still cannot reproduce the observations, and researchers speculated that nitrous acid (HONO) played a key role in PAN formation. For the first time we systematically assessed the impact of potential HONO sources on PAN formation mechanisms in eastern China using the Weather Research and Forecasting/Chemistry (WRF-Chem) model in February of 2017. The results showed that the potential HONO sources significantly improved the PAN simulations, remarkably accelerated the RO_x (sum of hydroxyl, hydroperoxyl, and organic peroxy radicals) cycles, and resulted in 80%–150% enhancements of PAN near the ground in the coastal areas of eastern China and 10%–50% enhancements in the areas around 35–40°N within 3 km during a heavy haze period. The direct precursors of PAN were aldehyde and methylglyoxal, and the primary precursors of PAN were alkenes with C > 3, xylenes, propene and toluene. The above results suggest that the potential HONO sources should be considered in regional and global chemical transport models when conducting PAN studies.     

The pollution levels, variation characteristics, sources and implications of atmospheric carbonyls in a typical rural area of North China Plain during winter

Atmospheric carbonyls were measured at a typical rural area of the North China Plain (NCP) from November 13 to December 24, 2017 to investigate the pollution characteristics, sources and environmental implications. Fifteen carbonyls were detected, and formaldehyde, acetaldehyde and acetone accounted for about 81% at most. The concentration of the total carbonyls in heavily polluted days was twice more than that in clean days. In contrast to other carbonyls, m-tolualdehyde exhibited relatively high concentrations in the clean days in comparison with the polluted days. The ratios of three principal carbonyls to CO showed similar daily variations at different pollution levels with significant daytime peaks. Multiple linear regression analysis revealed that the contributions of background, primary and secondary sources to three principal carbonyls showed similar variation trends from the clean level to the heavily polluted level. The OH formation rate of formaldehyde showed a similar variation trend to its photodegradation rate, reaching the peak value at noon, which is important to maintain relatively high OH levels to initiate the oxidation of various gas-phase pollutants for secondary pollutant formation at the rural site. OH radical consumption rate and ozone formation potential (OFP) calculations showed that formaldehyde and acetaldehyde were the dominant oxidative species among measured carbonyls. As for OH radical consumption, n-butyraldehyde and m-tolualdehyde were important contributors, while for ozone formation potential, n-butyraldehyde and propionaldehyde made significant contributions. In addition, the contribution of carbonyl compounds to secondary organic aerosol (SOA) formation was also important and needs further investigation.     

Characteristics and ozone formation potential of volatile organic compounds in emissions from a typical Chinese coking plant

Coking industry is an important volatile organic compounds (VOCs) emission source in China, however, detailed information on VOCs emissions is lacking. Therefore, we selected a typical mechanized coking plant and collected air samples according to the Emission Standard of Pollutants for Coking Chemical Industry (GB16171-2012). Using gas chromatography-mass spectrometry method, we analyzed the VOCs in the air samples, and applied maximum increment reactivity (MIR) rule to estimate ozone formation potential (OFP) of the VOCs emitted from the coke production. More than 90 VOCs species were detected from the coking plant, including alkanes, alkenes, alkynes, aromatic hydrocarbons, halogenated hydrocarbons and oxygenated VOCs. The concentrations of VOCs (ρ(VOCs)) generated at different stages of the coking process are significantly different. ρ(VOCs) from coke oven chimney had the highest concentration (87.1 mg/m³), followed by coke pushing (4.0 mg/m³), coal charging (3.3 mg/m³) and coke oven tops (1.1 mg/m³). VOCs species emitted from the coke production processes were dominated by alkanes and alkenes, but the composition proportions were different at the different stages. Alkenes were the most abundant emission species in flue gases of the coke oven chimney accounting for up to 66% of the total VOCs, while the VOCs emissions from coke pushing and coal charging were dominated by alkanes (36% and 42%, respectively), and the alkanes and alkenes emitted from coke oven top were similar (31% and 29%, respectively). Based on above results, reduction of VOCs emissions from coke oven chimney flue gases is suggested to be an effective measure, especially for alkenes.     

新型铁铜铝三元复合氧化物除磷性能与机制研究

采用共沉淀法制备了一种新型铁铜铝三元复合氧化物吸附剂,系统研究了其对磷的吸附行为,并对吸附磷前后的吸附剂进行了表征.吸附实验结果表明,铁铜铝三元复合氧化物对磷具有优异的吸附去除效能,Freundlich吸附等温线模型能更好地拟合其对磷的吸附,最大吸附量为62.6 mg·g-1(pH=7.0),显著高于多数文献报道的磷吸附剂;吸附速率较快,吸附动力学更符合Elovich模型;溶液pH对磷吸附有一定影响,随着pH的升高,磷吸附量降低,离子强度则影响不大;共存阴离子对磷吸附具有抑制作用,影响的大小顺序为SiO_3~(2-)SO_4~(2-)CO_3~(2-)Cl~-,而共存阳离子Ca2+和Mg2+则对磷吸附略有促进作用.Zeta电位、红外谱图(FTIR)和X射线光电子能谱(XPS)表征分析表明,磷在铁铜铝三元复合氧化物表面发生了特性吸附,磷酸根主要通过取代复合氧化物表面的羟基形成内表面络合物而被吸附去除.溶出实验结果表明,当pH在5.0~8.5范围内,Fe~(3+)、Cu~(2+)、Al~(3+)的溶出量均较低.由此可知,铁铜铝三元复合氧化物是一种具有良好应用前景的除磷吸附剂.     

碳氮比对活性污泥胞外聚合物的长期影响

以人工模拟废水为研究对象,采用4组SBR反应器（R₀,R₅,R₁₀和R₁₅）,重点考察了碳氮比（C/N）对胞外聚合物（EPS）含量及其组分（蛋白质（PN）、多糖（PS）和核酸（DNA））的影响.试验结果表明：C/N对EPS及其组分具有显著影响.随着C/N由0升高至15,EPS和紧密结合型胞外聚合物（TB-EPS）含量逐渐升高,而松散型胞外聚合物（LB-EPS）含量逐渐降低,EPS以TB-EPS为主（占77.4%~93.6%）.EPS和TB-EPS中的PN、PS和DNA含量随着C/N值升高而升高,LB-EPS中的PN、PS和DNA含量随C/N升高而降低.此外,随着C/N的增大,毛细吸水时间（CST）和污泥比阻（SRF）值显著增大,污泥的脱水性能变差.     

海底重燃油对海胆繁殖及其子代发育的影响

利用室内流水式粘油砾石柱模拟实际环境中的海底重燃油,研究了重燃油污染的孔隙水对成年海胆繁殖力、配子质量及子代胚胎发育的影响.结果表明,暴露结束后（7d）,暴露组海胆的排配子率显著降低（P=0.033）,同时雌海胆繁殖力也显著降低（P=0.036,（1957917±811471）个卵细胞）;卵细胞的直径和精子的受精能力并未受到海底重燃油的影响.子代继续暴露48h,发现亲代暴露加剧了子代胚胎畸形程度,表明亲代暴露的毒性可传递给子代.进一步利用整合毒性指数（ITI）检测毒性传递的性别差异发现,与母本效应相比（24和48h子代的ITI分别为0.54~1.45和1.1~2.57）,父本效应（24和48h子代的ITI分别为0.82~1.95和1.89~4.04）在毒性传递过程中起着关键作用.     

Inhibition of thrombin by functionalized C60 nanoparticles revealed via in vitro assays and in silico studies

The studies on the human toxicity of nanoparticles (NPs) are far behind the rapid development of engineered functionalized NPs. Fullerene has been widely used as drug carrier skeleton due to its reported low risk. However, different from other kinds of NPs, fullerene-based NPs (C₆₀ NPs) have been found to have an anticoagulation effect, although the potential target is still unknown. In the study, both experimental and computational methods were adopted to gain mechanistic insight into the modulation of thrombin activity by nine kinds of C₆₀ NPs with diverse surface chemistry properties. In vitro enzyme activity assays showed that all tested surface-modified C₆₀ NPs exhibited thrombin inhibition ability. Kinetic studies coupled with competitive testing using 3 known inhibitors indicated that six of the C₆₀ NPs, of greater hydrophobicity and hydrogen bond (HB) donor acidity or acceptor basicity, acted as competitive inhibitors of thrombin by directly interacting with the active site of thrombin. A simple quantitative nanostructure-activity relationship model relating the surface substituent properties to the inhibition potential was then established for the six competitive inhibitors. Molecular docking analysis revealed that the intermolecular HB interactions were important for the specific binding of C₆₀ NPs to the active site canyon, while the additional stability provided by the surface groups through van der Waals interaction also play a key role in the thrombin binding affinity of the NPs. Our results suggest that thrombin is a possible target of the surface-functionalized C₆₀ NPs relevant to their anticoagulation effect.     

Sulfur dioxide and o-xylene co-treatment in biofilter: Performance, bacterial populations and bioaerosols emissions

Sulfur dioxide(SO_2) and benzene homologs are frequently present in the off-gas during the process of sewage sludge drying. A laboratory scale biofilter was set up to co-treat SO_2 and o-xylene in the present study. SO_2 and o-xylene could be removed simultaneously in a single biofilter. Their concentration ratio in the inlet stream influenced the removal efficiencies. It is worth noting that the removal of SO_2 could be enhanced when low concentrations of o-xylene were introduced into the biofilter. Pseudomonas sp., Paenibacillus sp., and Bacillus sp. were the main functional bacteria groups in the biofilter. Sulfur-oxidizing bacteria(SOB) and o-xylene-degrading bacteria(XB) thrived in the biofilter and their counts as well as their growth rate increased with the increase in amount of SO_2 and o-xylene supplied. The microbial populations differed in counts and species due to the properties and components of the compounds being treated in the biofilter. The presence of mixed substrates enhanced the diversity of the microbial population. During the treatment process, bioaerosols including potentially pathogenic bacteria, e.g., Acinetobacter lwoffii and Aeromonas sp., were emitted from the biofilter. Further investigation is needed to focus on the potential hazards caused by the bioaerosols emitted from waste gas treatment bioreactors.