Cu–Mn–Ce ternary mixed-oxide catalysts for catalytic combustion of toluene

Cu–Mn, Cu–Mn–Ce, and Cu–Ce mixed-oxide catalysts were prepared by a citric acid sol–gel method and then characterized by XRD, BET, H₂-TPR and XPS analyses. Their catalytic properties were investigated in the toluene combustion reaction. Results showed that the Cu–Mn–Ce ternary mixed-oxide catalyst with 1:2:4 mole ratios had the highest catalytic activity, and 99% toluene conversion was achieved at temperatures below 220°C. In the Cu–Mn–Ce catalyst, a portion of Cu and Mn species entered into the CeO₂ fluorite lattice, which led to the formation of a ceria-based solid solution. Excess Cu and Mn oxides existed on the surface of the ceria-based solid solution. The coexistence of Cu–Mn mixed oxides and the ceria-based solid solution resulted in a better synergetic interaction than the Cu–Mn and Cu–Ce catalysts, which promoted catalyst reducibility, increased oxygen mobility, and enhanced the formation of abundant active oxygen species.     

A screening assay for thyroid hormone signaling disruption based on thyroid hormone-response gene expression analysis in the frog Pelophylax nigromaculatus

Amphibian metamorphosis provides a wonderful model to study the thyroid hormone (TH) signaling disrupting activity of environmental chemicals, with Xenopus laevis as the most commonly used species. This study aimed to establish a rapid and sensitive screening assay based on TH-response gene expression analysis using Pelophylax nigromaculatus, a native frog species distributed widely in East Asia, especially in China. To achieve this, five candidate TH-response genes that were sensitive to T3 induction were chosen as molecular markers, and T3 induction was determined as 0.2 nmol/L T3 exposure for 48 hr. The developed assay can detect the agonistic activity of T3 with a lowest observed effective concentration of 0.001 nmol/L and EC50 at around 0.118–1.229 nmol/L, exhibiting comparable or higher sensitivity than previously reported assays. We further validated the efficiency of the developed assay by detecting the TH signaling disrupting activity of tetrabromobisphenol A (TBBPA), a known TH signaling disruptor. In accordance with previous reports, we found a weak TH agonistic activity for TBBPA in the absence of T3, whereas a TH antagonistic activity was found for TBBPA at higher concentrations in the presence of T3, showing that the P. nigromaculatus assay is effective for detecting TH signaling disrupting activity. Importantly, we observed non-monotonic dose-dependent disrupting activity of TBBPA in the presence of T3, which is difficult to detect with in vitro reporter gene assays. Overall, the developed P. nigromaculatus assay can be used to screen TH signaling disrupting activity of environmental chemicals with high sensitivity.     

桂林市公共场所空气污染的检测与分析

采用甲醛检测仪、有机气体检测仪等测试分析了桂林市宾馆、商场、候车室、家具城、文化娱乐场等公共场所的甲醛和TVOC浓度。结果显示:候车室和文化娱乐场所的甲醛、TVOC合格率均为100%;宾馆、商场、家具城的TVOC合格率分别为98.7%、98.9%、95.0%,甲醛合格率分别为78.8%、91.1%、85.0%;皮革制品、家具板材等为主要的甲醛和TVOC污染源。     

城市安全供水综合指数研究-以太原为例

采集太原市不同区住户的自来水和12种瓶装水,分析了水中无机离子和挥发性有机物( VOCs)成分.结果表明,无机离子和VOCs的总浓度范围分别为1.08~354.18 mg/L和0.43~13.98 μg/L;自来水中的无机离子与VOCs 含量最高,约是瓶装水中浓度的三倍.加热与过滤处理措施均可改善自来水水质,对水中无机离子和VOCs的去除效果均可达19%~100%,其中过滤可能会引发VOCs的二次污染 .根据饮用水标准,使用饮用水水质指数( DWQI)模型对水质评价结果显示,太原市饮用水水质总体较好.     

低NOx环境异戊二烯促进甲苯生成甲基丁烯二醛的模拟实验

在低NO_x浓度条件下开展甲苯和异戊二烯复合体系的烟雾箱模拟实验,使用高时间分辨率的在线质子转移反应飞行时间质谱(PTR-TOF-MS)实时监测混合体系中反应物与产物的浓度变化情况,探究人为源与天然源交汇过程中, 自然源挥发性有机物 (BVOCs)对人为挥发性有机物(AVOCs)化学降解的影响.结果表明,异戊二烯与甲苯竞争OH自由基,从而抑制了甲苯的化学降解,该竞争反应开始得越早,抑制效果越显著.研究还发现异戊二烯会增强甲苯RO₂降解途径产物的产量,生成更多1,4不饱和-二羰基化合物(如丁烯二醛和甲基丁烯二醛)与二羰基化合物(如乙二醛和甲基乙二醛),其中甲基丁烯二醛增量最高可达38.6%.此外,异戊二烯快速氧化生成的RO₂自由基碳数更少,可能与甲苯氧化生成的RO₂自由基发生了快速的交叉反应,有利于甲苯RO自由基的生成及裂解,最终导致甲苯RO₂途径裂解产物的增加.     

Ozone episodes during and after the 2018 Chinese National Day holidays in Guangzhou: Implications for the control of precursor VOCs

The impact of reducing industrial emissions of volatile organic compounds (VOCs) on ozone (O₃) pollution is of wide concern particularly in highly industrialized megacities. In this study, O₃, nitrogen oxides (NOx) and VOCs were measured at an urban site in the Pearl River Delta region during the 2018 Chinese National Day Holidays and two after-holiday periods (one with ozone pollution and another without). O₃ pollution occurred throughout the 7-day holidays even industrial emissions of VOCs were passively reduced due to temporary factory shutdowns, and the toluene to benzene ratios dropped from ∼10 during non-holidays to ∼5 during the holidays. Box model (AtChem2-MCM) simulations with the input of observation data revealed that O₃ formation was all VOC-limited, and alkenes had the highest relative incremental reactivity (RIR) during the holiday and non-holiday O₃ episodes while aromatics had the highest RIR during the non-pollution period. Box model also demonstrated that even aromatics decreased proportionally to levels with near-zero contributions of industrial aromatic solvents, O₃ concentrations would only decrease by less than 20% during the holiday and non-holiday O₃ episodes and ozone pollution in the periods could not be eliminated. The results imply that controlling emissions of industrial aromatic solvents might be not enough to eliminate O₃ pollution in the region, and more attention should be paid to anthropogenic reactive alkenes. Isoprene and formaldehyde were among the top 3 species by RIRs in all the three pollution and non-pollution periods, suggesting substantial contribution to O₃ formation from biogenic VOCs.     

Wall losses of oxygenated volatile organic compounds from oxidation of toluene: Effects of chamber volume and relative humidity

Vapor wall losses can affect the yields of secondary organic aerosol. The effects of surface-to-volume (S/V) ratio and relative humidity (RH) on the vapor-wall interactions were investigated in this study. The oxygenated volatile organic compounds (OVOCs) were generated from toluene-H₂O₂ irradiations. The average gas to wall loss rate constant (k_gw) of OVOCs in a 400 L reactor (S/V = 7.5 m⁻¹) is 2.47 (2.41 under humid conditions) times higher than that in a 5000 L reactor (S/V = 3.6 m⁻¹) under dry conditions. In contrast, the average desorption rate constant (k_wg) of OVOCs in 400 L reactor is only 1.37 (1.20 under humid conditions) times higher than that in 5000 L reactor under dry conditions. It shows that increasing the S/V ratio can promote the wall losses of OVOCs. By contrast, the RH effect on k_gw is not prominent. The average k_gw value under humid conditions is almost the same as under dry conditions in the 400 L (5000 L) reactor. However, increasing RH can decrease the desorption rates. The average k_wg value under dry conditions is 1.45 (1.27) times higher than that under humid conditions in the 400 L (5000 L) reactor. The high RH can increase the partitioning equilibrium timescales and enhance the wall losses of OVOCs.     

壬基酚的环境生物地球化学研究进展及对新污染物管理的建议

近年来,我国大气环境、水环境和土壤环境质量得到一定的改善,“碧水蓝天”已经成为常态.但随着持久性有机污染物、内分泌干扰物、抗生素和微塑料等新污染物在环境中不断被检出,新污染物正逐步受到广泛的关注,壬基酚作为一种典型的内分泌干扰物也备受研究人员的关注.系统地概括了我国水体中壬基酚的环境行为和暴露水平,并基于风险商法和联合概率曲线法对壬基酚可能造成的生态风险进行了评估.结果表明,壬基酚对水生生物的毒性效应主要包括急性毒性、生长发育毒性、雌激素效应和繁殖毒性;壬基酚在我国主要流域水体中普遍存在,其浓度平均值在60～1 000 ng·L^-1,浓度最高值可达4 628 ng·L^-1;基于风险商法和联合概率曲线法的风险评估结果表明,壬基酚对我国主要流域里的水生生物均存在一定的风险.最后,总结了目前比较常用的壬基酚处理处置和风险管控技术,比较了国际上内分泌干扰物的监管方法,针对我国在新污染物环境管理中存在的问题,提出了针对性政策建议,研究结果可以为我国新污染物管理和管控提供参考.     

长三角区域人为源活性挥发性有机物高分辨率排放清单

基于长三角区域41个城市本地实测,结合美国EPA的SPECIATE 4.4数据库,建立了长三角区域人为源活性挥发性有机物(VOCs)高分辨率排放清单,分析了区域内VOCs的排放特征和组分构成;计算了VOCs的臭氧生成潜势(OFP)和二次有机气溶胶生成潜势(SOAP).结果表明,2017年,长三角区域人为源VOCs排放总量为4.9×10⁶ t,其中工艺过程源、工业溶剂使用源、移动源、生活源、储运源、农业源和废弃物处理源排放贡献分别为：34.3%、27.1%、19.5%、9.7%、6.1%、2.5%和0.4%.芳香烃和烷烃是VOCs的主要种类,均各占长三角VOCs排放总量的25%.工艺过程源、工业溶剂使用源、移动源和生活源OFP贡献率分别为38.3%、21.5%、16.4%和13.2%,SOAP贡献率分别为26.2%、34.1%、18.1%和17.9%,与VOCs排放量的主要贡献源基本一致.各城市VOCs重点排放行业存在较大差异,重点城市群以石化化工和装备制造为主,区域北部则以木材家具等涂装行业为主.计算表明,丙烯、间/对-二甲苯和乙烯是臭氧主要贡献源;甲苯、1,2,...     

复合污染条件下人为源VOCs的SOA生成研究进展

大气细颗粒物(PM_2.5)仍是我国空气质量持续改善的重大挑战.近年来,二次有机气溶胶(SOA)对PM_2.5的贡献日益凸显.因此,深入认识复合污染条件下SOA生成机制和影响因素可以为进一步降低PM_2.5提供重要理论依据.实验室模拟是深入认识SOA生成机制的关键途径,也是模式模拟参数化方案的可靠来源之一.主要综述了我国多污染物共存条件下典型人为源挥发性有机物(VOCs)的SOA生成研究进展,包括汽油蒸气VOCs、生物质燃烧VOCs和含氧VOCs形成SOA过程中,前体物浓度、芳香烃含量、无机气体、种子气溶胶和相对湿度(RH)等不同因素对SOA生成的影响;阐述了实际大气VOCs的SOA生成潜势及其影响因素,最后提出了目前在SOA机制研究方面存在的关键科学问题,并对未来的研究方向进行了展望.