固定化多酚氧化酶对水中苯酚和氯酚的去除

以壳聚糖/蒙脱土插层复合物为载体,吸附法制备固定化多酚氧化酶,并以此催化氧化去除水中的苯酚、4-氯苯酚和2,4-二氯苯酚.考察了固定化多酚氧化酶的制备条件,对酚类化合物的催化氧化条件、动力学特性以及固定化酶的重复使用性能.结果表明,固定化多酚氧化酶的最佳制备条件为p H 5.0,酶与载体质量比20 mg·g-1,固定化6 h,所得固定化酶的载酶量为12.12 mg·g-1,每克单位载体酶活为12.76×103U·g-1.固定化多酚氧化酶对酚类化合物的最佳去除条件为:苯酚溶液p H 7.0,温度30℃;4-氯苯酚溶液p H 5.0,温度20℃;2,4-二氯苯酚溶液p H 5.0,温度30℃.在最佳反应条件下,酶与底物质量比为20 mg·mg-1时,固定化多酚氧化酶对苯酚、4-氯苯酚和2,4-二氯苯酚溶液去除率分别为63.6%、85.8%和87.8%.苯酚、4-氯苯酚和2,4-二氯苯酚的米氏常数Km值依次减小,最大反应速率Vmax依次增大,表明固定化酶对2,4-二氯苯酚的亲和力最强,催化速度最快.固定化酶循环使用6次(24 h)后对苯酚、4-氯苯酚和2,4-二氯苯酚的去除率分别为15.7%、24.2%和27.8%.     

成都市臭氧重污染成因与来源解析

采用来源解析的方法对2020年成都市发生的一次较为严重的臭氧污染事件进行了研究.结果表明,此次污染过程呈现从清洁-污染-清洁的变化趋势,污染持续时间长达9d,最大臭氧小时浓度达到258.8μg/m3.气象因素在成都臭氧污染中的影响不可忽略,其中温度与臭氧浓度呈现显著正相关关系,东北风主要出现在污染前和污染后,可能起到稀...     

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.     

Ambient volatile organic compounds at a receptor site in the Pearl River Delta region: Variations, source apportionment and effects on ozone formation

We present the continuously measurements of volatile organic compounds（VOCs） at a receptor site（Wan Qing Sha, WQS） in the Pearl River Delta（PRD） region from September to November of 2017. The average mixing ratios of total VOCs（TVOCs） was 36.3 ± 27.9 ppbv with the dominant contribution from alkanes（55.5%）, followed by aromatics（33.3%）. The diurnal variation of TVOCs showed a strong photochemical consumption during daytime,resulting in the formation of ozone（O₃）. Five VOC sources were ...     

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.     

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.     

兰州市夏季挥发性有机物污染特征及来源解析

为研究兰州市夏季大气挥发性有机物（VOCs）污染特征和来源,采用实时在线监测仪器TH-300B （GC-MS/FID）等多种设备联用,于2021年7月开展为期1个月的综合观测.结果表明,监测期间总挥发性有机物ρ（TVOCs）为99.77μg·m^-3,烷烃占比最大,其次是芳香烃和含氧挥发性有机物（OVOCs）,烯炔烃和卤代烃占比较小,各组分浓度呈现早晚高,中午低的日变化特征.VOCs臭氧生成潜势（OFP）前10种物质贡献率占57.3%,二次有机气溶胶（SOA）生成潜势前10种物质贡献率占93.10%,以芳香烃和高碳烷烃为主,其中,甲苯和间/对-二甲苯对OFP和SOA贡献最大.采用正交矩阵因子分解法（PMF）进行污染来源解析,其中工业溶剂源（22.25%）、油漆涂料源（21.70%）和机动车尾气源（16.25%）是研究区环境空气中VOCs的主要来源;基于污染源排放清单法,2017年兰州市VOCs排放量为94761.6 t,主要来自溶剂使用源和移动源,贡献率分别为56.70%和18.03%.因此解决兰州大气复合污染问题,实现O₃和PM_2.5协同控制,应以工业溶剂排放和机动车管控为主,重点减少VOCs中甲苯和间/对-二甲苯等芳香烃化合物排放.     

芳香类有机物氯化生成消毒副产物的特性研究

选择有代表性的芳香类有机物,在含有腐殖酸的水溶液中进行氯化试验.测定三卤甲烷和卤乙酸的生成特性.并分析有机物的化学结构对生成消毒副产物的影响.结果表明.各受试物氯化生成消毒副产物的活性和反应速率排序为间苯二酚>对苯二酚>邻苯二酚>苯酚>苯胺>苯甲酸>硝基苯;芳香类有机物苯环上官能团的性质、数量和位置等影响消毒副产物的生成;间苯二酚的氯化反应可分为快速反应阶段和慢速反应阶段.