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.     

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.     

有机物辛醇／水分配系数的计算方法：分子碎片常数法

辛醇／水分配系数是表征有机污染物环境行为的重要参数之一，本文应用于碎片常数计算了１３０余个有机化合物的辛醇／水分配系数对数值，通过计算值与实测值的比较发现，两者之间表现出相当好的一致性，其平均绝对误差为０．１３５，此外，还探讨了该方法应用于不同类型有机污染物时需要注意的问题。     

Novel Co-Mg-Al-Ti-O catalyst derived from hydrotalcite-like compound for NO storage/decomposition

Catalysts of Co_1.5Mg_1.5/Al_0.9Ti_0.1O and Co_1.5Mg_1.5/AlO were successfully prepared by calcinations of corresponding hydrotalcite-like compounds at 800℃ for 4 hr. The derived oxides were of spinel phase and a small quantity of Ti substitution did not change the crystal purity. Their catalytic performance for the NO storage/decomposition was investigated. Ti incorporation enhanced the NO decomposition activity while has an opposite effect on the storage capacity of catalyst. In situ FT-IR spectra of the catalysts showed that the final adsorption species on the catalysts was coordinated nitrates/nitrites. In addition, NO storage/decomposition mechanism has been discussed on the basis of these observations.     

紫外光降解对生物过滤塔去除氯苯性能的影响机制研究

紫外-生物过滤联合工艺中的紫外单元促进了后续生物过滤单元的氯苯去除性能.为了进一步揭示紫外光降解对生物过滤塔运行性能的影响机制,本研究系统分析了紫外光降解对生物过滤塔填料层pH、生物膜特性和填料层结构特性等方面的影响.结果表明,氯苯紫外光降解产物导致了生物过滤单元填料层pH的下降(从pH 6～8降至pH 4～7);另外,紫外单元产生的臭氧降低了生物过滤单元生物膜厚度和生物膜的EPS含量,改善了生物膜的特性,提高了氯苯和营养物质在生物膜内的传质效率.同时,臭氧可以有效控制生物量过量积累,增加了填料层的比表面积(从784 m2.m-3增加至880 m2.m-3),优化了填料层的结构特性,提高了污染物的反应速率.上述各方面的综合作用最终促进了生物过滤单元的氯苯去除性能.     

长白山温带森林挥发性有机物的排放通量

2010年夏季,在长白山温带森林开展了挥发性有机物(VOC)排放通量以及气象参数、PAR的综合测量.VOC排放通量采用松弛涡度积累(RelaxedEddyAccumulation)技术在森林冠层上进行测量.初步发现长白山阔叶林主要排放α-蒎烯、β-蒎烯、莰烯、香桧烯、月桂烯、蒈烯、柠檬烯、罗勒烯、松油烯、繖花烃、萜品油烯、三环烯等.研究表明,长白山阔叶混交林VOC排放有明显的日变化——早晚较低和中午前后较高.2010年夏季,单萜烯总排放通量的平均值为0.242mg·m·h-2-1,其变化范围为0.005～1.668mg·m·h-2-1;各成分排放通量的平均值(和最大值)分别为α-蒎烯0.072(0.234)、莰烯0.028(0.356)、月桂烯0.027(0.433)、蒈烯0.023(0.173)、柠檬烯0.037(0.197)、罗勒烯0.016(0.168)、萜品油烯0.053(0.320)、繖花烃0.067(0.755)mg·m·h-2-1.研究还发现VOC排放通量与气温之间存在一定的联系.     

基于遥感资料的中国东部地区植被VOCs排放强度研究

本研究充分基于遥感资料获取中国东部地区叶面积指数和叶生物量的最新信息,并广泛调研了植被VOCs排放因子的最新研究进展,以2008—2010年的植被和气象的平均状态为背景,基于MEGAN排放模型,研究了中国东部地区植被VOCs(BVOCs)排放的时空分布特征.结果表明,我国东部地区BVOCs年排放总量为11.3×106t(以C计,下同),其中异戊二烯(ISOP)、单萜烯(MON)和其它VOC(OVOC)质量分数(下同),分别为44.9%、31.5%、23.6%.BVOCs排放呈现明显的季节变化特征,春、夏、秋、冬4个季节分别占全年的11.2%、71.8%、14.1%和3.0%.空间分布上,排放高值区主要分布于大小兴安岭、长白山脉、秦岭大巴山脉、东南丘陵、海南等植被茂密的区域,年均排放强度一般在1500～6000kg·km-·2a-1之间,福建、广东、江西、浙江、湖南、湖北等省份BVOCs的排放总量与平均排放强度均较高.本研究所得到的高时空分辨率的BVOCs排放清单,可以为区域环境与气候的数值模拟研究提供基础.