一个沿海城市大气臭氧的本地生成过程及其对前体物的敏感性

在威海市两个采样点用苏码罐采集了全空气样品,利用三级冷阱预浓缩-GC/MS方法离线测定了空气样品中109种大气挥发性有机物(VOCs).使用基于观测的MCM机理大气化学模式(OBM-MCM)分析了大气臭氧生成对VOCs组分的敏感性及本地生成过程.结果表明:观测期间两个采样点的总挥发性有机物(TVOCs)平均浓度分别为27.84×10~(-9)和17.85×10~(-9),对TVOCs贡献最大的均是烷烃.模拟分析表明,大气臭氧生成与前体物的控制关系存在空间差异性,在一个观测点受VOCs控制,而在另一个观测点受NO_x和VOCs共同控制;模拟结果还表明,臭氧生成对活性烃类最为敏感,但是,含氧有机物、卤代烃和高碳烷烃对臭氧生成的影响和贡献也不可忽视;此外,计算了日平均臭氧净生成速率P(O_3)_(net),分别为6.41×10~(-9) h~(-1)和3.22×10~(-9) h~(-1),臭氧的本地生成过程扮演重要角色.     

深圳市秋季大气OH自由基总反应性测量及其构成分析

羟基自由基(·OH)总反应性(k_(OH))是大气中所有·OH反应物的浓度与其·OH反应速率常数乘积的总和,对k_(OH)的直接测量有助于识别未知的·OH反应物种及提升·OH收支分析的准确度.因此,本研究建立了一套基于激光光解-激光诱导荧光技术的k_(OH)在线测量系统(LP-LIF),利用紫外脉冲激光在流动管内光解臭氧产生·OH,采用激光诱导荧光技术实时测量其与采样进入流动管的活性气体反应而导致的·OH浓度衰减,通过对该衰减进行指数拟合得到采样气的k_(OH).经实验室测试,LP-LIF系统对k_(OH)的测量灵敏度为1.2 s~(-1),时间分辨率5 min.应用该系统对2018年秋季深圳地区的大气k_(OH)进行为期1个月的连续测量,结合同步观测的·OH反应物浓度数据发现,k_(OH)观测值在10～30 s~(-1)之间,主要来自一氧化碳(14%)、氮氧化物(26%)和一次排放的挥发性有机物(24%).此外,由未测量的·OH反应物贡献的k_(OH)平均约23%,且在夜间和早晚高峰时段贡献较高,推测其主要来自溶剂涂料、石化工业及LPG机动车排放.     

Effects of atamp-charging coke making on strength and high temperature thermal properties of coke

The stamp-charging coke making process has some advantages of improving the operation environment, decreasing fugitive emission, higher gas collection efficiency as well as less environmental pollution. This article describes the different structure strength and high temperature thermal properties of 4 different types of coke manufactured using a conventional coking process and the stamp-charging coke making process. The 4 kinds of cokes were prepared from the mixture of five feed coals blended by the petrography blending method. The results showed that the structure strength indices of coke prepared using the stamp-charging coke method increase sharply. In contrast with conventional coking process, the stamp-charging process improved the coke strength after reaction but had little impact on the coke reactivity index.     

南京北郊秋季VOCs及其光化学特征观测研究

采用GC5000挥发性有机物在线监测系统和EMS系统,于2011年11月在南京北郊开展了为期一个月的连续观测,分别测量了大气中56种VOCs组分和反应性气体(NOx、CO和O3).结果表明,南京北郊的VOCs小时平均体积分数大约在48.17×10-9,日变化呈明显双峰型特征,受机动车影响比较显著,极小值出现在下午16:00,白天与O3浓度曲线呈负相关;VOCs的平均OH消耗速率常数约为3.26×10-12cm3.(molecule.s)-1,最大增量反应活性约为3.26 mol·mol-1;烯烃对OH消耗速率(LOH)和臭氧生成潜势(OFP)贡献率最大,芳香烃次之,而烷烃在大气中含量最为丰富,却并不是LOH和OFP主要贡献者;VOCs关键活性组分是乙烯、丙烯、1-丁烯、间,对-二甲苯及异戊二烯等物质;臭氧生成过程处于VOCs控制区.     

成都市春季O3污染特征及关键前体物识别

2018年4月在成都市区开展了臭氧（O₃）以及挥发性有机物（VOCs）等污染物的在线监测,搜集了成都市国控站点数据,对O₃污染特征进行分析,利用增量反应活性（RIR）的方法识别了O₃生成的关键前体物.结果表明,成都市2016~2018年的4月的O₃污染程度逐年加重,O₃日变化呈现单峰态;当温度大于20℃,风速处于1~1.5 m·s^-1,相对湿度小于65%时,O₃超标率在4月会高于80%;2018年4月,O₃超标天的NO_x日均浓度是非超标天的2.3倍,VOCs日均浓度是非超标天的2倍;人为源VOCs、CO、天然源VOCs和NO_x这4大类前体物在臭氧超标天对O₃的RIR值依次为2.4、0.87、0.06和-2.6,说明O₃处于VOCs控制区;从VOCs物种来看,间/对-二甲苯、乙烯、反-2-丁烯、丙烯、邻-二甲苯、甲苯、丙酮、异戊二烯、异戊烷和正丁烷等为O₃生成的关键活性VOCs物种.     

珠三角典型工业区挥发性有机物(VOCs)组成特征：含氧挥发性有机物的重要性

挥发性有机物(VOCs)是对流层大气的关键化学组分,其中工业排放是VOCs的重要来源之一.于2021年夏初在中国珠江三角洲的典型工业地区中开展了74种VOCs的在线观测.在整个观测期间,总挥发性有机物(TVOC)的体积分数平均值为(81.9±45.4)×10^-9.其中,含氧挥发性有机物(OVOCs)在TVOC中的占比最大,平均值为51.5%,并且其占比随TVOC体积分数的升高而逐渐增大.芳香烃在TVOC中的占比为19.4%.进一步分析发现,与工业活动相关的排放是工业区环境大气中芳香烃与OVOCs的主要来源.芳香烃和OVOCs对臭氧生成潜势(OFP)的贡献最为显著,在总OFP中的贡献率分别为56.4%和26.7%.此外,与烃类组分相比,OVOCs的大气化学活性同样较高,贡献了大气中总·OH反应活性的40.0%.二甲苯、甲苯、丙烯醛和乙酸乙酯对二次污染形成的贡献较大,在制定大气二次污染管控策略时应优先考虑.研究结果强调了工业地区中OVOCs对TVOC的重要贡献以及OVOCs在大气二次污染形成过程中的重要作用.     

广州大气中异戊二烯浓度变化特征、化学活性和来源分析

在广州番禺大气成分站(GPACS)应用在线监测仪器对异戊二烯进行长达1年的观测,获得异戊二烯浓度变化特征、大气化学活性和来源规律.结果表明:广州地区异戊二烯日均浓度为1.12 ppbv,由于受光照和温度影响较大,各月日均浓度在0.07~2.72 ppbv范围内波动.异戊二烯在冬季的日变化规律与其他季节不同,呈现双峰值变化,较大峰值出现在下午14:00,主要受光照和温度影响;较小峰值出现在晚上22:00左右,主要受机动车排放影响.采用最大增量活性(Maximum Incremental Reactivity,MIR)因子加权法和等效丙烯浓度法均发现异戊二烯的大气化学活性在监测的VOCs物种中最强,分别占总活性的15.45%和36.74%.通过异戊二烯与机动车标志性物质3-甲基戊烷、顺-2-丁烯的比值发现,广州地区异戊二烯在冬季夜晚主要来源于机动车排放,在秋季和春季夜晚也受到机动车排放影响,而夏季夜晚受机动车排放最不明显.这主要是由于在冬季、秋季和春季,监测点主要受到来自广州城区污染物输送的影响,而在夏季污染物从广州郊区输送使监测点受机动车排放的影响很小.异戊二烯与3-甲基戊烷、顺-2-丁烯在各季节的白天都没有线性关系,表明白天异戊二烯的排放受机动车的影响不大.     

Characterization of odorous charge and photochemical reactivity of VOC emissions from a full-scale food waste treatment plant in China

Food waste treatment plants (FWTPs) are usually associated with odorous nuisance and health risks, which are partially caused by volatile organic compound (VOC) emissions. This study investigated the VOC emissions from a selected full-scale FWTP in China. The feedstock used in this plant was mainly collected from local restaurants. For a year, the FWTP was closely monitored on specific days in each season. Four major indoor treatment units of the plant, including the storage room, sorting/crushing room, hydrothermal hydrolysis unit, and aerobic fermentation unit, were chosen as the monitoring locations. The highest mean concentration of total VOC emissions was observed in the aerobic fermentation unit at 21,748.2-31,283.3 μg/m³, followed by the hydrothermal hydrolysis unit at 10,798.1-23,144.4 μg/m³. The detected VOC families included biogenic compounds (oxygenated compounds, hydrocarbons, terpenes, and organosulfur compounds) and abiogenic compounds (aromatic hydrocarbons and halocarbons). Oxygenated compounds, particularly alcohols, were the most abundant compounds in all samples. With the use of odor index analysis and principal components analysis, the hydrothermal hydrolysis and aerobic fermentation units were clearly distinguished from the pre-treatment units, as characterized by their higher contributions to odorous nuisance. Methanthiol was the dominant odorant in the hydrothermal hydrolysis unit, whereas aldehyde was the dominant odorant in the aerobic fermentation unit. Terpenes, specifically limonene, had the highest level of propylene equivalent concentration during the monitoring periods. This concentration can contribute to the increase in the atmospheric reactivity and ozone formation potential in the surrounding air.     

Oxidation reactivity of 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) by Compound I model of cytochrome P450s

Alternative brominated flame retardants (BFRs) have become prevalent as a consequence of restrictions on the use of polybrominated diphenyl ethers (PBDEs). For risk assessment of these alternatives, knowledge of their metabolism via cytochrome P450 enzymes is needed. We have previously proved that density functional theory (DFT) is able to predict the metabolism of PBDEs by revealing the molecular mechanisms. In the current study, the reactivity of 1,2-bis(2,4,6-tribromophenoxy)ethane and structurally similar chemicals with the Compound I model representing the active site of P450 enzymes was investigated. The DFT calculations delineated reaction pathways which lead to reasonable explanations for products that were detected by wet experiments, meanwhile intermediates which cannot be determined were also proposed. Results showed that alkyl hydrogen abstraction will lead to bis(2,4,6-tribromophenoxy)ethanol, which may undergo hydrolysis yielding 2,4,6-tribromophenol, a neurotoxic compound. In addition, a general pattern of oxidation reactivity regarding the 2,4,6-tribromophenyl moiety was observed among several model compounds. Our study has provided insights for convenient evaluation of the metabolism of other structurally similar BFRs.     

Monitoring and modeling of disinfection by-products (DBPs)

In the United States, the newly promulgateddisinfectant/disinfection by-product (D/DBP) regulationsforce water treatment utilities to be more concerned withfinished and distributed water qualities. In this study,monitoring of DBP formation was conducted from three Frenchwater treatment plants trying to assess DBP variationsthrough time and space. Compared to the in-plant totaltrihalomethanes (TTHM) levels, TTHM levels in thedistribution system increased from less than 150% to morethan 300%. Significant variations for TTHM and bromate(BrO₃ ^-) levels throughout the seasons were alsoobserved; generally higher levels in the summer and lowerlevels in the winter. Combining chemical DBP models(empirical power functional models) and hydraulicsimulations, DBPs including TTHM and BrO₃ ^- weresuccessfully simulated from the full-scale monitoring data,indicating that empirical DBP model can be a potential toolto access DBP formation in actual plants. This study alsoprovides the protocols to assess DBP simulations in thewater treatment systems.