北京夏季大气HONO的监测研究

在2007-08-14～2007-08-24期间,利用差分光学吸收光谱（DOAS）技术,对北京市大气中HONO、NO₂和O₃等污染物进行了连续监测,分析了HONO和NO₂的日变化特征,讨论了夜间直接排放对HONO来源的贡献,进行了24 h和夜间13 h HONO非均相反应形成与黑碳气溶胶（BC）和相对湿度（RH）等要素的相关分析.结果表明,HONO和NO₂均在01:00左右达到峰值,HONO的另一峰值浓度出现在06:00,比NO₂第2个峰值出现时间07:00早1 h;夜间（19:00～次日07:00）直接排放对HONO的贡献最大达到31.3％,出现在20:00,平均贡献为15％;夜间HONO_corr/NO₂比率与BC和RH具有非常明显的相关性,说明HONO的非均相生成速率与NO₂的浓度以及反应介质BC表面的吸附水的浓度即RH成正比,得到夜间HONO平均转化率(HONO/NO₂)为0.8%·h^-1;而且RH的增加对HONO的非均相形成有利,但是当RH>80%对反应也将产生抑制作用,通过对监测期间的个例分析也证实了这一假设.     

Aerosol effects on ozone concentrations in Beijing: A model sensitivity study

Most previous O₃ simulations were based only on gaseous phase photochemistry. However, some aerosol-related processes, namely, heterogeneous reactions occurring on the aerosol surface and photolysis rate alternated by aerosol radiative influence, may affect O₃ photochemistry under high aerosol loads. A three-dimensional air quality model, Models-3/Community Multi-scale Air Quality-Model of Aerosol Dynamics, Reaction, Ionization, and Dissolution, was employed to simulate the effects of the above-mentioned processes on O₃ formation under typical high O₃ episodes in Beijing during summer. Five heterogeneous reactions, i.e., NO₂, NO₃, N₂O₅, HO₂, and O₃, were individually investigated to elucidate their effects on O₃ formation. The results showed that the heterogeneous reactions significantly affected O₃ formation in the urban plume. NO₂ heterogeneous reaction increased O₃ to 90 ppb, while HO₂ heterogeneous reaction decreased O₃ to 33 ppb. In addition, O₃ heterogeneous loss decreased O₃ to 31 ppb. The effects of NO₂, NO₃, and N₂O₅ heterogeneous reactions showed opposite O₃ concentration changes between the urban and extra-urban areas because of the response of the reactions to the two types of O₃ formation regimes. When the aerosol radiative influence was included, the photolysis rate decreased and O₃ decreased significantly to 73 ppb O₃. The two aerosol-related processes should be considered in the study of O₃ formation because high aerosol concentration is a ubiquitous phenomenon that affects the urban- and regional air quality in China.     

基于电化学传感器的大气NO2与O3监测研究

利用四电极电化学传感器开展大气NO₂和O₃监测研究.为解决温度和湿度对传感器响应的影响问题,提出了一种具有温湿度补偿与零点校正功能的大气NO₂和O₃测量结果校准模型,通过活性炭吸附特性获得干净的背景气体,实现传感器准确的零点校正,并利用实验系统实测数据结合多元线性回归方法获得校准模型参数.首先对传感器线性响应特性进行了测试,发现O₂和O₃的测量灵敏度分别为3.889 ppbv·mV^-1和4.107 ppbv·mV^-1.同时,在合肥西郊科学岛开展了为期2 d的大气NO₂和O₃连续观测,发现两者的浓度分别为0~30 ppbv和2~100 ppbv.最后将传感器观测结果与NO_x/O₃分析仪测量结果进行了回归分析,发现两者测得的NO₂线性拟合斜率为0.9701±0.0182,R²为0.8378,测得的O₃线性拟合斜率为0.9850±0.0101,R²为0.9431.研究表明,校准后的电化学传感器可用于大气NO₂和O₃的长期监测,可为推动大气环境监测技术发展提供新的思路.     

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.     

广州城市大气HOx化学过程初步研究

根据广州城市大气中OH自由基和其它污染物同步测量结果,计算了城市大气HO_x(OH+HO₂)化学过程中主要反应的转化速率,分析了城市大气化学过程的主要特征,并与清洁大气中的化学过程进行了对比.研究结果表明:广州城市大气中OH和HO₂总的生成速率分别约为4.5×10⁸分子/(cm³·s)和3.8×10⁸分子/(cm³·s),比清洁大气中要快得多;城市大气中的OH净生成主要来自气相HNO₂的光解,而OH的去除主要与VOCs、HCHO、NO₂和CO反应,有别于清洁大气.     

臭氧氧化饮用水过程中可同化有机碳生成的影响因素

研究臭氧化过程中,臭氧投加量、p H值和离子强度对可同化有机碳(assimilable organic carbon,AOC)生成量的影响.结果表明,臭氧投加量在1~5 mg·L~(-1)范围,AOC的生成量随着投加量的增加而增加,但过高的臭氧投加量(9 mg·L~(-1))反而导致AOC生成量下降.p H越高(6~9),AOC的生成量也越高.AOC的生成量随着离子强度的升高而下降.臭氧氧化强疏组分AOC的生成量最高,其次为弱疏,而极亲和中亲最低.研究发现,AOC的生成量与小分子有机物的SUVA有密切的关系,较低的SUVA产生较多的AOC.     

Heterogeneous uptake of nitrogen dioxide on Chinese mineral dust

Mineral dust is one of the major aerosols in the atmosphere. To assess its impact on trace atmospheric gases, in this work we present a laboratory study of the effect of temperature on the heterogeneous reaction of NO₂ on the surface of ambient Chinese dust over the temperature range from 258 to 313 K. The results suggest that nitrogen dioxide could mainly be adsorbed on these types of Chinese mineral dust reversibly with little temperature dependence. Similar to a previous study on NO₂ uptake on mineral aerosols, the uptake coefficients are mainly on the order of 10^− 6 for the Chinese dust, when BET areas are taken into account. HONO was observed as a product, and its formation and decomposition on Chinese mineral dust during the uptake processes were also studied. The complete dataset from this study was compiled with previous literature determinations. Atmospheric implications of the heterogeneous reaction between NO₂ and mineral dust are also discussed, in an effort to understand this important heterogeneous process.     

北京市大气光化学氧化剂污染研究

根据在北京市开展的光化学氧化剂系列研究,讨论北京市主要光化学氧化剂O₃,H₂O₂和有机过氧化物的污染浓度水平及其污染特征,探讨光化学氧化剂的形成机制及其主要影响因素。结果表明,北京市存在严重的光化学氧化剂污染,中关村大气臭氧(0₃)最大浓度不仅逐年递增,而O₃最大值的出现时间也提前,说明大气光化学活性逐年增强。光化学烟雾的重要产物过氧化氢(H₂O₂)和甲基过氧化氢(MHP)的浓度水平较高,最大浓度分别为3.69和3.26ug/m3。日益严重的大气NO_x污染为光化学氧化剂的生成提供了充足的前体物,北京市的大气污染己逐渐转为机动车尾气污染型,控制北京市光化学氧化剂污染的有效途径是降低NO_x排放。      

南京夏季大气臭氧光化学特征与敏感性分析

对流层臭氧（O₃）主要由氮氧化物（NO_x）和挥发性有机物（VOCs）经过一系列光化学反应生成,反应过程呈现复杂的非线性关系.为深入了解O₃的光化学特征及生成机制,利用2018年夏季大气O₃与VOCs的观测数据,结合大气零维框架模拟模型F0AM-MCM,研究O₃超标日和非O₃超标日的O₃光化学特征之间的差异性.观测结果表明,O₃超标日期间φ（O₃）和φ（TVOCs）的平均值分别为47.8×10^-9和49.0×10^-9,为非O₃超标日期间O₃（26×10^-9）和TVOCs（30×10^-9）体积分数的1.8倍和1.6倍.使用F0AM模型,借助EKMA曲线和RIR分析等识别O₃敏感性,发现南京市O₃超标日和非O₃超标日O₃的形成均主要受VOCs和NO_x的协同控制.F0AM-MCM模拟结果表明,在O₃超标日,·OH和HO₂的日平均混合比分别是非O₃超标日的1.3倍和1.8倍,表明O₃超标日期间具有更强的大气氧化能力,且·OH和HO₂的形成和损失速率也有明显的增加,表明自由基循环的增强.此外,O₃超标日的O₃生成速率明显高于非O₃超标日,从而导致了O₃超标日的O₃净生成速率明显高于非O₃超标日.以上发现提高了对南京夏季O₃超标日大气O₃光化学特征的认识.     

Observations of N2O5 and NO3 at a suburban environment in Yangtze river delta in China: Estimating heterogeneous N2O5 uptake coefficients

The nitrate radical (NO₃) and dinitrogen pentoxide (N₂O₅) play an important role in the nocturnal atmosphere chemistry. Observations of NO₃ radicals and N₂O₅ were performed in a semirural ground site at Tai'Zhou in polluted southern China using cavity ring down spectroscopy (CRDS) from 23 May to 15 June 2018. The observed NO₃ and N₂O₅ concentrations were relatively low, with 1 min average value of 4.4 ± 2.2 and 26.0 ± 35.7 pptV, respectively. The N₂O₅ uptake coefficient was determined to be from 0.027 to 0.107 based on steady state lifetime method. Fast N₂O₅ hydrolysis was the largest contributor to the loss of NO₃ and contributed to substantial nitrate formation, with an average value of 14.83 ± 6.01 µg/m³. Further analysis shows that the N₂O₅ heterogeneous reactions dominated the nocturnal NO_x loss and the nocturnal NO_x loss rate is 0.14 ± 0.02 over this region.     

O3/UV降解喹啉过程中不同氧化剂的相对重要性

研究O₃/UV降解自配喹啉水溶液时水体中存在的不同氧化剂对喹啉降解的相对重要性的结果表明,O₃和·OH是喹啉降解过程的主要氧化剂.通过靛蓝二磺酸钠法和·OH探针化合物(对氯苯甲酸)法分别测定了水体中的O₃浓度和·OH浓度,定量地计算了O₃和·OH在降解喹啉时的相对重要性,得到喹啉与·OH的二级反应速率常数为6.65×10⁹mol·(L·s)^-1.在本试验条件下,由·OH引起的喹啉去除率占总去除率的88%,而由O₃引起的喹啉去除率占总去除率的12%.提高水体中·OH的浓度有利于提高喹啉的总降解速率.     

基于DFT计算和实验研究无机氮对水中萘普生及其产物光解的影响

萘普生(NP)是一种广泛使用的消炎镇痛类药.本文研究了水中不同形态无机氮对萘普生及其两种重要的光解中间产物NP_1和NP_2光降解的影响.结果表明,NH~+_4对于NP及产物的光解几乎没有影响,NO~-_2和NO~-_3对NP、NP_1和NP_2的光解均表现出抑制作用.NO~-_2和NO~-_3对NP的影响主要是光屏蔽效应,而对NP_1和NP_2光解影响的主导因素是由光化学环境中产生的·NO、·NO_2同·OH的竞争关系造成的间接抑制.光化学环境中·OH、·NO_2、·NO氧化NP_1和NP_2的化学反应活化能垒呈现上升趋势(NP_1:7.0、21.2、54.4 kcal·mol~(-1);NP_2:34.5、47.1、70.3 kcal·mol~(-1)).活化能垒的差异表明,光化学反应体系中生成的·NO_2和·NO将会导致反应速率下降,这也诠释了NO~-_2和NO~-_3对NP_1和NP_2光解抑制的差异性.     

海洋厌氧氨氧化菌的富集培养及其脱氮特性

采用ASBR厌氧氨氧化反应器,通过接种胶州湾底泥,研究了海洋厌氧氨氧菌的富集培养及其脱氮特性.实验结果表明:海洋厌氧氨氧化菌的富集培养可分为4个阶段:菌体自溶期(1~15 d)、迟滞期(16~152 d)、活性提高期(153~183 d)与稳定运行期(184~192 d).与淡水厌氧氨氧化相比,其迟滞期(137 d)较长,活性提高期(30 d)较短,对基质浓度与HRT的变化更敏感,且由进出水导致的菌活性延迟时间为5 h,远长于淡水厌氧氨氧化菌,因此海洋厌氧氨氧化菌对新环境的适应能力更弱,更难富集培养.经过192 d运行,对NH_4~+-N与NO-2-N的去除率分别达到96.98%与95.66%,三氮转化比n(NH_4~+-N)∶n(NO-2-N)∶n(NO-3-N)为1∶(1.2±0.2)∶(0.22±0.06),接近理论比(1∶1.32∶0.26),NRRNH_4~+-N升至0.080 kg·(m~3·d)-1,海洋厌氧氨氧化菌活性显著提高,这标志着海洋厌氧氨氧化菌富集成功.反应器运行过程中,污泥逐渐由黑色泥状变为砖红色颗粒状,扫描电镜观察,该砖红色颗粒为表面光滑,排列紧密、有类似火山口形状的球状菌相互黏聚而成的菌团.     

NO3自由基与3种环醚的大气化学反应动力学研究

在自制的大气反应烟雾箱模拟实验装置中,利用相对速率法研究了3种工业常用溶剂四氢呋喃、1,3-二氧五环、1,4-二氧六环与NO3自由基在298 K±1 K和1.01×105 Pa条件下的反应,目的是通过了解这些挥发性有机化合物（volatile organiccompounds,VOCs）在大气中的降解反应动力学来评估这些化合物对环境可能造成的影响.利用配有氢火焰离子化检测器（FID）的气相色谱（GC）检测反应物浓度变化,测得NO3自由基与四氢呋喃的反应速率常数为（5.36±1.93）×10-15cm3·（molecule·s）-1,与文献报道值在误差范围内非常吻合,验证了实验装置和实验方法的可靠性.实验首次测定了298 K±1K和1.01×105 Pa条件下1,3-二氧五环以及1,4-二氧六环与NO3自由基反应的速率常数,分别为（1.84±0.70）×10-15cm3·（molecule·s）-1和（3.20±0.67）×10-16 cm3.（molecule·s）-1.利用所测反应速率常数估算这些化合物在大气中的平均寿命都在1 d甚至十几d,因此,其排放可能会对区域大气环境产生一定的影响.     

Evaluation and impact factors of indoor and outdoor gas-phase nitrous acid under different environmental conditions

As an important indoor pollutant, nitrous acid (HONO) can contribute to the concentration of indoor OH radicals by photolysis via sunlight penetrating into indoor environments, thus affecting the indoor oxidizing capability. In order to investigate the concentration of indoor HONO and its impact factors, three different indoor environments and two different locations in urban and suburban areas were selected to monitor indoor and outdoor pollutants simultaneously, including HONO, NO, NO₂, nitrogen oxides (NO_x), O₃, and particle mass concentration. In general, the concentration of indoor HONO was higher than that outdoors. In the urban area, indoor HONO with high average concentration (7.10 ppbV) was well-correlated with the temperature. In the suburban area, the concentration of indoor HONO was only about 1-2 ppbV, and had a good correlation with indoor relative humidity. It was mainly attributed to the heterogeneous reaction of NO₂ on indoor surfaces. The sunlight penetrating into indoor environments from outside had a great influence on the concentration of indoor HONO, leading to a concentration of indoor HONO close to that outdoors.     

Review of heterogeneous photochemical reactions of NOy on aerosol－A possible daytime source of nitrous acid (HONO) in the atmosphere

As an important precursor of hydroxyl radical, nitrous acid (HONO) plays a key role in the chemistry of the lower atmosphere. Recent atmospheric measurements and model calculations show strong enhancement for HONO formation during daytime, while they are inconsistent with the known sources in the atmosphere, suggesting that current models are lacking important sources for HONO. In this article, heterogeneous photochemical reactions of nitric acid/nitrate anion and nitrogen oxide on various aerosols were reviewed and their potential contribution to HONO formation was also discussed. It is demonstrated that HONO can be formed by photochemical reaction on surfaces with deposited HNO3 , by photocatalytic reaction of NO2 on TiO2 or TiO2 -containing materials, and by photochemical reaction of NO2 on soot, humic acids or other photosensitized organic surfaces. Although significant uncertainties still exist in the exact mechanisms and the yield of HONO, these additional sources might explain daytime observations in the atmosphere.     

Oxidation of diesel soot on binary oxide CuCr(Co)-based monoliths

Binary oxide systems (CuCr₂O₄, CuCo₂O₄), deposited onto cordierite monoliths of honeycomb structure with a second support (finely dispersed Al₂O₃), were prepared as filters for catalytic combustion of diesel soot using internal combustion engine's gas exhausts (O₂, NO_x, H₂O, CO₂) and O³ as oxidizing agents. It is shown that the second support increases soot capacity of aforementioned filters, and causes dispersion of the particles of spinel phases as active components enhancing thereby catalyst activity and selectivity of soot combustion to CO₂. Oxidants used can be arranged with reference to decreasing their activity in a following series: O₃ >> NO₂ > H₂O > NO > O₂ > CO₂. Ozone proved to be the most efficient oxidizing agent: the diesel soot combustion by O₃ occurs intensively (in the presence of copper chromite based catalyst) even at closing to ambient temperatures. Results obtained give a basis for the conclusion that using a catalytic coating on soot filters in the form of aforementioned binary oxide systems and ozone as the initiator of the oxidation processes is a promising approach in solving the problem of comprehensive purification of automotive exhaust gases at relatively low temperatures, known as the "cold start" problem.     

Identification of close relationship between atmospheric oxidation and ozone formation regimes in a photochemically active region

Understanding ozone (O₃) formation regime is a prerequisite in formulating an effective O₃ pollution control strategy. Photochemical indicator is a simple and direct method in identifying O₃ formation regimes. Most used indicators are derived from observations, whereas the role of atmospheric oxidation is not in consideration, which is the core driver of O₃ formation. Thus, it may impact accuracy in signaling O₃ formation regimes. In this study, an advanced three-dimensional numerical modeling system was used to investigate the relationship between atmospheric oxidation and O₃ formation regimes during a long-lasting O₃ exceedance event in September 2017 over the Pearl River Delta (PRD) of China. We discovered a clear relationship between atmospheric oxidative capacity and O₃ formation regime. Over eastern PRD, O₃ formation was mainly in a NO_x-limited regime when HO₂/OH ratio was higher than 11, while in a VOC-limited regime when the ratio was lower than 9.5. Over central and western PRD, an HO₂/OH ratio higher than 5 and lower than 2 was indicative of NO_x-limited and VOC-limited regime, respectively. Physical contribution, including horizontal transport and vertical transport, may pose uncertainties on the indication of O₃ formation regime by HO₂/OH ratio. In comparison with other commonly used photochemical indicators, HO₂/OH ratio had the best performance in differentiating O₃ formation regimes. This study highlighted the necessities in using an atmospheric oxidative capacity-based indicator to infer O₃ formation regime, and underscored the importance of characterizing behaviors of radicals to gain insight in atmospheric processes leading to O₃ pollution over a photochemically active region.     

北京大气中NO、NO2和O3浓度变化的相关性分析

臭氧（O₃）是城市污染大气中的首要光化学污染物,其变化规律与氮氧化物(NO_x=NO+NO₂)关系密切.采用49C臭氧分析仪和42CTL氮氧化物分析仪对北京城区O₃和NO_x浓度进行了连续观测,时间为2004-08～2005-07.结果显示,O₃和OX（O₃+NO₂）浓度在午后15:00左右出现峰值,NO_x呈双峰态日变化,在07:00和23:00左右出现峰值.不同季节污染物的浓度变化存在差异,O₃和NO_x浓度分别在夏季和冬季达到最大.NO_x浓度存在100×10^-9(体积分数)的“分界点”,NO_x低浓度时以NO₂为主,NO_x高浓度时NO占大部分.OX区域贡献和局地贡献存在明显的季节变化,前者主要受区域背景O₃的影响,在春季最大,后者主要受局地NO_x光化学反应的制约,在夏季最强,同时OX组分呈现显著的昼夜差异.     

失稳硝化膜生物反应器的性能恢复研究

对高水力负荷条件下丧失硝化功能的膜生物反应器进行恢复实验,将水力停留时间(HRT)从原来的5h延长到正常条件下可以实现完全硝化的10h后,在进水NH4+-N浓度为500mg.L-1的条件下反应器可去除99%的NH4+-N,但NO2--N出现严重积累,在60d的实验过程中NO2--N平均出水浓度为425mg.L-1.荧光原位杂交分析结果表明,氨氧化菌(AOBs)在总菌中的比例与恢复实验前没有变化,分别为12.9%(恢复实验期)和9.75%(恢复实验前),但氨氧化杆菌(Nitrosomonas)在AOBs中的比例从80%降低到40%;亚硝酸盐氧化细菌(NOBs)在总菌中的比例下降一半(从5.64%下降至2.84%),并以慢生型的Nitrospira为主.高NO2-含量和高胞外物浓度(497.1mg.L-1)可能是导致亚硝酸盐氧化功能难以恢复的主要原因.