化学电离技术在大气气溶胶质谱分析中的应用与展望

化学电离技术在大气气溶胶质谱分析中的应用已较为广泛.本文对化学电离质谱的结构与工作原理进行了简介,重点归纳总结了近年来化学电离质谱技术对大气自由基和痕量气体的测量、在有机气溶胶的外场观测和实验室研究中的应用与进展情况,探讨了目前研究中尚待解决的难点问题,并对化学电离质谱未来的研究工作及发展趋势进行了展望.     

连续测量大气·OH的化学电离飞行时间质谱仪的研制

搭建了一套化学电离飞行时间质谱仪用于连续测量大气·OH.该仪器采用了基于63Ni放射源的双管正交式结构大气压化学电离源电离大气中的·OH,最大程度地避免了试剂气体电离及滴定、转化反应间的相互干扰.63Ni放射源首先电离HNO3试剂气体得到试剂离子NO-3,·OH在反应管中与SO2反应最终转化为H2SO4,NO-3与H2SO4发生化学电离反应生成HSO-4离子,进入到质谱仪中进行检测,通过测量NO-3与HSO-4离子的强度,利用化学电离反应方程可直接计算出大气中OH的浓度.所研制仪器用于实验室内·OH的在线检测,在5 s内测得·OH的浓度为1.6×106个·cm-3,实验结果显示该仪器可用于原位连续测量大气中的超痕量自由基.     

Chemical composition of different size ultrafine particulate matter measured by nanoparticle chemical ionization mass spectrometer

New particle formation (NPF) is the primary source of nanoparticles and contributes a large number of concentrations of cloud condensation nuclei. In recent years, field campaigns and laboratory experiments have been conducted to promote cognition of the mechanism for NPF and its following growth processes. The chemical composition measurement of nanoparticles could help deepen understanding of the initial step of particulate matter formation. In this work, we developed a nanoparticle chemical ionization mass spectrometer to measure nanoparticles' chemical compositions during their initial growth stage. Meanwhile, a non-radioactive ion source was designed for aerosol charging and chemical ionization. Time of flight mass spectrometer coupled with integrated aerosol size selection and collection module would guarantee the picogram level detection limit and high-resolution ability to measure the matrix of ambient samples. The performance of this equipment was overall evaluated, including the transmission efficiency and collection efficiency of custom-built nano differential mobility analyzer, chemical ionization efficiency, and mass resolution of the mass spectrometer. The high sensitivity measurement of ammonium sulfate and methylammonium sulfate aerosols with diameters ranging from 10 to 25 nm could guarantee the application of this instrument in the ambient measurement.     

全自动阵列离子迁移谱仪连续监测挥发性有机化合物

为了拓宽离子迁移谱仪的检测范围、提高化合物的识别准确度,研制了一套阵列离子迁移谱仪,该仪器基于63 Ni源正离子模式、63Ni源负离子模式和真空紫外灯光电离模式的组合电离源,可以连续监测空气中挥发性有机化合物.仪器采用全自动的采样进样系统,同时检测了二甲基亚砜的正离子和二氯甲烷的负离子,实现了正负离子的同时检测.通过对阵列离子迁移谱图的综合解析,识别了63Ni源正离子模式下难以鉴别的丙烯腈、间二甲苯和丙酮.连续4 d定量测定丙酮样品,结果表明仪器对丙酮的线性检测范围为2个数量级,线性相关系数R优于0.995,相对标准偏差控制在4.0%～18.3%.采用动态跟踪法,连续24 h在线监测了模拟泄漏的丙烯酸甲酯,监测结果直接反映了其泄漏的时间和浓度.     

Significant contribution of spring northwest transport to volatile organic compounds in Beijing

High values of ozone (O₃) occur frequently in the dry spring season; thus, understanding the evolution characteristics of volatile organic compounds (VOCs) in spring is of great significance for preventing O₃ pollution. In this study, a total of 101 VOCs from April 16 to May 21, 2019, were quantified using an online gas chromatography mass spectrometer/flame ionization detector (GCMS/FID). The results indicated that the observed concentration of total VOCs (TVOCs) was 30.4 ± 17.0 ppbv, and it was dominated by alkanes (44.3%), followed by oxygenated VOCs (OVOCs) (17.4%), halocarbons (12.7%), aromatics (9.5%), alkenes (8.2%), acetylene (5.3%) and carbon disulfide (2.5%). The average mixing ratio of VOCs showed obvious diurnal variation (high at night, low during daytime). We conducted a source apportionment study based on 32 major VOCs using positive matrix factorization (PMF), and coal + biomass burning (25.2%), diesel exhaust (16.0%), gasoline exhaust + evaporation (17.4%), secondary + long-lived species (16.7%), biogenic sources (4.3%), industrial emissions (9.3%) and solvent use (11.2%) were identified as major sources of VOCs. In addition to local emissions, most of the atmospheric VOCs were derived from long-distance air masses (65.7%), and the average mixing ratio of VOCs in the northwest direction was 29.4 ppbv. Combined with the results of the potential source contribution function (PSCF) indicate that research should focus on the local emissions of combustion, transportation sources and solvents usage to control atmospheric VOCs. Additionally, transmission of the northwest air mass is an important component that cannot be ignored during spring in Beijing.     

西安市近地层空气离子与环境因子的关系研究

2009年8月至2010年7月在西安市16个采样点上开展了近地层空气离子浓度和温度、相对湿度、风速及可吸入颗粒物(PM10)等环境因子的观测,研究了西安市空气离子时空分布的基本特征,并利用空气离子浓度值对西安市的空气质量进行了评价.另外,详细分析了近地层空气负离子浓度与温度、相对湿度和PM10等主要环境因子之间的相互关...     

Atmospheric gaseous organic acids in winter in a rural site of the North China Plain

Organic acids are important contributors to the acidity of atmospheric precipitation,but their existence in the Chinese atmosphere is largely unclear.In this study,twelve atmospheric gaseous organic acids,including C₁-C₉ alkanoic acids,methacrylic acid,pyruvic acid,and benzoic acid,were observed in the suburb of Wangdu,Hebei Province,a typical rural site in the northern China plain from 16^th December,2018 to 22^nd January,2019,using a Vocus@Proton-Trans...     

Transient species in the ozonolysis of tetramethylethene

The reaction of alkenes with ozone has great effect on atmospheric oxidation, its transient species can produce OH radicals and contribute to the formation of secondary organic aerosols (SOA). In the present study, the reaction of tetramethylethene (TME) with ozone was investigated using self-assembled low temperature matrix isolation system. The TME and ozone were co-deposited on a salt plate at 15 K, and then slowly warmed up the plate. The first transient species primary ozonide (POZ) was detected, indicating that the reaction followed Criegee mechanism. Then POZ began to decompose at 180 K. However, secondary ozonide (SOZ) was not observed according to Criegee mechanism. Probably, Criegee Intermediate (CI) did not react with inert carbonyl of acetone, but with remaining TME formed tetra-methyl epoxide (EPO).     

膜进样-单光子电离/化学电离-质谱仪在线检测水中VOCs

介绍了自行研制的膜进样-单光子电离/化学电离-飞行时间质谱仪.光子能量为10.6 eV的真空紫外灯作为单光子电离的光源,同时利用光电子电离产生O 2＋试剂离子,用于待测物分子的化学电离,通过调节电离区的电场条件可在2 s之内实现2种电离模式的快速切换.水中挥发性有机物（VOCs）以50μm的硅橡胶膜进行快速富集,膜后加入吹扫气加快样品脱附,吹扫气体还可抑制质谱分析器中油气本底,提高信噪比.SPI模式下,甲基叔丁基醚的检出限达到2μg·L-1（10 s分析时间）;SPI-CI模式下,三氯甲烷检出限达到1μg·L-1（10 s分析时间）.该仪器已成功应用于模拟加油站附近地下水中的甲基叔丁基醚和饮用水消毒副产物中的挥发性有机物的快速检测.结果表明该仪器在水中挥发性有机物在线检测方面有着广阔的应用前景.     

A metal-OH group modification strategy to prepare highly-hydrophobic MIL-53-Al for efficient acetone capture under humid conditions

A series of highly-hydrophobic MIL-53-Al (MIL = Materials of Institut Lavoisier) frameworks synthesized via decoration of the Al-OH groups by alkyl phosphonic acid were developed as adsorbents for removing acetone from humid gas streams. The newly prepared materials were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), N₂ adsorption-desorption and thermogravimetric analysis (TGA). Their adsorption behaviors toward acetone vapor under dry and wet conditions were studied subsequently. Results showed that alkyl phosphonic acid was successfully grafted into MIL-53-Al skeleton through coordinating interaction with Al³⁺ generating [email protected]_x (x = 12, 14, 18). The [email protected]_x exhibited similar crystal structure and thermal stability to parent MIL-53-Al. Furthermore, the modified materials showed significantly enhanced hydrophobicity. The water vapor uptake of [email protected]₁₄ decreased by 72.55% at 75% relative humidity (RH). Dynamic adsorption experiments demonstrated that water vapor had almost no effect on the acetone adsorption performance of [email protected]₁₄. Under the condition of 90% RH, the acetone adsorption capacity of [email protected]₁₄ was 102.98% higher than that of MIL-53-Al. Notably, [email protected]₁₄ presented excellent adsorption reversibility and regeneration performance in 10 adsorption-desorption cycles. Taken together, the strategy of metal-OH group modification is an attractive way to improve the acetone adsorption performance over metal-organic frameworks (MOFs) under humid conditions. Besides, [email protected]₁₄ would be deemed as a promising candidate for capturing acetone in high moisture environment.     

Field measurements of dissociation of ammonium nitrate at a Beijing site

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Field measurements of dissociation of ammonium nitrate at a Beijing site

The atmospheric nitric acid, ammonia and ammonium nitrate aerosol was determined simultaneously in a Beijing site to teste quilibrium. Rather good agreement between measurements and theory was found at ambient temperature above 9oC at relative humidity below 70%. Below 9oC the kinetic constraints preventing rapid attainment equilibrium were observed. A procedure for calculation of dependence of NH4NO3 aerosol dissociation constants on temperature and relative humidity was given. The seasonal variation of concentration of NH3, total NH4+ and HNO3 was observed.The seasonal variation of concentration of HNO3 was caused by dissociation of aerosol of NH4NO3. The concentrations of NH3 were 1-2 order higher than those of HNO3. For formation of NH4NO3 aerosol the HNO3 was the control reagent. Any increase of HNO3 to formed from NOx would react with NH3 form NH4NO3 aerosol in Beijing area except for someday in summer time.     

北京地区大气温湿廓线对气溶胶垂直分布的影响

目的分析北京地区大气温湿廓线对气溶胶垂直分布的影响。方法利用北京地区2017年9月至2018年8月每日两次(08时和20时)的气象探空、地面PM_(2.5)浓度和气溶胶激光雷达消光系数资料,分析不同污染条件下大气温湿廓线与气溶胶消光系数廓线的关系。结果地面PM_(2.5)浓度和210m气溶胶消光系数的相关系数达到0.77。春季、秋季和冬季污染条件下的近地面消光系数约是清洁条件下的5倍,夏季污染条件下的近地面消光系数约是清洁条件下的3倍。相比清洁条件下,污染条件下各季节的大气温度垂直递减率偏小,并且低层大气相对湿度偏大。结论大气温度廓线代表大气层结稳定性,影响气溶胶的扩散高度,而相对湿度廓线与气溶胶吸湿增长密切相关,两者对气溶胶消光系数的垂直分布都有重要影响。     

北京市区大气氮沉降研究

2009年3～9月,使用离子交换树脂柱法对北京市区大气氮沉降进行了观测.2009年3～6月,北京市区大气硝态氮沉降平均值为40.59 mg.m-2,大气亚硝态氮沉降平均值为14.66 mg.m-2.2009年6～9月,北京市区大气硝态氮沉降平均值为75.13 mg.m-2,大气亚硝态氮沉降平均值为20.67 mg.m-2.观测表明,大气硝态氮和亚硝态氮沉降有明显的局部分异特点,沉降量大的地点主要是交通干线和热电厂周边地区,显示了大气硝态氮和亚硝态氮的线源和点源特征.2009年3～6月,北京市区大气氨态氮沉降平均值为12.19 mg.m-2.2009年6～9月,北京市区大气氨态氮沉降平均值为8.46 mg.m-2.结果表明,各观测点之间大气氨态氮沉降变化明显小于硝态氮和亚硝态氮,显示了大气氨态氮的非点源特征.     

Effect of air-exposed biocathode on the performance of a Thauera-dominated membraneless single-chamber microbial fuel cell (SCMFC)

To investigate the effect of air-exposed biocathode(AEB) on the performance of singlechamber microbial fuel cell(SCMFC), wastewater quality, bioelectrochemical characteristics and the electrode biofilms were researched. It was demonstrated that exposing the biocathode to air was beneficial to nitrogen removal and current generation. In Test 1 of 95%AEB, removal rates of ammonia, total nitrogen(TN) and chemical oxygen demand(COD)reached 99.34% ± 0.11%, 99.34% ± 0.10% and 90.79% ± 0.12%, respectively. The nitrogen removal loading rates were 36.38 g N/m~3/day. Meanwhile, current density and power density obtained at 0.7 A/m3 and 104 m W/m~3 respectively. Further experiments on opencircuit(Test 2) and carbon source(Test 3) indicated that this high performance could be attributed to simultaneous biological nitrification/denitrification and aerobic denitrification, as well as bioelectrochemical denitrification. Results of community analysis demonstrated that both microbial community structures on the surface of the cathode and in the liquid of the chamber were different. The percentage of Thauera, identified as denitrifying bacteria, maintained at a high level of over 50% in water, but decreased gradually in the AEB. Moreover, the genus Nitrosomonas, Alishewanella, Arcobacter and Rheinheimera were significantly enriched in the AEB, which might contribute to both enhancement of nitrogen removal and electricity generation.     

用离子交换树脂柱法观测长春市大气氮沉降

为了解城市环境中大气氮沉降的特点,于2008年9月—2009年9月,使用离子交换树脂柱法对长春市大气氮沉降进行了观测. 结果表明:观测期间,长春市大气硝态氮沉降量月均值为5.33 mg/m2>/sup>,亚硝态氮沉降量月均值为1.67 mg/m2>/sup>. 大气硝态氮和亚硝态氮沉降量有明显的局部分异特点,沉降量大的地点主要分布在交通干线和热电厂周边地区,显示了大气硝态氮的点源和线源特征. 大气氨氮沉降量月均值为3.10 mg/m2>/sup>; 各观测点间大气氨氮沉降量变化明显小于硝态氮和亚硝态氮,显示了大气氨氮的面源特征.      

Assessing the net atmospheric impacts of wood production and utilization

The main objective of the study was to calculate net atmospheric impacts for wood production and utilization in Finnish boreal forest conditions. Net atmospheric impacts were calculated by comparing net CO₂ exchanges of the wood production and utilization to the reference management regime. Net CO₂ exchanges were simulated with a life cycle assessment (LCA) tool for a Scots pine (Pinus sylvestris L.) stand (MT, Myrtillys-type) in central Finland (Joensuu region, 62°39 N, 29°37 E) over two consecutive rotation periods (100?+?100 years/200 years). Net atmospheric impacts were calculated both for sawn timber and pulpwood, and expressed in kgCO₂m^?3. According to the results, the production of pulp and sawn timber produced emissions of 0.20 and 0.59 kgCO₂m^?3 over the 200-year period, respectively, when the unmanagement regime was used as the reference management regime. When 50 % of the processing waste of timber was accounted as an instant emission to the atmosphere, the atmospheric impact increased to 0.55 kgCO₂m^?3 in pulpwood and to 1.27 kgCO₂m^?3 in sawn timber over the 200 year period. When turnover rates of sawn timber in the technosystem were decreased by 30 % and the share of energy use was decreased to 30 %, the atmospheric impact decreased by 17 % and 4 % for pulpwood and sawn timber, respectively, compared to the default wood degradation and energy use of 50 %. The utilized LCA approach provided an effective tool for approaching net atmospheric impacts originating from the ecosystem carbon (C) flows and variable wood utilization. Taking the ecosystem production and utilization of wood (i.e. degradation of technosystem C stock) into account, in terms of net CO₂ exchange, the mitigation possibilities of wood compared to other products can be accounted for more precisely in the future and C sequestration credited more specifically for a certain wood product.     

Effects of tourmaline on nitrogen removal performance and biofilm structures in the sequencing batch biofilm reactor

The effects of tourmaline on nitrogen removal performance and biofilm structures were comparatively investigated in two identical laboratory-scale sequencing batch biofilm reactors(SBBRs)(denoted SBBR1 and SBBR2) at different nitrogen loading rates(NLRs) varying from(0.24 ± 0.01) to(1.26 ± 0.02) g N/(L·day). SBBR1 was operated in parallel with SBBR2, but SBBR1 was filled with polyurethane foam loaded tourmaline(TPU) carriers and another(SBBR2) filled with polyurethane foam(PU) carriers. Results obtained from this study showed that the excellent and stable performance of SBBR1 was obtained. Ammonia nitrogen removal and total nitrogen removal were higher in SBBR1 than that in SBBR2 with increase of NLR. At an NLR of(0.24 ± 0.01) g N/(L·day), the majority of the spherical and elliptical bacteria were surrounded by the extracellular polymeric substance(EPS) and bacillus or filamentous bacteria in two SBBRs biofilms. When NLR increased to(1.26 ± 0.02) g N/(L·day), the clusters were more obvious in the SBBR1 biofilm than that in the SBBR2 biofilm. Bacteria in SBBR1 were inclined to synthesis more EPS, and the formed EPS could protect the bacteria from free ammonia(FA) under extreme condition NLR(1.26 ± 0.02) g N/(L·day). The results of polymerase chain reaction-denaturing gradient gel electrophoresis analysis showed that the microbial community similarity in SBBR2 decreased more obviously than that in SBBR1 with the increase of NLR, which the microbial community in SBBR1 was relatively stable.     

北京市MODIS气溶胶光学厚度与PM_(10)质量浓度的相关性分析

利用北京地区2012年1—12月NASA MODIS气溶胶光学厚度(AOD)和通过空气污染指数(API)转换得到的PM10质量浓度进行了相关性分析.结果发现,二者的直接相关程度较低,在引入季节变化的气溶胶标高且考虑了气溶胶的垂直分布后,进行标高订正,二者的相关系数有所提高;在考虑了湿度影响因子后,进行湿度订正,二者的相关系数显著提高;引入平均风速、平均气温和平均气压等气象因素,进行多元回归分析,相关系数进一步提高.证实了卫星遥感气溶胶光学厚度在经过垂直和湿度订正并考虑气象因素的情况下,可以作为监测北京地区颗粒物污染物地面分布的一个有效手段.     

Emission of particulate and gaseous pollutants from household laser processing machine

Indoor air quality (IAQ) directly affects the health of occupants. Household manufacturing equipment (HME) used for hobbies or educational purposes is a new and unexplored source of air pollution. In this study, we evaluated the characteristics of particulate and gaseous pollutants produced by a household laser processing equipment (HLPE). Various target materials were tested using a commercial HLPE under various operating conditions of laser power and sheath air flow rate. The mode diameters of the emitted particles gradually decreased as laser power increased, while the particle number concentration (PNC) and particle emission rate (PER) increased. In addition, as the sheath air flow rate quadrupled from 10 to 40 L/min, the mode diameter of the emitted particles decreased by nearly 25%, but the effect on the PNC was insignificant. When the laser induced the target materials at 53 mW, the mode diameters of particles were <150 nm, and PNCs were >2.0 × 10⁴ particles/cm³. Particularly, analyses of sampled aerosols indicated that harmful substances such as sulfur and barium were present in particles emitted from leather. The carcinogenic gaseous pollutants such as acrylonitrile, acetaldehyde, 1,3-butadiene, benzene, and C₈ aromatics (ethylbenzene) were emitted from all target materials. In an actual indoor environment, the PNC of inhalable ultrafine particles (UFPs) was >5 × 10⁴ particles/cm³ during 30 min of HLPE operation. Our results suggest that more meticulous control methods are needed, including the use of less harmful target materials along with filters or adsorbents that prevent emission of pollutants.