Roles of SO2 oxidation in new particle formation events

The oxidation of SO₂ is commonly regarded as a major driver for new particle formation (NPF) in the atmosphere. In this study, we explored the connection between measured mixing ratio of SO₂ and observed long-term (duration > 3 hr) and short-term (duration <1.5 hr) NPF events at a semi-urban site in Toronto. Apparent NPF rates (J₃₀) showed a moderate correlation with the concentration of sulfuric acid ([H₂SO₄]) calculated from the measured mixing ratio of SO₂ in long-term NPF events and some short-term NPF events (Category I) (R² = 0.66). The exponent in the fitting line of J₃₀ ~ [H₂SO₄]ⁿ in these events was 1.6. It was also found that SO₂ mixing ratios varied a lot during long-term NPF events, leading to a significant variation of new particle counts. In the SO₂-unexplained short-term NPF events (Category II), analysis showed that new particles were formed aloft and then mixed down to the ground level. Further calculation results showed that sulfuric acid oxidized from SO₂ probably made a negligible contribution to the growth of >10 nm new particles.     

Roles of SO2 oxidation in new particle formation events

The oxidation of SO₂ is commonly regarded as a major driver for new particle formation (NPF) in the atmosphere. In this study, we explored the connection between measured mixing ratio of SO₂ and observed long-term (duration > 3 hr) and short-term (duration < 1.5 hr) NPF events at a semi-urban site in Toronto. Apparent NPF rates (J₃₀) showed a moderate correlation with the concentration of sulfuric acid ([H₂SO₄]) calculated from the measured mixing ratio of SO₂ in long-term NPF events and some short-term NPF events (Category I) (R² = 0.66). The exponent in the fitting line of J₃₀ ~ [H₂SO₄]ⁿ in these events was 1.6. It was also found that SO₂ mixing ratios varied a lot during long-term NPF events, leading to a significant variation of new particle counts. In the SO₂-unexplained short-term NPF events (Category II), analysis showed that new particles were formed aloft and then mixed down to the ground level. Further calculation results showed that sulfuric acid oxidized from SO₂ probably made a negligible contribution to the growth of > 10 nm new particles.     

青岛沿海地区夏季和冬季新粒子生成特征对比

利用宽范围粒径谱仪（WPS）和电迁移率粒径分析仪（SMPS）对青岛沿海地区夏、冬两季大气颗粒物数浓度和粒径谱分布进行了实时测量,同时结合无机和有机气态前体物、大气颗粒物化学组分、气象参数以及后向气流轨迹,对新粒子生成（NPF）特征进行了分析对比.结果表明,在夏季,NPF事件发生频率较低,为18%.夏季NPF事件发生时,大气颗粒物数浓度可增加1~4倍,新粒子表观生成速率和增长速率（除7月20日特殊事件）分别为（5.2±4.3）cm^-3·s^-1和（6.5±2.2）nm·h^-1,相关分析结果暗示生物源有机物（BVOCs）对新粒子生成有促进作用,人为源有机物（AVOCs）起抑制作用.冬季,NPF事件发生频率为27%,新粒子表观生成速率和增长速率分别为（3.3±3.1）cm^-3·s^-1和（5.3±3.3）nm·h^-1,大气颗粒物总数浓度在NPF天和非NPF天无显著差异.与夏季相反,相关分析结果暗示冬季人为源有机物（AVOCs）对新粒子生成有促进作用,而生物源有机物（BVOCs）与新粒子生成的关系不明显.此外,新粒子增长到CCN粒径范围（>50 nm）的增长特征呈现季节性差异：在夏季,新粒子生成后可在光化学作用下直接增长到CCN粒径范围,而在冬季,新粒子需经历两阶段增长,第二阶段增长中颗粒态硝酸铵的生成方可使新粒子增长至CCN粒径范围.     

四川乡村点新粒子生成特征及其对云凝结核数浓度的贡献

为揭示成渝地区大气复合污染成因,选择乡村点资阳站的冬季,实测了颗粒物数浓度及其粒径谱分布、云凝结核(CCN),在二氧化硫、光解速率(JO1D)实测值基础上估算了新粒子生成的重要前体物气态硫酸的浓度.2012年12月5日到2013年1月5日观测期间,3~582nm颗粒物数浓度水平较高,平均值为(16072±9713)cm-3.颗粒物数谱分布呈现以积聚模态为主体的特征,占总颗粒物数浓度的46%,此比值高于我国北京、上海、广州等城市和珠江三角洲及长江三角洲的乡村点和背景点.在较高颗粒物凝结汇(CS)水平下[(4.3±3.6)×10-2s-1],甄别出7次新粒子生成(NPF)事件,占观测天数的23%.NPF事件发生时,颗粒物生成速率与增长速率分别为(5.2±1.4)cm-3s-1,(3.6±2.5)nm/h. NPF事件对CCN数浓度有明显贡献,NPF发生后CCN数浓度平均增长19%.     

南京市夏季大气气溶胶新粒子生成事件分析

研究了南京市夏季大气气溶胶数浓度的基本特征和气溶胶新粒子生成事件的形成条件及其影响因子.应用宽范围颗粒粒径谱仪(WPS)和双光路差分吸收光谱仪(DOAS)对南京市2010年7月大气气溶胶数浓度谱分布和污染气体(O3、SO2和NO2)进行了观测,并结合气象要素观测数据和后向轨迹模式模拟,探讨了南京市夏季大气气溶胶新粒子生成的条件及其影响因子.结果表明,南京市夏季10～500nm气溶胶平均数浓度为1.7×104cm-3,与北美和欧洲的一些典型城市观测值相近;10～25 nm气溶胶粒子数浓度占总数浓度的比例为25%.观测期间共出现6次新粒子生成事件,通过分析发现比较稳定的风速风向、较强的太阳辐射有利于南京夏季新粒子的形成.南京夏季新粒子生成事件的相对湿度条件在50%～70%,通过后向轨迹模式模拟的结果发现偏东风或偏南风带来的海洋性洁净气团有利于新粒子的生成.南京夏季新粒子生成事件发生时,10～25 nm气溶胶数浓度与SO2的浓度呈正相关,与O3的浓度呈负相关,而与NO2的浓度相关性较差.     

Photodegradation of methylmercury in Jialing River of Chongqing,China

Photodegradation (PD) of methylmercury (MMHg) is a key process of mercury (Hg) cycling in water systems, maintaining MMHg at a low level in water systems. However, we possess little knowledge of this important process in the Jialing River of Chongqing, China. In situ incubation experiments were thus performed to measure temporal patterns and influencing factors of MMHg PD in this river. The results showed that MMHg underwent a net demethylation process under solar radiation in the water column, which predominantly occurred in surface waters. For surface water, the highest PD rate constants were observed in spring (12 × 10^− 3 ± 1.5 × 10^− 3 m²/E), followed by summer (9.0 × 10^− 3 ± 1.2 × 10^− 3 m²/E), autumn (1.4 × 10^− 3 ± 0.12 × 10^− 3 m²/E), and winter (0.78 × 10^− 3 ± 0.11 × 10^− 3 m²/E). UV-A radiation (320–400 nm), UV-B radiation (280–320 nm), and photosynthetically active radiation (PAR, 400–700 nm) accounted for 43%–64%, 14%–31%, and 16%–45% of MMHg PD, respectively. PD rate constants varied substantially with the treatments that filtered the river water and amended it with chemicals (i.e., Cl⁻, NO₃⁻, dissolved organic matter (DOM), Fe(III)), which reveals that suspended particulate matter and water components are important factors in affecting the PD process. For the entire water column, the PD rate constant determined for each wavelength range decreased rapidly with water depth. UV-A, UV-B, and PAR contributed 27%–46%, 6.2%–12%, and 42%–65% to the PD process, respectively. PD flux was estimated to be 4.7 μg/(m²·year) in the study site. Our results are very important to understand the cycling characteristics of MMHg in the Jialing River of Chongqing, China.     

Effect of short-term regional traffic restriction on urban submicron particulate pollution

During the 2013 and 2015 Lanzhou International Marathon Events(LIME1 and LIME2),the local government made a significant effort to improve traffic conditions and air quality by implementing traffic restriction measures. To fill the gap in information on the effect of short-period(several hours)traffic control on urban air quality,submicron particle size distributions and meteorological data were measured simultaneously during June 2013 and June 2015 in urban Lanzhou. The number and surface area concentrations of particles in the100–200 nm range declined by 67.2% and 65.0% for LIME1 due to traffic control,while they decreased by 39.2% and 37.1% for LIME2. The impact of traffic restriction on air pollution near the sampling site lagged behind the traffic control period for LIME2. In addition,the effect of traffic restriction on air pollution near the sampling site was dependent on the distance between the relative orientation of the sampling site and traffic-restricted zones,as well as meteorological conditions such as wind direction. The influence of traffic restrictions on the particle concentrations differed for different particle sizes. The size range most affected by traffic restriction was 60–200 and 60–300 nm for number and surface area concentrations in the urban environment,respectively,while for the particle volume concentration it was the 100–600 nm range. This study will provide a basis for implementation of future urban traffic-induced particulate pollution control measures.     

Online single particle measurement of fireworks pollution during Chinese New Year in Nanning

Time-resolved single-particle measurements were conducted during Chinese New Year in Nanning, China. Firework displays resulted in a burst of SO_2, coarse mode, and accumulation mode(100–500 nm) particles. Through single particle mass spectrometry analysis, five different types of particles(fireworks-metal, ash, dust, organic carbon-sulfate(OC-sulfate), biomass burning) with different size distributions were identified as primary emissions from firework displays. The fireworks-related particles accounted for more than70% of the total analyzed particles during severe firework detonations. The formation of secondary particulate sulfate and nitrate during firework events was investigated on single particle level. An increase of sulfite peak(80SO_3~-) followed by an increase of sulfate peaks(97HSO_4~-+ 96SO_4~-) in the mass spectra during firework displays indicated the aqueous uptake and oxidation of SO_2 on particles. High concentration of gaseous SO_2, high relative humidity and high particle loading likely promoted SO_2 oxidation. Secondary nitrate formed through gas-phase oxidation of NO_2 to nitric acid, followed by the condensation into particles as ammonium nitrate. This study shows that under worm, humid conditions, both primary and secondary aerosols contribute to the particulate air pollution during firework displays.     

Responses of soil ammonia oxidizers to a short-term severe mercury stress

The responses of soil ammonia-oxidizing archaea(AOA) and ammonia-oxidizing bacteria(AOB) to mercury(Hg) stress were investigated through a short-term incubation experiment.Treated with four different concentrations of Hg(CK,Hg25,Hg50,and Hg100,denoting 0,25,50,and 100 mg Hg/kg dry soil,respectively),samples were harvested after 3,7,and 28 day incubation.Results showed that the soil potential nitrification rate(PNR) was significantly inhibited by Hg stress during the incubation.However,lower abundances of AOA(the highest in CK: 9.20 × 10~7 copies/g dry soil; the lowest in Hg50: 2.68 × 10~7 copies/g dry soil) and AOB(the highest in CK: 2.68 × 10~7 copies/g dry soil; the lowest in Hg50:7.49 × 10~6 copies/g dry soil) were observed only at day 28 of incubation(P 0.05).Moreover,only the community structure of soil AOB obviously shifted under Hg stress as seen through DGGE profiles,which revealed that 2–3 distinct AOB bands emerged in the Hg treatments at day 28.In summary,soil PNR might be a very useful parameter to assess acute Hg stress on soil ecosystems,and the community structure of soil AOB might be a realistic biological indicator for the assessment of heavy metal stress on soil ecosystems in the future.     

黄山大气气溶胶新粒子生长特性观测分析

利用2012年9月22日~10月28日黄山地区大气气溶胶、二氧化硫和臭氧观测数据,结合气象数据,分析气溶胶新粒子的生成-增长特征.分析发现,在33个有效观测日中,有新粒子生成-增长的观测日占总数的18.2%,其中晴天的发生频率为37.5%,新粒子生成-增长都开始于晴天上午,与无新粒子观测日相比,太阳辐射量、风速、SO2及O3浓度较高,环境温度和相对湿度较低.气溶胶新粒子的增长具有由小及大的特点,核模态气溶胶粒子(10~20nm)数浓度最先增加,爱根核模态粒子(20~50nm)数浓度随着时间推移逐渐增大,但浓度峰值依次下降,平均增长率为3.58nm/h. SO2浓度先于核模态气溶胶数浓度到达峰值,其氧化后的产物H2SO4为新粒子的核化提供前体物,并且参与新粒子的增长过程,当SO2浓度较低时,不会发生新粒子生长事件.     

大气细颗粒物的透射电子显微镜研究

利用透射电子显微镜(TEM)对北京市区和背景点的细颗粒物(PM2.5)的形貌特征和集聚状态进行分析,结合颗粒物能谱(EDX)和选区电子衍射(SAED)特征,将北京市大气细颗粒物分为烟尘集合体、飞灰、矿物颗粒、硫酸盐和有机颗粒等5种单颗粒类型,并讨论了它们的来源.TEM分析表明,北京市区和背景点大气细颗粒物中不同类型的单颗粒所占比例不同,表明市区和背景点细颗粒物的污染物源有所不同.研究还表明,不同类型的细颗粒之间常常发生聚集.     

Particle number size distribution and new particle formation: New characteristics during the special pollution control period in Beijing

New particle formation is a key process in shaping the size distribution of aerosols in the atmosphere.We present here the measurement results of number and size distribution of aerosol particles (10-1...     

Physico-chemical characterization and source tracking of black carbon at a suburban site in Beijing

Particles from ambient air and combustion sources including vehicle emission, coal combustion and biomass burning were collected and chemically pretreated with the purpose of obtaining isolated BC (black carbon) samples. TEM (transmission electron microscopy) results indicate that BC from combustion sources shows various patterns, and airborne BC appears spherical and about 50 nm in diameter with a homogeneous surface and turbostratic structure. The BET (Barrett–Emmett–Teller) results suggest that the surface areas of these BC particles fall in the range of 3–23 m²/g, with a total pore volume of 0.03–0.05 cm³/g and a mean pore diameter of 7–53 nm. The nitrogen adsorption–desorption isotherms are indicative of the accumulation mode and uniform pore size. O₂-TPO (temperature programmed oxidation) profiles suggest that the airborne BC oxidation could be classified as the oxidation of amorphous carbon, which falls in the range of 406–490°C with peaks at 418, 423 and 475°C, respectively. Generally, the BC characteristics and source analysis suggest that airborne BC most likely comes from diesel vehicle emission at this site.     

Monitoring atmospheric nitrous oxide background concentrations at Zhongshan Station, east Antarctica

At present,continuous observation data for atmospheric nitrous oxide(N_2O) concentrations are still lacking,especially in east Antarctica.In this paper,nitrous oxide background concentrations were measured at Zhongshan Station(69°22′25″S,76°22′14″E),east Antarctica during the period of 2008–2012,and their interannual and seasonal characteristics were analyzed and discussed.The mean N_2O concentration was 321.9 n L/L with the range of 320.5–324.8 n L/L during the five years,and it has been increasing at a rate of 0.29% year-1.Atmospheric N_2O concentrations showed a strong seasonal fluctuation during these five years.The concentrations appeared to follow a downtrend from spring to autumn,and then increased in winter.Generally the highest concentrations occurred in spring.This trend was very similar to that observed at other global observation sites.The overall N_2O concentration at the selected global sites showed an increasing annual trend,and the mean N_2O concentration in the Northern Hemisphere was slightly higher than that in the Southern Hemisphere.Our result could be representative of atmospheric N_2O background levels at the global scale.This study provided valuable data for atmospheric N_2O concentrations in east Antarctica,which is important to study on the relationships between N2 O emissions and climate change.     

Urease inhibitor reduces N losses and improves plant-bioavailability of urea applied in fine particle and granular forms under field conditions

A field lysimeter/mini plot experiment was established in a silt loam soil near Lincoln, New Zealand, to investigate the effectiveness of urea fertilizer in fine particle application (FPA), with or without the urease inhibitor N-(n-butyl) thiophosphoric triamide (NBPT - “Agrotain”), in decreasing nitrogen (N) losses and improving N uptake efficiency. The five treatments were: control (no N) and ¹⁵N-labelled urea, with or without NBPT, applied to lysimeters or mini plots (unlabelled urea), either in granular form to the soil surface or in FPA form (through a spray) at a rate equivalent to 100 kg N ha⁻¹. Gaseous emissions of ammonia (NH₃) and nitrous oxide (N₂O), nitrate (NO₃⁻) leaching, herbage dry-matter (DM) production, N-response efficiency, total N uptake and total recovery of applied ¹⁵N in the plant and soil varied with urea application method and with addition of NBPT. Urea with NBPT, applied in granular or FPA form, was more effective than in application without NBPT: N₂O emissions were reduced by 7-12%, NH₃ emissions by 65-69% and NO₃⁻ leaching losses by 36-55% compared with granular urea. Urea alone and with NBPT, applied in FPA form increased herbage DM production by 27% and 38%, respectively. The N response efficiency increased from 10 kg DM kg⁻¹ of applied N with granular urea to 19 kg DM kg⁻¹ with FPA urea and to 23 kg DM kg⁻¹ with FPA urea plus NBPT. Urea applied in FPA form resulted in significantly (P < 0.05) higher ¹⁵N recovery in the shoots compared with granular treatments and this was improved further when urea in FPA form was applied with NBPT. These results suggest that applying urea with NBPT in FPA form has potential as a management tool in mitigating N losses, improving N-response efficiency and increasing herbage DM production in intensive grassland systems.     

发动机燃用GTL柴油的排气颗粒数量及粒径分布规律

以一台汽车电控高压共轨柴油机为样机,采用发动机尾气颗粒粒径谱仪EEPS研究了发动机燃用天然气制油(GTL柴油)的排气颗粒数量及粒径分布规律.所用燃油分别为纯柴油(G0)、纯GTL柴油(G100)及GTL柴油掺混比为10%、20%的燃料(分别表示为G10、G20).试验工况为最大转矩转速1500r.min-1和标定转速2300r.min-1的负荷特性试验,负荷百分比分别为10%、25%、50%、75%和100%.结果表明:无论燃用柴油,还是GTL柴油或混合燃料,该机排气颗粒数量随粒径变化大都呈现明显的双峰对数分布状态,其排气核态颗粒的峰值粒径在10nm附近,聚集态颗粒峰值集中出现在40～50nm之间.随着GTL柴油配比的增加,各工况下不同粒径的颗粒数量大都持续下降,其中,排气核态颗粒数量明显下降,在高速高负荷下更为显著;而聚集态颗粒也较纯柴油有一定的降幅,其中,G20和G100柴油更为明显.     

Trace metals in atmospheric fine particles in one industrial urban city: Spatial variations, sources, and health implications

Trace metals in PM2.5were measured at one industrial site and one urban site during September, 2010 in Ji'nan, eastern China. Individual aerosol particles and PM2.5samples were collected concurrently at both sites. Mass concentrations of eleven trace metals(i.e., Al, Ti, Cr, Mn, Fe, Ni, Cu, Zn, Sr, Ba, and Pb) and one metalloid(i.e., As) were measured by inductively coupled plasma atomic emission spectroscopy(ICP-AES). The result shows that mass concentrations of PM2.5(130 μg/m3) and trace metals(4.03 μg/m3) at the industrial site were 1.3 times and 1.7 times higher than those at the urban site, respectively, indicating that industrial activities nearby the city can emit trace metals into the surrounding atmosphere. Fe concentrations were the highest among all the measured trace metals at both sites, with concentrations of 1.04 μg/m3at the urban site and 2.41 μg/m3at the industrial site, respectively. In addition, Pb showed the highest enrichment factors at both sites, suggesting the emissions from anthropogenic activities existed around the city. Correlation coefcient analysis and principal component analysis revealed that Cu, Fe, Mn, Pb, and Zn were originated from vehicular trafc and industrial emissions at both sites; As, Cr, and part of Pb from coal-fired power plant; Ba and Ti from natural soil. Based on the transmission electron microscopy analysis, we found that most of the trace metals were internally mixed with secondary sulfate/organic particles. These internally mixed trace metals in the urban air may have diferent toxic abilities compared with externally mixed trace metals.     

Exploring the impact of new particle formation events on PM2.5 pollution during winter in the Yangtze River Delta, China

New particle formation（NPF） events are an increasingly interesting topic in air quality and climate science. In this study, the particle number size distributions, and the frequency of NPF events over Hefei were investigated from November 2018 to February 2019. The proportions of the nucleation mode, Aitken mode, and accumulation mode were 24.59%,53.10%, and 22.30%, respectively, which indicates the presence of abundant ultrafine particles in Hefei. Forty-six NPF events occurred during the obser...     

A hydroxyl radical detection system using gas expansion and fast gating laser-induced fluorescence techniques

An OH radical measurement instrument based on Fluorescence Assay by Gas Expansion(FAGE)has been developed in our laboratory.Ambient air is introduced into a low-pressure fluorescence cell through a pinhole aperture and irradiated by a dye laser at a high repetition rate of 8.5 k Hz.The OH radical is both excited and detected at 308 nm using A-X(0,0)band.To satisfy the high efficiency needs of fluorescence collection and detection,a 4-lens optical system and a self-designed gated photomultiplier(PMT)is used,and gating is actualized by switching the voltage applied on the PMT dynodes.A micro channel photomultiplier(MCP)is also prepared for fluorescence detection.Then the weak signal is accumulated by a photon counter in a specific timing.The OH radical excitation spectrum range in the wavelength of 307.82–308.2 nm is detected and the excited line for OH detection is determined to be Q_1(2)line.The calibration of the FAGE system is researched by using simultaneous photolysis of H_2O and O_2.The minimum detection limit of the instrument using gated PMT is determined to be 9.4×10~5molecules/cm~3,and the sensitivity is 9.5×10~(-7)cps/(OH·cm~(-3)),with a signal-to-noise ratio of 2 and an integration time of 60 sec,while OH detection limit and the detection sensitivity using MCP is calculated to be 1.6×10~5molecules/cm~3and 2.3×10~(-6)cps/(OH·cm~(-3)).The laboratory OH radical measurement is carried out and results show that the proposed system can be used for atmospheric OH radical measurement.     

2015～2017年上海郊区大气新粒子生成特征

本研究利用扫描电迁移率粒径谱仪(SMPS)对上海郊区2015～2017年期间大气新粒子生成进行长期连续观测,结合气象要素、气态污染物和PM_(2.5)化学组分等数据,分析上海郊区新粒子生成特征.结果表明,上海郊区新粒子生成天(NPF)为172 d,占有效天数(942 d)的18. 3%;其中典型新粒子生成天(Event)和新粒子增长-缩小天(Shrinkage)分别为150 d和32 d;NPF天占比春、夏季最高,秋季次之,冬季最低.高温低湿、太阳辐射强、风速大和降雨量少的气象条件有利于新粒子生成;南风、西南风和西风期间Event天占比高,气团主要来自环太湖流域植被覆盖和农业种植区,而Non-NPF和Shrinkage天主导风向为东北、东到东南风.与非新粒子生成天(Non-NPF)相比,Event天各季度SO_2和O_3均高,表明气态硫酸和光化学反应为新粒子生成的关键因素; PM_(2.5)浓度并不均低于Non-NPF天,但PM_(10)值均更高,可能与多相光催化反应有关.Shrinkage天除O_3外,其他污染物浓度均最低,较低的气态前体物导致新粒子增长程度有限.PM_(2.5)化学组分显示,Event天NH_4~+、SO_4~(2-)和NO_3~-无机组分秋季平均浓度高于Non-NPF天,其他季节则相反;有机碳各季节平均浓度均高于Non-NPF天; Shrinkage天各组分浓度最低,但春、夏、冬季有机碳占比均高于Non-NPF天;因此有机物在上海郊区新粒子生成及增长过程中有重要贡献.