An online monitoring system for atmospheric nitrous acid (HONO) based on stripping coil and ion chromatography

A new instrument for measuring atmospheric nitrous acid(HONO) was developed,consisting of a double-wall glass stripping coil sampler coupled with ion chromatography(SC-IC).SC-IC is featured by small size(50 × 35 × 25 cm) and modular construction,including three independent parts:the sampling unit,the transfer and supporting unit,and the detection unit.High collection efficiency(> 99%) was achieved with 25 μmol/L Na2CO3 as absorption solution even in the presence of highly acidic compounds.This instrument has a detection limit of 8 pptv at 15 min time resolution,with a measurement uncertainty of 7%.Potential interferences from NOx,NO2+SO2,NO2+VOCs,HONO+O3,HNO3,peroxyacetyl nitrite(PAN) and particle nitrite were quantified in laboratory studies and were found to be insignificant under typical atmospheric conditions.Within the framework of the 3C-STAR project,inter-comparison between the SC-IC and LOPAP(long path liquid absorption photometer) was conducted at a rural site in the Pearl River Delta.Good agreement was achieved between the two instruments over three weeks.Both instruments determined a clear diurnal profile of ambient HONO concentrations from 0.1 to 2.5 ppbv.However,deviations were found for low ambient HONO concentrations(i.e.< 0.3 ppbv),which cannot be explained by previous investigated interference species.To accurately determine the HONO budget under illuminated conditions,more intercomparison of HONO measurement techniques is still needed in future studies,especially at low HONO concentrations.     

In situ monitoring of atmospheric nitrous acid based on multi-pumping flow system and liquid waveguide capillary cell

In the last four decades, various techniques including spectroscopic, wet chemical and mass spectrometric methods, have been developed and applied for the detection of ambient nitrous acid (HONO). We developed a HONO detection system based on long path photometry which consists of three independent modules i.e., sampling module, fluid propulsion module and detection module. In the propulsion module, solenoid pumps are applied. With solenoid pumps the pulsed flow can be computer controlled both in terms of pump stroke volume and pulse frequency, which enables the attainment of a very stable flow rate. In the detection module, a customized Liquid Waveguide Capillary Cell (LWCC) is used. The customized LWCC pre-sets the optical fiber in-coupling with the liquid wave guide, providing the option of fast startup and easy maintenance of the absorption photometry. In summer 2014, our system was deployed in a comprehensive campaign at a rural site in the North China Plain. More than one month of high quality HONO data spanning from the limit of detection to 5 ppb were collected. Intercomparison of our system with another established system from Forschungszentrum Juelich is presented and discussed. In conclusion, our instrument achieved a detection limit of 10 pptV within 2 min and a measurement uncertainty of 7%, which is well suited for investigation of the HONO budget from urban to rural conditions in China.     

Reactive uptake of NO2 on volcanic particles: A possible source of HONO in the atmosphere

The heterogeneous degradation of nitrogen dioxide (NO₂) on five samples of natural Icelandic volcanic particles has been investigated. Laboratory experiments were carried out under simulated atmospheric conditions using a coated wall flow tube (CWFT). The CWFT reactor was coupled to a blue light nitrogen oxides analyzer (NO_x analyzer), and a long path absorption photometer (LOPAP) to monitor in real time the concentrations of NO₂, NO and HONO, respectively. Under dark and ambient relative humidity conditions, the steady state uptake coefficients of NO₂ varied significantly between the volcanic samples probably due to differences in magma composition and morphological variation related with the density of surface OH groups. The irradiation of the surface with simulated sunlight enhanced the uptake coefficients by a factor of three indicating that photo-induced processes on the surface of the dust occur. Furthermore, the product yields of NO and HONO were determined under both dark and simulated sunlight conditions. The relative humidity was found to influence the distribution of gaseous products, promoting the formation of gaseous HONO. A detailed reaction mechanism is proposed that supports our experimental observations. Regarding the atmospheric implications, our results suggest that the NO₂ degradation on volcanic particles and the corresponding formation of HONO is expected to be significant during volcanic dust storms or after a volcanic eruption.     

Characterization of particle number size distribution and new particle formation in Southern China

Knowledge of particle number size distribution(PND) and new particle formation(NPF)events in Southern China is essential for mitigation strategies related to submicron particles and their effects on regional air quality,haze,and human health.In this study,seven field measurement campaigns were conducted from December 2013 to May 2015 using a scanning mobility particle sizer(SMPS) at four sites in Southern China,including three urban sites and one background site.Particles were measured in the size range of15-515 nm,and the median particle number concentrations(PNCs) were found to vary in the range of 0.3× 10~4-2.2 × 10~4 cn~(-3) at the urban sites and were approximately 0.2 × 10~4 cm~(-3) at the background site.The peak diameters at the different sites varied largely from 22 to 102 nm.The PNCs in the Aitken mode(25-100 nm) at the urban sites were up to 10 times higher than they were at the background site,indicating large primary emissions from traffic at the urban sites.The diurnal variations of PNCs were significantly influenced by both rush hour traffic at the urban sites and NPF events.The frequencies of NPF events at the different sites were0%-30%,with the highest frequency occurring at an urban site during autumn.With higher SO_2 concentrations and higher ambient temperatures being necessary,NPF at the urban site was found to be more influenced by atmospheric oxidizing capability,while NPF at the background site was limited by the condensation sink.This study provides a unique dataset of particle number and size information in various environments in Southern China,which can help understand the sources,formation,and the climate forcing of aerosols in this quickly developing region,as well as help constrain and validate NPF modeling.     

Effect of elevated tropospheric ozone on methane and nitrous oxide emission from rice soil in north India

Physiological changes in crop plants in response to the elevated tropospheric ozone (O₃) may alter N and C cycles in soil. This may also affect the atmosphere-biosphere exchange of radiatively important greenhouse gases (GHGs), e.g. methane (CH₄) and nitrous oxide (N₂O) from soil. A study was carried out during July to November of 2007 and 2008 in the experimental farm of Indian Agricultural Research Institute, New Delhi to assess the effects of elevated tropospheric ozone on methane and nitrous oxide emissions from rice (Oryza sativa L.) soil. Rice crop was grown in open top chambers (OTC) under elevated ozone (EO), non-filtered air (NF), charcoal filtered air (CF) and ambient air (AA). Seasonal mean concentrations of O₃ were 4.3 ± 0.9, 26.2 ± 1.9, 59.1 ± 4.2 and 27.5 ± 2.3 ppb during year 2007 and 5.9 ± 1.1, 37.2 ± 2.5, 69.7 ± 3.9 and 39.2 ± 1.8 ppb during year 2008 for treatments CF, NF, EO and AA, respectively. Cumulative seasonal CH₄ emission reduced by 29.7% and 40.4% under the elevated ozone (EO) compared to the non-filtered air (NF), whereas the emission increased by 21.5% and 16.7% in the charcoal filtered air (CF) in 2007 and 2008, respectively. Cumulative seasonal emission of N₂O ranged from 47.8 mg m⁻² in elevated ozone to 54.6 mg m⁻² in charcoal filtered air in 2007 and from 46.4 to 62.1 mg m⁻² in 2008. Elevated ozone reduced grain yield by 11.3% and 12.4% in 2007 and 2008, respectively. Global warming potential (GWP) per unit of rice yield was the least under elevated ozone levels. Dissolved organic C content of soil was lowest under the elevated ozone treatment. Decrease in availability of substrate i.e., dissolved organic C under elevated ozone resulted in a decline in GHG emissions. Filtration of ozone from ambient air increased grain yield and growth parameters of rice and emission of GHGs.     

Comparison of atmospheric nitrous acid measurements by annular denuder and differential optical absorption systems

As part of the Southern California Air Quality Study (SCAQS), nitrous acid (HONO) measurements were made at Long Beach, CA during the period 11 November–12 December 1987, using two distinctly different techniqes. One of these, the annular denuder method (ADM), used two denuders in tandem, coated with an alkaline medium to obtain 4- or 6-h integrated measurements. A small FEP Tefloncoated glass cyclone preceded the denuders to exclude coarse particles while minimizing loss or artifactual formation of HONO. Nitrite recoveries from the rear denuder were used to correct for sampling artifacts. In the second method, 15 min average HONO concentrations were measured with a differential optical absorption spectrometer (DOAS) coupled to a 25 m basepath, open multiple reflection system operated at a total optical path of 800 m. Period-averaged HONO concentrations from the two techniques were highly correlated (r = 0.94), with DOAS results averaging about 10% higher. However, ADM results were biased high at low HONO concentrations. HONO and NO concentrations showed a significant, positive correlation (r = 0.8), consistent with a common emission source (e.g. auto exhaust) for the two pollutants.     

Observation of atmospheric nitrous acid with DOAS in Beijing, China

Measurements of nitrous acid （HONO） and nitrogen dioxide （NO2） in Beijing City have been performed by means of a developed differential optical absorption spectroscopy （DOAS） system based on photodiode array （PDA）, during the autumn of 2004. HONO and NO2 were simultaneously identified by their characteristic absorption bands in the spectral region between 337 nm and 372 nm with high sensibility and time resolution. The concentrations of HONO exhibit obviously diurnal variation with a nocturnal maximum and a daytime minimum. The highest HONO value up to 11.8 μg/m^3 was observed during the night of 2/3 September. Possible sources of the observed HONO were discussed. Good correlation to NO2 indicates that NO2 is a main source component. The measurement also shows direct emission of HONO is an imnortant source in strongly polluted urban area.     

典型华北农村地区冬季HONO的浓度水平及来源分析

气态亚硝酸(HONO)容易光解,是对流层大气羟基自由基(·OH)的重要来源之一,对区域二次污染的形成具有重要作用.我国在大气HONO观测研究方面主要集中在一些城市区域,而在我国北方农村区域的研究还鲜见报道.为此,本文利用亚硝酸在线分析仪(long path absorption photo meter,LOPAP)于2017年11月在中国科学院农村环境研究站(河北省望都县东白陀村)开展了为期一个月的HONO外场观测,并分析了HONO的浓度水平、变化特征及收支情况.大气HONO的浓度在观测期间呈现夜间高、白天低的日变化特征,夜间最高浓度(体积分数,下同)可达约3. 70×10-9,中午最低浓度也维持在0. 10×10-9以上,表明农村区域存在比较强的HONO来源.采暖前后CO浓度显著提高,而HONO浓度无显著变化,说明供暖燃烧对HONO的贡献较小;夜间机动车直接排放在污染天气和清洁天气条件下对HONO的贡献分别为23. 20%和31. 20%,说明在污染天气条件下存在着某些较强的HONO源;夜间·OH与NO的均相反应HONO平均生成速率可高达0. 40×10-9h-1,比NO2的非均相反应HONO生成速率(0. 24×10-9h-1)高0. 67倍,是HONO的主要来源; HONO在白天存在着很强的未知源,其强度可达1. 37×10-9h-1,对于HONO的贡献达到50%左右.     

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.     

环境大气中半/中等挥发性有机物(S/IVOCs)的测量技术进展

总结了环境大气中半/中等挥发性有机物（S/IVOCs）的主要测量技术及其进展,重点介绍了基于气相色谱技术和化学电离质谱技术的测量方法.S/IVOCs的测量主要由气相色谱技术开始发展,并随着质谱技术的发展而不断发展.基于气相色谱技术的测量方法,能够直接测量非极性化合物,但在面对组分多达千万种的复杂体系时,传统的一维色谱相对耗时,而且由于峰容量不够,峰重叠现象十分严重,难以实现全组分的准确分离.新近发展的多维分离系统如全二维气相色谱,通过正交的分离系统,能够实现复杂体系中物种组分的准确、快速分离.目前基于化学电离质谱技术的在线测量方法已经逐渐应用于S/IVOCs的测量,虽然在物种定性方面相对较弱,但其可提供高时间分辨率的测量结果,帮助分析S/IVOCs在大气中的快速变化.在未来的研究中,高时间分辨率和全组分准确测量是S/IVOCs研究的关键.     

环境大气中半/中等挥发性有机物(S/IVOCs)的测量技术进展

总结了环境大气中半/中等挥发性有机物（S/IVOCs）的主要测量技术及其进展,重点介绍了基于气相色谱技术和化学电离质谱技术的测量方法.S/IVOCs的测量主要由气相色谱技术开始发展,并随着质谱技术的发展而不断发展.基于气相色谱技术的测量方法,能够直接测量非极性化合物,但在面对组分多达千万种的复杂体系时,传统的一维色谱相对耗时,而且由于峰容量不够,峰重叠现象十分严重,难以实现全组分的准确分离.新近发展的多维分离系统如全二维气相色谱,通过正交的分离系统,能够实现复杂体系中物种组分的准确、快速分离.目前基于化学电离质谱技术的在线测量方法已经逐渐应用于S/IVOCs的测量,虽然在物种定性方面相对较弱,但其可提供高时间分辨率的测量结果,帮助分析S/IVOCs在大气中的快速变化.在未来的研究中,高时间分辨率和全组分准确测量是S/IVOCs研究的关键.     

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.     

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.     

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.     

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.     

Intercomparison of tunable diode laser and gas filter correlation measurements of ambient carbon monoxide

An intercomparison that involved a standards intercomparison, interferant spiking tests and simultaneous ambient measurements was carried out between two CO measurement systems: a tunable diode laser absorption spectrometer (TDLAS) and a gas filter correlation, non-dispersive infrared absorption instrument (GFC). Both the TDLAS and the GFC techniques responded to CO. No major interferences were found for the TDLAS system; tested species included H₂O, O₃ and OCS. The GFC instrument exhibited no interference from H₂O or O₃, but only a relatively high upper limit could be placed on the O₃ interference. For CO measurements in ambient air at levels from 100 to 1500 ppbv, the results from the two instruments agreed within their combined uncertainties. On average the GFC technique was 6% higher than the TDLAS system, and there was no systematic, constant offset. The precision of the GFC instrument was about 10%, and the precision of the TDLAS system was better than 4%.     

基于Stacking集成学习模型的气态亚硝酸预测

建立了基于Stacking集成学习下气态亚硝酸（HONO）预测模型.利用非相干宽带腔增强吸收光谱（IBBCEAS）系统获得的北京城区HONO的浓度,结合HONO的来源,选取了O₃、CO、SO₂、NO、NO₂、NO_y、温度（T）、相对湿度（RH）、风速（WS）、j（HONO）、j（NO₂）、j（O¹D）作为特征数据,通过对HONO的平均日变化分析,将测量时间按小时转换为新特征.分别以极端梯度提升（XGBoost）、轻量化梯度促进机（LightGBM）以及随机森林（RF）算法构建基模型,采用5折交叉验证的方式划分训练集,将基模型输出的结果作为新特征集,并将新特征集作为第二层线性回归模型的输入,通过对这两层中的模型进行训练,最终得到Stacking集成学习HONO预测模型.通过对模型的特征重要度分析和计算夜间交通直接排放所占的贡献,表明CO是模型预测中重要的影响因子,说明机动车的直接排放是该区域冬季时期HONO的重要来源.利用测试集分别对单模型和融合后模型的预测性能进行评估,3个单模型的预测结果与测量值的相关系数都达到了0.91以上,其中Stacking融合后的模型性能最好,相关系数达到了0.94,平均绝对误差和均方根误差分别为0.307×10^-9和0.453×10^-9,结果表明基于Stacking集成学习方式下HONO预测模型的可解释性和推广性.     

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.     

A denuder technique for the measurement of nitrous acid in urban atmospheres

A new denuder set-up for the measurement of nitrous acid in polluted atmospheres is described here. The set-up is composed of one tetrachloromercurate-coated denuder for the removal of SO₂ and two downstream sodium carbonate-coated denuders for the determination of nitrous acid by the differential technique [Febo et al., 19, 1517–1530 1990]. The removal of SO₂ is necessary in order to avoid the formation of artifact nitrite on the sulfite layer which results from the interaction between atmospheric SO₂ and the Na₂CO₃ coating. Because of this mechanism, the measurement of HONO by means of the previously used NaClNa₂CO₃Na₂CO₃ denuder set-up is heavily biased in all cases when SO₂ and NO₂ are present at high concentration levels (e.g. urban environments).     

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.