Comparison of annular denuder and filter pack collection of HNO3 (g), HNO2((g), SO2 (g), and particulate-phase nitrate,nitrite and sulfate in the south-west desert

During the 15 January–4 February 1986 SCENES Special Study, a comparison study was conducted to determine atmospheric HNO₃ (g), HNO₂ (g), SO₂ (g), and particle-phase nitrate, nitrite and sulfate sampled with annular diffusion denuder and filter pack sampling systems for 12-h periods. The results of the ion chromatographic analyses of the denuder and filter extracts from the annular denuder system showed that an average of 88% of the total nitrate measured was HNO₃ (g), 97% of the total nitrite was HNO₂ (g), and 91% of the total sulfur was present as SO₂ (g). Analyses of the various gas-phase species collected by replicate annular denuder systems indicated that a precision of ± 3% to ± 18% was achieved using these denuders. The good agreement in HNO₃ (g) concentrations observed between the filter pack and the denuder (r²=0.873, slope=1.06±0.03, intercept=0±3.5 nmol m⁻³) results from the fact that the majority of the atmospheric nitrate consisted of HNO₃ (g), which minimized any positive artifact in HNO₃(g) due to loss of HNO₃(g) from particles collected in the filter pack. The particulate-phase nitrate correlation between the two sampling systems was not as good (r²=0.709, slope=0.519±0.045, intercept =0±1.2 nmol m⁻³) because the lower percentage of nitrate present as the particulate species was more affected by the loss of particulate nitrate during sampling with the filter pack.     

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).     

气态污染物和气溶胶在线检测装置(GAC)测量结果评估

气态污染物和气溶胶在线检测装置(GAC)是一种连续收集、测量气态污染物和气溶胶水溶性组分的装置. 分别将GAC的测量结果与二氧化硫(SO₂)分析仪、差分吸收光谱(DOAS)、颗粒物-液体转换采集系统(PILS)和膜采样法的测量结果进行比对. 结果表明:GAC对SO₂吸收完全,测量结果稳定可靠;GAC测量的气态亚硝酸(HONO)质量浓度比DOAS测量值略偏高,原因可能是在相对湿度较高的条件下GAC对HONO的测量受到了NO₂的干扰;GAC和PILS测量的硫酸盐、硝酸盐和氯离子质量浓度〔分别以ρ(SO₄2-),ρ(NO₃-)和ρ(Cl-)计〕均有较好的相关性,将ρ_GAC (SO₄2-)校正到与PILS相同的粒径范围后,与ρ_PILS (SO₄2-)的系统偏差仅为-2%;GAC与膜采样法测量的ρ(SO₄2-)具有较好的相关性(R20.96),而二者的ρ(NO₃-)相关性较差,原因可能是硝酸盐在膜采样过程中有损失,使膜采样法的测量结果偏低.      

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.     

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.     

Nitrous and nitric acid measurements at sites in South-East England

Measurements of HONO and HNO₃ have been made using annular denuder samplers at sites in south-east England. Whilst concentrations of HNO₃ exhibited a diurnal variation, with a maximum in mid-afternoon nitrous acid shows the opposite diurnal cycle with maximum levels at night due to daytime photolysis. Concentrations of HONO increase with those of NO₂, and elevated nighttime HONO level appear to be followed by high levels of HNO₃ the following day. Average concentrations of HONO (0.45± 0.26 ppb in 24 h samples are comparable to those of HNO₃ (0.56±0.36 ppb in 24 h samples), each representing about 5–10% of the concentration of NO₂. Although NO₂ oxidation provides the source of HNO₃ concentrations of the two compounds are not related, presumably since the formation of NH₄NO₃ aerosol limits HNO₃ concentrations at out site.     

A comparison of measurements of atmospheric ammonia by filter packs,transition-flow reactors,simple and annular denuders and fourier transform infrared spectroscopy

Using data obtained during the 1985 Nitrogen Species Methods Comparison Study (1988,Atmospheric Environment22, 1517), several measurement methods for sampling ambient NH₃ are compared. Eight days of continuous measurements at Pomona College, a smog receptor site in Los Angeles, provided an extensive data base for comparing the following methods: Fourier transform i.r. spectroscopy (FTIR), three filter pack configurations, a simple and an annular denuder, and the transition flow reactor. FTIR was defined as the reference method and it reported hourly NH₃ concentrations ranging from > 60 to 2280 nmol m⁻³ (1.5−57ppb) during the course of the study, the highest values coming from the influence of nearby livestock operations.Although only limited quality assurance procedures were carried out, the following conclusions can, nevertheless, be drawn: most of the methods correlated highly with the FTIR method (correlation coefficientr > 0.96); generally, the linear regression slopes were close to unity and the intercepts were insignificantly different from zero at the 95% confidence level); relative to the FTIR average values, (1) for 4–6 h sampling periods, the averages of the three filter packs from three research groups were 83–130% and the annular denuder average was 87%, and (2) for 10–12 h sampling periods, the simple denuder averaged 90% and the two transition flow reactors were 77–98%. Possible reasons for the reported systematic biases are presented, but these are not able to fully explain the large range of differences reported by the various methods.     

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.     

Laboratory tests of KI and alkaline annular denuders

Annular denuders coated with KI and with alkaline solutions have been tested for their ability to remove atmospheric pollutants including ozone, NO₂, SO₂, formaldehyde, methyl nitrate and peroxyacetyl nitrate. Tests were carried out at flow rates of 0.4–2.0 ℓ min⁻¹, using particle-free ambient air as well as purified air to study the effect of atmospheric CO₂ on alkaline denuder performance. Denuders coated with KI were efficient in removing O₃, NO₂, SO₂ (> 95%) and PAN (84±3%) but not methyl nitrate (44%) and formaldehyde (<5%). Selective removal of PAN from NO₂, and vice versa, could be obtained with annular denuders coated with NaOH, which removed 100% PAN and ⩽15% NO₂, and with alkaline guaiacol, which removed ⩾99% NO₂ and ⩽6% PAN.     

A long path differential optical absorption spectrometer and epa-approved fixed-point methods intercomparison

Differential optical absorption spectrometry (DOAS) has been used by a number of investigators over the past 10 years to measure a wide range of gaseous air pollutants. Recently OPSIS AB, Lund, Sweden has developed and made commercially available a DOAS instrument that has a number of features which make the unit attractive for field monitoring studies in both remote and urban areas. The DOAS is composed of a broad band light source (emission between 200 and 1000 nm) and a receiver-spectrometer assembly. The spectral data from the spectrometer are processed in real time using a PC computer to calculate the concentrations of the pollutants programmed to be monitored by the system. The distance between the light source and receiver can range from 100 to 2000 m, depending on the pollutant to be monitored and species concentrations. In September and October of 1989 an OPSIS AB DOAS was operated in the Research Triangle Park, NC on the roofs of the two main Environmental Protection Agency laboratories. The distance between the light source and receiver was 557 m and the pollutants monitored were SO₂, NO₂, O₃, HCHO and HNO₂. Comparisons between the federal reference and equivalent fixedpoint methods measuring SO₂, O₃ and NO₂ and simultaneous data derived from the DOAS had correlations typically greater than 0.90 during the evaluation.     

NitroMAC: An instrument for the measurement of HONO and intercomparison with a long-path absorption photometer

NitroMAC (French acronym for continuous atmospheric measurements of nitrogenous compounds) is an instrument which has been developed for the semi-continuous measurement of atmospheric nitrous acid (HONO). This instrument relies on wet chemical sampling and detection using high performance liquid chromatography (HPLC)-visible absorption at 540 nm. Sampling proceeds by dissolution of gaseous HONO in a phosphate buffer solution followed by derivatization with sulfanilamide/N-(1-naphthyl)-ethylenediamine. The performance of this instrument was found to be as follows: a detection limit of around 3 ppt with measurement uncertainty of 10% over an analysis time of 10 min. Intercomparison was made between the instrument and a long-path absorption photometer (LOPAP) during two experiments in different environments. First, air was sampled in a smog chamber with concentrations up to 18 ppb of nitrous acid. NitroMAC and LOPAP measurements showed very good agreement. Then, in a second experiment, ambient air with HONO concentrations below 250 ppt was sampled. While NitroMAC showed its capability of measuring HONO in moderate and highly polluted environments, the intercomparison results in ambient air highlighted that corrections must be made for minor interferences when low concentrations are measured.     

高分辨率气溶胶光学厚度在珠三角及香港地区区域颗粒物监测中的应用研究

利用最新的MODlS(中分辨率成像光谱仪)气溶胶光学厚度(AOD)反演算法,反演珠江三角洲及香港地区2008年高分辨率(1 km x1 km)AOD分布,并与AERONET观测数据进行了验证(r=0.917).分析了2008年珠江三角洲及香港地区5个站点地面监测PM10质量浓度与反演的AOD数据相关性.结果表明:两者直...     

A comparison of calibration and measurement techniques for gas chromatographic determination of atmospheric peroxyacetyl nitrate (PAN)

A 24 day intercomparison study of peroxyacetyl nitrate (PAN) measurement was conducted in Egbert, Ontario, in February–March 1989. Two GC/ECD systems and one GC using a luminolchemiluminescence based detection device were involved. To separate the influence of calibration errors vs possible chromatographic interferences, a series of laboratory standards (gaseous PAN concentrations determined by either i.r. or by chemiluminescence) were exchanged. For all three GCs the results of analysis of standard samples were within ±25% of the standard concentration. For ambient air PAN measurements (concentrations ranging from 0.15 to 2 ppb), plots of each set of measurement data regressed against those of the other two techniques were obtained. Linear regression of the data from ambient air analysis for the two GC/ECD systems yielded a slope and intercept of 1.14±0.01 and −0.03±0.05, respectively (r = 0.995). The plot of the Luminol-based GC against the AES GC/ECD yielded a slope of 1.08±0.03 and an intercept of 0.08±0.24 (r = 0.864). The results demonstrated the reliability of the chemiluminescence calibration technique, and indicated that the luminol-based PAN measurement device can yield accurate and sensitive measurements of ambient PAN concentrations.     

Interactions of aerosols (ammonium sulfate,ammonium nitrate and ammonium chloride) and of gases (HCl,HNO3) with fogwater

The concentrations of aerosols (NH₄NO₃, (NH₄)₂SO₄ and NH₄Cl) and of gases (HCl_(g), HNO_3(g), NH_3(g) were determined by denuder methods under different conditions (in the absence of fog, before, during and after fog events). At this site situated in an urban region, high concentrations of the gaseous strong acids HCl_(g) and HNO_3(g) are observed. NH₄Cl and NH₄NO₃ aerosols represent a major fraction of the Cl⁻ and NO₃⁻ aerosols (<2.4 μm)collected by denuders. During a fog event, very high concentrations of SO₄²⁻ were found in small aerosols, which are attributed to the aqueous phase oxidation of SO₂ under the influence of high pH due to the presence of NH₃. Differences in SO₄²⁻ concentrations measured in aerosols (<2.4 μm) and in fog droplets were probably due to mass-transport limitations of the SO₂ oxidation. Ammonium sulfate aerosols represent in some cases a significant fraction of the total S present (SO_2(g) + SO₄²⁻. Soluble aerosols and gases contribute to the composition of fogwater and are released again after fog dissipation.     

Measurement of atmospheric elemental carbon: Real-time data for Los Angeles during summer 1987

Two fundamentally different techniques for measuring atmospheric elemental carbon (EC) aerosol were compared to validate the methods. One technique, photoacoustic spectroscopy, was used to measure the optical absorption (λ = 514.5 nm) of in situ atmospheric aerosol in real time. This optical absorption can be converted to EC concentration using the appropriate value of the absorption cross-section for C, so that a comparison could be made with the second technique, thermal-optical analysis of filter-collected samples, which measures the collected EC by combustion. Solvent extraction of the filter samples prior to the thermal analysis procedure was required to minimize errors due to pyrolysis of organic carbon. Excellent 1:1 correlation of atmospheric EC concentrations resulted for measurements by the photoacoustic method vs the thermal method over coincident sampling times. The linear regression gave y = 1.006 (±0.056) x+0.27 (±0.56) with r = 0.945 (n = 41), where y is the photoacoustic EC concentration and x is the thermal elemental carbon concentration, both in μg m⁻³. This data set was collected in Los Angeles as part of the Southern California Air Quality Study (SCAQS) during the summer 1987, and supplements the results of an earlier, more limited data set taken in Dearborn, MI. The diurnal variability of EC aerosol in Los Angeles during SCAQS, as determined by photoacoustic spectroscopy, is discussed.     

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.     

Formation of HNO2 on aerosol surfaces during foggy periods in the presence of NO and NO2

A commercial Differential Optical Absorption Spectrometer (DOAS), measuring trace gases absorbing in the u.v./vis region was used for obtaining information on aerosol parameters (e.g. total surface) based on the observed Mie scattering. This procedure allows simultaneous measurements of trace gas concentrations and aerosol parameters within the same air volume. A series of measurements of HNO₂, NO₂, NO, SO₂ and aerosol parameters was performed at Ispra in northern Italy. The observations show a rapid formation of gaseous HNO₂ during foggy episodes and give direct evidence of an important contribution of reactions on wet aerosols to the transformation of tropospheric NO_x into HNO₂.     

化学发光法和DOAS测定NOx的对比研究

分析了化学发光法和差分吸收光谱法(DOAS)测定环境中氮氧化物的原理及相应分析仪器的系统结构,指出了化学发光法氮氧化物分析仪的技术瓶颈及差分吸收光谱法的难点和关键技术。并对两种方法的优缺点及发展趋势进行分析。实验表明,化学发光法与差分吸收光谱法测定的结果具有很好的相关性。     

天津市冬季蜂窝状溶蚀器涂层溶液最适浓度研究

在特定时间特定地点利用溶蚀器PM2.5采样系统进行PM2.5采样前,应首先确定溶蚀器涂层溶液最适浓度.为确定在天津市冬季利用蜂窝状溶蚀器PM2.5采样系统采样的最优化条件,于2014年1月1日~2月24日,在南开大学理化楼楼顶进行蜂窝状溶蚀器涂层溶液最适浓度的条件实验.结果表明:在天津地区冬季, 蜂窝状溶蚀器的碳酸钠涂层溶液最适浓度为4%,柠檬酸涂层溶液最适浓度为5%; 环境空气中HCl气体对PM2.5中Cl-的质量浓度测定影响不大,而HNO3、SO2、NH3等酸/碱性气体对PM2.5中相对应离子的质量浓度测定影响较大.     

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.