Evaluation and Evolution of MAX-DOAS-observed Vertical NO_2 Profiles in Urban Beijing

Multiaxis differential absorption spectroscopy(MAX-DOAS) is a newly developed advanced vertical profile detection method, but the vertical nitrogen dioxide(NO_2) profiles measured by MAX-DOAS have not yet been fully verified. In this study, we perform MAX-DOAS and tower gradient observations to simultaneously acquire tropospheric NO_2 observations in the Beijing urban area from 1 April to 31 May 2019. The average values of the tropospheric NO_2 vertical column densities measured by MAX-DOAS and the tropospheric monitoring instrument are 15.8 × 10~(15) and 12.4 × 10~(15) molecules cm~(-2), respectively, and the correlation coefficient R reaches 0.87. The MAX-DOAS measurements are highly consistent with the tower-based in situ measurements, and the correlation coefficients R from the ground to the upper air are 0.89(60 m), 0.87(160 m), and 0.76(280 m). MAX-DOAS accurately measures the trend of NO_2 vertical profile changes,although a large underestimation occurs by a factor of two. By analyzing the NO_2 vertical profile, the NO_2 concentration reveals an exponential decrease with height. The NO_2 vertical profile also coincides with the evolution of the boundary layer height. The study shows that the NO_2 over Beijing mainly originates from local sources and occurs in the boundary layer, and its vertical evolution pattern has an important guiding significance to better understand nitrate production and ozone pollution.     

大气NO2柱浓度多轴差分吸收光谱测量技术及应用

介绍了以太阳散射光为光源的多轴差分吸收光谱技术（Multi-Axis Differential Optical Absorption Spectroscopy,简称MAX-DOAS）,以及MAX-DOAS仪器试验应用.试验中选取中午仪器测量的天顶散射光光谱为参考光谱即Fraunhofer参考光谱,并将测量光谱进行消噪、波长校准以及去除Fraunhofer结构处理.利用分子吸收光学厚度和Ring效应光学厚度对处理后的测量光谱进行最小二乘法拟合,反演出了大气NO2差分斜柱浓度（Differential Slant Column Densities,简称DSCD）.分析了天津武清NO2的差分斜柱浓度反演结果,用简单快捷的几何法将NO2差分斜柱浓度转化成对流层垂直柱浓度（Vertical Column Densities,简称VCD）.研究表明,MAX-DOAS可以有效地监测污染地区对流层NO2的垂直柱浓度.     

Relationship between Lightning Activity and Tropospheric Nitrogen Dioxide and the Estimation of Lightning-produced Nitrogen Oxides over China

To better understand the relationship between lightning activity and nitrogen oxides(NOX) in the troposphere and to estimate lightning-produced NOX(LNOX) production in China more precisely, spatial and temporal distributions of vertical column densities of tropospheric nitrogen dioxide(NO_2VCDs) and lightning activity were analyzed using satellite measurements. The results showed that the spatial distribution of lightning activity is greater in the east than in the west of China, as with NO_2 VCDs. However, the seasonal and annual variation between lightning and NO_2 density show different trends in the east and west. The central Tibetan Plateau is sparsely populated without modern industry, and NO_2 VCDs across the plateau are barely affected by anthropogenic sources. The plateau is an ideal area to study LNOX. By analyzing 15 years of satellite data from that region, it was found that lightning density is in strong agreement with annual, spatial and seasonal variations of NO_2 VCDs, with a correlation coefficient of 0.79 from the linear fit. Combining Beirle's method and the linear fit equation,LNOXproduction in the Chinese interior was determined to be 0.07(0.02–0.27) Tg N yr~(-1) for 1997–2012, within the range of 0.016–0.384 Tg N yr~(-1) from previous estimates.     

Assessment of the Uncertainties in the NO2 and O3 Measurements by Visible Spectrometers

The column amounts of nitrogen dioxide (NO2) and ozone (O3) were measured using a visible spectrometer based on the twilight zenith-sky technique at two observatories located at similar latitudes in the northern part of Japan separated by a distance of 150 km. The measurements began in April 1991 at the Moshiri Observatory (44.4°N, 142.3°E) and in April 1994 at the Rikubetsu Observatory (43.5°N, 143.8°E). Since weather conditions and the possible influence from tropospheric pollution were not always identical at these two observatories, the overall accuracy of the measurements was studied comparing these data sets. The first year data obtained at a solar zenith angle of 90 degrees indicated that the NO2 slant column values at sunrise and sunset agreed within 0.36 and 0.54 × 1016 cm-2, respectively, corresponding to 5 % (June) and to 12 % (December) of the columns. The O3 values agreed within 0.76 × 1019 cm-2, corresponding to 4 % (March) 6 % (August) of the columns, although a part of the difference was systematic. The O3 column amounts were also compared to those obtained by the Dobson spectrometer at Sapporo (43.5°N, 143.8°E), whose latitude is similar to these observatories. When an air mass factor of 17.5 was used, the two-year Moshiri vertical column values agreed with the Dobson direct sun values to within 15 Dobson Units, or 3 6 % of the column. The difference between the two values was found to be due partly to the change in the air mass factor caused by seasonal and day-to-day changes in the shape of the O3 vertical profiles. These results confirm the reliability of the NO2 and O3 measurements by visible spectrometers at these sites for the Network for the Detection of Stratospheric Change (NDSC).     

Satellite Measurements of Tropospheric Column O<Subscript>3</Subscript> and NO<Subscript>2</Subscript> in Eastern and Southeastern Asia: Comparison with a Global Model (MOZART-2)

Satellite measurements of tropospheric column O₃ and NO₂ in eastern and southeastern Asia are analyzed to study the spatial and seasonal characteristics of pollution in these regions. Tropospheric column O₃ is derived from differential measurements of total column ozone from Total Ozone Mapping Spectrometer (TOMS), and stratospheric column ozone from the Microwave Limb Sounder (MLS) instrument on the Upper Atmosphere Research Satellite (UARS). The tropospheric column NO₂ is measured by Global Ozone Monitoring Experiment (GOME). A global chemical and transport model (Model of Ozone and Related Chemical Tracers, version 2; MOZART-2) is applied to analyze and interpret the satellite measurements. The study, which is based on spring, summer, and fall months of 1997 shows generally good agreement between the model and satellite data with respect to seasonal and spatial characteristics of O₃ and NO₂ fields. The analysis of the model results show that the industrial emission of NO_x (NO + NO₂) contributes about 50%–80% to tropospheric column NO₂ in eastern Asia and about 20%–50% in southeastern Asia. The contribution of industrial emission of NO_x to tropospheric column O₃ ranges from 10% to 30% in eastern Asia. Biomass burning and lightning NO_x emissions have a small effect on tropospheric O₃ in central and eastern Asia, but they have a significant impact in southeastern Asia. The varying effects of NO_x on tropospheric column ozone are attributed to differences in relative abundance of volatile organic compounds (VOCs) with respect to total nitrogen in the two regions.     

利用GOME卫星资料分析北京大气NO2污染变化

利用GOME (Global Ozone Monitoring Experiment, 全球臭氧监测实验) 1996年1月—2002年12月NO₂对流层柱浓度月平均卫星遥感资料以及根据北京市2001年1月1日—2002年12月31日NO₂污染指数数据计算出的地面NO₂日均质量浓度值, 分析了北京市城市大气NO₂污染变化的季节变化特征以及年际变化, 并将2001年1月—2002年12月北京上空GOME NO₂对流层柱浓度月平均值变化与北京市地面NO₂日均质量浓度月平均值变化进行了比较, 结果表明两者随时间的变化趋势具有较好的一致性, 据此可以利用GOME NO₂对流层柱浓度月平均卫星遥感资料来分析特定区域大气NO₂的季节变化和年际变化。     

An ozone depletion event in the sub-arctic surface layer over Hudson Bay,Canada

During the Tropospheric Ozone Production about the Spring Equinox (TOPSE) program, aircraft flights during April 7–11, 2000 revealed a large area air mass capped below ∼500 m altitude over Hudson Bay, Canada in which ozone was reduced from normal levels of 30–40 ppbv to as low as 0.5 ppbv. From some of the in-situ aircraft measurements, back-trajectory calculations, the tropospheric column of BrO derived from GOME satellite measurements, and results from a regional model, we conclude that the event did not originate from triggering of reactive halogen release in the sub-Arctic region of Hudson Bay but resulted from such an event occurring at higher latitudes over the islands of the northern Canada Archipelago and nearby Arctic Ocean with subsequent transport over a distance of 1,000–1,500 km to Hudson Bay. BrO _x remained active during this transport despite considerable changes in the conditions of the underlying surface suggesting that chemical recycling during transport dominated any local halogen input from the surface. If all of the tropospheric column density of BrO is distributed uniformly within the surface layer, then the mixing ratio of BrO derived from the satellite measurements is at least a factor of 2–3 larger than derived indirectly from in situ aircraft measurements of the NO/NO₂ ratio.     

INTEX-B NO2排放源在中国地区的应用与检验

将INTEX-B排放源应用到空气质量模型Model3-CMAQ中,对中国地区对流层NO₂的浓度分布进行了数值模拟,并与OMI卫星对流层NO₂资料进行了对比和验证。结果表明：将INTEX-B排放源应用到Model3-CMAQ模式,模拟的NO₂浓度在中国地区的分布、季节变化规律与卫星资料所得结果一致。敏感性试验表明,工业及电厂排放对NO₂的浓度贡献最大,而交通排放的贡献相对较小,两种排放均主要集中在京津、长江三角洲等经济发达地区。     

华北平原固城站NO2对流层柱浓度变化特征

基于2008年9月—2010年9月河北固城生态与农业气象试验站多轴差分吸收光谱仪 (multi-axis differential optical absorption spectroscopy, MAX-DOAS) 获得的太阳散射光谱观测,反演计算该地区NO₂对流层柱浓度,分析其季节、日变化特征以及不同来源输送的影响,并与同期NO₂地面观测资料和卫星产品进行对比分析。发现固城站NO₂对流层柱浓度冬高 (5.14×1016 cm-2) 夏低 (1.28×1016 cm-2);日变化形态在四季均呈现中午低、傍晚高的特征,且冬季最明显。与北京城市区域同期的观测相比,冬季固城站观测值略低,而在春、夏季则偏低较显著。地面风玫瑰图分析显示,来自SW, SSW, NE方向及ENE方向的污染输送对其贡献最大。与地面、卫星NO₂观测的对比表明,MAX-DOAS反演的NO₂柱浓度与地面观测浓度具有一致的季节和日变化特征,卫星反演的NO₂对流层柱浓度产品在华北平原农村地区存在系统性低估。     

INTEX-B NO_2排放源在中国地区的应用与检验

将INTEX-B排放源应用到空气质量模型Model3-CMAQ中,对中国地区对流层NO2的浓度分布进行了数值模拟,并与OMI卫星对流层NO2资料进行了对比和验证。结果表明：将INTEX-B排放源应用到Model3-CMAQ模式,模拟的NO2浓度在中国地区的分布、季节变化规律与卫星资料所得结果一致。敏感性试验表明,工业及电厂排放对NO2的浓度贡献最大,而交通排放的贡献相对较小,两种排放均主要集中在京津、长江三角洲等经济发达地区。     

Responses of the tropospheric ozone and odd hydrogen radicals to column ozone change

The response of tropospheric ozone to a change in solar UV penetration due to perturbation on column ozone depends critically on the tropospheric NO _x (NO+NO₂) concentration. At high NO _x or a polluted area where there is net ozone production, a decrease in column ozone will increase the solar UV penetration to the troposphere and thus increase the tropospheric ozone concentration. However, the opposite will occur, for example, at a remote oceanic area where NO _x is so low that there is net ozone destruction. This finding may have important implication on the interpretation of the long term trend of tropospheric ozone. A change in column ozone will also induce change in tropospheric OH, HO₂, and H₂O₂ concentrations which are major oxidants in the troposphere. Thus, the oxidation capacity and, in turn, the abundances of many reduced gases will be perturbed. Our model calculations show that the change in OH, HO₂, and H₂O₂ concentrations are essentially independent of the NO _x concentration.     

风廓线雷达对大气折射率结构常数的探测研究

基于湍流散射理论,构建了风廓线雷达（WPR）强度信息对大气折射率结构常数的估算方法。经过对WPR多种探测模式探测数据的估算分析,发现雷达参数的确切选用、信噪比(SNR)测量方法的合理性以及信号累积得益的认定对大气折射率结构常数的准确估算有较大的影响,为此提出适合WPR多种探测模式对该估算值规范化处理方法。利用北京两部对流层风廓线雷达五种探测模式于2005年获取的部分观测数据,进行了规范化计算及对比分析。结果表明,邻近时刻的不同风廓线雷达探测估算结果有较好的一致性,其垂直分布结构合理,呈指数形式, 统计结果与国内外的分析研究结果较为吻合。     

Environmental Process and Convergence Belt of Atmospheric NO2 Pollution in North China

Both surface environmental monitoring and satellite remote sensing show that North China is one of the regions that are heavily polluted by NO2. Using the NO2 monitoring data from 18 major cities in the region, the tropospheric NO2 column density data from the Ozone Monitoring Instrument (OMI) on the Aura satellite, and the observations from the China Meteorological Administration network, this paper analyzes a regional NO2 pollution event in February 2007 over North China, examines the convergence of the pollutant, and identifies its correlation with the atmospheric background conditions. The results show that daily mean NO2 concentrations derived from surface observations are consistent with the mean values of the OMI measurements, with their correlation coefficient reaching 0.81. The correlations of NO2 concentration with general weather patterns and sequential changes of temperature structure from 925 hPa down to the surface indicate that the weather fronts, high pressure and low pressure systems in the atmosphere play a role in changing the temporal and spatial evolutions of NO2 through removing, accumulating or converging of the pollutant, respectively. It is also found that the eastern Taihang Mountains is most heavily polluted by NO2 in North China. Based on a model that correlates NO2 column density with surface wind vector, the relation of the NO2 concentrations in six major cities in North China to the surrounding wind field is analyzed. The results show that the maximum wind field is associated with the highest frequency of pollution events, and under certain large-scale atmospheric conditions together with the topographic effect, small- and meso-scale wind fields often act to transport and converge pollutants, and become a major factor in forming the heaviest NO2 pollution event in North China. Analysis of the causes for the severe NO2 pollution event in this study may shed light on understanding, forecasting, and mitigating occurrences of heavy NO2 pollution.     

Slant Column Measurements of O3 and NO2 During the NDSC Intercomparison of Zenith-Sky UV-Visible Spectrometers in June 1996

In June 1996, 16 UV-visible sensors from 11 institutes measured spectra of the zenith sky for more than 10 days. Spectra were analysed in real-time to determine slant column amounts of O3 and NO2. Spectra of Hg lamps and lasers were measured, and the amount of NO2 in a cell was determined by each spectrometer. Some spectra were re-analysed after obvious errors were found. Slant columns were compared in two ways: by examining regression analyses against comparison instruments over the whole range of solar zenith angles; and by taking fractional differences from a comparison instrument at solar zenith angles between 85° and 91°. Regression identified which pairs of instruments were most consistent, and so which could be used as universal comparison instruments. For O3, regression slopes for the whole campaign agreed within 5% for most instruments despite the use of different cross-sections and wavelength intervals, whereas similar agreement was only achieved for NO2 when the same cross-sections and wavelength intervals were used and only one half-day's data was analysed. Mean fractional differences in NO2 from a comparison instrument fall within ±7% (1-sigma) for most instruments, with standard deviations of the mean differences averaging 4.5%. Mean differences in O3 fall within ±2.5% (1- sigma) for most instruments, with standard deviations of the mean differences averaging 2%. Measurements of NO2 in the cell had similar agreement to measurements of NO2 in the atmosphere, but for some instruments measurements with cell and atmosphere relative to a comparison instrument disagreed by more than the error bars.     

Deriving Temporal and Vertical Distributions of Methane in Xianghe Using Ground-based Fourier Transform Infrared and Gas-analyzer Measurements

Methane(CH4) is one of the most important greenhouse gases in the atmosphere, making it worthwhile to study its temporal and vertical distributions in source areas, e.g., North China. For this purpose, a ground-based high-resolution Fourier transform infrared spectrometer(FTIR), the Bruker IFS 125 HR, along with an in-situ instrument, the Picarro G2301, were deployed in Xianghe County(39.8°N,117.0°E), Hebei Province, China. Data have been recorded since June2018. For the FTIR measurements, we used two observation modes to retrieve the mole fraction of CH4: the Total Carbon Column Observing Network(TCCON) method(retrieval algorithm: GGG2014), and the Network for the Detection of Atmospheric Composition Change(NDACC) method(retrieval algorithm: SFIT4). Combining FTIR with in-situ measurements, we found the temporal and vertical distributions of atmospheric CH4 within three vertical layers(near the ground, in the troposphere, and in the stratosphere), and throughout the whole atmosphere. Regarding the diurnal variation of CH4 near the ground, the concentration at night was higher than during the daytime. Regarding the seasonal variation,CH4 was low in spring and high in summer, for all three vertical layers. In addition, there was a peak of CH4 in winter near the ground, both in the troposphere and the whole atmosphere. We found that variation of CH4 in the tropospheric column was close to that of the in-situ measurements near the ground. Furthermore, the variations of CH4 in the stratospheric column could be influenced by vertical motions, since it was higher in summer and lower in winter.     

青藏高原闪电与NO_2的分析及中国内陆地区LNO_x产量的估算

为了进一步认识闪电活动与对流层氮氧化物的关系及更准确地估算中国地区闪电产生的氮氧化物(LNOx)总量,选取人口稀疏,工业生产水平较低的青藏高原地区作为研究区域,基于LIS(Lightning Imaging Sensor)和GOME-2(The Global Ozone Monitoring Experiment-2)卫星探测仪资料,分析了青藏高原中部区域2009年1月至2012年2月闪电与对流层NO2垂直浓度(VCD)月均值资料的时空分布特性和相关性。在此基础上,结合Beirle et al.(2004)的LNOx估算方法,估算了中国内陆地区的LNOx产量。结果表明:青藏高原地区对流层NO2与闪电与在年际趋势、空间分布及季节变化上保持很好的一致性,闪电密度与NO2VCD的线性拟合相关系数为0.84,这表明青藏高原地区NOx受人为源影响小,是研究LNOx的理想区域。基于拟合结果,估算得到中国内陆地区LNOx的年均产量为0.15(0.03~0.38)Tg(N)a-1。这一结论进一步缩小了以往研究中中国地区LNOx产量估算的不确定范围,有助于更清楚地认识闪电在中国气候变化中的重要作用。     

华北地区香河站对流层NO_2的MAX-DOAS光谱仪观测及变化特征分析

利用中国科学院大气物理研究所香河大气探测综合试验站2010年3月至2012年2月(2年)的多轴差分吸收光谱仪(MAX-DOAS)观测数据和32 m高塔常规气象资料,反演了华北地区香河站对流层NO2柱浓度,分析了该区域NO2柱浓度的季节变化特征。研究表明:可见光455~485 nm、紫外330~370 nm都可以作为MAX-DOAS工作波段很好地反演NO2;香河地区NO2柱浓度夏季最低,几乎保持在2×1016 cm–2以下,春、秋季次之,在3×1016 cm–2上下小范围浮动,冬季最高,可达4.5×1016 cm–2;月平均最低值出现在7月,最高值出现在11月。NO2柱浓度与风速、风向密切相关:来自东边唐山方向的风,风速越大时NO2浓度越高,因为唐山是NO2的高值区之一;其它方向风速越大,浓度越低。春、夏两季NO2柱浓度日变化趋势比较平缓,秋、冬两季日变化明显,秋季正午偏高,冬季早晚偏高。     

Intercomparison of remote measurements of stratospheric NO and NO2

During the 1982 and 1983 Balloon Intercomparison Campaigns, the vertical profile of stratospheric NO₂ was measured remotely by nine instruments and that of NO by two. Total overhead columns were measured by two more instruments. Between 30 and 35km, where measurements overlapped, agreement between NO profiles was within ±30%, which is better than the accuracies claimed by the experimenters. Between 35 and 40km there was similarly good agreement between NO₂ profiles, but below 30km, differences of greater than a factor three were found. In the second Campaign, NO₂ values from most instruments agreed within their quoted errors, except that the Oxford radiometer gave much lower values; but the first Campaign and the column measurements show a more uniform spread of results.These differences below 30km could not be resolved, but new laboratory measurements are planned which should do so.     

Flux between soil and atmosphere, vertical concentration profiles in soil, and turnover of nitric oxide: 2. Experiments with naturally layered soil cores

Intact soils cores were taken with a stainless steel corer from a sandy podzol and a loamy luvisol, and used to measure the flux (J) of NO between soil and atmosphere and the vertical profile of the NO mixing ratios (m) in the soil atmosphere, both as function of the NO mixing ratio (m _a) in the atmosphere of the headspace. These measurements were repeated after stepwise excavation of the soil column from the top, e.g. by removing the upper 2 cm soil layer. The gaseous diffusion coefficients of NO in the soil cores were either computed from soil porosity or were determined from experiments using SF6. The NO fluxes (J) that were actually measured at the soil surface were compared to the fluxes which were calculated either from the vertical NO profiles (J _c ) or from the NO production and uptake rates (J _m ) determined in the excavated soil samples. In the podzol, the actually measured (J) and the calculated (J _m , J_m) NO fluxes agreed within a factor of 2. In the luvisol, the measured NO fluxes (J) and those calculated from the vertical NO profiles (J _c ) also agreed well, but in the upper 6 cm soil layer the NO fluxes (J _m ) calculated from NO production and uptake rates were up to 7 times higher than the measured NO fluxes. This poor agreement was probably due to the inhomogeneous distribution of NO production and consumption processes and the change of diffusivities within the top layers of the luvisol. Indeed, the luvisol showed a pronounced maximum of the NO mixing ratios at about 6 cm depth, whereas the podzol column exhibited a steady and exponential decrease of the NO mixing ratios with depth. The inhomogeneities in the luvisol were confirmed by incubation of the soil cores under anoxic conditions. This treatment resulted in production of NO at several depths indicating a zonation of increased potential activities within the luvisol profile which may have biased the modelling of the NO surface flux from turnover measurements in soil samples. Inhomogeneities could be achieved even in homogenized soil by fertilization with nitrate solution.     

地基曙暮光光谱观测反演平流层O3和NO2柱含量

用差分光学吸收光谱(DOAS)方法,从曙暮光天顶散射可见光光谱资料反演了北京上空的O3和NO2柱含量,并对反演结果进行了验证和误差分析.斜柱含量的反演采用了线性和非线性最小二乘拟合方法,拟合时考虑了O3、NO2和H2O的吸收、Ring效应和散射的影响;斜柱含量除以空气质量因子转换成垂直柱含量.空气质量因子的计算使用伪球面DISORT辐射传输模式.O3和NO2总量的检验分别用北京的Dobson O3资料和卫星SAGE Ⅱ的NO2廓线资料.反演的O3总量与Dobson O3总量相比偏差小于10%;NO2总量与SAGE Ⅱ的偏差约20%.