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1.
The intensive field study POPCORN (Photo-Oxidant Formation by Plant Emitted Compounds and OH Radicals in North-Eastern Germany) was carried out in a rural area of North-Eastern Germany during August 1994. An overview of the objectives, measurements and major results of this campaign is presented. Measurements of a set of relevant atmospheric trace compounds, including the hydroxyl radical, along with meteorological data were performed to increase the understanding of OH radical chemistry and photo-oxidant formation. Additionally, plant emissions and the exchange of trace gases between a maize field and the atmosphere were investigated. Budgets of selected trace gases were calculated to assess the relative importance of local sources, chemistry or transport. Intercomparisons between measurement techniques were a central issue of POPCORN and included measurements of OH, hydrocarbons, formaldehyde, photolysis frequencies and vertical fluxes. OH radical concentrations were measured simultaneously by LIF (Laser Induced Fluorescence) and DOAS (Differential Optical Absorption Spectroscopy). Both methods showed good agreement. Maximum OH concentrations were around 107 cm–3 and the diurnal cycles closely followed the rate of primary production via ozone photolysis. Generally, the trace gas composition during POPCORN was characterized by relatively low concentrations of most compounds, e.g. CO: 85–200 ppb, ethane: 0.6–2 ppb, and moderate NOx levels: 0.5–5 ppb (at noontime). Concentrations of individual biogenic volatile organic compounds (VOC) were mostly well below 100 ppt. However, formaldehyde and acetaldehyde which partly originate from biological sources were observed at mixing ratios of some ppb.  相似文献   

2.
At the atmosphere simulation chamber SAPHIR in Jülich both Laser-Induced Fluorescence Spectroscopy (LIF) and Long-Path Differential Optical Laser Absorption Spectroscopy (DOAS) are operational for the detection of OH radicals at tropospheric levels. The two different spectroscopic techniques were compared within the controlled environment of SAPHIR based on all simultaneous measurements acquired in 2003 (13 days). Hydroxyl radicals were scavenged by added CO during four of these days in order to experimentally check the calculated precisions at the detection limit. LIF measurements have a higher precision (σ= 0.88×106 cm–3) and better time resolution (Δt = 60 s), but the DOAS method (σ= 1.24×106 cm–3, Δt = 135 s) is regarded as primary standard for comparisons because of its good accuracy. A high correlation coefficient of r = 0.95 was found for the whole data set highlighting the advantage of using a simulation chamber. The data set consists of two groups. The first one includes 3 days, where the LIF measurements yield (1 – 2) ×106 cm–3 higher OH concentrations than observed by the DOAS instrument. The experimental conditions during these days are characterized by increased NOx concentration and a small dynamic range in OH. Excellent agreement is found within the other group of 6 days. The regression to the combined data of this large group yields unity slope without a significant offset.  相似文献   

3.
Tropospheric hydroxyl radical (OH) concentrations were measured by laser-induced fluorescence (LIF) during the POPCORN field campaign in August 1994 at a rural site in the North East of Germany. Ambient air spectra were recorded by tuning the laser wavelength over a spectral region covering the Q11(3), Q21(3), and P11(1) rotational transitions of the (0-0) band in the A-X system of OH around 308 nm. The observed spectra clearly identify the OH radical in the atmosphere. Besides the OH absorption lines there was no sign of any other narrow-band spectral structure nearby demonstrating the high specificity of the method. For OH measurements with a typical time resolution of 60–100 seconds per data point the laser wavelength was tuned repetitively over small spectral intervals covering the peak position of the P11(1) OH-line and background positions. A total of 2300 measurements were recorded including diurnal cycles of OH with more than 300 data points. The OH as well as the LIF background signal data will be presented. In a first analysis the background signal will be characterized and the correlation between OH and the ozone photolysis frequency will be derived.  相似文献   

4.
An open-path cavity ring-down spectroscopy (CRDS) instrument for measurement of atmospheric iodine monoxide (IO) radicals has been tested in the laboratory and subsequently deployed in Roscoff on the north-west coast of France as part of the Reactive Halogens in the Marine Boundary Layer (RHaMBLe) project in September 2006. In situ measurements are reported of local IO mixing ratios in the marine boundary layer. To obtain these mixing ratios, accurate absorption cross sections of IO are required at the selected wavelengths used for spectroscopic measurements. Absorption cross sections at the bandheads of the IO A2Π3/2–X2Π3/2 (3,0) and (2,0) vibronic bands were thus verified by a combination of spectral simulation methods, inter-comparison of prior determinations of cross-sections at high and low spectral resolution, and by measurement of rates of loss of IO by its self-reaction. The performance of the open-path CRDS instrument was tested by measuring concentrations of NO2 in ambient air, both within and outside the laboratory, with results that were in excellent agreement with a previously validated continuous wave CRDS apparatus for NO2 detection. During the RHaMBLe campaign, the open-path CRDS instrument was located within a few metres of the shoreline and operated at wavelengths close to 435 nm to detect the absorption of light by trace levels of IO. The IO mixing ratios were obtained on two days, peaked close to low tide, and were approximately 5–10 times higher than values calculated from column densities previously reported by long-path, differential optical absorption spectroscopy (DOAS) in coastal regions. The typical detection limit of the instrument was estimated to be 10 pptv of IO, with some fluctuation around this value depending on the conditions of wind and atmospheric aerosol particles, and the total accumulation time was 30 s for each data point. The observations of relatively high concentration of IO, compared to the values previously reported by DOAS, are consistent with the concurrent observations using a LIF (Laser induced Fluorescence) instrument (Whalley et al. in press). The first such measurements of localized IO by CRDS and LIF should contribute to an improved understanding of the chemistry of halogen compounds and the formation of iodine oxide aerosol particles in the marine boundary layer.  相似文献   

5.
Absolutely calibrated in-situ measurements of tropospheric hydroxyl radicals, formaldehyde, sulfur dioxide, and naphthalene (C10H8) were performed by long-path laser absorption spectroscopy during the field campaign POPCORN. The absorption light path was folded into an open optical multiple reflection cell with a mirror separation of 38.5 m. Using a light path length of 1848 m and an integration time of 200 s, the average 1-detection limits of OH, HCHO, SO2 and C10H8 during POPCORN were 8.7 · 105 cm–3, 8.3 · 109 cm–3, 2.4 · 109 cm–3, 1.5 · 108 cm–3, respectively. In total, 392 identifications of OH in air spectra were made in a rural environment between August 5 and August 23, 1994. We present and discuss OH absorption spectra and diurnal OH concentration profiles of three days which are representative for measurements under different pollution conditions during POPCORN. The observed maximum and median OH radical concentrations are 1.3 · 107 OH/cm3 and 4.0 · 106 OH/cm3, respectively. The measured diurnal variation of the OH concentration shows a good correlation with the primary formation reaction of OH radicals which is the photolysis of ambient ozone. Deviations from this correlation in the morning and evening hours, when the OH concentration is higher than expected from the ozone photolysis, demonstrate the importance of other photochemical HOx production pathways during POPCORN.  相似文献   

6.
Free Radicals and Fast Photochemistry during BERLIOZ   总被引：4，自引：0，他引：4  
The free radicals OH, HO2, RO2, and NO3 are known to be the driving force for most chemical processes in the atmosphere. Since the low concentration of the above radicals makes measurements particularly difficult, only relatively few direct measurements of free radical concentrations have been reported to date.We present a comprehensive set of simultaneous radical measurements performed by Laser Induced Fluorescence (LIF), Matrix Isolation –Electron spin Resonance (MI-ESR), Peroxy Radical Chemical Amplification (PERCA), and Differential Optical Absorption Spectroscopy (DOAS) during the BERLIner OZonexperiment (BERLIOZ) during July and August of 1998 near Berlin, Germany. Most of the above radical species were measured by more than one technique and an intercomparison gave good agreement. This data set offered the possibility to study and quantify the role of each radical at a rural, semi-polluted site in the continental boundary layer and to investigate interconnections and dependencies among these free radicals.In general (box) modelled diurnal profiles of the different radicals reproduced the measurements quite well, however measured absolute levels are frequently lower than model predictions. These discrepancies point to disturbing deficiencies in our understanding of the chemical system in urban air masses.In addition considerable night-time peroxy radical production related to VOC reactions with NO3 and O3 could be quantified.  相似文献   

7.
南京北郊冬季大气SO2、NO2和O3的变化特征   总被引：1，自引：0，他引：1  
利用差分吸收光谱仪DOAS（differential optical absorption spectroscopy）,对2007年11月—2008年1月南京北郊大气SO2、NO2和O3进行了观测。结合Parsivel降水粒子谱仪和自动气象站的资料,对冬季大气污染气体的浓度变化规律及降水和风速风向对其的影响进行了分析。结果表明,南京北郊大气SO2浓度较高,呈明显双峰特征,分别在12时（北京时,下同）和00时达最大,受附近排放源的影响最大,东风及南风时比静风时SO2浓度更高。降水对SO2湿清除效果明显,清除系数平均为0.168 h-1。NO2气体呈明显单峰特征,在18时达最高值。南京北郊是NO2源区之一,主要受附近高速公路汽车尾气排放源的影响。静风时NO2浓度最高。O3浓度受NO2的影响较明显。O3日变化呈单峰特征,在15时达最大值,静风时O3浓度最低。降水对O3的间接影响较明显,在降水时,白天由于太阳辐射较弱,O3浓度降低;夜晚NO浓度较低,使得O3浓度升高。  相似文献   

8.
The 2.4-dinitrophenylhydrazine coated silica cartridge technique (DSC) was used for the measurements of HCHO and CH3CHO during the POPCORN campaign in August 1994. A total number of 505 measurements was carried out using an automatic sampling system. The sampling time for each measurement was 30 minutes. During the first two weeks of the campaign samples were taken every 3 hours and during the last two weeks every 30 minutes. No significant diurnal variation of HCHO and CH3CHO was observed. The average mixing ratios of HCHO and CH3CHO were 1.8 ±1.0 ppb and 1.4 ±1.3 ppb. The results for HCHO are in a good agreement with simultaneous measurements by differential optical absorption spectroscopy (DOAS). The absence of a strong diurnal variation of the HCHO mixing ratio can be explained by production and destruction processes during day and night. The measured mixing ratios of HCHO and CH3CHO, especially the mixing ratios during night, are a strong indication that during the POPCORN campaign the maize was a local source of HCHO and CH3CHO.  相似文献   

9.
Degradation of isoprene, m-xylene, n-octane, propene, and methacrolein by hydroxyl radicals has been studied in the simulation chamber SAPHIR under burden of trace gases as they are typical for the moderately polluted planetary boundary layer. Measured time series of the hydrocarbon mixing ratios and the OH concentrations were used to determine the rate constants. The hydrocarbons were measured with gas chromatography and proton transfer reaction mass spectrometry. OH was measured with the Jülich DOAS (differential optical absorption spectroscopy) instrument. In all cases except methacrolein good agreement was found with the reference rate constants taken from the Master Chemical Mechanism (MCM3.1). The data for methacrolein are consistent with the results of Karl et al. (J. Atmos. Chem 55, 2006, doi:) who reported a 12% smaller value. The degradation of hydrocarbons provides an independent method to analyse precision and accuracy of the OH measurements. A precision of better than 4% over a period of nearly 4 months was found. The accuracy is within the limitations given by the light absorption cross section of OH. Both results are consistent with earlier results by Hausmann et al. (J. Geophys. Res. 102:16011–16022, 1997).  相似文献   

10.
利用差分吸收光谱仪DOAS(differential optical absorption spectroscopy),对2007年11月-2008年1月南京北郊大气SO_2、NO_2和O_3进行了观测.结合Parsivel降水粒子谱仪和自动气象站的资料,对冬季大气污染气体的浓度变化规律及降水和风速风向对其的影响进行了分析.结果表明,南京北郊大气SO_2浓度较高,呈明显双峰特征,分别在12时(北京时,下同)和00时达最大,受附近排放源的影响最大,东风及南风时比静风时SO_2浓度更高.降水对SO_2湿清除效果明显,清除系数平均为0.168h~(-1).NO_2气体呈明显单峰特征,在18时达最高值.南京北郊是NO_2源区之一,主要受附近高速公路汽车尾气排放源的影响.静风时NO_2浓度最高.O_3浓度受NO_2的影响较明显.O_3日变化呈单峰特征,在15时达最大值,静风时O_3浓度最低.降水对O_3的间接影响较明显,在降水时,白天由于太阳辐射较弱,O_3浓度降低;夜晚NO浓度较低,使得O_3浓度升高.  相似文献   

11.
Observations of the Nitrate Radical in the Marine Boundary Layer   总被引：3，自引：0，他引：3  
A study of the nitrate radical (NO3) has been conducted through a series of campaigns held at the Weybourne Atmospheric Observatory, located on the coast of north Norfolk, England. The NO3 concentration was measured in the lower boundary layer by the technique of differential optical absorption spectroscopy (DOAS). Although the set of observations is limited, seasonal patterns are apparent. In winter, the NO3 concentration in semi-polluted continental air masses was found to be of the order of 10 ppt, with an average turnover lifetime of 2.4 minutes. During summer in clean northerly air flows, the concentration was about 6 ppt with a lifetime of 7.2 minutes. The major loss mechanisms for the radical were investigated in some detail by employing a chemical box model, constrained by a suite of ancillary measurements. The model indicates that during the semi-polluted conditions experienced in winter, the major loss of NO3 occurred indirectly through reactions of N2O5, either in the gas-phase with H2O, or through uptake on aerosols. The most important direct loss was via reactions of NO3 with a number of unsaturated nonmethane hydrocarbons. The cleaner air masses observed during the summer were of marine origin and contained elevated concentrations of dimethyl sulfide (DMS), which provided the major loss route for NO3. The box model was then used to investigate the conditions in the remote marine boundary layer under which DMS will be oxidised more rapidly at night (by NO3) than during the day (by OH). This should occur if the concentration of NO2 is more than about 60% that of DMS.  相似文献   

12.
利用 2008年1-12月南京北郊O3、NO2及SO2质量浓度连续观测资料,分析了南京北郊气体污染物(O3、NO2、SO2) 的质量浓度变化规律。结果表明：南京北郊O3浓度夏季较高,日变化曲线呈单峰型,NO2和SO2浓度夏季较低,日变化曲线呈双峰型,NO2与O3的日变化呈现负相关关系,该地区SO2浓度整体较高,夏季周末效应NO2和SO2较O3更明显。  相似文献   

13.
Three different techniques used tomeasure atmospheric formaldehyde were compared duringa field campaign carried out at a clean maritime siteon the West coast of Ireland. Two spectroscopictechniques Differential Optical AbsorptionSpectroscopy (DOAS) and Tunable Diode Laser AbsorptionSpectroscopy (TDLAS), together with a glass coil/Hantzschreaction/fluorescence technique, wereemployed for measurements of atmospheric formaldehydeof the order of a few hundred pptv. The betteragreement was observed between the fluorescence andDOAS instruments.Two DOAS instruments were compared to the glasscoil/Hantzsch reaction/fluorescence technique at asemi-polluted site on the North Norfolk coast, U.K.,where concentrations of formaldehyde were observed atlevels up to 4 ppbv. A very good agreement wasobserved between the two instruments.The glass coil/Hantzsch reaction/fluorescence and theTDLAS instruments were also deployed simultaneously inorder to measure indoor air inside a mobile laboratorylocated at the Imperial College Silwood Park site nearAscot, U.K. The doors of the mobile laboratory wereleft open in order to obtain the backgroundformaldehyde concentrations. Closing them afterwardsallowed us to observe the increase in concentrationsas a result of indoor emissions. The agreement betweenthe two instruments was outstanding (correlationcoefficient was 99%).The results from this study showed that of the fourinstruments included in this intercomparison the glasscoil/Hantzsch reaction/fluorescence technique provedthe most suitable for continuous measurements offormaldehyde in the background atmosphere.  相似文献   

14.
《大气与海洋》2013,51(4):325-338
Abstract

A portable ground‐based instrument has been constructed for the automated measurement of vertical column abundances of a number of gases pertinent to stratospheric ozone chemistry. The instrumentation is described in this paper and results are presented from the first set of field measurements, made during the Middle Atmosphere Nitrogen TRend Assessment (MANTRA) 1998 field campaign at Vanscoy, Saskatchewan, Canada. Zenith‐sky spectra in the near ultraviolet and visible wavelength regions were recorded for a period of seven days, prior to and following the launch of the MANTRA balloon on 24 August 1998. The spectra were then analysed using the differential optical absorption spectroscopy (DOAS) technique in conjunction with a radiative transfer model to determine vertical column amounts of ozone and NO2. Ozone measurements compared favourably with concurrent observations by ozonesondes, a Brewer spectrophotometer, and satellite instruments. Vertical NO2 columns were in broad agreement with those determined by the Global Ozone Monitoring Experiment (GOME) satellite instrument.  相似文献   

15.
不同天气条件下脉冲激光风廓线仪测风性能   总被引：1，自引：1，他引：0       下载免费PDF全文
将2012年5月21日-8月16日广东省湛江市东海岛气象观测站内脉冲激光风廓线仪WINDCUBE V2与气象站内的100 m测风塔进行同步观测试验,在经过观测数据同步性调整、有效性检验和代表性样本筛选基础上,分大小风和有无降雨天气过程,对杯式测风仪、超声风速仪与激光风廓线仪的同步测风数据进行比较,结果显示:脉冲激光风廓线仪与杯式测风仪测量水平风参数的相关性较好,10 min平均风速、风向的线性拟合度均大于0.99,3 s阵风风速的拟合度大于0.96,湍流强度的拟合度大于0.67,风速标准差的拟合度大于0.79;大风情况下,激光风廓线仪对风参数的测量效果更佳。无降雨情况下,激光风廓线仪的测量效果较降雨时略好,10 min降水量小于15 mm的降雨对这款激光风廓线仪的风速、风向、湍流强度、3 s阵风风速的测量没有显著影响,对风速标准差有一定影响。当水平风速增大和有降雨时,激光风廓线仪对垂直速度的测量效果欠佳。该对比分析可为激光风廓线仪观测数据的可靠性提供参考。  相似文献   

16.
A field-based intercomparison study of a(DOAS) instrument (OPSIS AB, Sweden) andcommercial Differential Optical Absorption Spectroscopydifferent point-sample monitoring techniques (PM, basedon an air monitoring station, an air monitoring vehicle, and various chemical methods) was conducted inBeijing from October 1999 to January 2000. The mixing ratios of six trace gases including NO, NO2, SO2,03, benzene, and toluene were monitored continuously during the four months. A good agreement betweenthe DOAS and PM data was found for NO2 and SO2. However, the concentrations of benzene, toluene,and NO obtained by DOAS were significantly lower than those measured by the point monitors. Theozone levels monitored by the DOAS were generally higher than those measured by point monitors. Theseresults may be attributed to a strong vertical gradient of the NO-O3-NO2 system and of the aromatics atthe measurement site. Since the exact data evaluation algorithm is not revealed by the manufacturer ofthe DOAS system, the error in the DOAS analysis can also not be excluded.  相似文献   

17.
A differential optical absorption spectroscopy (DOAS)-like algorithm is developed to retrieve the column-averaged dry-air mole fraction of carbon dioxide from ground-based hyper-spectral measurements of the direct solar beam. Different to the spectral fitting method, which minimizes the difference between the observed and simulated spectra, the ratios of multiple channel-pairs——one weak and one strong absorption channel——are used to retrieve X CO2 from measurements of the shortwave infrared (SWIR) band. Based on sensitivity tests, a super channel-pair is carefully selected to reduce the effects of solar lines, water vapor, air temperature, pressure, instrument noise, and frequency shift on retrieval errors. The new algorithm reduces computational cost and the retrievals are less sensitive to temperature and H2O uncertainty than the spectral fitting method. Multi-day Total Carbon Column Observing Network (TCCON) measurements under clear-sky conditions at two sites (Tsukuba and Bremen) are used to derive X CO2 for the algorithm evaluation and validation. The DOAS-like results agree very well with those of the TCCON algorithm after correction of an airmass-dependent bias.  相似文献   

18.
A field-based Intercomparison study of a commercial Differential Optical Absorption Spectroscopy (DOAS) instrument (OPSIS AB, Sweden) and different point-sample monitoring techniques (PM, based on an air monitoring station, an air monitoring vehicle, and various chemical methods) was conducted in Beijing from October 1999 to January 2000. The mixing ratios of six trace gases including NO, NO2, SO2, O3, benzene, and toluene were monitored continuously during the four months. A good agreement between the DOAS and PM data was found for NO2 and SO2. However, the concentrations of benzene, toluene, and NO obtained by DOAS were significantly lower than those measured by the point monitors. The ozone levels monitored by the DOAS were generally higher than those measured by point monitors. These results may be attributed to a strong vertical gradient of the NO-O3-NO2 system and of the aromatics at the measurement site. Since the exact data evaluation algorithm is not revealed by the manufacturer of the DOAS sys  相似文献   

19.
Accurate OH and HO2 (collectively called HOx) measurements by laser-induced fluorescence (LIF) may be contaminated by spurious signals from interfering atmospheric chemicals or from the instrument itself. Interference tests must be conducted to ensure that observed OH signal originates solely from ambient OH and is not due to instrument artifacts. Several tests were performed on the Penn State LIF HOx instrument, both in the laboratory and in the field. Theseincluded measurements of the instrument's zero signal by using either zero air or perfluoropropylene to remove OH, examination of spectral interferences from naphthalene, sulfur dioxide, and formaldehyde, and tests of interferences by addition of suspected interfering atmospheric chemicals, including ozone, hydrogen peroxide, nitrous acid, formaldehyde, nitric acid, acetone, and organic peroxy radicals (RO2). All tests lacked evidence ofsignificant interferences for measurements in the atmosphere, including highly polluted urban environments.  相似文献   

20.
Continuous data of aerosol optical thickness monitored using differential optical absorption spectroscopy (DOAS) are correlated with the concentration of ground-measured suspended particulate matter (SPM). A high correlation is found between the DOAS and the ground SPM data, making it possible to calculate the mass extinction efficiency of the aerosols in the atmosphere. It is found that the value of mean mass extinction efficiency (MEE) varies over a range of 2.6–13.7m2 g?1, with smaller and larger values occurring for size distributions dominated by coarse and fine particles, respectively.  相似文献   

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