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1.
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2.
In situ measurements of [OH], [HO2] (square brackets denote species concentrations), and other chemical species were made in the tropical upper troposphere (TUT). [OH] showed a robust correlation with solar zenith angle. Beyond this dependence, however, [OH] did not correlate to its primary source, the product of [O3] and [H2O] ([O3]?[H2O]), or its sink [NOy]. This suggests that [OH] is heavily buffered in the TUT. One important exception to this result is found in regions with very low [O3], [NO], and [NOy]. Under these conditions, [OH] is highly suppressed, pointing to the critical role of NO in sustaining OH in the TUT and the possibility of low [OH] over the western Pacific warm pool due to strong marine convections bringing NO-poor air to the TUT. In contrast to [OH], [HOx] ([OH] + [HO2]) correlated reasonably well with [O3]?[H2O]/[NOy], suggesting that [O3]?[H2O] and [NOy] are the significant source and sink, respectively, of [HOx].  相似文献   

3.
A detailed photochemical box model was used to investigate the key reaction pathways between OH, HO2 and RO2 radicals during the summer and winter PUMA field campaigns in the urban city-centre of Birmingham in the UK. The model employed the most recent version of the Master Chemical Mechanism and was constrained to 15-minute average measurements of long-lived species determined in situ at the site. The results showed that in the summer, OH initiation was dominated by the reactions of ozone with alkenes, nitrous acid (HONO) photolysis and the reaction of excited oxygen atoms atoms with water. In the winter, ozone+alkene reactions were the primary initiation route, with a minor contribution from HONO photolysis. Photolysis of aldehydes was the main initiation route for HO2, in both summer and winter. RO2 initiation was dominated by the photolysis of aldehydes in the summer with a smaller contribution from ozone+alkenes, a situation that was reversed in the winter. At night, ozone+alkene reactions were the main radical source. Termination, under all conditions, primarily involved reactions with NO (OH) and NO2 (OH and RCO3). These results demonstrate the importance of ozone+alkene reactions in urban atmospheres, particularly when photolysis reactions were less important during winter and at nighttime. The implications for urban atmospheric chemistry are discussed.  相似文献   

4.
Atmospheric hydroxyl (OH), hydroperoxy (HO2), total peroxy (HO2 and organic peroxy radicals, RO2) mixing ratios and OH reactivity (first order OH loss rate) were measured at a rural site in central Pennsylvania during May and June 2002. OH and HO2 mixing ratios were measured with laser induced fluorescence (LIF); HO2 + RO2 mixing ratios were measured with chemical ionization mass spectrometry (CIMS). The daytime maximum mixing ratios were up to 0.6 parts per trillion by volume (pptv) for OH, 30 pptv for HO2, and 45 pptv for HO2 + RO2. A parameterized RACM (Regional Atmospheric Chemistry Mechanism) box model was used to predict steady state OH, HO2 and HO2 + RO2 concentrations by constraining the model to the measured OH reactivity and previously measured volatile organic compound (VOC) distributions. The averaged model calculations are generally in good agreement with the observations. For OH, the model matched the observations for day and night, with an average observed-to-modeled ratio of 0.80. In previous studies such as PROPHET98, nighttime NO was near 0 pptv and observed nighttime OH was significantly larger than modeled OH. In this study, nighttime observed and modeled OH agree to within measurement and model uncertainties because the main source of the nighttime OH was the reaction HO2 + NO → OH + NO2, with the NO being continually emitted from the surrounding fertilized corn field. The observed-to-modeled ratio for HO2 is 1.0 on average, although daytime HO2 is underpredicted by a factor of 1.2 and nighttime HO2 is over-predicted by a factor of ∼2. The average measured and modeled HO2 + RO2 agree well during daytime, but the modeled value is about twice the measured value during nighttime. While measured HO2 + RO2 values agree with modeled values for NO mixing ratios less than a few parts per billion by volume (ppbv), it increases substantially above the expected value for NO greater than a few ppbv. This observation of the higher-than-expected HO2 + RO2 with the CIMS technique confirms the observed increase of HO2 above expected values at higher NO mixing ratios in HO2 measurements with the LIF technique. The maximum instantaneous O3 production rate calculated from HO2 and RO2 reactions with NO was as high as 10–15 ppb h−1 at midday; the total daily O3 production varied from 13 to 113 ppbv d−1 and was 48 ppbv d−1 on average during this campaign.  相似文献   

5.
For atmospheric photochemistry, clouds can significantly affect actinic flux distributions. In this paper, we examine the effects of convective clouds on the three-dimensional distribution of the spectral actinic flux and on photolysis frequencies for various chemical species. Three-dimensional solutions of the UV-VIS radiative transfer equation are produced using the Spherical Harmonic Discrete Ordinary Method solution technique. This solver uses as input the 3-D cloud characteristics simulated by a dynamical cloud model. The ultraviolet and visible spectra are divided into 5 intervals in order to explore the wavelength dependency of the cloud effect on the actinic flux. Results show that the distribution of the actinic flux over the cloud domain is far from homogeneous and depends primarily on the cloud extinction associated with the hydrometeors. Maximum actinic flux is found at the top edge of the cloud and is related to scattering by ice crystals. The actinic flux is enhanced by a factor of 2 to 5, compared to clear air values, above, at the top edge, and around the cloud. The 3-D actinic flux is used to calculate the photolysis rates for some chemical species (e.g. NO2, O3, and HCHO). Forcomputing photolysis rates, a discretized spectral representation of the absorption wavelengths is used in the model. The calculated photolysis rates are distributed inhomogeneously throughout the cloud, and maxima are found in regions where the actinic flux is enhancement is large. Temperature effects on absorption are found in the photolysis frequencies of some species. Finally, the potential importance of this photolysis enhancement on photochemistry is studied using box model simulations. Results show that enhanced OH concentrations are found in the upper troposphere (120–200%) overthe clouds and changes in ozone production rates (+15%) are obtained in quasi-steady state conditions.  相似文献   

6.
Reported are the results from a comparison of OH,H2O2CH3OOH, and O3 observationswithmodel predictions based on current HOx–CH4reaction mechanisms. The field observations are thoserecorded during the NASA GTE field program, PEM-Tropics A. The major focus ofthis paper is on thosedata generated on the NASA P-3B aircraft during a mission flown in the marineboundary layer (MBL) nearChristmas Island, a site located in the central equatorial Pacific (i.e.,2° N, 157° W). Taking advantage of thestability of the southeastern trade-winds, an air parcel was sampled in aLagrangian mode over a significantfraction of a solar day. Analyses of these data revealed excellent agreementbetween model simulated andobserved OH. In addition, the model simulations reproduced the major featuresin the observed diurnalprofiles of H2O2 and CH3OOH. In the case ofO3, the model captured the key observational feature whichinvolved an early morning maximum. An examination of the MBL HOxbudget indicated that the O(1D) + H2Oreaction is the major source of HOx while the major sinks involveboth physical and chemical processes involving the peroxide species,H2O2 and CH3OOH. Overall, the generally goodagreement between modeland observations suggests that our current understanding ofHOx–CH4 chemistry in the tropical MBL isquite good; however, there remains a need to critically examine this chemistrywhen both CH2O and HO2are added to the species measured.  相似文献   

7.
Using long path UV absorption spectroscopy we have measured OH concentrations close to the earth's surface. The OH values observed at two locations in Germany during 1980 through 1983 range from 0.7×106 to 3.2×106 cm-3. Simultaneously we measured the concentrations of O3, H2O, NO, NO2, CH4, CO, and the light non methane hydrocarbons. We also determined the photolysis rates of O3 and NO2. This allows calculations of OH using a zero dimensional time depdendent model. The modelled OH concentrations significantly exceed the measured values for low NO x concentrations. It is argued that additional, so far unidentified. HO x loss reactions must be responsible for that discrepancy.  相似文献   

8.
Photochemical box modelling was undertaken to investigate OH and HO2 radical chemistry during summer and winter field campaigns in the urban city-centre of Birmingham in the UK. The model employed the most recent version of the Master Chemical Mechanism (v3.1) and was constrained to 15-minute average measurements of long-lived species determined in situ at the site. The model was used to predict OH and HO2 concentrations for comparison with measurements made by the fluorescence assay by gas expansion technique. Whilst there was generally good agreement between the modelled and measured OH concentrations, particularly during summer, there was sometimes a significant model under-prediction during daylight hours, which significantly skews the overall model: measured agreement. There were less measured data available for HO2, but the agreement between model and measurement for the days where measurements existed were less good than for OH, with one or two exceptions. The modelled:measured ratios between the hours of 11:00–15:00 h for OH were 0.58 and 0.50 for summer and winter respectively. For HO2, the same ratios were 0.56 in the summer and 0.49 in the winter. Sensitivity studies were conducted to attempt to understand the model-measurement discrepancy. The predicted radical concentrations were particularly sensitive to changes in NOX concentrations. Constraining the model to the observed HO2 concentrations made the OH predictions worse. These results highlight the fact that there are many complexities in urban areas and that more highly-instrumented campaigns are required in the future to further our understanding.  相似文献   

9.
An instrument for measuringtropospheric OH/HO2 radicals by laser-inducedfluorescence developed in our laboratory is presentedin detail. It is based on FAGE (fluorescence assay bygas expansion) technique and OH is both excited anddetected at 308 nm corresponding to its A-X(0,0) band.The alignment of the laser beam, the design of thesample gas inlet, and the devices for the fluorescencedetection are optimized so as to reduce the backgroundsignal while keeping the OH sensitivity as high aspossible. A thermalized position of the expanding gasbeam is probed in our system and we did not observe asevere decrease of the HOx sensitivities under humidconditions. An optical fiber is used for deliveringthe laser light to the fluorescence detection cellmounted outside at a high position. Thus the laserbeam alignment is by far simplified and is made highlyreproducible, once settled properly. For thecalibration, two methods are employed: a system withlaser absorption measurements of OH and a system ofsimultaneous photolysis of H2O and O2. Thecalibration factors are compared well within thecombined uncertainty. Using the latter system, theconversion efficiency of HO2 to OH by NO additionis measured to be around 90%. The detection limitsfor OH and HO2 (S/N = 2) are estimated to be3.3 × 106 and 3.6 × 106cm–3 at noon,respectively, with an integration time of 1 min. Theresults of test observations at our institute are alsopresented.  相似文献   

10.
南京地区大气颗粒物影响近地面臭氧的个例研究   总被引：4，自引：0，他引：4  
通过对2008年4月2～7日南京地区地面气象观测数据以及两个站点空气质量(O3、NOx、PM10)监测资料的分析, 发现O3和PM10之间存在一定程度的反相关。利用一个光化学箱模式对该个例中大气颗粒物影响近地面臭氧的过程进行模拟, 结果发现大气颗粒物浓度的升高使得气溶胶光学厚度增加20％～40%, 导致NO2和O3近地面光解率下降20%～30%, OH和HO2自由基浓度分别减少20%～50%, 造成O3净生成率下降30%～40%。研究表明, 颗粒物对光化学过程的抑制造成了大气氧化能力的降低, 是近地面臭氧浓度减少的可能原因。  相似文献   

11.
Measurements of formaldehyde (HCHO) were made at the Cape Verde Atmospheric Observatory between November 2006 and June 2007 using the Long-Path Differential Optical Absorption Spectroscopy (LP-DOAS) technique. Observations show that typical HCHO mixing ratios ranged between 350 and 550 pptv (with typical 2-σ uncertainties of ~110 pptv), with several events of high HCHO, the maximum being 1,885?±?149 pptv. The observations indicate a lack of strong seasonal or diurnal variations, within the uncertainty of the measurements. A box model is employed to test whether the observations can be explained using known hydrocarbon photochemistry; the model replicates well the typical diurnal profile and monthly mean values. The model results indicate that on average 20% of HO2 production and 10% of OH destruction can be attributed to the mean HCHO levels, suggesting that even at these low average mixing ratios HCHO plays an important role in determining the HOx (HO2+OH) balance of the remote marine boundary layer.  相似文献   

12.
High levels of uncertainty in non-methane volatile organic compound （NMVOC） emissions in China could lead to significant variation in the budget of the sum of hydroxyl （OH） and peroxy （HO2,RO2） radicals （ROx =OH ＋ HO2 ＋ RO2） and the ozone production rate [P（O3）],but few studies have investigated this possibility,particularly with three-dimensional air quality models.We added diagnostic variables into the WRF-Chem model to assess the impact of the uncertainty in anthropogenic NMVOC （AVOC） emissions on the ROx budget and P（O3） in the Beijing-Tianjin-Hebei region,Yangtze River Delta,and Pearl River Delta of China.The WRF-Chem simulations were compared with satellite and ground observations,and previous observation-based model studies.Results indicated that 68％ increases （decreases） in AVOC emissions produced 4％-280％ increases （2％-80％ decreases） in the concentrations of OH,HO2,and RO2 in the three regions,and resulted in 35％-48％ enhancements （26％-39％ reductions） in the primary ROx production and ～ 65％ decreases （68％-73％ increases） of the P（O3） in Beijing,Shanghai,and Guangzhou.For the three cities,the two largest contributors to the ROx production rate were the reaction of O1D ＋ H2O and photolysis of HCHO,ALD2,and others; the reaction of OH ＋ NO2 （71％-85％） was the major ROx sink; and the major contributor to P（O3） was the reaction of HO2 ＋ NO （～ 65％）.Our results showed that AVOC emissions in 2006 from Zhang et al.（2009） have been underestimated by ～ 68％ in suburban areas and by ＞ 68％ in urban areas,implying that daily and hourly concentrations of secondary organic aerosols and inorganic aerosols could be substantially underestimated,and cloud condensation nuclei could be underestimated,whereas local and regional radiation was overestimated.  相似文献   

13.
Isoprene peroxy radical isomerizations (1,5- and 1,6-H shifts) have recently been proposed as important pathways regenerating and recycling HOx (OH?+?HO2) in the atmosphere under low-NOx conditions (Peeters et al. Phys. Chem. Chem. Phys. 28: 5935?C5939 2009; da Silva et al. Environ. Sci. Technol. 44:250?C256 2010). Evaluation and comparison of the isoprene peroxy radical isomerization mechanisms from recent studies have been performed against isoprene-NOx experiments conducted in the UNC dual outdoor smog chambers. Five different kinetic mechanisms were tested in this study, including the original Master Chemical Mechanism (MCM) v3.1; two modified MCM mechanisms both implementing isoprene peroxy radical isomerization reactions but with different rate coefficients; the Carbon Bond 6 (CB6) mechanism; and the ISO-UNC mechanism. Sensitivity analyses of the unsaturated hydroxyperoxy aldehydes (HPALDs) reaction mechanisms under fast isomerization have also been performed. The results indicate that the fast isomerization mechanism and the mechanisms with high OH yields from HPALDs photolysis both significantly enhance HOx estimates with increasing isoprene/NOx ratios. However, O3 predictions, as well the isoprene decay rates are substantially overestimated. Our results suggest that given the current state of our knowledge, it is difficult to improve both HOx levels and maintain reasonable O3 simulations using the Peeters et al. (Peeters et al. Phys. Chem. Chem. Phys. 28: 5935?C5939 2009) mechanism.  相似文献   

14.
An instrument is developed for the measurement of peroxy radical using chemical amplification coupled with NO2-luminol chemiluminescence detection. The chain length of 147 ± 10 (1σ) is determined by an HO2 source that uses the photolysis of water vapor under 184.9 nm in air. A Nafion system equipped with a Nafion tube of ~2.2 mm external diameter and 350 mm length is employed in the PERCA instrument (Nafion-PERCA system). When flowing an air sample containing HO2 through the Nafion system, it is found that - 94.6 % of HO2 is removed. In contrast, only 17.8 % of RO2 radicals (a mixtures of CH3O2 and CH3C(O)O2 with a ratio of 1.1:0.9) are removed. The results indicate the Nafion system has a good selective removing performance of HO2 radical during the PERCA measurement. Therefore, the method could be applied to ambient and laboratory measurements of absolute concentrations of RO2 as well as the sum of HO2 and RO2.  相似文献   

15.
Summary We have used a multi-phase cloud photochemistry model to investigate the influence of dissolved iron (Fe) and copper (Cu) on the in-cloud production and loss of ozone and ozone-related species. Comparison of the results of our simulations with and without Fe and Cu reactions for three different photochemical scenarios (marine, averaged continental and polluted continental) indicate that Fe and Cu reactions, depending upon the scenario considered, can either increase or decrease the predicted rate of loss of ozone and ozone related species. For the marine and averaged continental scenarios the rate of loss of ozone in the aqueous-phase was decreased by as much as 45% and 70%, respectively, when Fe and Cu reactions were considered. For polluted continental conditions, the rate of loss of ozone in the aqueous phase increased with a factor 2 for low metal concentrations up to a factor 20 for high metal concentrations. In all three scenarios inclusion of the Fe and Cu reactions results in cloud droplets becoming more efficient sinks for gas-phase HO2 and also enhances OH production. The net effect of the decreased losses of ozone from the aqueous phase and the effect of the cloud droplets on HO2 and OH determine the overall impact on ozone and ozone related species, for each of the situations considered. Overall, when Fe and Cu reactions were included the marine cloud was found to be a less efficient sink for ozone, and averaged continental and polluted continental clouds were more efficient sinks for ozone (O3 losses doubled in the averaged continental scenario). The higher OH flux in the aqueous phase also enhances the rate at which organic compounds, such as formaldehyde and formic acid, are oxidized in the cloud.With 4 Figures  相似文献   

16.
Modelling studies were performed with the multiphase mechanism RACM-MIM2ext/CAPRAM 3.0i to investigate the tropospheric multiphase chemistry in deliquesced particles and non-precipitating clouds using the SPACCIM model framework. Simulations using a non-permanent cloud scenario were carried out for two different environmental conditions focusing on the multiphase chemistry of oxidants and other linked chemical subsystems. Model results were analysed by time-resolved reaction flux analyses allowing advanced interpretations. The model shows significant effects of multiphase chemical interactions on the tropospheric budget of gas-phase oxidants and organic compounds. In-cloud gas-phase OH radical concentration reductions of about 90 % and 75 % were modelled for urban and remote conditions, respectively. The reduced in-cloud gas-phase oxidation budget increases the tropospheric residence time of organic trace gases by up to about 30 %. Aqueous-phase oxidations of methylglyoxal and 1,4-butenedial were identified as important OH radical sinks under polluted conditions. The model revealed that the organic C3 and C4 chemistry contributes with about 38 %/48 % and 8 %/9 % considerably to the urban and remote cloud / aqueous particle OH sinks. Furthermore, the simulations clearly implicate the potential role of deliquescent particles to operate as a reactive chemical medium due to an efficient TMI/HOx,y chemical processing including e.g. an effective in-situ formation of OH radicals. Considerable chemical differences between deliquescent particles and cloud droplets, e.g. a circa 2 times more efficient daytime iron processing in the urban deliquescent particles, were identified. The in-cloud oxidation of methylglyoxal and its oxidation products is identified as efficient sink for NO3 radicals in the aqueous phase.  相似文献   

17.
Two recent gas-phase chemical kinetic mechanisms for tropospheric ozone formation, one based on the lumped-structure approach (CB05) and the other based on the lumped-molecule approach (RACM2), are compared for simulations of ozone over Europe. The host air quality model is POLAIR3D of the Polyphemus modeling platform. A one-month period (15 July to 15 August 2001) is simulated. Model performance is satisfactory with both mechanisms. Overall, the two mechanisms give similar results with a domain-averaged difference of 3 ppb and a mean fractional absolute difference of 5% (values averaged over the month for the daily 8-h average maximum ozone concentrations). This difference results from different treatments in the two mechanisms for both inorganic and organic chemistry. Differences in the treatment of the inorganic chemistry are due mainly to differences in the kinetics of two reactions: NO + O3 \(\longrightarrow\) NO2 + O2 and NO + HO2 \(\longrightarrow\) NO2 + OH. These differences lead to a domain-averaged difference in ozone concentration of 5%, with RACM2 kinetics being more conducive to ozone formation. Differences in the treatment of organic chemistry lead to a domain-averaged difference in ozone concentration of 3%, with CB05 chemistry being more conducive to ozone formation. This average difference results in part from compensating effects among various VOC classes and some significant differences are identified at specific locations (the coastline of northern Africa and eastern Europe: 9%) and for specific organic classes (aldehydes, biogenic alkenes and aromatics). Differences in the treatment of the organic chemistry result from various aspects. For some VOC classes, such as aldehydes and biogenic alkenes, the more detailed explicit treatments using more model species in RACM2 lead to either greater or lower reactivity depending on the assumptions made for the oxidation products. For other VOC species, such as aromatics, the assumptions made about the major chemical oxidation pathways (aromatic alcohol formation in CB05 vs. ring opening in RACM2) affect the ozone formation significantly. Reconciliation of different chemical kinetic mechanisms will require experimental data to reduce current uncertainties in the kinetic (e.g., NO oxidation) and mechanistic (e.g., aromatics oxidation) representations of major chemical pathways.  相似文献   

18.
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19.
The HO x (OH and HO2) production rate in indoor air caused by radon decay was measured by the chemical amplification technique. The average HO x production rate was found to be (4.31±0.07)×105 HO x per Rn decay per second (Bq) within the range of relative humidity from 3.4 to 55.0 percent at 22 °C. This work providedG(HO x )-value, 7.86±0.13 #/100 eV in air by directly measuring [HO x ] from radiolysis of water vapor. It is also found that there is no obvious relationship between the HO x production rate and the relative humidity in this range. Therefore, this work provides both the basic data for the evaluation of radioactive pollution in indoor air as well as a potentially useful way to produce HO x concentrations in air.  相似文献   

20.
Simultaneous measurements of ozone and ozoneprecursors were made during a field campaign atSchauinsland in the Black Forest and in the valleynorth of Schauinsland that channels the flow ofpolluted air from the city of Freiburg to the site.From the decay of hydrocarbons and NOx between the twomeasuring sites and the known rate coefficients, theconcentration of OH radicals was calculated. From abudget analysis of OH and HOx it is concluded that therelatively high OH concentrations (5–8 ×106cm-3) in the presence of high NO2concentrations cannot be explained by the knownprimary sources. The budget can be closed if efficientrecycling of OH via HO2 is assumed to occur andthat, based on the measured hydrocarbons, 2 HO2molecules are formed for each OH radical that reactswith a hydrocarbon molecule. This assumption is inaccordance with the budget of Ox obtained from ourmeasurements and with results from earliermeasurements of alkylnitrates and peroxy radicals atSchauinsland. A possible conclusion is that the decayof precursors and production of photooxidants in urbanplumes proceeds at a faster rate than is currentlyassumed. The potential role of biogenichydrocarbons for the radical budget is alsodiscussed.  相似文献   

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