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1.
The rate of deposition of reactive gaseous pollutants onto indoor surfaces is examined, taking into account mass transport processes and the kinetics of gas-surface interactions. A conceptual model for predicting indoor deposition velocities is proposed, and approximate analysis based on this model is used to obtain algebraic expressions for the deposition velocity of reactive gases under three model airflow conditions: (1) forced laminar convection parallel to a flat plate, (2) laminar natural convection flow along an isothermal vertical plate, and (3) homogeneous turbulence in an enclosure. Numerical simulations are used to refine the approximate analysis results and to predict reactive gas deposition under laminar natural convection flow in an enclosure. The kinetics of gas-surface interactions are modeled in terms of the reaction probability γ, defined as the fraction of pollutant molecular collisions with a surface that result in irreversible removal. Values of γ for the reaction of ozone with surfaces are obtained from published reaction chamber and tube penetration experiments. For common indoor materials, values range from as low as O(10−7) for glass and aluminium to O(10−5–10−4) for materials such as bricks, concrete and latex paint. Our results indicate that ozone deposition occurs at the transport-limited rate when γ > − 3 × 10−4 for typical indoor air flow conditions, and that ozone deposition can be predicted by surface kinetics alone if γ < ∼ 5 × 10−7.  相似文献   

2.
Methyl nitrate, CH3ONO2, was measured by electron capture gas chromatography (EC-GC) under conditions which allowed resolution of methyl nitrate, PAN, and several chlorinated hydrocarbons. Calibrations involved both EC-GC andNOx chemiluminescence and were in agreement with independent calibrations involving i.r. spectroscopy. The rate constant for photolysis of methyl nitrate in sunlight was< 2.3 × 10−6s−1. Detection limits of field instruments were 0.1–0.4 ppb. Some 3000 EC-GC chromatograms grams of ambient air recorded between June and December 1987, during the Southern California Air Quality Study (SCAQS) at up to nine Southern California locations yielded only seven possible, but unlikely observations of methyl nitrate. Thus, methyl nitrate was only a minor component among nitrogenous air pollutants during SCAQS. The measured CH3ONO2/PAN ratios of<0.003–0.2 during SCAQS are discussed in terms of available kinetic data for PAN unimolecular decomposition (a major source of methyl nitrate), PAN thermal decomposition and CH3ONO2 photolysis.  相似文献   

3.
甲醛(HCHO)是大气光化学重要污染物之一,为研究西南地区郊区大气夏季甲醛污染特征选取了四川省成都市新津区进行大气甲醛观测,结合NOx、O3、PAN、J-value、温湿度、风速风向、天气数据进行分析.观测期间成都市新津区夏季甲醛浓度为0.76×10-9~12.50×10-9V/V),均值为3.47×10-9±2.05×10-9V/V),呈现明显的日变化规律.结合数据分析可知,一次人为排放源在成都郊区夏季日间甲醛贡献中占比较低.观测期间甲醛受光照的影响较大,与O3、PAN、J-value普遍呈现一致的变化规律,因此成都市夏季日间甲醛主要来源为甲醛前体物的二次光化学反应.  相似文献   

4.
臭氧在冰晶及硫酸铵和亚硫酸铵渗溶冰晶上的粘着系数   总被引:3,自引:0,他引:3  
利用流动管式反应器,在220-260K温度范围内,实验测量了臭氧在低温冰晶及硫酸铵和亚硫酸铵渗溶冰晶表面上的粘着系数.结果表明:臭氧在低温冰晶表面上的粘着系数随温度升高而增大, 其粘着系数为1.3×10-7-2.7×10-6; 臭氧在硫酸铵和亚硫酸铵渗溶冰晶表面上的粘着系数与二者浓度呈非线性关系; 利用实验结果估算了臭氧在极地平流层云中存留寿命约为56d, 臭氧在主要组成为水的冰晶表面上的损耗不容忽视.  相似文献   

5.
Previous measurements of peroxyacetyl nitrate(PAN) in Asian megacities were scarce and mainly conducted for relative short periods in summer. Here, we present and analyze the measurements of PAN, O3, NOx, etc., made at an urban site(CMA) in Beijing from 25 January to 22 March 2010. The hourly concentration of PAN averaged 0.70 × 10 9mol/mol(0.23 × 10 9–3.51 × 10 9mol/mol) and was well correlated with that of NO2but not O3, indicating that the variations of the winter concentrations of PAN and O3in urban Beijing are decoupled with each other. Wind conditions and transport of air masses exert very significant impacts on O3, PAN, and other species. Air masses arriving at the site originated either from the boundary layer over the highly polluted N-S-W sector or from the free troposphere over the W-N sector. The descending free-tropospheric air was rich in O3, with an average PAN/O3ratio smaller than 0.031, while the boundary layer air over the polluted sector contained higher levels of PAN and primary pollutants, with an average PAN/O3ratio of 0.11. These facts related with transport conditions can well explain the observed PAN-O3decoupling. Photochemical production is important to PAN in the winter over Beijing. The concentration of the peroxyacetyl(PA) radical was estimated to be in the range of 0.0014 × 10 12–0.0042 × 10 12 mol/mol. The contributions of the formation reaction and thermal decomposition to PAN's variation were calculated and found to be significant even in the colder period in air over Beijing, with the production exceeding the decomposition.  相似文献   

6.
Scavenging of sulfates and nitrates—two most common ions leading the cloudwater acidity—was investigated during field studies atop a site in Mt. Mitchell (35°44′05″N, 82°17′15″W) State Park where the highest peak (2038 m MSL) of the eastern U.S. is located. Experiments were conducted during the growing seasons (15 May–30 September) of 1986 and 1987 using an instrumented meteorological tower (16.5 m tall) and a passive cloudwater collector. A cloud episode that occurred on 12 October 1987, was also comprehensively investigated. Clouds were frequently observed in which the Fraser fir and red spruce stands stayed immersed 28% and 41% of the time during the 1986 and 1987 seasons, respectively. Rate of cloudwater deposition on the forest canopy was determined using an inferential cloud deposition model. It was found by analysing nine short duration (lasting 8 h or less) and 16 long duration cloud events that the ionic concentration (SO42− and NO3) is inversely proportional to the rate (Ic) of cloudwater deposition (in mm h−1) and can be expressed by the following relationship: [SO42−] = aIcb or [NO3] = aIcb. Theoretical arguments leading to these relationships are presented. The b values for predicting NO32− concentration are found in the range of 0.14–1.24 (mean = 0.48) for short duration and 0.062–0.63 (mean = 0.27) for long duration cloud events, respectively. The corresponding b values for predicting NO3 concentrations are 0.19–1.16 (mean = 0.49) and 0.072–0.59 (mean = 0.27), respectively. When the b parameter was between 0.2 and 0.6, the correlation coefficients between measured and predicted ionic concentrations were found to exceed 0.7. The parameter a is shown to represent the maximum ionic flux for a given cloud event. The ratio of the a parameter for SO42− to NO3 varied between 1.75 and 6.95, indicating that the SO42− contributes to the total ionic concentration substantially more than the NO3 leading to the conclusion that the cloudwater acidity is primarily due to the presence of sulfuric acid which has been demonstrated to cause foliar injury and growth retardation in red spruce trees. The above parameterization is similar to the one that is frequently used to relate ionic concentration in precipitation to the rainfall rate. In order to understand physico-chemical processes leading to the proposed parameterization schemes, meteorological and chemical variables are comprehensively analysed for one short duration and two long duration cloud events. The concentrations of principal ions (SO42−, NO3, H+ and NH4+) during the short duration cloud events were found to be much higher than those during the long duration ones, especially at colder temperatures. Such short cloud events have a potential of causing foliar narcosis in red spruce stands because of unusually acidic cloudwater to which these stands stay exposed intermittently during each growing season.  相似文献   

7.
We have measured, using a conventional discharge-flow resonance-fluorescence technique, the rates of reaction between the hydroxyl radical and a series of halogenated ethanes and ethers for the temperature range 230–423 K. Our measurements gave the following Arrhenius expressions (units are cm3 molecule−1 s−1): CF2HCH3 (HFC-152), 14.2 × 10−13 exp-(1050/T); CF2ClCH3 (HCFC-142b), 2.6 × 10−13 exp-(1230/T); CFCl2CH3 (HCFC-141b), 5.8 × 10−13 exp-(1100/T); CF3CFH2 (HFC-134a), 5.8 × 10−13 exp-(1350/T); CF3CF2H (HFC-125), 2.8 × 10−13 exp-(1350/T); CF3CCl2H (HCFC-123), 11.8 × 10−13 exp-(900/T); CF2HOCF2CFClH, (enflurane), 6.1 × 10−13 exp-(1080/T); CFH2OCH(CF3)2, (sevoflurane), 15.3 × 10−13 exp-(900/T). In two cases, we measured rate constants only at room temperature: CF3CClBrH (halothane), 6 × 10−14 and CF2HOCClHCF3 (isoflurane), 2.1 × 10−14.We also report the following values for the integrated absorption cross-sections of the compounds in the spectral region 800–1200 cm−1 in units of cm−2 atm−1: CF2HCH3, 1155; CF2ClCH3, 1422; CFCl2CH3, 1995; CF3CFH2, 2686; CF3CF2H, 1970, CF3CCl2H, 1411; CF3CClBrH, 1400; CF2HOCF2CFClH, 4800; CF2HOCClHCF3, 3900; CFH2OCH(CF3)2, 2550. We use our measurements to calculate ozone depletion potentials and greenhouse warming potentials relative to CFCl3 for each compound.  相似文献   

8.
Twenty-eight radiochemical 14C tracer measurement of tropospheric hydroxyl radical (OH) concentrations were obtained at a rural site near Washington State University, Pullman, WA (117°W, 47°N). Diurnal OH concentration variations were observed for the five days between 9 August and 14 August 1990. These data made it possible to estimate the midday precision and detection limit of the radiochemical OH measurement method. Experiments performed at a peak O3 photolysis rate J (O(1D)) of (3.0±0.2) × 10−5 s−1 yielded a mean midday OH concentration of (5.6±0.1 (1σ)) × 106 cm−3. Other data put an upper bound of 16% on fluctuations of instrument sensitivity. Low-light or nighttime background OH concentrations were less than (2.6±2) × 105 cm−3. A lower detection limit of 105 cm−3 was obtained when extra care was taken with the low-level 14C counting procedure.  相似文献   

9.
By using a 4-m3 chamber, photochemical aerosol formation from mixtures of aromatic hydrocarbons (AHCs) and nitrogen oxides (NOx) was studied with the main purpose of determining the aerosol yield. Altogether, 18 aromatic species were investigated, including toluene, xyluene, xylenes, ethylbenzene and methoxybenzene. Evolution of the aerosol was monitored through the measurement of the total number ([CN]) and volume (V) concentrations. Aerosol-forming potential of different aromatics was examined in terms of the maximum growth rates of [CN] and V. By putting dry sheath air into an electrical aerosol analyzer, the net organic volume concentration (Vd) was obtained; then a relation was established between Vd and the C mass concentration, and was used to determine the aerosol yield as defined by the ratio of the particulate C mass to the C mass of the reacted HC. It was found that the yields were larger for toluene, ethylbenzene, and o- and m-ethyltoluene (3.0, 3.1, 3.3 and 3.7%, respectively) but smaller for para-substituted toluene derivatives (< 1.5%).  相似文献   

10.
Atmospheric dry deposition of ions to branches of native Pinus contorta and Pinus monticola (natural surfaces), and nylon filters and Whatman paper filters (surrogate surfaces) were measured in the summer of 1987 in the vicinity of Emerald Lake Watershed (ELW) of the Sequoia National Park located on the western slope of the Sierra Nevada in California. Deposition fluxes of airborne NO3, NH+4 and SO2−4 to native pines at the ELW were much higher than in the eastern Sierra Nevada, but several times lower than deposition fluxes to natural and surrogate surfaces at the highly polluted site in the San Gabriel Mountains of southern California. Deposition fluxes of NO3 and NH4+ to the natural and surrogate surfaces at the ELW were much higher than deposition of SO42−, providing the importance of N compounds in atmospheric dry deposition in this part of the western U.S. A deficit of inorganic anions in materials deposited to various surfaces indicated a possibility of substantial participation of organic acids in atmospheric dry deposition processes. Nylon and paper filters proved to be poor surrogate surfaces for the estimation of ionic dry deposition to conifer branches.  相似文献   

11.
The rate constants for the gas-phase reactions of sabinene and camphene, two monoterpenes emitted from vegetation, with OH and NO3 radicals and O3 have been determined at 296±2 K and one atmosphere total pressure of air. The OH and NO3 radical reaction rate constants were determined using relative rate techniques. Using rate constants of k(OH + isoprene) = 1.01 × 10−10 cm3 molecule−1 s−1, k(NO3 + trans-2-butene) = 3.87 × 10−13 cm3 molecule−1 s−1 and k(NO3 + 2-methyl-2-butene) = 9.33 × 10−12 cm3 molecule−1 s−1, the following OH and NO3 radical reaction rate constants (in cm3 molecule−1 s−1 were obtained: OH radical reaction; sabinene, 1.17 × 10−10 and camphene, 5.33 × 10−11; NO3 radical reaction; sabinene, 1.01 × 10−11, and camphene, 6.54 × 10−13. The absolute O3 reaction rate constants determined were (in cm3 molecule−1 s−1 units): sabinene, 8.07 × 10−17, and camphene, 9.0 × 10−19. These rate constants are compared to literature data for other structural-related alkenes and monoterpenes.  相似文献   

12.
Aerosol light absorption (babs) has been measured in real-time in Los Angeles with a validated photoacoustic technique, and its impact on visibility degradation has been examined. These measurements were collected during ten days in the summer of 1987 for the Southern California Air Quality Study (SCAQS). Aerosol babs (λ = 514.5 nm) varied from an hourly average value of 7 × 10−6 m−1 in the 3–4 and 4–5 a.m. periods of 13 July to 9 × 10−5 m−1 in the 7–8 a.m. period of both 28 August and 3 September. This babs, which is due solely to elemental carbon (EC) showed a distinct diurnal pattern with low values at night, increasing around sunrise to higher values through mid-afternoon. Comparison of these data with aerosol light scattering data clearly illustrates that the contribution of aerosol light absorption to visibility degradation increases in importance under less polluted conditions. Other urban and rural studies show similar results.  相似文献   

13.
Porous S-doped bismuth vanadate with an olive-like morphology and its supported iron oxide (y wt.% FeOx/BiVO4-δS0.08, y = 0.06, 0.76, and 1.40) photocatalysts were fabricated using the dodecylamine-assisted alcohol-hydrothermal and incipient wetness impregnation methods, respectively. It is shown that the y wt.% FeOx/BiVO4-δS0.08 photocatalysts contained a monoclinic scheetlite BiVO4 phase with a porous olive-like morphology, a surface area of 8.8-9.2 m^2/g, and a bandgap energy of 2.38-2.42 eV. There was co-presence of surface Bi^5+, Bi^3+, V^5+, V^3+, Fe^3+, and Fe^2+ species in y wt.% FeOx/BiVO4-δS0.08. The 1.40 wt.% FeOx/BiVO4-δS0.08 sample performed the best for Methylene Blue degradation under visible-light illumination. The photocatalytic mechanism was also discussed. We believe that the sulfur and FeOx co-doping, higher oxygen adspecies concentration, and lower baudgap energy were responsible for the excellent visible-light-driven catalytic activity of 1.40 wt.% FeOx/BiVO4-δS0.08.  相似文献   

14.
Atmospheric dry deposition to branches of Pinus contorta and P. albicaulis was measured during summer 1987 in a sub-alpine zone at Eastern Brook Lake Watershed (EBLW), eastern Sierra Nevada, California. Results are presented as deposition fluxes of NO3, SO42−, PO43−, Cl, F, NH4+, Ca2+, Mg2+, Na+, K+, Zn2+, Fe3+, Mn2+, Pb2+ and H+, and compared with other locations in California and elsewhere. Deposition fluxes of anions and cations to the pine branches were low, several times lower than the values determined near the Emerald Lake Watershed (ELW), another sub-alpine location in the western Sierra Nevada. The sums of deposition fluxes of the measured cations and anions to pine surfaces were similar, in contrast to the ELW location where the sums of cation fluxes were much higher than the sums of anion fluxes. A strong positive correlation between depositions of NO3 and NH4+, as well as SO42− and Ca2+, suggested that large portions of these ions might have originated from particulate NH4NO3 and CaSO4 deposited on pine surfaces. An estimated total N dry deposition (surface deposition of NO3 and NH4+ and internal uptake of NO2 and HNO3) to the forested area of the EBLW was 29.54 eq ha−1 yr (about 414 g H ha−1 yr−1).  相似文献   

15.
大气中丙烷光氧化臭氧生成活性的烟雾箱模拟   总被引:1,自引:1,他引:0  
黄丽华  莫创荣  徐永福  贾龙 《环境科学》2012,33(8):2551-2557
利用自制光化学烟雾箱模拟了丙烷和NOx大气光化学反应,研究了相对湿度以及丙烷与NOx初始浓度比值对臭氧生成的影响.实验表明,臭氧最大值及丙烷的臭氧生成活性最大值(IRmax)都随相对湿度的增大而减小.低相对湿度时,臭氧最大值大约出现在反应的22 h,IRmax变化范围为0.023 1~0.039 1;而高相对湿度时,臭氧最大值大约出现在反应的16 h,IRmax变化范围为0.017 2~0.032 0.在反应的20 h内,前12 h内相对湿度对丙酮的生成量影响不大,12 h后低相对湿度时丙酮生成量更大.在实验的4~20 h内,相对湿度为17%时,丙酮浓度为153×10-9~364×10-9;而相对湿度为62%时,丙酮浓度为167×10-9~302×10-9.臭氧最大值随着丙烷与NOx初始浓度比值增加而减少,在低相对湿度时线性负相关性更好.另外,还利用了MCM丙烷子机制对反应进行了数值模拟,并与实验结果进行比较,发现两者还存在较大的偏差.  相似文献   

16.
采用在线仪器监测分析2017年夏季天津气象铁塔220 m观测平台大气中过氧乙酰硝酸酯(PAN)和O_3的体积分数,并结合气象观测资料和后向轨迹分析PAN和O_3的输送特征.观测期间PAN和O_3体积分数平均值分别为(0.73±0.56)×10~(-9)和(53±25)×10~(-9),最大小时体积分数分别为3.49×10~(-9)和137×10~(-9),PAN和O_3体积分数具有相似的日变化特征,白昼PAN和O_3浓度高于夜间,且PAN和O_3浓度相关系数(R2=0.52)显著高于夜间(R2=0.21).观测期间偏南风下PAN和O_3浓度最高,偏东风下最低,风玫瑰图和后向轨迹聚类分析都表明,来源于西南方向的气流轨迹对应的污染物浓度最高,途经渤海和河北、辽宁沿海地区的偏东气流对应的PAN和O_3体积分数最低,边界层内输送对PAN和O_3的体积分数分布起到了重要作用.  相似文献   

17.
The evaporation rates of ammonium chloride and ammonium nitrate were measured by continuously and rapidly removing gaseous NH3 and HNO3 or HCl from aerosols in an annular denuder. The experiments gave the evaporation rates in terms of mass loss of chloride or nitrate which can be expressed conveniently as the rates of reduction of aerosol radius with time. Both dry aerosols (humidity 30–60% r.h.) and aqueous aerosols (humidity ca 97% r.h.) were studied. Dry aerosols evaporate at rates of −1.05 Å s−1 for NH4Cl and −0.45Å s−1 for NH4NO3, while the evaporation rates of aqueous aerosols expressed as for equivalent dry particles are −4.52 Å s−1 for NH4Cl and −0.49 Å s−1 for NH4NO3. The experimentally measured rates are independent of particle radius and remarkably low compared with those predicted from existing theories of aerosol evaporation, thus implying that there is an unknown kinetic constraint to the achievement of equilibrium at atmospheric temperature and pressures.  相似文献   

18.
北京城区夏季O3化学生成过程   总被引:3,自引:2,他引:1  
选取2007年7月1日—8月31日中的21个晴空日,利用观测资料和光化学箱模式计算了北京城区测点的O3生成速率G(O3)和O3生成效率OPE.结果表明,21个晴空日中G(O3)日最高小时值分布在(18~82)×10-9h-1之间;在O3污染和非污染日G(O3)最高值的平均水平无显著差异,且与Ox浓度之间不存在一致的对应关系,表明O3化学生成过程不能全面解释地面O3浓度的累积,物理传输过程对测点O3实测浓度有显著作用;各个化学过程对G(O3)的贡献率对比结果显示,HO2 在 NO向NO2的转化中贡献最大;OPE值分布在2.8~5.8之间,总体水平为4.1±0.1;OPE值与NOx浓度之间为非线性关系,OPE值随NOx浓度的增加而减少,表明消减测点附近VOCs排放能有效降低O3浓度.  相似文献   

19.
Concentrations of S(IV) were measured in cloudwater at Great Dun Fell and compared with theoretical HSO3 assuming equilibrium between aqueous and gaseous phases in cloud. Detectable concentrations of S(IV) in the range of 1 × 10−6 to 17.2 × 10−6 mol dm−3 were observed only in samples which contained low H2O2 concentrations, generally <1 × 10−6 mol dm−3. Concentrations of S(IV) were below the detection limit of 1 × 10−6 mol dm−3 in samples which contained hign H2O2 levels (1 × 10−6−80 × 10−6 mol dm−3) confirming that either SO2 or H2O2 acts as the limiting reagent in the oxidation of SO2 in cloudwater.Equilibrium HSO3 concentrations were estimated from the measured cloudwater pH, the gas phase SO2 concentration and the ambient temperature and found to be on average about 5 times lower than the measured S(IV) concentrations. The possible role of formaldehyde in stabilizing S(IV) in cloudwater is discussed. The kinetic data available in the literature suggest that the complexation reaction between S(IV) and HCHO is too slow to account for the observed difference between measured and calculated S(IV) concentrations over the typical lifetime of clouds in our study.S(IV) accounted for up to 10% of the SO42− measured in stored cloudwater samples.  相似文献   

20.
邹宇  邓雪娇  李菲  殷长秦 《环境科学》2019,40(4):1634-1644
通过对广州番禺大气成分站(GPACS)的光化学相关污染物(O3、PAN、VOCs、NO2、NO)以及气象要素进行观测,分析2010~2016年期间发生在广州地区一次典型光化学污染过程.结果表明,该光化学污染过程期间,O3和PAN总体体积分数比较高,最大O3小时体积分数为140.6×10-9,而最大PAN小时体积分数为4.7×10-9.NO整体体积分数较低,对O3的化学滴定和PAN的去除影响较小.NO2整体体积分数较高、辐射较强和风速较低则有利于O3和PAN的形成和积累.PAN和O3具有一定的线性关系(R2=0.55),而形成PAN和O3前体物VOCs物种不完全相同影响着它们的线性关系,在生成PAN的VOCs物种中,乙烯、丙烷、异戊二烯和甲苯所占的比例较大,而对臭氧生成潜势较大的物种有异戊二烯、1,3,5-三甲苯、丙烯、间,对-二甲苯以及甲苯.对PA自由基体积分数进行估算,发现它的日均值体积分数在0.11×10-12~0.16×10-12范围变化,远高于其它地区,表明此次发生的光化学反应较为强烈.  相似文献   

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