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1.
The oxidation of SO2 is commonly regarded as a major driver for new particle formation (NPF) in the atmosphere. In this study, we explored the connection between measured mixing ratio of SO2 and observed long-term (duration > 3 hr) and short-term (duration <1.5 hr) NPF events at a semi-urban site in Toronto. Apparent NPF rates (J30) showed a moderate correlation with the concentration of sulfuric acid ([H2SO4]) calculated from the measured mixing ratio of SO2 in long-term NPF events and some short-term NPF events (Category I) (R2 = 0.66). The exponent in the fitting line of J30 ~ [H2SO4]n in these events was 1.6. It was also found that SO2 mixing ratios varied a lot during long-term NPF events, leading to a significant variation of new particle counts. In the SO2-unexplained short-term NPF events (Category II), analysis showed that new particles were formed aloft and then mixed down to the ground level. Further calculation results showed that sulfuric acid oxidized from SO2 probably made a negligible contribution to the growth of >10 nm new particles.  相似文献   

2.
The oxidation of SO2 is commonly regarded as a major driver for new particle formation (NPF) in the atmosphere. In this study, we explored the connection between measured mixing ratio of SO2 and observed long-term (duration > 3 hr) and short-term (duration < 1.5 hr) NPF events at a semi-urban site in Toronto. Apparent NPF rates (J30) showed a moderate correlation with the concentration of sulfuric acid ([H2SO4]) calculated from the measured mixing ratio of SO2 in long-term NPF events and some short-term NPF events (Category I) (R2 = 0.66). The exponent in the fitting line of J30 ~ [H2SO4]n in these events was 1.6. It was also found that SO2 mixing ratios varied a lot during long-term NPF events, leading to a significant variation of new particle counts. In the SO2-unexplained short-term NPF events (Category II), analysis showed that new particles were formed aloft and then mixed down to the ground level. Further calculation results showed that sulfuric acid oxidized from SO2 probably made a negligible contribution to the growth of > 10 nm new particles.  相似文献   

3.
The content of the water-soluble fraction of power-plant fly ash from nine power plants burning brown and black coal varied in the range 0.43–1.34%. It was found, on the basis of chemical analysis and X-ray diffraction measurements, that the soluble fraction consists mostly of anhydrous CaSO4, 3MgSO4.CaSO4, Na2Ca(SO4)2 and other double sulphates. The sample from one power plant burning black coal also contained CaCO3, CaO and K2CO3. The nucleation activity of the original ash sample, the ash without the water-soluble fraction and the separated fraction was found by the methods of nucleation deposition and the freezing of water drops. These measurements demonstrated that the soluble components, which, by themselves, exhibit low nucleation activity, considerably increase the nucleation activity of the ash when associated with the ash particles.  相似文献   

4.
The acid snow/rain model [describedin Part I, Kitada et al., Atmospheric Environment27A, 1061–1076, 1993] was applied to investigate transport/transformation/deposition of acidic species in association with snow-precipitating cloud over the Japan Sea in winter. The model results showed: (1) The snow-precipitating clouds generated by relatively weak convective motions tend to trap aerosols of sulfate and nitrate and soluble gases such as SO2 and HNO3 below cloud levels, thus keeping their concentrations at higher levels than those for no-cloud situations. The mechanisms involved are: transfer of gas- and aerosol-phase species to cloud-phase through absorption and nucleation scavenging, then their transfer from cloud to snow through riming, and subsequent release from sublimating snow back to gas- and aerosol-phases below cloud base. (2) In-cloud oxidation enhanced the overall conversion of SO2 to SO42− by some 25% with respect to no-cloud situation after 12 h. Furthermore, contributions to the oxidation were 77.4%, 21.1% and 1.5% for S(IV)H2O2, S(IV)O2 with catalysts of Fe3+ + Mn2+ and S(IV)O3 reactions, respectively. (3) The sulfate wet deposited by precipitating snow for 12 h was due mostly to in-cloud scavenging and in-cloud oxidation, i.e. 66% by nucleation scavenging and the remaining by in-cloud oxidation of S(IV), while the contribution of below-cloud scavenging was negligible. (4) The adsorption process of HNO3 onto the surface of falling snow was found to account for major below-cloud scavenging of snow, and thus in contrast to SO42−, the below-cloud scavenging contributed very significantly to the nitrate wet deposition. Throughout the stimulation, below-cloud scavenging was responsible for 75% of the snow-NO3 formation. Therefore, taking account of this process in acid snow models is important.  相似文献   

5.
A time-dependent finite difference model in three levels combined with a puff model to account for subgrid effects close to single sources was used to calculate hour-to-hour concentration distributions. Measurements from several selected stations were used to account from time variation in background concentrations. For each hour, weight was given to observed values in areas that were not influenced by local sources.Results of concentration calculations based on hourly data on emission and dispersion are validated by measured time series of SO2 and NOx at five stations. A combination of hourly nephelometer readings and 12-h measurements of small particles at three stations are compared with calculated values.Hourly observed and calculated values from two periods (3 January–15 March 1988 and 18 April–24 June 1988) were used for the evaluation of the model for calculating hourly pollution concentrations in each square kilometre. The results showed that prediction of short-term average concentrations (e.g. hourly data) are usually poorly correlated with observations at the same time and location. Slight displacement errors may cause point-to-point correlation to be poor as a result of errors in input data.The pattern of NOx concentration variation with time was reproduced well at all stations. A subgrid model taking into account the influence of nearby roads would probably improved the model for NOx at some stations. For SO2 and small particles, industrial sources have the dominant influence and the correspondence between observed and calculated values were improved by taking into account spatial uncertainty and an hourly variation in background concentrations.  相似文献   

6.
SO_2是北京大气中重要的污染气体.为探讨亚太经合组织(APEC)峰会前后北京大气SO_2的垂直分布及其对二次硫酸盐(SO_4~(2-))生成的影响,我们于2014年10月21日至11月30日在地面和北京325 m气象塔260 m高度处同步开展了气体SO_2和亚微米颗粒物中硫酸盐(SO_4~(2-))实时连续在线观测.结果显示,采暖前,北京地面SO_2浓度较低,但高层由于显著受到区域输送的影响浓度较高,两层污染物变化趋势也存在明显差异.采暖后,即APEC后,受本地供暖排放影响,SO_2和SO_4~(2-)浓度显著增加,两层的总体差异也相应减小,变化趋势也更为一致.湿度对SO_2的液相转化起关键作用.我们发现近地面SO_2的转化率(SOR)显著高于260 m,这主要与地面较高的湿度相关.事实上,SOR随着湿度增加而迅速增大,进一步凸显了湿度对SO_2液相氧化的影响.另外,我们也发现SO_2特别是260 m在低湿范围(RH40%)内随湿度增加而逐渐升高,但在高湿范围(RH50%)内则呈下降趋势,说明不同湿度范围内的来源或者生成机制可能有所不同.SO_4~(2-)和PM_(2.5)浓度均随着湿度的增加而增加,但不同湿度范围,增加速率不同.通过相关性和和后向轨迹分析表明,区域输送(特别是途经北京西部和南部的气团)和本地燃煤排放分别是采暖前后污染物的主要来源.  相似文献   

7.
Time-resolved single-particle measurements were conducted during Chinese New Year in Nanning, China. Firework displays resulted in a burst of SO_2, coarse mode, and accumulation mode(100–500 nm) particles. Through single particle mass spectrometry analysis, five different types of particles(fireworks-metal, ash, dust, organic carbon-sulfate(OC-sulfate), biomass burning) with different size distributions were identified as primary emissions from firework displays. The fireworks-related particles accounted for more than70% of the total analyzed particles during severe firework detonations. The formation of secondary particulate sulfate and nitrate during firework events was investigated on single particle level. An increase of sulfite peak(80SO_3~-) followed by an increase of sulfate peaks(97HSO_4~-+ 96SO_4~-) in the mass spectra during firework displays indicated the aqueous uptake and oxidation of SO_2 on particles. High concentration of gaseous SO_2, high relative humidity and high particle loading likely promoted SO_2 oxidation. Secondary nitrate formed through gas-phase oxidation of NO_2 to nitric acid, followed by the condensation into particles as ammonium nitrate. This study shows that under worm, humid conditions, both primary and secondary aerosols contribute to the particulate air pollution during firework displays.  相似文献   

8.
The modeling of rain composition for a convective shower (Tucson, AZ, 10 September 1977) and a frontal precipitation event (Den Helder, Holland, 12 December 1978) is performed in this paper by including the pollutant species and wet scavenging mechanisms into the mass transport equation of the sequential sampling model described in Part I of this series. The results indicate that: (1) the major scavenging mechanisms of most pollutants in convective showers appear to be similar to those in frontal precipitations; (2) the major scavenging mechanisms of NH4 and NO3 are gas absorption, whereas the absorption of SO2 by aqueous drops and oxidation of S(IV) by H2O2 and O3 in the aqueous phase are the major formation and scavenging mechanisms for SO4; (3) the scavenging by raindrops in the below-cloud region is the dominant removal mechanism for coarse particles, whereas nucleation is the major scavenging mechanism for submicrometer particles; (4) H2O2 is the most important oxidant responsible for the oxidation of S(IV) and the formation of sulfate in precipitation; (5) the contributions of both (SO2 + H2O2) and (SO2 + O3) reactions to sulfate concentration in precipitation are larger for convective precipitation than for frontal precipitation.  相似文献   

9.
Meteorological and chemical conditions during the July 1988 Bermuda-area sampling appear to have been favorable for conversion of sulfur gases to particulate excess sulfate (XSO4). Observed average XSO4 and SO4 concentrations of 11 and 2.1 nmol m−3, respectively, at 15 m a.s.l. in the marine boundary layer (MBL) upwind of Bermuda, indicate that conversion of SO2 to XSO4, over and above homogeneous conversion, may be necessary to explain the > 5.0 average molar ratio of XSO4 to SO2. Given an observed cloud cover of <15% over the region and the <3 nmol m−3 SO3 concentrations observed by aircraft, heterogeneous conversion mechanisms, in addition to cloud conversion of SO2, are necessary to explain the observed 11 nmol XSO4 m−3.Aerosol water content, estimated as a function of particle size distribution plus consideration of SO2 mass transfer for the observed particle size distribution, shows that SO2 was rapidly transferred to the sea-salt aerosol particles. Assuming that aqueous-phase SO2 reaction kinetics within the high pH sea-salt aerosol water are controlled by O3 oxidation, and considering mass-transfer limitations, SO2 conversion to XSO4 in the sea-salt aerosol water occurred at rates of approximately 5% h−1 under the low SO2 concentration, Bermuda-area sampling conditions. All of the 2 nmol XSO4 m−3 associated with sea-salt aerosol particles during low-wind-speed, Bermuda-area sampling can be explained by this conversion mechanism. Higher wind speed, greater aerosol water content and higher SO2 concentration conditions over the North Atlantic are estimated to generate more than 4 nmol XSO4 m−3 by heterogeneous conversion of SO2 in sea-salt aerosol particles.  相似文献   

10.
A method for estimating the upwind SO2 emissions associated with individual wet SO42− deposition events has been developed. The relationship between these estimates and wet SO42− concentrations was examined at six Utility Acid Precipitation Study Program Sites (UAPSP) for the 1979–1986 period. Using Spearman correlation coefficients and the Bonferroni experimentwise criterion for statistical significance it was found that upwind emissions and concentrations were significantly related (p < 0.05). However, correlation's were sensitive to site location, time upwind of the emissions and season, and ranged from −0.03 to 0.50. Correlations were weaker at sites located west of the high emission region in the midwestern U.S.A. and stronger at sites further away and to the east of this region. There was a decrease in the strength of the correlations from the warm season to the cold season. It was also found that differences in meteorology between events obscured the relationship between emissions and concentrations. The effects of variations in ambient temperature and precipitation amount on wet SO42− concentrations were taken into account by calculating partial correlation coefficients. A higher percentage of the resulting correlations were found to be statistically significant and the differences between sites decreased. This suggested that meteorological variability had a confounding influence on the detection of a link between concentrations and emissions. This influence should be considered when studying source-receptor relationships.  相似文献   

11.
Sulfate, nitrate and ammonium(SNA) are the dominant species in secondary inorganic aerosol, and are considered an important factor in regional haze formation. Size-fractionated aerosol particles for a whole year were collected to study the size distribution of SNA as well as their chemical species in Shanghai. SNA mainly accumulated in fine particles and the highest average ratio of SNA to particulate matter(PM) was observed to be 47% in the fine size fraction(0.49–0.95 μm). Higher sulfur oxidation ratio and nitrogen oxidation ratio values were observed in PM of fine size less than 0.95 μm. Ion balance calculations indicated that more secondary sulfate and nitrate would be generated in PM of fine size(0.49–0.95 μm). Sulfur K-edge X-ray absorption near-edge structure(XANES) spectra of typical samples were analyzed. Results revealed that sulfur mainly existed as sulfate with a proportion(atomic basis) more than 73% in all size of PM and even higher at 90% in fine particles. Sulfate mainly existed as(NH4)2SO4 and gypsum in PM of Shanghai. Compared to non-haze days, a dramatic increase of(NH4)2SO4 content was found in fine particles on haze days only, which suggested the promoting impact of(NH4)2SO4 on haze formation. According to the result of air mass backward trajectory analysis, more(NH4)2SO4 would be generated during the periods of air mass stagnation. Based on XANES, analysis of sulfate species in size-fractionated aerosol particles can be an effective way to evaluate the impact of sulfate aerosols on regional haze formation.  相似文献   

12.
Sulfuric anhydrides,generated from the cycloaddition reaction of SO3with carboxylic acids,have been revealed to be potential participants in the nucleation process of new particle formation (NPF).Hence the reaction mechanisms of typical aromatic acids (benzoic acid (BA),phenylacetic acid (PAA),phthalic acid (PA),isophthalic acid (mPA),and terephthalic acid(PTA)) with SO3to generate the corresponding aromatic sulfuric anhydrides were investigated by density functional theory...  相似文献   

13.
兰州市大气重污染气象成因分析   总被引:18,自引:8,他引:10  
兰州市曾经是全国乃至全世界空气污染最严重的城市之一,重度空气污染特征明显.根据兰州市环境保护局公布的大气污染数据及气象局的气象观测数据,采用时间序列法和相关统计方法对兰州市2002—2011年空气污染指数(Air Pollution Index,API)大于200的大气重污染特征进行研究,并探析了其气象学成因.结果表明,静稳型重污染发生天数约占重污染发生总天数的77%,而沙尘型重污染只占23%.静稳型重污染是兰州市最主要的大气重污染类型,它往往存在PM10、SO2和NO2三种污染物同步累积的过程,持续时间长,主要发生在冬季;而沙尘型重污染持续时间短,由于外来高浓度沙尘输送的影响,PM10浓度会急剧升高,而SO2和NO2浓度则会明显下降(SO2、NO2浓度明显低于静稳型重污染),几乎都发生在春季.对它们的成因分析表明:静稳型重污染的气象学成因主要是风速小,稳定能量大,大气环境稳定度大,不利于湍流扩散,本地源污染物持续积累造成;沙尘型重污染气象学成因主要是春季气候干燥,相对湿度低,造成大风沙尘天气,给兰州市输送大量沙尘颗粒形成大气重污染.此研究结果可为兰州市大气重污染的防治提供科学依据.  相似文献   

14.
成都市冬季相对湿度对颗粒物浓度和大气能见度的影响   总被引:7,自引:5,他引:2  
刘凡  谭钦文  江霞  蒋文举  宋丹林 《环境科学》2018,39(4):1466-1472
利用成都市城区2015年12月的连续在线观测数据,如相对湿度(RH)、能见度、颗粒物(PM10、PM2.5和PM1)浓度、气态污染物(SO2和NO2)浓度以及PM2.5中SO42-和NO3-浓度,探讨RH对颗粒物浓度和大气能见度的影响.结果表明,高颗粒物浓度和高RH协同作用导致低能见度事件.观测阶段,PM2.5在PM10中的平均比重为64%,表明成都市冬季细颗粒物污染严重;随着RH增加,PM2.5/PM10显著增加,表明高RH会加重细颗粒物污染.随着PM2.5浓度增加,能见度呈幂指数下降;在相同PM2.5浓度下,RH越高,能见度越低.当颗粒物浓度较低时,RH对能见度的影响作用较强;当颗粒物浓度较高时,大气消光主要由PM2.5浓度控制,RH对能见度的影响减弱.当RH大于70%时,硫氧化率(SOR)和氮氧化率(NOR)的均值分别从0.27和0.11(RH小于40%)增长至0.40和0.19,表明较高RH对二次硫酸盐和硝酸盐的生成有显著的促进作用,二次硫酸盐和硝酸盐单独或协同影响空气质量.  相似文献   

15.
华楠  尚玥  谢鸣捷 《环境科学》2023,44(2):593-601
为了解新冠疫情期间极端减排情景下南京市PM2.5的化学组成和来源变化,对南京市2020年1~3月和2021年6~8月两次疫情管控前后PM2.5化学组分(水溶性无机离子、碳质组分和无机元素)的小时观测结果进行分析.结果表明,NO-3浓度在两次疫情管控期间比管控前分别下降52.9%和43.0%,高于NH+4(46.4%和31.6%)和SO42-(33.8%和16.5%).由于观测点位于交通干道附近,元素碳(EC)的下降幅度(35.4%和20.6%)高于有机碳(OC; 11.1%和16.2%).结合以上丰量组分特征比值的变化,推断疫情管控对交通排放的影响比工业活动更显著.各主要丰量组分浓度在疫情管控前后的连续变化过程表明,来自本地交通排放的NOx对PM2.5中NO-3的形成有重要贡献,并且是短期内本地PM2.5...  相似文献   

16.
Fe203 particle catalysts were experimentally studied in the low temperature selective catalytic reduction (SCR) of NO with NH3. The effects of reaction temperature, oxygen concentration, [NH3]/[NO] molar ratio and residence time on SCR activity were studied. It was found that Fe203 catalysts had high activity for the SCR of NO with NH3 in a broad temperature range of 150-270℃, and more than 95% NO conversion was obtained at 180℃ when the molar ratio [NH3]/[NO] = 1, the residence time was 0.48 seconds and 02 volume fraction was 3%. In addition, the effect of SO2 on SCR catalytic activity was also investigated at the temperature of 180℃. The results showed that deactivation of the Fe2O3 particles occurred due to the presence of SO2 and the NO conversion decreased from 99.2% to 58% in 240 min, since SO2 gradually decreased the catalytic activity of the catalysts. In addition, X-ray diffraction, Thermogravimetric analysis and Fourier transform infrared spectroscopy were used to characterize the fresh and deactivated Fe2O3 catalysts. The results showed that the deactivation caused by SO2 was due to the formation of metal sulfates and ammonium sulfates on the catalyst surface during the de-NO reaction, which could cause pore plugging and result in suppression of the catalytic activity.  相似文献   

17.
PM2.5和O3浓度超标是我国大气污染的主要特征,研究两种典型污染时段的细颗粒化学组成、混合状态和来源对治理大气污染具有重要意义.2016年11月10—20日广东省鹤山市先后出现了PM2.5和O3超标的污染事件.污染期间,采用SPAMS(单颗粒气溶胶质谱仪)对细颗粒进行实时采样分析,共采集到有正负化学组成信息的颗粒422 944个,占总颗粒数的19.2%.基于单颗粒质谱数据特征,使用自适应共振神经元网络算法(ART-2a),对单颗粒数据进行自适应分类.颗粒物划分为OC(有机碳)、EC(元素碳)、ECOC(元素-有机碳混合)、HOC(高分子有机碳)、Pb-rich(富铅)、Si-rich(富硅)、LEV(左旋葡聚糖)、K-Secondary(钾二次)、Na-rich(海盐)和HM(重金属)颗粒共10类.结果表明:两个PM2.5污染时段EC颗粒和K-Secondary颗粒的占比高,EC颗粒分别占46.5%和61.1%,K-Secondary颗粒分别占14.3%和10.3%;O3污染时段EC颗粒占比(39.4%)最高,其次是OC颗粒占比17.0%;两种污染时段OC组分与HSO4-和NO3-的混合程度都有明显的上升,说明污染有利于有机气溶胶的老化.由源解析结果可知,PM2.5污染时段,细颗粒主要来源于燃煤、机动车尾气和扬尘,而O3污染时段细颗粒主要来源于燃煤、生物质燃烧和扬尘;此外,两种污染时段燃煤源对细颗粒的贡献都有较大提升.研究显示,控制燃煤源的排放对污染物的降低有着重要影响.   相似文献   

18.
In this study, the effects of a diesel oxidation catalyst (DOC) coupled with a catalyzed diesel particulate filter (CDPF) with different catalyst loadings on the power, fuel consumption, gaseous and particulate emissions from a non-road diesel engine were investigated. Results showed that the after-treatment had a negligible effect on the power and fuel consumption. The reduction effect of the DOC on the CO and hydrocarbon (HC) increased with the engine load. Further reductions occurred coupling with the CDPF. Increasing the catalyst loading resulted in a more significant reduction in the HC emissions than CO emissions. The DOC could increase the NO2 proportion to 37.9%, and more NO2 was produced when coupled with the CDPF below 250°C; above 250°C, more NO2 was consumed. The after-treatment could reduce more than 99% of the particle number (PN) and 98% of the particle mass (PM). Further reductions in the PN and PM occurred with a higher CDPF catalyst loading. The DOC had a better reduction effect on the nucleation particles than the accumulation ones, but the trend reversed with the CDPF. The DOC shifted the particle size distribution (PSD) to larger particles with an accumulation particle proportion increasing from 13% to 20%, and the geometric mean diameter (GMD) increased from 18.2 to 26.0 nm. The trend reversed with the CDPF and the accumulation particle proportion declined to less than 10%. A lower catalyst loading on the CDPF led to a higher proportion of nucleation particles and a smaller GMD.  相似文献   

19.
二氧化硫胁迫下拟南芥miRNA表达谱分析   总被引:1,自引:0,他引:1  
以拟南芥为材料,利用高通量测序技术并结合生物信息学分析方法,检测二氧化硫(SO_2)处理后拟南芥植株的小分子RNA表达谱,筛选SO_2胁迫响应microRNAs(miRNAs)分子,研究植物miRNAs对逆境胁迫的应答机制.结果发现,30 mg·m~(-3) SO_2处理72 h后,拟南芥地上组织小分子RNA长度分布发生改变,在对照组和SO_2组中均有大量特有的小分子RNA序列,说明SO_2胁迫可诱导拟南芥小分子RNA的表达改变.SO_2胁迫诱导186个保守miRNA和16个新miRNA分子差异表达,其靶基因主要涉及转录调控、信号转导、代谢、刺激响应等生理过程.差异表达的miR160和miR393可通过生长素信号途径调控植株生长发育,参与植物对SO_2的胁迫响应.本研究揭示了植物中参与SO_2胁迫应答的miRNA种类及作用机制,进一步阐明了miRNAs在植物抗逆应答过程中的作用.  相似文献   

20.
Ozone (O3) is an important atmospheric oxidant. Black carbon (BC) particles released into the atmosphere undergo an aging process via O3 oxidation. O3-aged BC particles may change their uptake ability toward trace reducing gases such as SO2 in the atmosphere, leading to different environmental and health effects. In this paper, the heterogeneous reaction process between O3-aged BC and SO2 was explored via in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Combined with ion chromatography (IC), DRIFTS was used to qualitatively and quantitatively analyze the sulfate product. The results showed that O3-aged BC had stronger SO2 oxidation ability than fresh BC, and the reactive species/sites generated on the surface had an important role in the oxidation of SO2. Relative humidity or 254 nm UV (ultraviolet) light illumination enhanced the oxidation uptake of SO2 on O3-aged BC. The oxidation potentials of the BC particles were detected via dithiothreitol (DTT) assay. The DTT activity over BC was decreased in the process of SO2 reduction, with the consumption of oxidative active sites.  相似文献   

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