春季黄海边界层内海盐细粒子氯亏损及混合状态研究

为了解海盐气溶胶和亚洲出流污染物的相互影响,对2001年春季黄海边界层内观测的气溶胶细粒子可溶离子浓度(AGE-Asia中NCAR C-130飞机航测)进行了研究.所分析的6个航段(航段1～航段6)都位于黄海中部(124.0°E～125.1°E,34.3°N～36.4°N)的大气边界层内.离子摩尔比和相关分析表明,在所...     

The spatial distribution and particle size of some inorganic nitrogen,sulphur and chlorine species over the North Sea

The use of filter packs and a cascade impactor during a series of research cruises in the southern area of the North Sea has yielded detailed spatial distribution patterns of aerosol concentrations, Cl⁻, NO₃⁻, SO₄²⁻¹ and NH₄⁺ and gaseous concentrations, HCl, HNO₃ and NH₃. The overall distribution of the atmospheric concentrations closely parallels published modelled results for metallic species. The chemical transformations of these aerosols and gases are investigated together with their interactions with the seasalt aerosol. Aerosol chloride loss is greatest in the more polluted areas, whilst concentrations products of NH₃ with HNO₃ and HCl appear insufficient to sustain the existence of NH₄NO₃ and NH₄Cl. Nitrate is associated predominantly with larger particles and appears to be present substantially as a surface coating on marine aerosol. The total dry deposition input for nitrogen species is calculated for the southern sector with extrapolation to the whole of the North Sea, using particle size weighted deposition velocities of 0.63 and 0.21 cm s⁻¹ for NO₃⁻¹ and NH₄⁺, respectively, and literature-derived values for the gaseous constituents. Finally the use of air-mass back trajectories illustrates the role of source regions in influencing the chemical composition of the North Sea atmosphere.     

The removal of nitric acid to atmospheric particles during a wintertime field study

A field was conducted in Warren, MI, during the 1987/88 winter period to examined the reaction of HNO₃ with particulate salt from road deicing. Samples of gases and particles were collected on a daily basis over a 4-month period. If HNO₃ reacts with particulate salt, particles of sodium nitrate will be formed and gaseous hydrochloric acid will be released. Thus, during the periods of high salt concentrations, one would expect increases in HCl and particulate NO₃⁻ and a decrease in HNO₃. The effect was observed, although the total amount of NaNO₃ formed was not large. The increase in particulate NO₃⁻ did not appear in the large particle mode. Although more than 40% of the salt was present as very large particles (> 8 μm), most of the surface area was associated with small particles. Since the reaction occurred at the particle surface, the NO₃⁻ appeared in the small particle mode. Large-particle nitrate has been observed in association with sea salt and crustal particles and has also been attributed to reactions with HNO₃. These cases will be reconsidered based on the road salt results.     

厦门春季气溶胶特征初探

1993年春季对厦门市大气气溶胶进行了研究,其中包括对3种不同粒径的气溶胶质量浓度?气溶胶元素浓度?气溶胶离子浓度?气溶胶酸度和酸化缓冲能力的研究?结果表明:厦门大气气溶胶质量浓度接近于国家一级标准,细粒子的气溶胶的贡献较高;气溶胶中元素含量较高的为Ca,Al,Fe和S等;在厦门地区气溶胶中NH+₄和SO2-₄主要分布在细粒子中,Ca2+和Mg2+则多分布在粗粒子中,并且其值远小于华南地区;气溶胶中细粒子的酸性大于粗粒子,且酸化缓冲能力远低于粗粒子。      

Kinetics of evaporation of ammonium chloride and ammonium nitrate aerosols

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.     

Formic acid and acetic acid measurements during the Southern California Air Quality Study

As part of the Southern California Air Quality Study (SCAQS), ambient levels of gas phase formic acid and acetic acid have been measured at four locations: a ‘control’ site (San Nicholas Island), a source-dominated coastal site (Long Beach) and two inland smog receptor sites (Claremont and Palm Springs). Samples were collected on alkaline traps and were analyzed by size exclusion liquid chromatography with ultraviolet detection. Levels of gas phase formic acid (up to 19 ppb) and acetic acid (up to 17 ppb) exhibited diurnal (frequent night-time maxima), spatial and seasonal variations. During summer smog episodes, concentrations increased from 0.6 ppb at the ‘control’ site to up to 13–19 ppb at the inland smog receptor sites reflecting primary emissions and in situ formation during transport inland. The acetic acid/formic acid (A/F) ratio decreased from coastal to inland sites. At the coastal site levels of both acids and the A/F ratio were substantially higher during the fall than during the summer.     

Scavenging ratios and deposition of sulphur,nitrogen and chlorine species in eastern England

Measurements of wet deposited NH₄⁺, SO₄²⁻, NO₃⁻ and Cl⁻, as well as airborne concentrations of these species and gaseous HNO₃, HCl and NH₃, have been made at a site in eastern England. Scavenging ratios based solely upon aerosol-associated species and upon aerosol plus gaseous airborne species are presented and compared with literature values. It appears that HCl and HNO₃ have only a rather minor influence upon wet deposition at our site. Gaseous NH₃ influences ground-level air chemistry appreciably, but scavenging ratios for NH₄⁺ are low, even when based upon aerosol NH₄⁺ concentrations alone, presumably due to altitudinal gradients in this species. The problems inherent in interpretation of scavenging ratios are discussed. Deposition of nitrogen in various chemical forms is estimated from rainwater and air composition. If a transport-limited deposition velocity is assumed for ammonia gas, dry deposition of this species accounts for around 40% of total nitrogen deposition to the ground.     

Kinetic and thermodynamic behaviour of volatile ammonium compounds in industrial and marine atmospheres

Measurements of volatile ammonium aerosol compounds and respective acidic and basic gaseous precursors were taken at an industrial site emitting HCl, HNO₃ and NH₃ and at a marine suburban location.Because of fresh industrial emissions the gaseous acid and base concentration products show values orders of magnitude higher than thermodynamic equilibrium previsions, at the industrial site. To our knowledge these are the first published field measurements that strongly confirm that gas-particle equilibrium conditions are not attained instantaneously in the atmosphere and that kinetic constraints play an important role on gas-particle conversion for ammonium chloride and ammonium nitrate compounds. The results permit to conclude that, for temperature conditions lower than 15°C, transformation rates are not high, several minutes being necessary, at least, for the equilibrium between gaseous precursors and ammonium particulate products to be reached.At the marine suburban location a diurnal variation was observed for gaseous and particulate compounds in agreement with known emission and transformation mechanisms. The behaviour of nitric and hydrochloric acids in the marine atmosphere can be better explained if kinetic limitations are considered for the reaction of HNO₃ with NaCl aerosol particles and for the transference of acids and ammonia to the particulate phase.     

Wintertime measurements of aerosol acidity and trace elements in Wuhan,a city in central China

A 2-week intensive ambient aerosol study was conducted in December 1988 in Wuhan (Hubei Province), a city of nearly 2 million located on the Yangtze River in central China (P.R.C.). This is an industrial region where soft coal burning is widespread, and emission controls for vehicles and industrial facilities are minimal. The sampling site was located in one of the civic centers where residential and commercial density is highest. An Andersen dichotomous sampler was operated with Teflon membrane filters to collect fine (d_p < 2.5 μmad) and coarse (2.5 ⩽ d_p < 10 μmad) particles for total mass and element determinations. An annular denuder system (ADS) was used to collect fine fraction aerosols for analyses of ionic species including strong acidity (H⁺).The study was conducted between 18 and 30 December, which was rainless, consistently cool (3–10°C) and overcast, but without fog or acute stagnation. Fine particulate mass (PM, as μ m⁻³) averaged 139 (range 54–207); coarse PM averaged 86 (range 29–179). Trace element concentrations were also high. Crustal elements (Si, Al, Ca and Fe) were found primarily in the coarse fraction, while elements associated with combustion (S, K, Cl, Zn and Se) were enriched in the fine fraction. The concentrations of arsenic and selenium were evidence of a large source of coal burning, while vanadium levels (associated with fuel oil use) were not especially enriched.Despite the seemingly high PM loadings, ionic concentrations were not especially high. The average composition of soluble fine aerosol species (in neq m⁻³) were SO₄²⁻: 520 (range 180–980), NO₃⁻: 225 (range 50–470), Cl⁻: 215 (range 20–640), and NH₄⁺: 760 (range 280–1660). A deficit in accountable FP components (total mass compared to the total of ionic plus element masses) as well as the black appearance of collected materials indicate an abundance of carbonaceous aerosol, as high as 100 μ m⁻³. (total mass compared to the total of ionic plus element masses) as well as the black appearance of collected materials indicate an abundance of carbonaceous aerosol, as high as 100 μ m⁻³Aerosol acidity was negligible during most monitoring periods, H⁺: 14 (range 0–50 neq m⁻³, equivalent to 0–2.5 μm m⁻³ as H₂SO₄). Sulfur dioxide, measured by the West-Gaeke method for part of the study, concentrations were low. Although not directly measured, the aerosol measurments suggested that gaseous HCl (from refuse incineration) and NH₃ (animal wastes) concentrations might have been high. Higher aerosol acidity might be expected if HCl sources were more prominent and not neutralized by local ammonia or other base components.     

海陆风环流中海盐气溶胶对大气影响的模拟

采用WRF-CMAQ模式对2013年9月9~13日珠江口一次典型海陆风过程进行数值模拟,并进一步探讨了在此类型环流系统下,海盐气溶胶及其对大气环境的影响.结果表明：珠江口附近海风环流一般在14：00左右开始形成,17：00左右发展最旺盛,且在珠江口沿岸形成扇形风系.在海陆风环流影响下,珠江三角洲地区陆地上Na⁺浓度从17：00开始增加,次日02：00左右达到最大,10：00以后开始下降.海盐气溶胶存在明显的氯亏损现象,其中白天的氯亏损情况远比晚上严重,细粒径的氯亏损情况比粗粒径严重.设置有无海盐气溶胶排放的敏感性试验进行对比研究发现：考虑海盐排放后,珠江口地区HCl,SO₄^2-,NO₃^-的浓度均有增加,其中,HCl和NO₃^-的增加较多,SO₄^2-较少.HCl浓度增加的高值在Cl^-高值之前;SO₄^2-浓度变化主要受海盐气溶胶排放中的硫酸盐组分影响;NO₃^-浓度变化则主要受氯亏损机制和NO₃^-干沉降过程共同影响.     

Aerosols in Santiago de Chile: A study using receptor modeling with X-ray fluorescence and single particle analysis

Between 15 January and 26 February 1987, 51 fine and coarse mode aerosol samples were collected at the Universidad de Santiago de Chile Planetarium using a dichotomous sampler. The samples were analyzed by X-ray fluorescence for up to 17 elements (Mg, Al, Si, P, S, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Br and Pb). Aerosol particles were individually studied by Electron Probe Microanalysis (EPMA) and Laser Microprobe Mass Analysis (LAMMA). The data set consisting of aerosol elemental concentrations and meteorological variables was subjected to Principal Factor Analysis (PFA), allowing the identification of six fine mode particle source classes (soil, industrial, sulfate particles, traffic, residual oil, wood-burnings), and five coarse mode particle source classes (soil, industrial, traffic, residual oil, sulfate particles). Both PFA solutions explained about 81 and 90% of the total variance in the data set, respectively. The regression of elemental mass concentrations on the Absolute Principal Factor Scores allowed the estimation of the contribution of the different source classes to the Santiago aerosol. Within the fine fraction, secondary SO₄²⁻ particles were responsible for about 49% of the fine mode aerosol mass concentration, while 26, 13, 6.4 and 5.6% were attributed to wood-burning/car exhausts, residual oil combustion, soil dust/metallurgical, and soil dust/wood-burning releases, respectively. The coarse fraction source apportionment was mainly dominated by soil dust, accounting for 74% of the coarse mode aerosol mass concentration. A composite of soil dust and industrial release accounted for 13%; a composite of secondary sulfates contributed with 9%; a composite of soil dust and automotive emissions, and secondary sulfates were responsible for 4 and 0.03% of the coarse aerosol mass concentration, respectively. EPMA results are in satisfactory agreement with those from the bulk analysis and allowed the identification of eight particle types in both fine and coarse mode aerosols, pertaining to different source classes, namely soil, seaspray, secondary SO₄²⁻, metallurgical emissions and biomass burning release. EPMA also evidenced that one of the most abundant particle types corresponded to marine aerosol, having an average diameter of 0.7 μm for the fine mode and 2.2 μm for the coarse mode aerosol. LAMMA results indicate that, in fact, seaspray has been transported into the city of Santiago de Chile airshed, suffering several transformations and a sulfur enrichment. This analytical technique also provided evidence of the abundance of carbon-rich particles, which were not detected by either the bulk X-ray analysis or EPMA; they are probably due to fossil-fuel combustion releases.     

厦门海岸气溶胶中氯亏损研究

对厦门海岸两个采样点大气气溶胶进行观测分析,研究发现在1号采样点由于人为排放的影响,使粗、细粒径气溶胶中Cl^－/Na⁺比值大于1.16,研究还表明,在人为污染较轻的２号采样点,当粗粒径气溶胶中Na⁺/Ca²⁺比值大于1.0,细粒径气溶胶中Na⁺/Ca²⁺比值大于2.0时,气溶胶中Cl^-/Na⁺比值小于1.16,存在氯亏损现象,反之,气溶胶中存在氯富集。前者是由于二次反应产生;后者由于人为一次排放源的贡献所致。     

氯化钙种子气溶胶对甲苯二次有机气溶胶与氨形成含氮有机物的影响

苯系物光氧化反应形成的二次有机气溶胶(SOA)是大气细粒子的重要组成部分.SOA羧酸和二元醛组分能与氨反应形成有机酸铵和咪唑类含氮有机物,它们能够吸收205 nm和270 nm的紫外辐射,是棕色碳的主要组分.氯化钙等无机种子气溶胶具有较大的比表面积,可为气相羰基化合物和氨提供凝结与反应载体,从而影响含氮有机物的形成.基于此,本文利用烟雾腔研究氯化钙种子气溶胶存在时甲苯SOA与氨的反应,采用紫外-可见分光光度计测量产物溶液在205 nm和270 nm处的吸光度,并定性研究不同浓度、湿度和酸度的氯化钙种子气溶胶对含氮有机物形成的影响.结果表明:氯化钙种子气溶胶能够促进甲苯SOA含氮有机物的形成;含氮有机物的生成浓度随着氯化钙种子气溶胶浓度和pH值的增加而逐渐增大.但当氯化钙种子气溶胶为碱性时,OH~-会与凝结的有机酸发生酸碱中和反应并抑制二元醛化合物水合形成四醇产物,从而不利于含氮有机物的生成;水分子的增加占据了氯化钙种子气溶胶表面的吸附活性位点,氨被吸附和凝结的量减少,从而导致含氮有机物的生成浓度随着相对湿度的增大而降低.本研究可为人为源SOA棕色碳的形成机制和化学组成研究提供实验依据.     

Determination of aerosol strong acidity losses due to interactions of collected particles: Results from laboratory and field studies

Existing methods of measuring atmospheric aerosol strong acidity adequately prevent neutralization of fine-particle acidity by removing course alkaline particles and gaseous ammonia from air samples. However, these techniques do not consider particle interactions on the collection medium; therefore, they may still underestimate the actual aerosol acidity. Assessment of acid neutralization due to such interactions is made possible using annular denuder technology in conjuction with a newly designed filter pack. The amount of sulfate-related acidity neutralized by the collected ammonium nitrate (and possibly ammonium chloride and organic acid ammonium salts) is determined. Laboratory data suggest that large fractions of sulfate-related aerosol acidity are neutralized by ammonium nitrate particles during collection on filter media. Field data from the Harvard Acid Aerosol Health Effects Study also suggest that ammonium nitrate and possibly other ammonium salts, such as ammonium chloride, neutralize collected acid aerosols. For low-acid aerosol concentrations, the correction factor is significant; whereas, for high-acid concentrations, correction is negligible.     

北京郊区农田夏季大气颗粒物质量和离子成分谱分布特征

农业活动是大气颗粒物的重要来源之一.为了研究北京郊区农田大气颗粒物质量和离子成分的分布,探讨其来源,本研究使用8级串联撞击式采样器MOUDI采集了2004年夏季北京远郊菜地的大气颗粒物样品,测量了0.18～18μm粒径段颗粒物质量和水溶性无机离子的粒径分布.细粒子的主要离子成分是SO₄^2-、NO₃^-和NH₄⁺,与温度、湿度和光照等条件相关,推测主要来自农田释放的NH₃与光化学生成的酸性物种的反应.细粒子中的K⁺可能来自植物的排放和生物质的燃烧.粗粒子中Ca²⁺、Mg²⁺、NO₃^-和SO₄^2-可能主要来自土壤颗粒物通过机械过程进入大气,以及其后酸性物种和土壤颗粒物表面的化学反应.研究结果表明,施用的化肥和土壤可能是决定农田大气中颗粒物的重要因素,北京远郊菜地对大气颗粒物可能有着重要的贡献.     

Measurements of atmospheric HNO3, HCl and associated species on a small network in eastern England

Measurements of gaseous HNO₃, HCl and NH₃ and particulate NO₃⁻, SO₄²⁻, Cl⁻ and NH₄⁺ have been made at a small network of sites in eastern England using sampling intervals from 3 h to 7 days. Both HCl and HNO₃ are spatially rather uniform, with some variation apparently due to spatial variations in NH₃, which stoichiometrically exeeded the sum of both gaseous acids. Mean concentrations of NH₃, HCl and HNO₃ between February 1987 and January 1988 were 1.90, 0.67 and 1.01 μg m⁻³, respectively. Pollution roses revealed low NH₃ concentrations, and high associated HCl and HNO₃ with winds from the North Sea. HCl, but not HNO₃ showed an appreciable elevation in concentration on the sector NW from our site, which we speculate may be due to the large capacity of coal-fired power stations in this upwind sector. Three-hourly data have been examined for diurnal effects and its is concluded that nocturnal formation of NO₃⁻ is occurring.     

Chemical characterization of size-resolved aerosols in four seasons and hazy days in the megacity Beijing of China

Size-resolved aerosol samples were collected by MOUDI in four seasons in 2007 in Beijing. The PM₁₀ and PM_1.8 mass concentrations were 166.0 ± 120.5 and 91.6 ± 69.7 μg/m³, respectively, throughout the measurement, with seasonal variation: nearly two times higher in autumn than in summer and spring. Serious fine particle pollution occurred in winter with the PM_1.8/PM₁₀ ratio of 0.63, which was higher than other seasons. The size distribution of PM showed obvious seasonal and diurnal variation, with a smaller fine mode peak in spring and in the daytime. OM (organic matter = 1.6 × OC (organic carbon)) and SIA (secondary inorganic aerosol) were major components of fine particles, while OM, SIA and Ca^2 + were major components in coarse particles. Moreover, secondary components, mainly SOA (secondary organic aerosol) and SIA, accounted for 46%–96% of each size bin in fine particles, which meant that secondary pollution existed all year. Sulfates and nitrates, primarily in the form of (NH₄)₂SO₄, NH₄NO₃, CaSO₄, Na₂SO₄ and K₂SO₄, calculated by the model ISORROPIA II, were major components of the solid phase in fine particles. The PM concentration and size distribution were similar in the four seasons on non-haze days, while large differences occurred on haze days, which indicated seasonal variation of PM concentration and size distribution were dominated by haze days. The SIA concentrations and fractions of nearly all size bins were higher on haze days than on non-haze days, which was attributed to heterogeneous aqueous reactions on haze days in the four seasons.     

Characteristics of mass distributions of aerosol particle and its inorganic water-soluble ions in summer over a suburb farmland in Beijing

Agricultural activity is one of the most important sources of aerosol particles. To understand the mass distribution and sources of aerosol particles and their inorganic water-soluble ions in a suburb farmland of Beijing, particle samples were collected using a microorifice uniform deposit impactor (MOUDI) in the summer of 2004 in a suburb vegetable field. The distribution of the particles and their inorganic water-soluble ions in the diameter range of 0.18–18 μm were measured. The dominant fine particle ions were SO₄ ²⁻, NO₃ ⁻, and NH₄ ⁺. The association of day-to-day variation of the concentration of these ions with temperature, humidity, and solar radiation suggested that they are formed by the reaction of NH₃ released from the vegetable field with the acid species produced from photochemical reactions. Fine particle K⁺ is likely from vegetation emission and biomass burning. Coarse particles like Ca²⁺, Mg²⁺, NO₃ ⁻, and SO₄ ²⁻ are suggested to come from the mechanical process by which the soil particle entered the atmosphere, and from the reaction of the acid species at the surface of the soil particle. The results show that fertilizer and soil are important factors determining the aerosol particle over agricultural fields, and vegetable fields in suburban Beijing contribute significantly to the aerosol particle. Translated from Environmental Science, 2006, 27(2): 193–199 [译自: 环境科学]     

不同酸性气体及相对湿度对海盐氯损耗过程的影响

使用在广州南村站、深圳竹子林站及西涌站的MARGA仪器实测资料,分析了不同酸性气体及相对湿度对海盐氯损耗过程的影响.在分析深圳竹子林站、西涌站的海盐氯损耗中发现,竹子林站氯损耗平均为48.0％,西涌站海盐氯损耗平均为56.9％,氯损耗的峰值一般出现于下午14时.西涌站、竹子林站和广州南村站酸性气体和碱性气体均以HNO2、SO2、NH3为主,但各站点的比例分布不同,西涌站以HNO2最多(42％),SO2(32％)次之;竹子林站以NH3与SO2为主,百分比分别为36％和34％;广州南村站以SO2为主(58％),NH3次之(20％);而三站HNO3所占比例很小,均为7％.另外,分析了HCl的来源,主要关注了海盐粒子中的NaCl与HNO3反应、NH4Cl的挥发及H2SO4与NaCl的反应这3个来源,发现西涌站与竹子林站HCl和HNO3之间的线性关系较好(R2西涌=0.689,R2竹子林=0.594),说明西涌站与竹子林站的HCl主要来源于NaCl与HNO3反应过程中Cl被HNO3置换而成;而广州南村站二者线性关系较差(R2南村=0.295),说明还存在其他的损耗机制.在研究相对湿度对氯损耗的影响中发现,相对湿度低时氯损耗更容易发生.     

Identification of sources of lead in the atmosphere by chemical speciation using X-ray absorption near-edge structure (XANES) spectroscopy

Sources of Pb pollution in the local atmosphere together with Pb species, major ions, and heavy metal concentrations in a size-fractionated aerosol sample from Higashi-Hiroshima(Japan) have been determined by X-ray absorption near-edge structure(XANES) spectroscopy, ion chromatography, and ICP-MS/AES, respectively. About 80% of total Pb was concentrated in fine aerosol particles. Lead species in the coarse aerosol particles were PbC2O4, 2PbCO3·Pb(OH)2, and Pb(NO3)2, whereas Pb species in the fine aerosol particles were PbC2O4, PbSO4, and Pb(NO3)2. Chemical speciation and abundance data suggested that the source of Pb in the fine aerosol particles was different from that of the coarse ones. The dominant sources of Pb in the fine aerosol particles were judged to be fly ash from a municipal solid waste incinerator and heavy oil combustion. For the coarse aerosol particles, road dust was considered to be the main Pb source. In addition to Pb species, elemental concentrations in the aerosols were also determined. The results suggested that Pb species in size-fractionated aerosols can be used to identify the origin of aerosol particles in the atmosphere as an alternative to Pb isotope ratio measurement.