The Drop Size-Dependence of Iron and Manganese Concentrations in Clouds and Fogs: Implications for Sulfate Production

Differences in total iron and manganese concentrations between large (d > 23 m) and small (4 < d < 23 m) cloud and fog drops were investigated at four locations in the United States. The study examined coastal stratus and stratocumulus clouds in southern California and northern Oregon, frontal and orographic clouds at Mt. Mitchell, North Carolina, and radiation fogs in California's San Joaquin Valley. The speciation of iron as a function of drop size was also examined in some fog samples from the San Joaquin Valley. Total iron and manganese concentrations were generally higher in large drops than in small drops in clouds sampled at Mt. Mitchell and along the southern California coast. These species were typically enriched in small drops at the Oregon coast and San Joaquin Valley sites. Ratios of dissolved Fe(III) to total dissolved Fe ranged from 0.88 to 0.93 in small fog drops. Non-uniform distributions of iron and manganese across the drop size spectrum can influence rates of metal catalyzed S(IV) autooxidation. Approximately 50% of the sampled clouds were calculated to experience autooxidation rate enhancements greater than 30% due to variations in drop acidity and catalyst concentrations with drop size.     

Evolution of the fogwater composition in Strasbourg (France) from 1990 to 1999

The chemical composition of fogwater has been studied in the city of Strasbourg (France) from 1990 to 1999. During these years, fogwater samples have been collected and analysed for major ions and trace metals. This paper reports on the analysis of the collected dataset. The analysis revealed a significant decrease in acidity of approximately one pH unit over the course of the study. This decrease in acidity appears to be linked to a decrease in SO_2(g) and the resulting SO₄²⁻. Trace metal concentrations have also strongly decreased over the 10-year period. Pb concentrations, following the elimination of leaded gasoline, decreased by more than one order of magnitude.     

The Influence of Oxalate on Fe-Catalyzed S(IV) Oxidation by Oxygen in Aqueous Solution

This study demonstrates that oxalate has a strong inhibiting effect onFe-catalyzed S(IV) oxidation by oxygen in aqueous solution. While thepseudo-first order rate constant of S(IV) oxidation was determined to be1.6 × 10³ M^-1 s^-1 in experimentswithout oxalate, the oxidation of S(IV) was totally inhibited at a molarconcentration ratio of iron:oxalate = 1:5 at an oxalate concentration of 4M. Under these conditions, the Fe(II)/Fe(III) ratio remained nearlyconstant during the observed reaction time. The determined rate constants wereindependent of the initial oxidation state of iron. However, with increasingconcentrations of oxalate, a longer induction period is observed forexperiments with iron initially in the Fe(II) oxidation state.     

Model Simulations on the Variability of Particulate MSA to Non-Sea-Salt Sulfate Ratio in the Marine Environment

A box model was constructed to investigate connections between the particulate MSA to non-sea-salt sulfate ratio, R, and DMS chemistry in a clean marine boundary layer. The simulations demonstrated that R varies widely with particle size, which must be taken into account when interpreting field measurements or comparing them with each other. In addition to DMS gas-phase chemistry, R in the submicron size range was shown to be sensitive to the factors dictating sulfate production via cloud processing, to the removal of SO₂ from the boundary layer by dry deposition and sea-salt oxidation, to the entrainment of SO₂ from the free troposphere, to the relative concentration of sub- and supermicron particles, and to meteorology. Three potential explanations for the increase of R toward high-latitudes during the summer were found: larger MSA yields from DMS oxidation at high latitudes, larger DMSO yields from DMS oxidation followed by the conversion of DMSO to MSA at high latitudes, or lower ambient H₂O₂ concentrations at high latitudes leading to less efficient sulfate production in clouds. Possible reasons for the large seasonal amplitude of R at mid and high latitudes include seasonal changes in the partitioning of DMS oxidation to the OH and NO₃ initiated pathways, seasonal changes in the concentration of species participating the DMS-OH reaction pathway, or the existence of a SO₂ source other than DMS oxidation in the marine boundary layer. Even small anthropogenic perturbations were shown to have a potential to alter the MSA to non-sea-salt sulfate ratio.     

我国空气污染状况及其对人体健康的影响

为了解我国空气污染状况,收集了1991～1993年全国城市污染物浓度的资料,这些污染物包括二氧化硫、氮氧化物和悬浮颗粒物,分析指出我国某些地区污染物浓度比较大,各种污染物都有不同程度的超标,然后讨论制定污染指数及相应的对人体健康的影响。       

大气污染预测的理论和方法研究进展

介绍中国科学院 “九五”重大科研项目 “大气污染预测的理论和方法研究”的研究意义、目标和具体的研究内容, 同时对已取得的重要研究进展和阶段性成果作简要介绍     

The influence of medium-range transport on O3 levels at a rural site in Israel

Simultaneous ozone measurements were made at a rural site, 25 km SSW of the city of Jerusalem, and in the center of the city during a period of 28 months. The ozone data were supplemented by SO₂, NO/NO _x ,and meteorological measurements at both sites. Elevated ozone concentrations were recorded at the rural site, mostly during the spring months (May and June) during which the monthly averages and the monthly averages of the daily 30 min maximum levels equalled those measured in the city. During the summer months, both average and peak levels were lower at the rural site by 20 and 35 ppb. The increased ozone levels at the rural site were accompanied by a parallel increase of SO₂ and NO _x ,suggesting hat the excess ozone at the rural site is a result of a transformation during transport of air pollutants from coastal sources.     

长沙市API指数时空变化特征及气象条件影响

利用长沙站2007—2012年逐日空气污染指数(Air Pollution Index,API)资料,对逐日空气污染指数、逐日空气质量级别等变化的差异进行了研究,其中包括了长沙空气质量的月变化、季节变化和年变化等,并利用湖南省地面气候背景资料及长沙市地面逐日观测资料,包括日平均气压、日降水量、日最高最低气温等,分析了长沙的API指数变化与气象因子的关系。结果表明:1)长沙2007—2012年每年的首要污染物均为可吸入颗粒物(PM10),其中在秋、冬两季污染尤为严重,API指数每年10月份出现极大值,1月份出现次大值。2)2007—2012年,长沙轻度污染及以上天数有逐年减少的趋势。这可能与长沙市在该时段秋冬季降水偏多、春季连阴雨时间长及夏季气温高等因素有关。3)长沙市API指数与日平均气压呈显著正相关,与日平均、日最高、日最低气温及日平均风速均呈显著负相关。     

Sulfur dioxide in rain clouds: Gas-liquid scavenging efficiencies and wet deposition rates in the presence of formaldehyde

The interaction of formaldehyde with SO₂ dissolved in the aqueous phase of clouds leads to the formation of hydroxymethane sulfonate. The impact of this process upon the gas-liquid equilibrium distribution of SO₂ in rain clouds and the ensuing wet SO₂ precipitation rate is explored. Model vertical SO₂ distributions are derived from observational data for three atmospheric regions: continental polluted, continental remote, and marine. The wet deposition rate for SO₂ in the polluted atmosphere increases by about a factor of two in the presence of formaldehyde compared with its absence. The effect is much stronger in the remote atmosphere leading to a potentially significant enhancement of wet SO₂ deposition. In the marine atmosphere, wet deposition of SO₂ may contribute as much as 35% to the total removal rate for SO₂ by all processes including dry deposition and chemical conversion to sulfate.     

北京地区平均最大混合层厚度的时间变化特征

大气混合层厚度是大气环境质量影响预测中所需的重要参数。应用Holzworth干绝热法计算最大混合层厚度的基本原理,采用王式功等提出的逐步逼近法计算了北京观象台站1970—2007年的最大混合层厚度,分析了最大混合层厚度38年的变化和月平均值的年变化特征,同时应用2004—2007年同期的北京地区空气质量等级与同期大气混合层厚度逐月分布频率进行比较。结果表明,北京观象台的平均最大混合层厚度自1970—1998年有逐年减小趋势,1998年达到最小值,而从1998—2007年有逐年增加趋势,年平均最大混合层厚度与年降水日数有较为明显的负相关关系。最大混合层厚度的年变化表现出冬季低和夏季高的特征,且在夏季的7月和8月出现一个相对的低谷。空气质量等级与同期大气混合层厚度逐月分布频率表明,较高的最大混合层厚度出现频率较大的月,空气质量等级为1级和2级出现的频率高,而较低的最大混合层厚度出现频率较大的月,其空气质量等级为3级和4级出现的频率高。     

CAPPS模式在石家庄市应用的效果检验

根据《气象部门空气质量预报质量考核和管理暂行办法》,对CAPPS系统在石家庄市空气质量预报中的应用效果进行检验,对CAPPS1.0和CAPPS2.0的预报能力和产生的误差进行了对比分析。结果表明:CAPPS2.0的整体预报水平高于CAPPS1.0,但其预报值多偏高于监测值,这是导致冬季首要污染物正确性评分偏低、夏季高污染预报能力偏低的主要原因。CAPPS系统对前日污染实况依赖性强,预报结果滞后,对高浓度污染日的预报准确率仅为13%,预报能力偏低。     

2002年广西三城市空气质量状况及与气象条件的关系

根据广西重点环境保护城市南宁、桂林、北海三城市空气质量自动监测数据监测到二氧化硫(SO2),二氧化氮(NO2),可吸入颗粒物(PM10)的日均浓度数据计算的空气污染指数API,结果表明:2002年三城市空气质量状况整体为1级"优"或2级"良",仅南宁市出现过轻度污染共10d,达到了国家环境保护总局对城市环境规定的标准。     

Features of the atmospheric cycle of aerosol trace elements and sulphur dioxide revealed by baseline observations in Canada

Selected applications of baseline aerosol, SO₂ and deposition chemistry observations in Canada are reviewed to illustrate how new insight can be gained into features of the atmospheric pathway of trace substances such as sources, transformation and removal. A strong annual variation in Arctic aerosol concentration is a manifestation of particle residence times that are much longer in winter than in summer. Differences in the variation of SO₄ ⁼ and V concentrations in the Arctic winter are due to SO₂ oxidation. The mean rate of oxidation between November and April ranges from 0.04 to 0.25%/h and is a minimum in December, January and February. Br measured on filters in the Arctic peaks in concentration later (March and April) than anthropogenic particulate matter suggesting photochemical production. Acidity in Arctic aerosol and in glacial ice are correlated. The relationship yields a best estimate of acidity in the absence of anthropogenic influences of 5.8 mole/l. Coincident air and precipitation measurements of sulphur oxides indicate that on average in eastern Canada 60% of SO₄ ⁼ in rain originates from SO₂ oxidation in the storm. Trends in Arctic ice core acidity and SO₂ emissions in Europe are similar, that is, little variation in the first half of the century and a marked increase since the mid 1950's. This is consistent with meteorological and chemical evidence linking Arctic air pollution with Eurasian sources.     

Spatial and temporal variations of methanesulfonic acid and non sea salt sulfate in Antarctic ice

A simultaneous glaciochemical study of methanesulfonic acid (MSA) and non-sea-salt sulfate (nss-SO₄ ^-) has been conducted on the Antarctic plateau (South Pole, Vostok) and in more coastal regions. The objective was to investigate marine sulfur emissions in very remote areas. Firstly, our data suggest that MSA and nss-SO₄ present in antarctic ice are mainly marine in origin and that DMS emissions have been significantly modulated by short term (eg. El Nino Southern Oscillation events) as well as long term climatic changes in the past. Secondly, our study of spatial variations of these two sulfur species seems to indicate that the atmosphere of coastal antarctic regions are mainly supplied by local DMS emissions whereas the atmosphere of the high plateau is also influenced by DMS emissions from more temperate marine latitudes. Thirdly, our study of the partitioning between MSA and nss-SO₄ suggest that the temperature could have been an important parameter controlling the final composition of the high southern latitude atmosphere over the last climatic cycle; colder temperature favoring the formation of MSA. However, our data also support a possible role played by changes in the transport pattern of marine air to the high antarctic plateau.     

城市与乡村大气中非甲烷烃(NMHCs)差异

在北京工业大学(城市点)和天津市宝邸县新安镇(乡村点)两个观测点进行了大气中非甲烷烃(NMHCs)的现场取样。从2006年4月16日至5月12日,分两批共获取约80个样本,检出55个组分,其中烷烃25个,烯烃19个,芳香烃10个。从非甲烷烃所含成分及其浓度的观测结果可见,城、乡两地大气中总烃(TNMHCs)平均浓度分别是438.1±173.1μg/m~3、193.8±184.4μg/m~3,城市是乡村的2.3倍,而TNMHCs的低值乡村只有城市的1/5。     

城市空气污染持续维持机制研究 I.2002年西安市空气污染持续维持过程分析及其气象成因

为研究城市大气污染持续过程的形成机制及区域输送问题, 利用 2002 年西安市环境监测站 SO2、NO2和PM10日平均污染物浓度资料分析了西安市大气污染的时空分布特征及其与气象条件的关系。分析结果表明: 一年中西安出现3天以上空气质量为3级以上的持续污染过程18次, 累计污染超标日为192天, 出现3级以上的概率为53%。西安市区的污染物以可吸入颗粒物为主, PM10污染超标日较多。重点分析了2002年1月9~12日造成西安市持续污染过程的气象条件及天气形势, 可见4天的气象条件有着共同的特点: 平均风速小, 气温较低, 出现逆温, 相对湿度较大。西安地处高压后部, 气压较低, 高空为较平直的西北气流, 天气形势持续稳定。     

On the Measurement of PANs by Gas Chromatography and Electron Capture Detection

A fast, automated, gas chromatographic system for the airborne measurement of PAN and a series of its homologues is described and its performance is evaluated. Response factors for PAN, PPN, APAN, PiBN, and MPAN have been determined and are discussed with regard to ECD response and to potential losses in the analytical system. Calibration methods used for these tasks are described and compared. The results from this work should help investigators who are employing the widely used GC/ECD method for the measurement of peroxyacyl nitrates to evaluate peaks of PAN homologues that cannot be calibrated for by using the reported response factors.     

S(IV) Autoxidation in Atmospheric Liquid Water: The Role of Fe(II) and the Effect of Oxalate

The reactivity of dissolved iron compounds towards different pollutants and photooxidants in atmospheric liquid water depends upon the oxidation state and speciation of iron. Our measurements of the oxidation state of dissolved iron eluted from aerosol particles (Dae: 0.4–1.6 m) collected in the urban atmosphere of Ljubljana showed that a large fraction of the iron content is present as Fe(II). The concentration ratio [Fe(II)]/[Fe(III)] varied between 0.9 and 3.1. The kinetics of S(IV) autoxidation catalyzed by Fe(II) under the conditions representative for acidified atmospheric liquid water and the influence of oxalate on this reaction under dark conditions was investigated. The reaction rate is the same if Fe(II) or Fe(III) is used as a catalyst under the condition that Fe(II) can be oxidized in Fe(III), which is the catalytically active species. Oxalate has a strong inhibiting effect on the S(IV) autoxidation in the presence of Fe(II). The reaction is autocatalytic with an induction period, that increases with higher concentrations of oxalate. The inhibiting effect of oxalate differs according to whether iron is initially in the Fe(II) or Fe(III) state. However, in both cases the inhibition by oxalate is a result of the formation of complexes with the catalyst.     

忻州市空气质量日报与预报方法

采用环保监测部门大气质量监测点污染物的自动采样数据，根据常规气象观测资料和数值预报产品，输入城市中各监测点的污染物指数后，就可以较为及时准确地预报出未来空气质量，计算结论与环保部门会商后通过电视等多种媒体面向社会公众服务。污染指数的预报准确率达76％。     

Tropospheric transformation products of a series of hydrofluorocarbons and hydrochlorofluorocarbons

The products of the Cl-atom initiated reactions of a series of hydrofluorocarbons (HFCs) and hydrochlorofluorocarbons (HCFCs) in air have been investigated at 298 K and one atmosphere (740 Torr total pressure) of air. The products observed and quantified and their yields (%) were as follows: from CHF₂Cl (HCFC-22), C(O)F₂ (100%); from CHFCl₂ (HCFC-21), C(O)FCl (100%); from CH₂FCl (HCFC-31), HC(O)F (100%); from CH₃F (HFC-41), HC(O)F (100%); from CH₃CFCl₂ (HCFC-141b), C(O)FCl (100%); from CH₃CF₂Cl (HCFC-142b), C(O)F₂ (100%); from CH₃CHF₂ (HFC-152a), C(O)F₂ (92%); from CHCl₂CF₃ (HCFC-123), CF₃C(O)Cl (98%); from CHFClCF₃ (HCFC-124), CF₃C(O)F (101%); and from CHF₂CF₃ (HFC-125), C(O)F₂ (100%). The reaction mechanisms are discussed.