燃煤工业城市大气细颗粒物中水溶性无机离子的季节变化特征及来源解析——以邯郸市为例

为探究典型燃煤工业城市邯郸市的大气细颗粒物(PM2.5)污染水平及水溶性无机离子特征,于2016年1—12月采集了当地大气PM2.5样品,然后利用离子色谱法测得水溶性无机离子的组分,分析了不同季节水溶性无机离子随PM2.5的浓度变化特征。通过对PM2.5中的阴离子、阳离子进行分析发现,SO4^2-、NO3^-和NH4^+在春夏秋冬四季均为PM2.5中的主要离子成分,SO4^2-、NO3^-和NH4^+的浓度之和在春夏秋冬四季占各季节总的水溶性无机离子浓度的百分比分别为84.6%、77.4%、89.9%、62.5%。其中,在春季和冬季含量最高的3种离子分别是NO3^-、SO4^2-和NH4^+,夏季含量最高的3种离子分别是SO4^2-、NH4^+和NO3^-,而秋季含量最高的3种离子分别是NH4^+、SO4^2-和NO3^-。相关性分析发现,2016年春季、夏季和秋季PM2.5为酸性,冬季为碱性。SO4^2-、NO3^-、NH4^+浓度分析表明,冬季PM2.5中的一次建筑扬尘排放较多。通过主成分分析法得出,PM2.5中水溶性无机离子主要来源于二次转化和生物质燃烧。     

南通市冬季PM2.5中水溶性离子污染特征

根据南通市2016和2017年冬季大气多参数站自动监测PM2.5数据和在线离子色谱分析仪Marga监测的PM2.5中水溶性离子数据,分析了南通市冬季PM2.5中水溶性离子污染特征。结果表明,南通市2016和2017年冬季,ρ(PM2.5)分别为58和54μg/m 3,均高出其年均值(14μg/m^3);ρ(水溶性离子)总占ρ(PM2.5)百分比分别为74.5%和74.3%;二次离子ρ(NO3^-、SO4^2-和NH4^+)占ρ(PM2.5)百分比分别为66.8%和66.6%;各水溶性离子占比大小依次为:NO3^-、SO4^2-、NH4^+、Cl^-、K^+、Na^+、Ca^2+、Mg^2+。对ρ(NO3^-)/ρ(SO 4^2-)分析表明,移动源已经成为南通市冬季的主要污染源,且呈逐年增强趋势。对氯氧化率和硫氧化率的分析表明,南通市冬季存在较明显的二次污染,SO2的转化程度大于NO2。除Na^+和Mg^2+外,其他离子与PM2.5均呈显著相关性,NO3^-、SO4^2-与NH4^+之间的相关系数最高,Cl^-与除Na^+外的所有阳离子均呈显著相关性。     

重庆市大气TSP中水溶性无机离子的化学特征

于2001至2002年在重庆市7个采样点采集了TSP,进行了水溶性无机离子分析。结果发现,SO42-离子浓度最高,其浓度范围为6.32~20.96μg/m3;Ca2 次之,其浓度范围0.78~7.47μg/m3;SO42-、NO3-和NH4 三种离子占TSP质量的8.05%~20.96%。Ca2 、K 与SO42-和NO3-都有很好的相关性,[NO3-]/[SO42-]比值较低(均值为0.4),说明重庆市区普遍使用含硫燃煤。SO42-浓度冬季最高,主要与冬季燃煤的消耗增大有关,NO3-季节明显,与NO3-的形成环境温度密切相关。水溶性无机离子质量浓度有较明显的区域差异,中心城区采样点离子质量浓度高于距离中心城区较远的采样点。     

浅谈离子色谱法连续对多种阴离子进行定性和定量分析

介绍了离子色谱法连续测定样品中F^-、Cl^-、NO3^-、SO4^2-8的浓度，体现了当代离子色谱的发展潮流．     

北京市大气颗粒物的浓度水平和离子物种的化学形态

用离子色谱法测定了 1 998年 1 1月至 1 999年 2月期间的 2 4个总悬浮颗粒物 (TSP)样品中 NH+ 4、NO- 3、SO2 - 4和Na+ 质量浓度。研究结果表明 ,北京市冬季大气颗粒物中离子物种的化学形态可以分为三种情况 :污染严重时 ,离子物种以 H2 SO4 、NH4 HSO4 、Na NO3为主要存在形态 ,气溶胶酸性强 ;污染轻时 ,离子物种以 (NH4 ) 2 SO4 、Na NO3为主要存在形态 ,气溶胶呈弱酸性 ;中等污染时 ,离子物种以 (NH4 ) 2 SO4 、NH4 HSO4 、Na NO3几种化学形态存在 ,气溶胶呈中等酸性     

南京市冬季PM2.5中水溶性离子污染特征研究

基于城市超级站对2018年12月—2019年2月南京市在线水溶性离子污染特征进行研究。结果表明：监测期间水溶性无机离子(WSIs)质量浓度均值为45.7μg/m3,占PM2.5的67.8%,各离子排序为NO3-＞ SO42-＞NH4+＞Cl-＞K+＞Ca2+＞Na+＞Mg2+。二次离子（SNA）是PM2.5主要组分,大气气溶胶呈中性。各离子日变化存在差异,SNA变化趋势和WSIs基本一致。南京市冬季存在明显SO2和NO2向SO42-和NO3-二次转化;NO3-/SO42-均值为1.96,移动源增量大于固定源。通过相关性和三相聚类分析可知,SNA主要结合方式为(NH4)2SO4和NH4NO3。主成分分析表明,南京市冬季PM2.5中水溶性离子主要来源是二次转化,燃煤、生物质燃烧和土壤建筑扬尘也有贡献。     

离子色谱法测定降水中部分阴离子含量的测量不确定度评定

通过对离子色谱法测定降水中F^-、Cl^-、NO3^-、SO4^2- 测量不确定度的分析，找出导致不确定度的因素。对测量不确定度进行计算和评定，结果表明，影响其测量不确定度的主要因素是标准曲线精密度。     

离子色谱分析中淋洗液对Cl^-的测定影响

PIC-8型离子色谱仪测定样品中的Cl^-、NO3^-、SO4^2-时，通过对样品中加入淋洗液与不加入淋洗液的测定结果进行比较分析，可以看出淋洗液的添加对NO3^-、SO4^2-测定结果不产生影响，但对Cl^-有较大影响，通过保持相同实验条件可以避免这一情况的发生，同时也减少了操作步骤，缩短分析时间，提高了工作效率．     

杭州城区春节PM2.5中水溶性离子在线观测

利用大气细颗粒物水溶性组分在线连续监测分析系统(AIM-URG9000D),考察了杭州城区春节期间PM2.5中无机水溶性离子的浓度变化范围,探讨了这些离子的日变化特征和影响因素,同时分析了集中燃放烟花爆竹对水溶性离子浓度的影响。结果表明,SO2-4、NO-3、NH+4是PM2.5中水溶性离子的主要成分,分别占全部水溶性组分的33.3%、28.4%、19.4%;强致癌物质NO-2浓度为2.07μg/m3,远大于膜采样结果;NO-3与SO2-4的质量比为0.85,表明机动车尾气排放导致的大气污染正逐步加重;各水溶性离子有着各自不同的日变化规律。相关性分析表明,NH+4与NO-3、SO2-4的相关系数分别为0.92、0.81;K+、Cl-、Mg2+3者之间的相关系数均在0.9以上。烟花爆竹燃放期间,PM2.5浓度急剧上升,Cl-、SO2-4、K+、Mg2+浓度分别达到燃放前的18、6、53、76倍。     

石家庄市大气颗粒物中水溶性无机离子污染特征研究

用超声萃取－离子色谱法分析了石家庄市大气颗粒物中8种水溶性无机离子。结果表明，NO3－、SO2－4、NH4＋及 Ca2＋为主要组分；各个离子的质量浓度均有季节及空间变化差异；不同粒径颗粒物中 SO2－4和 NO3－相关性均很好，NH4＋与 SO2－4、NO3－在细颗粒物中具有良好的相关性，Ca2＋在粗粒子中与 NO3－和 SO2－4的相关性也较好。SO2－4／NO3－质量比季节变化表明，春、夏季固定源与流动源对大气颗粒物贡献相当，秋季流动源贡献较大，冬季固定源贡献较大。PM2．5中SO2与SO2－4、NO2与 NO3－转化率表明，SO2－4、NO3－主要是由二次转化而来。     

Atmospheric aerosol concentration level and chemical characteristics of water-soluble ionic species in wintertime in Beijing,China

Total suspended particulate (TSP) samples were collected during wintertime from November 24, 1998 to February 12, 1999 in Beijing. Ionic species including Cl-, NO3(-), SO4(2-), Na+, NH4(+), K+, Mg2+ and Ca2+ were determined by Ion Chromatography (IC). The sum average concentration of all the determined ions accounted for 18.9% of the TSP concentration, and SO4(2-) appeared the dominant ion with an average concentration of 30.84 microg m(-3); the sum mass concentration of SO4(2-), NO3(-), Ca2+ and NH4(+) accounted for about 83.2% of all the eight ions measured. The study indicated that the chemical form of sulfate and ammonium varies with TSP concentration levels. During heavy pollution periods, the average TSP concentration was 0.66 mg m(-3), and the NH4(+)/SO4(2-) molar ratio was low (0.58). It indicated that sulfate may present as CaSO4 and (NH4)2SO4 x CaSO4 x 2H2O. When TSP concentration (average 0.186 mg m(-3)) was relatively low, the NH4(+)/SO4(2-) molar ratio was 1.94, close to the theoretical ratio of 2 of (NH4)2SO4. Under this condition (NH4)2SO4 is expected to exist as the major form of sulfate. When the TSP concentration level was medium (average 0.35 mg m(-3)), the NH4+/SO4(2-) molar ratio appeared an average value (1.27), (NH4)2SO4, (NH4)2SO4 x CaSO4 x 2H2O and CaSO4 are expected to be present in those aerosol particles. Meteorological conditions including wind speed and wind direction were related to the TSP concentration level.     

2017年厦门金砖会晤期间PM2.5的化学特征及来源

为了探讨厦门金砖会晤期间的排放控制措施以及天气形势对大气颗粒物污染特征的影响,于2017年8月10日至9月10日对厦门气态污染物、细颗粒物(PM2.5)中的水溶性离子以及有机碳(OC)、元素碳(EC)等主要化学成分开展了高时间分辨率的在线监测。根据空气质量管控措施和天气形势将研究期分为6个阶段。管控前、管控期Ⅰ(非台风)和管控期Ⅱ(非台风) PM2.5质量浓度分别为(33. 12±9. 48)、(30. 30±17. 00)、(16. 01±4. 71)μg/m^3。管控期Ⅰ(台风)和管控期Ⅱ(台风) PM2.5质量浓度分别为(12. 40±3. 73)、(12. 45±3. 28)μg/m^3。结果表明:管控期Ⅰ(非台风)阶段受静稳天气的影响,管控效果削弱,PM2.5质量浓度下降幅度小;台风对颗粒物质量浓度下降的影响比管控更显著。管控初期,PM2.5中二次无机离子的质量浓度下降明显;台风对碳质组分质量浓度的影响不如无机组分显著。PMF源解析结果表明,二次无机源是PM2.5主要来源,随着管控措施的实行,扬尘源的贡献从21%降低到6%,而机动车源的贡献降幅不明显。台风期间SO4^2-、NO3^-、SO2、NO2以及硫酸盐氧化比值(SOR)均明显低于非台风期间,氮氧化比值(NOR)反而升高。台风和非台风期间NOR的日变化特征一致,NOR与阳离子的相关性分析结果表明,台风或高风速海风期间NOR与Na^+呈现很强的正相关性,说明海盐粒子可促进NO2非均相反应生成NO3-。     

The Influence of a Coal-Fired Power Plant in Turkey on the Chemical Composition of Rain Water in a Certain Region

In this study, the chemical composition of the rainwater in Yatağan, which is a region surrounding a coal power plant was investigated from February to April 2002. Rainwater samples were obtained from Yatağan, located northwest of Muğla City in Turkey. pH values and concentrations of major ions (Ca²⁺, Na⁺, K⁺, , , ) in the rainwater samples were analyzed. The pH varied from 5.1 to 7.9 with an average of 6.7 which was in alkaline range considering 5.6 as the neutral pH of cloud water in equilibrium with atmospheric CO₂. In the total of 30 rain events, only three events were observed with water in the acidic range (<5.6), which occurred after continuous rains. The equivalent concentration of components followed the order: Ca²⁺ > > Na⁺ > > > K⁺ > H⁺. The anion and cation concentrations in the rainwater samples showed a high sulphate concentration (131 μEq/l), as well as high sodium (40 μEq/l) and calcium (298 μEq/l) concentrations. These values indicate that one probable source of the high sodium concentration is fly ash, after the coal burning process and the power plant can be effective on level concentrations in rainwater. In addition, the dust-rich local and surrounding limestone environment might have caused the high concentration of Ca²⁺ in rainwater of the Yatağan Basin. Due to a large contribution of these cations to the sulphate neutralization action, the rainwater of this region displays only a moderate acidity, which does not cause significant environmental impact.     

基于Berthollet反应示波极谱法测定水中微量氨

在亚硝基铁氰化钾存在下,氨在氢氧化钠介质中与苯酚、次氯酸钠反应,其产物靛酚在滴汞电极上产生－灵敏的吸附波,ＮＨ３－Ｎ在０．００３～０．２２ｍｇ／Ｌ内,导数峰电流与其呈良好的线性关系。用于环境水中ＮＨ３－Ｎ的测定,其相对标准偏差小于３％,回收率为９７％～１０５％,方法具有较好的选择性。     

Characterization and diurnal variation of size-resolved inorganic water-soluble ions at a rural background site

Water-soluble inorganic ions in aerosol samples have been studied. The sample collection took place during summer in 2003 at a European background site which is operating within the framework of the European Monitoring and Evaluation Program. Gent type PM10 stacked filter unit (SFU) samplers were operated in parallel on a day and night basis to collect particles in separate coarse (2.0-10 microm) and fine (<2.0 microm) size fractions. Particulate masses were measured gravimetrically; the filters from one of the SFU samplers were analyzed by particle-induced X-ray emission spectrometry (PIXE) and instrumental neutron activation analysis (INAA). Filters from the other SFU sampler were analyzed by ion chromatography (IC) for major inorganic anions (MSA-, NO2(-), NO3(-), Cl-, Br-, SO4(2-), oxalate) and cations (Na+, K+, NH4(+), Mg2+, Ca2+). The water-soluble inorganic ions measured were responsible for 44% and 16% of the total fine and coarse particulate mass, respectively. In the fine size fraction, the main ionic components were SO4(2-) and NH4(+) accounting for about 90% of fine ionic mass. In the coarse fraction the main ionic components were Ca2+ and NO3(-), followed by SO4(2-). Significant day and night difference in the mass concentrations was observed only for fine NO3(-). The molar ratios of fine NH4(+) to SO4(2-) indicated their complete neutralization to (NH4)2SO4. According to the cation-to-anion ratios the coarse particles were alkaline, while the fine particles were slightly acidic or neutral. By comparing the corresponding concentrations obtained from PIXE/INAA and IC, we determined the water-extractable part of the individual species. We also investigated the effect of long-range transported air masses on the local air concentrations, and we found that the air quality of this background monitoring station was affected by regional pollution sources.