沈阳市城区采暖期PM2.5中水溶性离子的化学特征

2013年11月—2014年3月采暖期在沈阳市沈河区设置采样点采集环境空气中的PM2.5。利用离子色谱法测定PM2.5中水溶性无机离子,分析PM2.5中水溶性无机离子的组成和污染特征等。结果表明,沈阳市冬季采暖期PM2.5平均质量浓度为106μg/m3,PM2.5中总水溶性离子占PM2.5的比例为41.7%,含量较高的二次离子依次为SO2-4、NO-3、NH+4,三者均有较好的相关性,SO2-4以(NH4)2SO4形式存在,采暖期PM2.5偏酸性。     

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。     

广州市灰霾期PM10的化学组成对能见度的影响

采集广州市大气可吸入颗粒物(PM10)样品,并分别对冬、夏两季灰霾和非灰霾期PM10中有机碳(OC)、元素碳(EC)和水溶性离子进行分析。广州市灰霾期大气PM10中的主要化学成分按质量浓度大小排序为OC>NO3->SO24->NH4+>EC(非灰霾期则依次为OC>SO24->EC>NH4+>NO3-),其质量浓度分别为非灰霾期的4.7、12.5、3.7、3.2和2.3倍。相关性分析表明,灰霾期总碳[TC(OC+EC)]及NO3-的质量浓度对大气能见度的降低起主要作用,而非灰霾期则主要是TC和SO24-。     

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。     

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。     

采暖期大气颗粒物PM1.0和PM2.5中水溶性离子污染特征

为了解采暖期大气PM_(1.0)和PM_(2.5)中水溶性离子污染特征,采集哈尔滨市2014年11月至2015年3月采暖期PM_(1.0)和PM_(2.5)的样品,进而分析其中的水溶性离子(F-、Cl-、NO-3、SO2-4、Na+、NH+4、K+、Mg2+、Ca2+)的质量浓度。结果表明:PM_(1.0)和PM_(2.5)中的水溶性离子具有相同的变化趋势。采暖期间PM_(1.0)和PM_(2.5)中9种水溶性离子质量浓度总和分别为25.4~60.7μg/m~3和38.8~78.0μg/m~3。在PM_(1.0)和PM_(2.5)中NH+4、NO-3、SO2-4占比较高,而F-、Mg2+占比较低。PM_(1.0)和PM_(2.5)中9种水溶性离子质量浓度均为夜间大于白天。在PM_(1.0)和PM_(2.5)中,Mg2+和NH+4、F-和Cl-呈显著相关,说明它们来自相似的污染源,在PM_(1.0)中的K+和Ca2+显著相关,故它们受相似的污染源的影响。根据酸度与各离子的相关性,得出SO2-4和NH+4是控制大气颗粒物酸碱性的主要离子。另外,气象因素对PM_(1.0)和PM_(2.5)的浓度有影响。     

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。     

典型矿业城市大气颗粒物水溶性离子分布特征

利用2014年7月和2015年1月在淮南市不同功能区采集的大气颗粒物样品，分析其水溶性离子时空和粒径分布特征。结果表明：夏季和冬季粗、细粒子中总水溶性离子质量浓度均值分别为（13.45±4.53）μg/m3、（27.81±17.65）μg/m3和（12.87±8.37）μg/m3、（85.08±35.41）μg/m3。淮南市大气颗粒物中主要的水溶性离子为Ca2+、NO-3和SO2-4。冬季各功能区PM2.5中总水溶性离子质量浓度普遍高于夏季。大气颗粒物中水溶性离子主要来源于土壤源、工业污染及二次转化，冬季二次污染源主要以流动源污染为主，而夏季流动源和固定源污染贡献接近。     

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.     

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.     

Characterization of ionic composition of TSP and PM10 during the Middle Eastern Dust (MED) storms in Ahvaz, Iran

Because of the recent frequent observations of major dust storms in southwestern cities in Iran such as Ahvaz, and the importance of the ionic composition of particulate matters regarding their health effects, source apportionment, etc., the present work was conducted aiming at characterizing the ionic composition of total suspended particles (TSP) and particles on the order of ～10?μm or less (PM(10)) during dust storms in Ahvaz in April-September 2010. TSP and PM(10) samples were collected and their ionic compositions were determined using an ion chromatography. Mean concentrations of TSP and PM(10) were 1,481.5 and 1,072.9?μg/m(3), respectively. Particle concentrations during the Middle Eastern Dust (MED) days were up to four times higher than those in normal days. Ionic components contributed to only 9.5% and 11.3% of the total mass of TSP and PM(10), respectively. Crustal ions were most abundant during dust days, while secondary ions were dominant during non-dust days. Ca(2+)/Na(+) and Cl(-)/Na(+) ratios can be considered as the indicators for identification of the MED occurrence. It was found that possible chemical forms of NaCl, (NH(4))(2)SO(4), KCl, K(2)SO(4), CaCl(2), Ca(NO(3))(2), and CaSO(4) may exist in TSP. Correlation between the anionic and cationic components suggests slight anion and cation deficiencies in TSP and PM(10) samples, though the deficiencies were negligible.     

Study on Size Distribution of Total Aerosol and Water-Soluble Ions During an Asian Dust Storm Event at Jeju Island, Korea

Soil dust particles transported from loess regions of the Asian continent, called Asian dust, highly influences the air quality of north-eastern Asia and the northern Pacific Ocean. In order to investigate the effects of these dust storms on the chemical composition of atmospheric aerosol particles with different size, measurements of size distributions of total aerosol and major ion species were carried out on Jeju Island, Korea during April 2001. Juju Island was chosen for the study because the levels of emissions of anthropogenic air pollutants are very low. A 5-stage cascade impactor was used to sample size-fractionated aerosol particles. Samples were analyzed for major water-soluble ions using Dionex DX-120 ion chromatograph. The average mass concentration of total aerosol was found to be 24.4 and 108.3 microg m(-3) for non-Asian dust and Asian dust periods, respectively. The total aerosol size distribution, measured during the non-Asian dust period, was bimodal, whereas the coarse particles dominated the size distribution of total aerosol during the Asian dust period. It was found that SO4(2-), NH4+ and K+ were mainly distributed in fine particles, while Cl-, NO3-, Na+, Mg2+ and Ca2+ were in coarse particles. Although SO4(2-) was mainly distributed in fine particles, during the Asian dust period, the concentrations in coarse particles were significantly increased. This indicates heterogeneous oxidation of SO2 on wet surfaces of basic soil dust particles. The NH4+ was found to exist as (NH4)2SO4 in fine particles, with a molar ratio of NH4+ to SO4(2-) of 2.37 and 1.52 for non-Asian dust and Asian dust periods, respectively. Taking into account the proximity of the sampling site to the sea, and the observed chloride depletion, coarse mode nitrate, during the non-Asian dust period, is assumed to originate from the reaction of nitric acid with sodium chloride on the surfaces of sea-salt particles although the chloride depletion was not shown to be large enough to prove this assumption. During the Asian dust period, however, chloride depletion was much smaller, indicating coarse nitrate particles were mainly produced by the reaction of nitric acid with surfaces of basic soil particles. Most chloride and sodium components were shown to originate from sea-salt particles. Asian dust aerosols, arriving at Jeju Island, contained considerable amounts of sea-salt particles as they passed over the Yellow Sea. Ca2+ was shown to be the most abundant species in Asian dust particles.     

桂林市细颗粒物部分典型排放源的粒径谱及成分分析

采用在线单颗粒气溶胶质谱技术源解析方法,对桂林市PM2.5典型排放源的粒径和化学成分进行质谱分析,采集燃煤/燃气源、工业工艺源、扬尘源、油烟源4类共计7个典型排放源。结果表明,桂林市4类排放源细颗粒物的粒径分布为0.25~1.25μm,80%以上的细颗粒分布在0.2~1.0μm的小粒径范围,峰值约0.68μm。细颗粒物离子成分含有Na~+、Mg~+、K~+、NH~+4、Fe~+、Pb~+、Cd~+、V~+、Mn~+、Li~+、Al~+、Ca~+、Cu~+、Zn~+、Cr~+、CN~-、PO_3~-、NO_2~-、NO_3~-、Cl~-、SO_4~(2-)、SiO_3~-等成分,桂林市细颗粒物为元素碳、有机碳元素碳、有机碳、富锰颗粒、富铁颗粒、富钾颗粒、矿物质、左旋葡聚糖以及其他金属等9类。     

Characterization and optimization of an online system for the simultaneous measurement of atmospheric water-soluble constituents in the gas and particle phases

In this work we present the results of extensive characterization and optimization of the Ambient Ion Monitor-Ion Chromatograph (AIM-IC) system, an instrument developed by URG Corp. and Dionex Inc. for simultaneous hourly measurements of the water-soluble chemical composition of atmospheric fine particulate matter (PM(2.5)) and associated precursor gases. The sampling assembly of the AIM-IC consists of an inertial particle size-selection assembly, a parallel-plate wet denuder (PPWD) for the collection of soluble gases, and a particle supersaturation chamber (PSSC) for collection of particles, in series. The analytical assembly of the AIM-IC consists of anion and cation IC units. The system detection limits were determined to be 41 ppt, 5 ppt, and 65 ppt for gas phase NH(3(g)), SO(2(g)), and HNO(3(g)) and 29 ng m(-3), 3 ng m(-3), and 45 ng m(-3) for particle phase NH(4)(+), SO(4)(2-), and NO(3)(-) respectively. From external trace gas calibrations with permeation sources, we determined that the AIM-IC is biased low for NH(3(g)) (11%), SO(2(g)) (19%), and HNO(3(g)) (12%). The collection efficiency of SO(2(g)) was found to strongly depend on the composition of the denuder solution and was found to be the most quantitative with 5 mM H(2)O(2) solution for mixing ratios as high as 107 ppb. Using a cellulose membrane in the PPWD, the system responded to changes in SO(2(g)) and HNO(3(g)) within an hour, however for NH(3(g)), the timescale can be closer to 20 h. With a nylon membrane, the instrument response time for NH(3(g)) was significantly improved, becoming comparable to the responses for SO(2(g)) and HNO(3(g)). Performance of the AIM-IC for collection and analysis of PM(2.5) was evaluated by generating known number concentrations of ammonium sulfate and ammonium nitrate particles (with an aerodynamic diameter of 300 nm) under laboratory conditions and by comparing AIM-IC measurements to measurements from a collocated Aerosol Mass Spectrometer (AMS) during a field-sampling campaign. On average, the AIM-IC and AMS measurements agreed well and captured rapid ambient concentration changes at the same time. In this work we also present a novel inlet configuration and plumbing for the AIM-IC which minimizes sampling inlet losses, reduces peak smearing due to sample carryover, and allows for tower-height sampling from the base of a research tower.