2006-2020年上海市闵行区大气降水化学特征及来源分析

为研究上海市闵行区大气降水化学特征及来源,以2006—2020年上海市闵行区大气降水监测数据为依据,对大气降水量、pH值、电导率(EC)和主要离子进行了统计分析。结果表明:2006—2020年上海市闵行区大气降水呈酸性,pH值范围为4.41~5.19,酸雨频率呈下降趋势;EC变化范围为1.26~3.67 mS/m,平均值为2.32 mS/m;夏季pH值最高,酸雨发生频率、EC和总离子浓度最低,冬季pH值最低,总离子浓度最高。大气降水中各离子组分浓度占比大小排序为:SO^(2-)_(4)>NH^(+)4>NO^(-)3>Ca^(2+)>Cl^(-)>Na^(+)>Mg^(2+)>F^(-)>K^(+),主要阴、阳离子SO^(2-)_(4)、Ca^(2+)和NH^(+)4浓度呈明显下降趋势,NO^(-)3浓度变化较平稳;SO 2-4与NO^(-)3的浓度比范围为0.94~3.59,呈波动下降趋势,降雨类型由硫酸型逐步转为混合型。因子分析及相关性分析显示,因子1中所有的离子成分都有较大的载荷,各离子在来源上可能具有一定的共性,Ca^(2+)与Mg^(2+)、K^(+)表现出显著相关,其可能来源于地壳组分;Cl^(-)与K^(+)、Mg^(2+)、Ca^(2+)的相关性显著,Mg^(2+)、K^(+)与Cl^(-)、Na^(+)有强相关性,表明海洋输送及生物质燃烧对大气降水化学组成的影响;NO_(3)^(-)、SO^(2-)_(4)和NH^(+)4在因子2中为高荷载,且有很好的相关性,它们可能有相似的来源或形成化合物共同存在。     

2016-2020年济南市大气降水化学组分变化特征及来源分析

基于2016—2020年济南市城区国控点降水监测数据,应用因子分析、相关分析、富集因子分析以及正定矩阵因子分解模型(PMF)对济南市大气降水化学组分特征及来源进行了综合评价与分析。结果表明:2016—2020年济南市大气降水呈弱碱性,pH值为6.01~8.03,呈波动下降趋势;电导率(EC)为47.6~97.4μS/cm,平均值为70.99μS/cm,远高于我国降水背景点值;济南市降水类型为硫酸、硝酸混合型降水,SO^(2-)_(4)对济南市降水酸化贡献较高;大气降水中各离子组分浓度大小排序为:NH^(+)4>Ca^(2+)>SO^(2-)_(4)>NO^(-)_(3)>Cl->Na^(+)>Mg^(2+)>K^(+)>F^(-),主要阴、阳离子SO^(2-)_(4)和NH^(+)4浓度呈现逐年下降趋势;因子分析和相关性分析显示,各离子之间存在一定的共源性。富集因子分析结果表明,SO 2-4、NO-3和Cl-主要为人为源贡献,Ca^(2+)、Mg^(2+)和K^(+)受土壤源贡献较大;PMF模型结果显示,扬尘源除了是Ca^(2+)的主要贡献源外,也是NO-3的主要贡献源之一。二次污染源是济南大气降水无机离子的主要来源,占比为37.88%,其次为燃煤源和扬尘源,占比分别为23.91%和22.59%。     

克拉玛依市大气降水化学的统计学分析

运用相关分析、因子分析和聚类分析等统计学分析方法,对2009—2010年新疆克拉玛依市的大气降水化学组成和分布特征进行分析。结果表明,SO4^2-、Cl^-、Ca^2＋和Na^＋是降水中主要离子。降水的pH值、电导率、降水量和各离子组份均呈现明显的正偏态分布,降水样品以低离子含量的样本为主,因子分析和聚类分析2种分类方法分析降水中水溶性离子主要分为3类。SO4^2-、Cl^-、Mg^2＋、F^-主要来自人为活动的贡献,K^＋、Ca^2＋主要来源于土壤和沙尘等地壳,H^＋与其他阴、阳离子间并未表现出明显的相关关系,表明研究区域的降水酸度是所有致酸离子和各种离子综合作用的结果,而不是降水中某个单一的离子组份确定的。     

淮南市降水化学组成特征与来源分析

2013—2014年,逐次采集淮南城市大气降水样品,对其离子化学组分进行分析测试,并利用酸度分析、中和因子和富集系数等方法对其酸碱物质平衡和离子来源进行了分析。化学组分分析结果表明,淮南城市降水pH为6.23~7.03,雨量加权平均值为6.68,整体上降水没有呈现酸化,大部分酸性物质能被碱性物质中和。主要阴离子为SO_4~(2-)、NO_3~-,雨量加权平均值分别为147.02、62.16μeq/L,两者分别占阴离子总浓度的60.3%、25.3%;主要阳离子为Ca~(2+)、NH_4~+,雨量加权平均值分别为126.42、96.43μeq/L,分别占阳离子总浓度的44.9%、34.3%。利用富集系数法计算结果表明,SO_4~(2-)、NO_3~-主要来源于人为活动排放,Cl~-主要为海洋输入,而Ca~(2+)、Mg~(2+)、K~+则主要来自陆源输入和人为活动。     

金华市大气降水的化学组成特征及来源解析

对2004年大气降水样品监测资料的综合分析和研究表明,金华市降水样品pH值的分布范围在3.64~6.76之间,降水的酸雨率为79.3%。SO24-和NO-3是降水中主要的阴离子,分别占降水中阴离子总量的66.1%和21.7%。NH 4和Ca2 是降水中含量最高的阳离子,分别占阴离子总量的56.6%和33.4%。降水中这些离子的浓度水平一般比世界上其它地方高,但大大低于国内的北方地区。由于降水中缺乏足够的中和物质,大约76%的降水酸度被NH 4、Ca2 和K 等碱性成分中和。陆源型离子Ca2 、Mg2 和K 以及海盐性离子Na 和Cl-之间存在明显的相关关系,另外Ca2 和SO24-、Mg2 和SO24-、Mg2 和NO-3以及Mg2 和Cl-之间也可以观察到比较好的相关关系。土壤和海水的富集系数表明,研究区域的Ca2 和K 主要来源于岩石/土壤风化,SO24-和NO-3主要归因于人为活动的影响。     

重庆黔江区大气降水的化学特征及来源分析

通过2013年6月—2014年5月对黔江区大气降水的化学组成分析研究表明,降水样品的p H值分布范围在4.91~7.32之间;SO2-4是降水中主要的阴离子,占阴离子总量的68.9%,Ca2+是降水中含量较高的阳离子,占阳离子总量的41.4%;SO2-4/NO-3浓度比为6.78,表明降水类型为硫酸盐型。陆源性离子Ca2+、Mg2+以及海源性离子Na+和Cl-之间存在明显的相关关系。海水和土壤的富集系数表明,研究区域的SO2-4和NO-3主要归因于人为活动的影响。     

湖南省大气湿沉降化学研究

以湖南省1999～2001年的酸雨监测数据为基础,运用统计学和线性回归分析方法研究了位于中国中南部的重酸雨区湖南省的大气降水的酸度和化学组成的分布特征以及季节变化规律。结果表明,大气降水以SO_4~(2-)为主,占总离子量的31％,大气降水阴阳离子基本平衡。降水年平均pH值为4.86,以春季酸度最大,降水离子总量以冬季最大。研究结果同时表明,降水酸度是主要酸性离子和主要碱性离子共同作用的结果,而且([H~+]+[NH_4~+])/([SO_4~(2-)]+[NO_3~-])比值的变化能较好的反映降水过程中强酸离子的中和现象。     

乌鲁木齐近十二年(1997~2009)降水中化学组分变化趋势分析

通过对乌鲁木齐市近12年(1997~2009)降水的化学组分分析,表明大气环境中的年际pH值在6.04~7.42间波动。∑阴离子所占百分比约为∑阳离子2倍。SO^2-₄和Ca²⁺分别是阴离子和阳离子中占比重最大的离子,直接影响降水的化学性质。近年来,SO^2-₄在阴离子中所占比重呈下降趋势,而NO^-₃则逐年增加,说明乌鲁木齐市在控制燃煤型污染方面采取的措施取得了一定效果,而机动车尾气污染日益加重,大气环境中各阴离子的组分比例在不断变化。     

天津市PM10和PM2.5中水溶性离子化学特征及来源分析

2011年5月—2012年1月在天津市南开区设立采样点,采集大气中PM10和PM2.5样品。采用离子色谱法测定颗粒物中水溶性无机阴离子、阳离子成分,分析其主要组成、季节变化及污染来源。结果表明,天津市PM10中离子平均浓度为71.2μg/m3,占PM10质量浓度的33.7%。PM2.5中离子平均浓度为54.8μg/m3,占PM2.5质量浓度的39.6%。NH+4、SO2-4、NO-3等二次离子含量较大,且夏季含量均为最高。颗粒物总体呈酸性,PM10中∑阳离子/∑阴离子平均值为0.92,PM2.5中该比值为0.75。来源分析发现,PM10可能主要来源于海盐、工业源、二次反应及土壤和建筑尘等,PM2.5则主要来源于海盐污染源、二次反应及生物质燃烧。     

杭州夏季一次降雨过程雨水中全氟化合物及主要化学组分的变化特征

采用分段采样的方式收集杭州市2018年8月2日—3日一场降水样品，测定其中16种全氟化合物（PFCs）及主要化学组分浓度。结果发现，此次降雨过程水样的pH值范围为5.04～5.32，均为弱酸性降水，酸雨类型为复合型，检出的主要阳离子为NH+4，主要阴离子为SO2-4和NO-3；样品中检出7种中短链PFCs，包括2种全氟烷基磺酸（PFSAs）和5种全氟烷基羧酸（PFCAs），ΣPFCs质量浓度范围为4.41 ng/L～25.2 ng/L，主要污染因子全氟辛酸（PFOA）质量浓度范围为096 ng/L～13.1 ng/L；降雨过程对大气污染清除作用的统计结果表明，区域大气环境中的主要化学组分及除全氟丁酸（PFBA）之外的PFCs污染主要吸附在云下大气颗粒物上；雨水中各污染因子浓度变化特征及相关性统计结果提示，杭州市大气中PFCAs和PFSAs两类PFCs可能来自不同的污染源。     

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.     

Statistical approaches for hydrogeochemical characterization of groundwater in West Delhi, India

Parametric statistical approaches, correlations and multiple linear regressions were used to develop models for the interpretation of hydrogeochemical parameters in the Western part of Delhi state, India. The hydrogeochemical parameters indicated that the groundwater quality is not safe for consumption. The water is moderately saline and the salinity level is increasing over time. There is also the problem of nitrate pollution. The correlation between electrical conductivity (EC) and other water quality parameters except potassium (K(+)), nitrate (NO(3)(-)) and bicarbonate (HCO(3)(-)) is significantly positive and Ca(++)+ Mg(++)/Na(+)+ K(+) is significantly negative. In predicting EC, the multiple R(2) values of 0.996 and 0.985 indicate that 99.6% and 98.5% variability in the observed EC could be ascribed to the combined effect of Na(+), HCO(3)(-), Cl(-), SO(4)(--), NO(3)(-) and Ca(++)+ Mg(++) for the year of 2005 and 2006 respectively. Out of 99.6% of the variability in EC in 2005, 51.2% was due to Cl(-) alone, and 8.5%, 12.5%, 6.1%, 14.7% and 6.7% were due to Na(+), HCO(3)(-), SO(4)(--), NO(3)(-) and Ca(++) + Mg(++). Similarly in 2006, out of 98.5% of the variability in EC, 48.5% was due to Cl(-) alone, and 10.4%, 12.7%, 5.3%, 17.2% and 4.4% were due to Na(+), HCO(3)(-), SO(4)(--), NO(3)(-) and Ca(++)+ Mg(++). The analysis shows that a good correlation exists between EC, Cl(-) and SO(4)(--) either individually or in combination with other ions and the multiple regression models can predict EC at 5% level of significance.     

Atmospheric deposition of major ions and trace metals near an industrial area,Jordan

Al, Cd, Cr, Cu, Fe, Mn, Pb, Zn, NH4+, Mg2+, Ca2+, Na+, K+, Cl-, NO3- and SO4(2-), along with pH were determined in wet and dry deposition samples collected at Al-Hashimya, Jordan. Mean trace metal concentrations were similar or less than those reported for other urban regions worldwide, while concentrations of Ca2+ and SO4(2-) were the highest. The high Ca2+ concentrations were attributed to the calcareous nature of the local soil and to the influence of the Saharan dust, while the high concentrations of SO4(2-) were attributed to the influence of anthropogenic sources and Saharan dust soil. Except for SO4(2-), NO3-, and Ca2+, dry deposition fluxes of measured metals and ions were higher than their corresponding wet deposition fluxes. The high annual average pH values recorded for wet and dry deposition samples were attributed to the neutralization of acidity by alkaline species. Cd, Cr, Cu, Pb, Zn, NO3- and SO4(2-) were enriched in wet and dry deposition samples relative to crustal material, and a significant anthropogenic contribution to these elements and ions is tentatively suggested. Finally, the possible sources and the main factors affecting the concentrations of the measured species are discussed.     

山西省大气降水水质评价

为了解山西省大气降水水质状况、主要污染物及区域分布规律，山西省水文部门于1984年开始对大气降水进行监测。在全省9个地市布设测点，分别为：太原市、大同市、长治市、榆次市、临汾市以及吕梁、忻州、阳泉、运城地区。监测项目为H^2 、电导率、Ca^2 、Mg^2 、K^2 、Na^2 、NH4^2 、SO4^2-、NO3^-、Cl^-、CO3^-、HCO3^-、F^-。结果表明，除吕梁、忻州地区外。山西省各地市均有酸雨发生，但酸雨发生的频率不高，全省年平均为3．3％；酸雨的酸性程度也不高，对生态可造成明显影响的降水次数不多；山西省酸雨为典型的硫酸型，酸雨中硫酸与硝酸的质量浓度比值远高于全国平均值。     

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.     

Atmospheric wet deposition of soluble macro-nutrients in the Cilician Basin, north-eastern Mediterranean sea

In order to estimate wet deposition atmospheric fluxes of macro-nutrients into the eastern Mediterranean coastal waters, soluble inorganic phosphate (PO4(3-)), nitrate (NO3-) and nitrite (NO2-) concentrations in precipitation (from February 1996 to June 1997) have been measured at a coastal sampling site, Erdemli, Turkey. Water-soluble inorganic PO4(3)-P, a reactive, bioavailable, limiting macro-nutrient in the oligotrophic waters of the eastern Mediterranean was studied with respect to its contribution to biological productivity. Reactive PO4(3-)-P and NO2(-) + NO3(-)-N concentrations were found to be highly variable in rainwater samples. One of the aims of the study was to determine the contribution of dust transport to the soluble macro-nutrient budget of the eastern Mediterranean. No differences were found between the mean reactive P and NO(2-) + NO3(-)-N concentrations of "red rain" and normal rain events. Most likely as a result of low solubility of crustal phosphorus, dust episodes were not found to be important sources of reactive P, in terms of wet deposition. The annual wet deposition fluxes of reactive PO4(3-)-P and NO2(-) + NO3(-)-N into the Cilician Basin were respectively estimated to be 0.010 g P m(-2) per year and 0.23 g N m(-2) per year, which are comparable to the fluxes from land-based sources in the north-eastern Mediterranean. The incorporation of water soluble bioavailable PO4(3-)-P and NO2(-) + NO3(-)-N delivered via atmospheric wet deposition could be responsible for approximately 3.3% (0.40 g C m(-2) per year) and 11.0% (1.31 g C m(-2) per year) respectively, of the mean annual new production in the north-eastern Mediterranean.     

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。     

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。     

西安城北地区秋季PM_(2.5)中的矿尘颗粒污染特征

采用单颗粒气溶胶飞行时间质谱仪(Single Particle Aerosol Mass Spectrometer,SPAMS)对西安市大气矿尘颗粒物进行连续12 d在线分析,共采集到107 425个同时含有正负质谱信息的矿尘颗粒,矿尘颗粒物占PM_(2.5)样本数的8.44%。结果表明,矿尘颗粒物的正离子碎片成分以Na~+、K~+、Al~+、Ca~+、CaO~+、Fe~+为主,同时还含有Pb~+等,负离子碎片成分以NO~-_2和NO~-_3为主,另外还含有HSO~-_4、SiO~-_3、HSiO~-_3、H(NO_3)~-_2等。在西安市大气细颗粒物中,矿尘颗粒物中贡献较大的几类(如含钙、含铁、铁氧颗粒物等)大多是老化的成分。将观测阶段采集到的矿尘颗粒纳入本地污染源谱进行来源分析,其主要来源为扬尘源、工业源、燃煤源和汽车尾气源等。