临安一次沙尘暴过程影响气溶胶物理化学特性演变的初步分析

文章利用2002年3月29日～4月4日在浙江临安大气本底污染监测站观测的气溶胶粒子质量谱、离子与元素成分的数据,结合TOMS卫星的气溶胶指数资料和轨迹模式,重点分析在北方沙尘暴输送影响期间临安气溶胶质量浓度尺度分布的演变特点以及气溶胶化学成分与不同空气来源的关系。初步分析结果显示,受北方沙尘暴天气影响,临安气溶胶质量浓度、离子、元素浓度有明显的尺度分布演变。这种演变与污染物来源和大气污染物的气粒转化有关。沙尘影响前和结束后临安地区气溶胶主要以细粒子为主(<2.1μm),峰值粒径0.65～2.1μm,而受北方地区的沙尘暴影响,峰值粒径偏移到2.1～3.3μm,且在7～11μm间出现另一个峰值,同时临安气溶胶粗粒子中矿物元素显著增加。从离子成分看,在整个观测期间SO^2-₄与NH⁺₄在细粒子段有很好的一致性,而SO^2-₄,NO^-₃与Ca²⁺在粗粒子段有很好的相关,尤其是沙尘影响期间NO^-₃与Ca²⁺有很好的对应关系,表现出较明显的表面非均相反应特征     

河北汤泉地热流体水文地球化学特征及其成因

提要：汤泉位于河北省遵化市西北部,为山前丘陵地貌,地热资源丰富。本文通过对该地区地热流体研究发现：Na⁺、Ca²⁺、K⁺、Mg²⁺与SO^2-₄、HCO^-₃、Cl^-、NO^-₃是该地区地下热水的主要成分,水化学类型主要为SO^2-₄-Na⁺型,属于未污染的天然弱碱性水;流体中F^-含量平均为9.36 mg/l,远高于国家地下水质量标准ⅴ级;可溶性SiO₂的含量可作为地热温标;地热流体总矿化度平均为782.33 mg/l,属于淡水;为中等腐蚀型水,不结碳酸钙垢,无CaSO₄?2H₂O垢和SiO₂垢生成的可能;地热流体属于含岩盐地层溶滤的陆相沉积水;根据氢氧稳定同位素可知,河北汤泉地热流体主要来源于大气降水。     

多种矿物流体包裹体中液相阴阳离子的同时测定

地质流体研究是地球科学领域的研究热点,矿物流体包裹体中成分是认识地质流体的关键。群体包裹体液相成分分析的传统方法大多采用单通道离子色谱分析阴离子,原子吸收光谱或电感耦合等离子体原子发射光谱分析阳离子,分析方法适用矿物种类少,单矿物需要量大（3g以上）。本文使用双通道离子色谱仪,经过大量条件实验,优化了样品爆裂、提取等前处理分析条件,确认了不同矿物可检测的离子,并采用富集方法将样品需要量由常规的3.00g减少到300mg,实现了石英、方解石、萤石、闪锌矿、石榴子石、磁铁矿和黄铁矿等多种矿物流体包裹体液相成分中Li⁺、Na⁺、K⁺、Mg²⁺、Ca²⁺、F^-、Cl^-、Br^-、NO₂^-、NO₃^-、SO₄^2-等阴阳离子的同时分析。所建立的离子色谱同时分析矿物流体包裹体液相微量成分分析方法简便、快速,成本低,用样量少,扩大了矿物种类的分析范围,为成矿流体研究提供了更加直接、有效的信息。     

广东省顺德肝癌多发区病因探讨

根据顺德肝癌病多发区与周边正常区土壤、水地球化学特征对比,结合病区人文景观探讨顺德肝癌病因,分析认为病区水中NH₄⁺, NO₂^-, NO₃-的显著异常(高含量)是主要病因。     

WMO区域本底站气溶胶特征分析*

文章通过2002年8月12~27日和2003年7月20日~8月1日在浙江临安县的WMO区域空气污染本底站临安站所采集的气溶胶样品的质量浓度,水溶性离子,有机碳/元素碳(OC/EC)及部分化学元素的特征分析,并与1991年夏季(8月22~28日)气溶胶的某些特征比较,初步研究结果为:1991年至2003年夏季的气溶胶TSP,PM11和PM2.1浓度均呈现出减少的趋势,但是PM11/TSP和PM2.1/PM11则有增加的趋势。1991年、2002年和2003年PM11/TSP的值为90 % 左右,PM2.1/PM11 分别为46.52 % , 69.33 % 和72.29 % ,说明气溶胶以小粒子为主,小粒子又以细粒子为主。1991年、2002年和2003年浓度最高的离子为SO^2-₄,其次为NH^＋₄。其中SO^2-₄占所测离子浓度的百分数分别为65.39 % ,57.75 % 和57.27 % ,并且主要以(NH₄)₂SO₄,(K)₂SO₄和(Na)₂SO₄的形式存在。各离子浓度占所测离子浓度的百分数基本上不随年代变化,具有一定稳定性。2002年和2003年气溶胶中的OC浓度分别为29.91μg/m³和14.14μg/m³,均为各自的组分之首。2002年和2003年OC的比值PM2.1/PM11分别为64.63 % 和77.71 % ,EC的比值PM2.1/PM11分别为69.89 % 和87.17 % ,可见气溶胶中OC和EC主要存在于PM2.1的粒子中。元素富集因子分析表明,自然源与人为源对气溶胶中的元素都有重要的贡献。主因子分析结果显示PM2.1和PM11元素源基本相同,自然源主要是地壳、土壤尘和海盐, 人为源主要是煤飞灰(煤和焦碳)、冶炼工业和道路机动车辆的排放、废物处理、垃圾焚烧及建筑工业粉尘等。     

贵阳市区地表/地下水化学与锶同位素研究

贵阳市及邻近地区地表和地下水的化学与Sr同位素组成变化反映了典型喀斯特地区地表/地下水文系统的水-岩反应和城市污染特征:水体中的化学溶解物质主要来源于碳酸盐岩(石灰岩和白云岩)的风化作用和膏岩层的溶解,其次为人为污染物的输入;污染物以K⁺,Na⁺,Cl^-,SO^2-₄,NO^-₃为主,枯水期因大气降水补给小而受人为活动影响较大;丰水期和枯水期地表/地下水的化学组成变化说明地表/地下水交换活跃,地下水环境容易受到人为活动影响。     

天山东部冰川雪坑离子浓度特征的对比研究

对2004年获取的天山奎屯河哈希勒根51号冰川1个雪坑和哈密庙尔沟平顶冰川4个雪坑的离子浓度特征进行了研究,结果表明：Ca²⁺、NO^-3和SO₄^2-是哈密庙尔沟平顶冰川雪坑雪层和积累区雪坑底部冰中的主要离子（尤其是Ca²⁺ ）,其雪层中的主要阳离子关系可在底部冰中得以较好的反映,但雪层中各离子浓度与海拔的相关性不明显,可能与海拔的跨度较小和挖取的雪坑较疏有关;雪坑底部冰中的离子浓度与海拔间明显的相关性说明淋融作用随着海拔升高、气温降低而逐渐减弱。SO₄^2-和Ca²⁺是奎屯河哈希勒根51号冰川雪坑中的主要离子（尤其是SO₄^2-）,其雪坑离子化学特征与哈密庙尔沟平顶冰川差别较大,可能与哈密庙尔沟平顶冰川处于塔克拉玛干沙漠、古尔班通古特沙漠和鄯善沙漠的下风向相关,还可能与雪层内淋融作用的强弱和沉积通量的高程效应有关。哈密庙尔沟平顶冰川积累区雪坑中NH₄⁺、NO₃^-和K⁺的Cs/Ci较Ca²⁺、Mg²⁺和Na⁺要大,奎屯河哈希勒根51号冰川Na⁺和NH4⁺的“雪冰比”较Cl-、SO₄^2-、Mg²⁺和Ca²⁺要大,说明这两条冰川雪坑中的Ca²⁺和Mg²⁺信号较其它离子可能更易于在冰芯记录中保存下来,为冰芯研究和古气候记录的恢复提供了保障。     

电感耦合等离子体质谱法测定硫时不同形态硫的影响

电感耦合等离子体质谱(ICP-MS)常常被应用于矿石、蛋白质和化石燃料等材料中硫含量的测定。文章综合研究比较了四极杆电感耦合等离子体质谱(Q-ICP-MS)和扇形磁场电感耦合等离子体质谱(SF-ICP-MS)测定硫的灵敏度、检出限及空白干扰。重点考察了两种不同的样品介质(水和2% HNO₃)中不同形态的硫对SF-ICP-MS测定硫信号的影响,并且深入研究了影响的原因。结果表明,硫含量相同但形态不同的含硫阴离子(S^2-、S₂O₃^2-、SO₃^2-、SO₄^2-)在2%的HNO₃介质中的信号比在水介质中的信号稳定,2%的HNO₃更适合于作为ICP-MS测定硫的介质。在2%的HNO₃介质中,S^2-、SO₃^2-中S的ICP-MS测量灵敏度(即标准曲线的斜率)分别为7828 cps/(μg·L^-1)、5528 cps/(μg·L^-1),SO₄^2-和S₂O₃^2-的测量灵敏度分别是为1321 cps/(μg·L^-1)、1299 cps/(μg·L^-1)。S^2-和SO₃^2-的灵敏度分别约为SO₄^2-的6倍和4倍;而S₂O₃^2-的灵敏度与SO₄^2-基本一致。主要原因在于S^2-、SO₃^2-形态的硫在HNO₃介质中形成了气态的H₂S和SO₂,相当于提高了雾化效率,从而使这两种形态硫的灵敏度大幅度提高。     

试论早子沟金矿成矿作用过程中地幔流体的参与

早子沟金矿地处夏河—合作—岷县区域性深大断裂带南侧,在时空上受断裂和壳幔混合岩浆双重控制。通过对矿床主要控矿因素、矿石稀土地球化学、流体包裹体及S、H、O、Pb同位素的系统研究,在探讨成矿流体来源的基础上,对地幔流体参与金矿成矿作用的可能性进行了探讨。研究表明：矿石稀土元素配分模式表现出轻稀土富集的特征;矿床流体包裹体气相成分主要为H₂O和CO₂,含少量CH₄、N₂等,液相成分阳离子以Na⁺、K⁺为主,含少量Ca²⁺ 、Mg²⁺,阴离子以SO₄^2-、Cl^-为主;黄铁矿、辉锑矿矿物的?啄³⁴ S_v-CDT介于-10. 30‰ ~ -4. 9‰之间,平均-8. 33‰,反映成矿作用过程有地层硫的加入;氢、氧同位素显示成矿流体既有岩浆水和地幔初生水的参与,亦有大气降水的加入;矿石铅同位素组成显示铅来源于壳幔的混合。以上说明成矿流体具多源性,暗示地幔流体参与了矿床成矿作用。     

碎屑岩储层成岩流体演化与储集性及油气运移关系探讨——以塔里木盆地满西地区上奥陶统-石炭系海相碎屑岩储层为例

碎屑岩储层中次生孔隙的发育主要为长石、岩屑及胶结物等的溶蚀,而溶蚀强度与流体成分密切相关。塔里木盆地满西地区从上奥陶统—石炭系不同层位、不同地区碎屑岩样品中包裹体的均一温度有差异,分为3个均一温度区间。包裹体流体绝大部分为不成熟氧化性、酸性流体;不同井区、不同层段、不同类型砂岩包裹体的阴离子浓度变化较大,石英加大边中含的包裹体总体阴离子组成单一,浓度低,而方解石胶结物、石英胶结物中包裹体组成复杂,浓度变化很大。储层物性与HCO^-₃、CO^2-₃、Cl^-离子浓度变化大致呈正相关关系,而与NO^-3、SO^2-₄离子浓度关系不明显,甚至有相反的变化趋势;研究区有3期油气运移。     

祁连山老虎沟12号冰川积雪化学特征及环境意义

2012年6月在祁连山老虎沟12号冰川采集雪坑和表层雪样品, 结合相关分析法、 海盐示踪法、 气团轨迹法等方法, 对冰川积雪的主要化学离子特征、 来源及环境意义进行分析研究.结果表明, 积雪中平均离子浓度Ca²⁺>SO₄^2->NH₄⁺>NO₃^->Cl^->Na⁺>Mg²⁺>K⁺. 雪坑中Ca²⁺是主要的阳离子, SO₄^2-是主要的阴离子; 各种离子在雪坑中的平均浓度要远大于表层雪, 而且雪坑中的化学离子浓度峰值与污化层有着很好的对应性.同时, 与青藏高原、 中亚天山、 阿尔泰山以及北半球其他区域高海拔雪冰化学特征进行比较, 发现祁连山老虎沟12号冰川区积雪化学特征受亚洲粉尘源区陆源矿物影响较大.然而, 雪坑中的离子(尤其是Na⁺和Cl^-)除了陆源矿物粉尘之外, 部分还来源于海洋源.结合NOAA Hysplit模型对冰川区积雪化学离子来源进行了后向轨迹反演验证.     

Water soluble components of PM10 Chongqing, China

The concentrations of water soluble ions (Na⁺, NH₄ ⁺, K⁺, Mg²⁺, Ca²⁺, NO₃ ^-, Cl^-, and SO ₄ ^2- ) in PM₁₀ samples collected on cellulose filters by a medium-volume cascade impactor were determined, which were obtained from three kinds of areas in Chongqing: industrial area (Jiulongpo district), commercial and residential area (Jiangbei district) and background area (Jinyun Mountain in the Beibei district). The results showed that except for the background site, the annual average values of PM₁₀ are 23% – 61% higher than the national air quality standard (GradeII) (0.1 mg/m³), even that the value of the control site is still 20% higher than American standard (0.05 mg/m³). This implied that serious pollution of fine particles occurred in Chongqing. Nine kinds of soluble ions in water of PM₁₀ were analyzed by ion chromatography (IC) and the annual average concentrations follow the order of [SO ₄ ^2- ] > [NO³ _-] > [Cl^-] > [F^-], and [Ca²⁺] > [NH₄ ⁺] > [K⁺] > [Na⁺] > [Mg²⁺]. Their values were different in these areas: the industrial area > the commercial and living area > the control area. As for NH_{4 +}, K⁺, Ca²⁺, NO₃ ^- and SO ₄ ^2- , their seasonal average concentrations show a similar variation trend: the values in spring and fall were higher than those in summer and winter. The seasonal average concentrations of [Cl^-], [F^-], [Na⁺] and [Mg²⁺] are much lower than those of other ions. However, the concentrations of [Na⁺] changed more greatly in different seasons than those of the other three ions. Correlation coefficients showed that the three areas have been polluted by coal smoke and dust to different extents, while some local resources of pollution should be taken into consideration as well.     

Chemistry and source identification of wet precipitation in a rural watershed of subtropical China

South China is one of the regions severely suffering from acid rain in the world.However,few systematic studies of rural precipitation chemistry have been performed in comparison with the extensive studies on their urban counterparts of this region.In order to characterize the current acid rain status and identify its possible sources in the rural area of South China,we analyzed precipitation collected event by event from a rural forested watershed in southern Anhui Province between March 2007 and February 2010.The results showed that the concentrations of major ions within precipitation in the studied rural area were significantly lower than those reported for the urban areas of the same latitude in China.Nevertheless,the precipitation acidity(with an average pH value of 4.49) and the frequency of acid rain(95%) were considerably high.The relatively high ratio of(SO42+ NO 3)/(Ca2+ +NH4+) was the main cause of acid rain in this rural area,as SO 2 and NO x were the main precursors of acid rain,while Ca2+ and NH4+acted as the dominant neutralizers to the acidity.Source identification indicated that Ca2+ and Mg2+ mainly were derived from alkaline dust,SO42,NO 3 and NH4+originated mainly from anthropogenic sources such as industrial and agricultural activities,most Na +,Cl,K + and some of Mg2+ were derived from the sea.The results suggested that the major ions within precipitation in the rural area of South China were related to the meso-scale and long-range transport of particles and aerosols in the air.     

Mass-size distribution of PM10 and its characterization of ionic species in fine (PM2.5) and coarse (PM10−2.5) mode, New Delhi, India

Size distribution of PM₁₀ mass aerosols and its ionic characteristics were studied for 2 years from January 2006 to December 2007 at central Delhi by employing an 8-stage Andersen Cascade Impactor sampler. The mass of fine (PM_2.5) and coarse (PM_10?2.5) mode particles were integrated from particle mass determined in different stages. Average concentrations of mass PM₁₀ and PM_2.5 were observed to be 306 ± 182 and 136 ± 84 μg m^?3, respectively, which are far in excess of annual averages stipulated by the Indian National Ambient Air Quality Standards (PM₁₀: 60 μg m^?3 and PM_2.5: 40 μg m^?3). The highest concentrations of PM_10?2.5 (coarse) and PM_2.5 (fine) were observed 505 ± 44 and 368 ± 61 μg m^?3, respectively, during summer (June 2006) period, whereas the lower concentrations of PM_10?2.5 (35 ± 9 μg m^?3) and PM_2.5 (29 ± 13 μg m^?3) were observed during monsoon (September 2007). In summer, because of frequent dust storms, coarse particles are more dominant than fine particles during study period. However, during winter, the PM_2.5 contribution became more pronounced as compared to summer probably due to enhanced emissions from anthropogenic activities, burning of biofuels/biomass and other human activities. A high ratio (0.58) of PM_2.5/PM₁₀ was observed during winter and low (0.24) during monsoon. A strong correlation between PM₁₀ and PM_2.5 (r ² = 0.93) was observed, indicating that variation in PM₁₀ mass is governed by the variation in PM_2.5. Major cations (NH₄ ⁺, Na⁺, K⁺, Ca²⁺ and Mg²⁺) and anions (F^?, Cl^?, SO₄ ^2? and NO₃ ^?) were analyzed along with pH. Average concentrations of SO₄ ^2? and NO₃ ^? were observed to be 12.93 ± 0.98 and 10.33 ± 1.10 μg m^?3, respectively. Significant correlation between SO₄ ^2? and NO₃ ^? in PM_1.0 was observed indicating the major sources of secondary aerosol which may be from thermal power plants located in the southeast and incomplete combustion by vehicular exhaust. A good correlation among secondary species (NH⁺, NO₃ ^? and SO₄ ^2?) suggests that most of NH₄ ⁺ is in the form of ammonium sulfate and ammonium nitrate in the atmosphere. During winter, the concentration of Ca²⁺ was also higher; it may be due to entrainment of roadside dust particles, traffic activities and low temperature. The molar ratio (1.39) between Cl^? and Na⁺ was observed to be close to that of seawater (1.16). The presence of higher Cl^? during winter is due to western disturbances and probably local emission of Cl^? due to fabric bleaching activity in a number of export garment factories in the proximity of the sampling site.     

天山乌鲁木齐河源1号冰川融水径流水化学特征研究

2006年和2007年的整个消融期内,在天山乌鲁木齐河源1号冰川末端水文控制点逐日定时采集融水径流样品,对样品的主要可溶离子、pH、电导率EC、总溶解固体TDS和悬移质颗粒物SPM进行了分析. 结果表明：天山乌鲁木齐河源1号冰川融水径流离子类型为Ca²⁺-HCO₃^--SO₄^2-,呈弱碱性. 融水径流中TDS变化受日径流量调节显著,表现为消融初期和末期浓度较高,消融强烈时浓度较低;SPM以细颗粒物质为主,各粒度组分含量变化幅度较大,且质量浓度SSC年内变化与TDS呈相反的变化趋势. 融水径流中离子组成主要受岩石风化作用影响,离子摩尔比值和Piper图分析表明,控制冰川径流离子组成的主要过程是碳酸盐、黄铁矿和长石类矿物风化作用.     

玉龙雪山地区大气降水中粉尘颗粒物特征研究

以在玉龙雪山地区采集的大气降水样品为主要研究载体,分析了大气降水中粉尘颗粒物随时间的变化特征和影响大气降水中粉尘含量的潜在因素. 结果表明：大气降水中颗粒物浓度和典型粉尘特征化学离子含量的变化具有很好的一致性,且季风期末大气降水中的微粒含量显著升高,显示了明显的季节性变化特征. 丽江市和甘海子盆地大气降水中粉尘化学离子含量(SO₄^2-,Mg²⁺,Ca²⁺,K⁺,NH₄⁺,NO₃^-,粉尘浓度)之间具有较好的相关性,反映了这些离子共同的来源. 降水中pH值和电导率的变化很大程度上受到粉尘活动的影响,海盐气溶胶粒子对玉龙雪山地区大气降水中典型粉尘微粒(除Cl^-和部分Na⁺之外)的沉降没有贡献. 此外,降水化学和微粒分析表明,丽江市区的大气环境不排除人为活动的影响.     

Study of precipitation chemistry over an industrial city

The growing trend of industrialization has marked impact on the atmospheric chemistry around the globe. Such impacts are also predicted for developing countries like India. Acid precipitation due to secondary pollutants is one of them. The present investigation was conducted with an aim of studying the precipitation chemistry over Asansol city, India during the monsoon season. The rain water samples, collected on event basis during the period of June to September 2006, were analyzed for HCO₃ ^?, Cl^?, SO₄ ^2?, NO₃ ^?, NH₄ ⁺, K⁺, Na⁺, Mg²⁺, Ca²⁺ and pH using standard procedures. The study revealed that the precipitation was alkaline in nature with mean pH value of 6.08. Dominant anion in rain water samples was HCO₃ ^? (36 %), whereas Ca²⁺ was highest among the cations (53 %). The observed acidic events, based on pH value, were only 17 %, indicating the alkaline components effectively neutralize rain water over the area. This was also supported by the total alkaline to acid ion ration of 1.05. The ratio of (NO₃-^?+Cl^?) and SO₄ ^2? was >1, indicating that acidic properties were influenced by HNO₃ and HCl. In the ratio between (Ca²++NH₄ ⁺) and (NO₃ ^?+SO₄ ^2?), values >1 were obtained, indicating significant alkaline influence, which effectively prevented acid depositions in the area.     

Characterization of PM10 in the ambient air during Deepawali festival of Rajnandgaon district, India

Deepawali is one of the main festivals for Hindu religion which falls in the period October–November every year with great fireworks display. In this study, we investigated the levels of water soluble ions and heavy metals—during the fireworks festival in Rajnandgaon, Central India. The chemical compositions and noise level distributions are reported from the sampling site. First time during Deepawali, air quality was studied in this area, The Aerosol samples of PM₁₀ (particle aerodynamic diameter <10 μm) are collected in October 24–28, 2011. Aims of the present studies are (1) To describe the particulate concentrations and associated chemical species during Deepawali festival, (2) To recognize the noise level in Deepawali festival. For study, the samples were collected in glass fiber filter paper and analyzed for the major water soluble ions F^?, Cl^?, NO₃ ^?, SO₄ ^2?, Na²⁺, NH₄ ⁺, K⁺, Ca²⁺, and Mg²⁺ employing ion chromatograph. Concentration of heavy metals was analyzed by ICP-MS and was observed to occur in order Fe > Zn > Pb > Ni > Cr > Cd. The result revels that all concentration are above the permissible limit fixed by CPCB, USPEA, and WHO standard. It is concluded that the burning of fireworks during Deepawali festival was the main source of heavy metals and ion.     

Impact of anthropogenic and natural processes on the chemical compositions of precipitation at a rapidly urbanized city in Northwest China

In this study, the chemical composition of precipitation was applied as an indicator to study the influence of urbanization on the atmosphere in Qilian County, a northwest city in China. The results showed that the annual mean pH calculated from the concentration of H⁺ was 7.35 due to alkaline ion neutralization, and Ca²⁺ had the largest contribution. Ca²⁺ and SO₄ ^2? were the most abundant ions, accounting for 45 and 17%, respectively, of the total ion mass. The correlation coefficient between SO₄ ^2? and NO₃ ^? reaching 0.85 in the urban area indicated the same source. The highest concentration of sulfate in spring was probably related to the strong wind in Northwest China, while the concentration of nitrate was the highest in winter suggesting that most of the nitrate originated from coal combustion, not vehicle emission. The application of factor and cluster analysis indicated that 38.43% of the SO₄ ^2? and 16.97% of the NO₃ ^? in Qilian County were from crustal sources, while 61.5% of the SO₄ ^2? and 83.03% of the NO₃ ^? originated from the human activities. The back trajectory analysis indicated that the pollution emitted from the surrounding areas also made a great contribution to the local atmospheric quality. Thus the communication and cooperation mechanisms with surrounding cities and improvement of energy consumption efficiency should be strengthened in the next few years.