不同材质滤膜测量大气颗粒物质量浓度和化学组分的适用性

为提高不同粒径段大气颗粒物质量浓度及化学组成测量数据的准确性,使用惯性撞击式采样器对北京、千烟洲和鼎湖山3个站点的大气颗粒物分9个粒径段进行了采集,从质量浓度偏差和化学组成的角度进行了方法学探讨.结果表明,在恒温25℃、恒湿50%平衡条件下,称量石英材质的采样膜获得的PM2.1质量浓度相对于TEOM在线PM2.5观测结果的正偏差为20%左右,正偏差诱因是环境空气相对湿度过高.干燥(10% 湿度,25℃)微环境平衡处理方法有利于采样后膜片中H2O析出,使得上述正偏差降低至8%.通过条件实验,确定了石英膜采样前后在干燥器中放置72h平衡后称重、差减获得各级质量浓度的方法,可将偏差控制在可接受范围之内.基于这种方法获得的PM2.1质量浓度与TEOM在线PM2.5观测结果呈显著线性相关(R2=0.89,P<0.05).为达到通过化学成分重构质量浓度的需求,建立了同步使用石英膜采集样品并用于水溶性成分、有机碳和元素碳含量分析,而使用纤维素膜采样后用于金属元素分析的方案.应用上述方案对样品进行了全化学分析,对PM2.1质量进行了重构,重构获得的质量浓度与称重获得PM2.1质量浓度也呈显著线性相关(R2=0.89,P<0.05).     

不同材质滤膜测量大气颗粒物质量浓度和化学组分的适用性——以安德森分级采样器为例

为提高不同粒径段大气颗粒物质量浓度及化学组成测量数据的准确性,使用惯性撞击式采样器对北京、千烟洲和鼎湖山3个站点的大气颗粒物分9个粒径段进行了采集,从质量浓度偏差和化学组成的角度进行了方法学探讨.结果表明,在恒温25℃、恒湿50%平衡条件下,称量石英材质的采样膜获得的PM2.1质量浓度相对于TEOM在线PM2.5观测结果的正偏差为20%左右,正偏差诱因是环境空气相对湿度过高.干燥(10%湿度,25℃)微环境平衡处理方法有利于采样后膜片中H2O析出,使得上述正偏差降低至8%.通过条件实验,确定了石英膜采样前后在干燥器中放置72h平衡后称重、差减获得各级质量浓度的方法,可将偏差控制在可接受范围之内.基于这种方法获得的PM2.1质量浓度与TEOM在线PM2.5观测结果呈显著线性相关(R2=0.89,P0.05).为达到通过化学成分重构质量浓度的需求,建立了同步使用石英膜采集样品并用于水溶性成分、有机碳和元素碳含量分析,而使用纤维素膜采样后用于金属元素分析的方案.应用上述方案对样品进行了全化学分析,对PM2.1质量进行了重构,重构获得的质量浓度与称重获得PM2.1质量浓度也呈显著线性相关(R2=0.89,P0.05).     

沙尘暴PM2.5水溶和有机成分对巨噬细胞的损伤

用超纯水或二氯甲烷从甘肃省武威市和内蒙古包头市采集的沙尘暴细颗粒物(PM2.5)中提取水溶成分和有机成分,于体外处理大鼠肺泡巨噬细胞4h,测定细胞谷胱甘肽(GSH)和丙二醛(MDA)含量、质膜ATP酶活性、膜表层和膜脂疏水区流动性、胞质内游离钙离子(Ca2+)浓度以及细胞培养液中乳酸脱氢酶(LDH)和酸性磷酸酶(ACP)活性.结果表明,沙尘暴PM2.5水溶成分可抑制质膜Ca2+-Mg2+-ATP酶、Na+-K+-ATP酶活性,降低质膜表层和膜脂疏水区流动性,增加胞质LDH外渗,并使细胞脂质过氧化作用增强、抗氧化能力减弱,但对ACP和Ca2+浓度影响不大;有机成分除引起胞质LDH渗漏、质膜Na+-K+-ATP酶活性下降外,对其它测定指标的影响无统计学意义.说明沙尘暴PM2.5水溶和有机成分均可对肺泡巨噬细胞产生毒性,其中水溶成分的毒性作用大于有机成分.     

鄱阳湖水体颗粒物对3种典型藻类的生长及絮凝作用

研究了鄱阳湖水体颗粒物对3种典型藻类的生长及絮凝作用.以铜绿微囊藻(蓝藻)、四尾栅藻(绿藻)和菱形藻(硅藻)为研究对象,鄱阳湖采集沉积物为悬浮颗粒物,利用500 m L玻璃锥形瓶作为小型、光照均一体系,于此体系中研究了颗粒物对藻类生长的影响,使用混凝试验搅拌仪分别研究了颗粒物粒径、浓度和体系p H对颗粒物絮凝沉降藻细胞的影响.在小型光照均一体系中,20 mg·L-1(鄱阳湖悬浮颗粒物低浓度)和80 mg·L-1(鄱阳湖悬浮颗粒物高浓度)颗粒物对3种藻类的生长影响均较小.在颗粒物投加量为0.02 g·L-1时,60~300目颗粒物均促进藻类的絮凝沉降,并且随着颗粒物粒径(D50)的增大,藻细胞的絮凝沉降效率逐渐减小,而且粒径在1~25μm部分的颗粒在此过程中占主导地位.当颗粒物投加量由0.02 g·L-1升至1.28 g·L-1时,3种藻的絮凝沉降效率随之提高.在颗粒物投加量为0.02 g·L-1时,铜绿微囊藻、四尾栅藻和菱形藻的絮凝沉降效率仅为11.08%、15.87%和7.50%,当颗粒物浓度升至1.28 g·L-1时,3种藻的絮凝沉降效率分别达42.33%、41.72%、28.98%.在p H值6~10范围内,随着p H升高,颗粒物对蓝藻、绿藻的絮凝沉降作用逐渐减小,絮凝沉降效率分别从p H为6时的36.10%、35.07%降到p H为10时的16.25%、12.59%;而对硅藻的絮凝沉降作用不明显.由此可见,鄱阳湖水体颗粒物影响藻类的絮凝沉降过程,使藻类的群落结构发生变化.     

HILIC/LC-MS直接分离测定大气颗粒物中的15种有机胺

本文建立了一种基于亲水作用液相色谱柱(HILIC)和液相色谱-质谱联用(LC-MS)的大气颗粒物有机胺的直接测定方法。颗粒物样品经甲醇提取、富集、浓缩后,对不同色谱柱与分析条件进行测试、对比,发现HILIC色谱柱可有效分离有机胺类化合物,高浓度以及低pH值的缓冲溶液可缩短大部分有机胺的保留时间,而流动相中有机相比例增加会延长保留时间。优化的HILIC/LC-MS分析方法可同时测定11种脂肪胺、2种脂环胺、1种芳香胺及1种醇胺,结合内标的有机胺标准曲线的线性相关系数R²为0.991—0.999。本方法的检出限(S/N=3)为0.59—75.46 ng·mL^-1,加标回收率为59%—92%,具有较高的精密度。该方法初步应用于青岛冬季大气细颗粒物样品中有机胺的测定,为大气有机胺的深入研究提供了方法参考与技术支撑。     

组合液膜对自配淋洗液中Cd的提取回收效果

淋洗法是解决土壤重金属污染的有效方法之一,其对土壤Cd污染的治理效果较好,但需对Cd污染土壤进行淋洗后的含Cd淋洗废液进行再生和回收利用.为了克服传统液膜分离技术不稳定、膜溶液易流失等缺陷.采用P204（磷酸二异辛酯）为络合剂的组合液膜提取技术对自配土壤淋洗液中Cd2+进行提取,考察水相pH、w（P204）、接受相酸浓度、膜相与接受相体积比、接收相不同酸、水相初始c（Cd2+）对Cd2+提取率的影响,并提出动力学方程,进一步研究Cd2+在多金属离子分离条件.结果表明:①络合剂与Cd2+形成络合物在液膜系统中传输,最佳提取条件为pH 4.2、w（P204）5.0%、接受相酸浓度4.0 mol/L、膜相与接受相体积比1:3,接收相酸种类对提取率影响不明显;②水相c（Cd2+）越低,提取率越高;③基于传质动力学模型,建立了回收系数与水相pH和w（P204）的关系方程,分别为P_c=（3.20×104+2.03×1010[H+]2）-1和P_c-1=3.208×104+1.742[C0]-2,得到Cd2+通过料液和膜边界层的厚度（d_w）为17.8 μm,络合物通过膜的扩散系数（D_m0）为7.61×10-8 m2/s.研究显示,在最佳提取条件下,初始c（Cd2+）为5.0×10-3 mol/L时,240 min内提取率可达93%,通过调节多金属离子体系中Cd2+的提取条件与参数,或调节每种金属提取条件与参数,进行反复提取,Cd2+可以与其他重金属成功分离.      

流动注射仪测定水中硫化物方法探讨

采用德国布朗卢比AA3型流动注射分析仪测定水中硫化物,通过在线处理释放出H2S气体,在酸性介质中与对氨基二甲基苯胺和三氯化铁反应,生成亚甲蓝染料,于660nm处比色测定.方法检出限为0.004mg/L,标准曲线有很好的稳定性,灵敏度大大提高,精密度和准确度较好,操作简便易行,能满足大批量水样以及应急监测及时准确分析的需...     

两种水源性诺如病毒富集方法的比较

评估阳离子膜吸附-洗脱法和阴离子膜吸附-洗脱法在富集水源性诺如病毒（NV）过程中的病毒回收效果、消耗时间及使用成本,可以获得更适用于水源性诺如病毒实际监测工作的较优富集方法.以无锡市疾病预防控制中心保存的诺如病毒阳性标准质粒为模板,采用荧光定量RT-PCR（反转录酶-聚合酶链反应）方法绘制病毒定量标准曲线,并应用于病毒的绝对定量.将含诺如病毒的粪便悬液先稀释成3个不同浓度,并加入灭菌水中,分别经过阴离子膜（硝酸纤维素滤膜）或阳离子膜（Nanoceram膜）吸附洗脱,最终相同体积洗脱液提取核酸后用荧光定量RT-PCR方法进行绝对定量,并进一步计算最终病毒回收率.结果表明:①样本病毒浓度为8×101~8×1010 copies/μL时,病毒拷贝数的lg对数值与C_t（荧光定量PCR中达到设定阈值所经过的循环数）呈线性关系.②随着样本病毒浓度的增加,阴离子膜法和阳离子膜法的病毒回收率都相应增加.③当检测样本中病毒浓度分别为8×101、4×102 copies/μL时,阴离子膜法回收率分别为22.2%±4.1%和36.8%±6.2%,阳离子膜法回收率分别为17.4%±1.5%和28.8%±6.1%,说明阴离子膜吸附-洗脱法对病毒的富集回收率显著高于阳离子膜吸附-洗脱法（P < 0.05）.研究显示,综合富集效果、耗费时间和成本等因素,阴离子膜吸附-洗脱法比阳离子膜吸附-洗脱法更适用于日常水源性诺如病毒的富集工作.      

酸性火山玻璃的脱玻化作用

本文阐述了酸性火山玻璃发生脱玻现象后的X射线衍射特征、镜下(偏光及扫描电镜)特征和形貌特征,重点讨论了对酸性火山玻璃脱玻化途径有重要影响的网络结构因素和化学成分因素,最终提出酸性火山玻璃的五种脱玻化途径及相应产物:SiO_2±H_2O纯架状、架状网络→“石英”质;SiO_2+Al_2O_3+H_2O±其它成分架状、层状网络→“伊毛缟石”质;SiO_2+Al_2O_3+K_2O(Na_2O,CaO)架状、层状网络→长石质;酸性火山玻璃(含不同的挥发份)架状、层状、链状网络→粘土质及其它可能的产物;SO_2+Al_2O_3+K_2O(Na_2O)+CaO、FeO、MgO(群聚?)等土挥发份层状、链状网络→绿泥石、辉石、闪石。     

大气中有机氯农药分析方法研究

采用GC-ECD标准曲线法测定大气中17种有机氯农药,采用索氏提取、旋转蒸发仪和氮吹仪浓缩前处理方法,测定空白加标精密度、准确度,样品加标精密度、准确度和方法检出限,结果表明大气中空白加标精密度、准确度分别在7.4～19.5%和81.7～114%之间,检出限在0.06～0.23 ng/m3之间。     

Spatial and temporal patterns in summertime sulfate aerosol acidity and neutralization within a metropolitan area

A study of sulfate aerosol acidity in Metropolitan Toronto was conducted during the summer of 1986. Fine-fraction aerosol (<2.5-μm) were collected using Teflon membrane filters and analyzed for major ionic species (H⁺, NH⁺₄, NO⁻₃, SO²⁻₄). Samples were collected for 6 weeks at three study sites: one in the Center City and the others 13 km (WNW) and 20 km (NE) away. There were very strong correlations among the three sites with respect to measured aerosol species (r² > 0.9 for 24-h data). However, spatial variations in the magnitude of aerosol acidity were observed during sulfate episodes. For example, the peak concentrations for all sites occurred on 25–26 July 1986. While the 24-h data for sulfate were quite uniform at the three sites (34, 34 and 35 μg m⁻³), H⁺ concentrations were 9.4, 8.3 and 6.0 μg m⁻³ (as H₂SO₄) for the NE, WNW and Center City sites, respectively. For most of the summertime episodes, the downtown area also had lower aerosol acidity compared to the two sites in suburban areas.     

Speciation of ammonium-containing species in atmospheric aerosols

A method for the speciation and separate determination of inorganic ammonium salts in atmospheric aerosols has been developed. It is based on sampling by an annular denuder-filter-pack system, in order to avoid chemical artifacts followed by thermal dissociation of NH₄NO₃ and NH₄Cl from the Teflon pre-filter, and collection of evolved gases on back-up filters. The predominant form of thermostable sulfate partially or totally neutralized by NH₃ is then identified and quantified from pH and [H⁺]/[SO₄²⁻] ratio measurements. Results of field experiments performed near Rome show that NH₄NO₃ and (NH₄)₂SO₄ constitute the major species of the fine particle fraction.NH₄Cl represents approximately one-fifth of NH₄NO₃ and one-tenth of the total ammonium species in terms of mass concentration.     

Processes affecting concentrations of aerosol strong acidity at sites in eastern England

Concentrations of aerosol strong acidity and related species have been measured at sites in eastern England using a sampler in which ammonia is pre-separated by a denuder. High concentrations occurred at a coastal site and were associated with air advected over the North Sea. At inland sites, ammonia concentrations were higher and the aerosol was more substantially neutralized. Daytime concentrations of aerosol H⁺ exceeded those measured at night, despite higher daytime levels of ammonia, presumably due to more effective production of H₂SO₄ during daytime hours. Concentrations of acidic aerosols were within the range 0–178 neq m⁻³, well below those observed at many eastern North American sites with lower concentrations of ammonia.     

Wintertime measurements of aerosol acidity and trace elements in Wuhan,a city in central China

A 2-week intensive ambient aerosol study was conducted in December 1988 in Wuhan (Hubei Province), a city of nearly 2 million located on the Yangtze River in central China (P.R.C.). This is an industrial region where soft coal burning is widespread, and emission controls for vehicles and industrial facilities are minimal. The sampling site was located in one of the civic centers where residential and commercial density is highest. An Andersen dichotomous sampler was operated with Teflon membrane filters to collect fine (d_p < 2.5 μmad) and coarse (2.5 ⩽ d_p < 10 μmad) particles for total mass and element determinations. An annular denuder system (ADS) was used to collect fine fraction aerosols for analyses of ionic species including strong acidity (H⁺).The study was conducted between 18 and 30 December, which was rainless, consistently cool (3–10°C) and overcast, but without fog or acute stagnation. Fine particulate mass (PM, as μ m⁻³) averaged 139 (range 54–207); coarse PM averaged 86 (range 29–179). Trace element concentrations were also high. Crustal elements (Si, Al, Ca and Fe) were found primarily in the coarse fraction, while elements associated with combustion (S, K, Cl, Zn and Se) were enriched in the fine fraction. The concentrations of arsenic and selenium were evidence of a large source of coal burning, while vanadium levels (associated with fuel oil use) were not especially enriched.Despite the seemingly high PM loadings, ionic concentrations were not especially high. The average composition of soluble fine aerosol species (in neq m⁻³) were SO₄²⁻: 520 (range 180–980), NO₃⁻: 225 (range 50–470), Cl⁻: 215 (range 20–640), and NH₄⁺: 760 (range 280–1660). A deficit in accountable FP components (total mass compared to the total of ionic plus element masses) as well as the black appearance of collected materials indicate an abundance of carbonaceous aerosol, as high as 100 μ m⁻³. (total mass compared to the total of ionic plus element masses) as well as the black appearance of collected materials indicate an abundance of carbonaceous aerosol, as high as 100 μ m⁻³Aerosol acidity was negligible during most monitoring periods, H⁺: 14 (range 0–50 neq m⁻³, equivalent to 0–2.5 μm m⁻³ as H₂SO₄). Sulfur dioxide, measured by the West-Gaeke method for part of the study, concentrations were low. Although not directly measured, the aerosol measurments suggested that gaseous HCl (from refuse incineration) and NH₃ (animal wastes) concentrations might have been high. Higher aerosol acidity might be expected if HCl sources were more prominent and not neutralized by local ammonia or other base components.     

北京中关村地区气溶胶的酸性测量

为了研究大气气溶胶的酸性及其粒径分布,笔者利用自制环状扩散管和三级撞击式组合采样器采样,ｐＨ测量和傅利叶红外光谱技术测量相结合,于１９９４处冬季至１９９５年冬季在北京中关村地区进行了采样分析。结果表明,北京中关村地区气溶胶存在酸性组成,且酸性主要分布于粒径１．５μｍ以下的细粒子中,测得的细粒子最大酸度为５６．６ｎｍｏｌ．ｍ＾－３,各冬季１９９４年冬季和１９９５年夏季气溶胶酸性较强,日平均一般在５ｍ     

The chemistry of dews and frosts in indianapolis,Indiana

Dews and frosts forming on chemically clean Teflon surfaces were sampled for pH and ion concentrations during a 13-month period in urban Indianapolis, Indiana. We predicted that dews forming in this polluted atmosphere would be acidic due to absorption of SO₂, NO₂ and CO₂, but that frost pH would be neutral due to the lack of gas absorption. However, measured pH ranged from 6.0 to 7.2, and dew and frost pH were not significantly different. Anion and cation concentrations did not differ between dews and frosts, implying similar mechanisms and rates for scavenging of atmospheric chemicals. Sulfite and nitrite were present in many samples, indicating SO₂ and NO₂ absorption by both dews and frosts. The presence of ions (K⁺, Ca²⁺, Mg²⁺, Na⁺) lacking gaseous sources suggested that sedimentation of aerosols, primarily carbonates and salts, from surrounding agricultural lands occurred into dews and frosts as they formed. Carbonate deposition may have been responsible for near-neutral dew and frost pH. Dews sampled from sugar maple leaves were depleted of ammonium and enriched in other ions, but did not differ substantially in pH, compared to dews simultaneously sampled from Teflon. Temporal (overnight) sampling of dews on Teflon showed that dew chemistry changed substantially during the course of the night.     

Vapor adsorption artifact in the sampling of organic aerosol: Face velocity effects

The concentration (μgC m⁻³) of aerosol organic carbon as determined by collection with quartz fiber filters was found to exhibit a significant decrease with increasing filter face velocity. A similar face velocity dependence was found for organic carbon on back-up quartz fiber filters behind either quartz fiber front filters (QQ combination) or Teflon membrane front filters (TQ combination). Additionally, the concentration of organic carbon on the back-up filter in the TQ combination was always greater than on the back-up filter in the QQ combination. The most likely explanation for these observations is the adsorption or organic vapors onto the filter medium itself. The amount of organic carbon adsorbed onto the quartz fiber front filter can be approximated by measuring the amount of organic carbon on a quartz fiber back-up filter behind a Teflon front filter with both filter combinations sampling at the same face velocity. Making the correction in such a manner removes most of the face velocity dependence inthe resultant concentrations. For 24 h sampling in Portland, Oregon, at a face velocity of 40 cm s⁻¹, the correction exceeded 50% for uncorrected organic carbon concentrations of 2 μgC m⁻³ but decreased to 15% at 16 μgC m⁻³.     

Transported acid aerosols measured in southern Ontario

During the period 29 June 1986–9 August 1986, a field health study assessing the acute health effects of air pollutants on children was conducted at a summer girls' camp on the northern shore of Lake Erie in SW Ontario. Continuous air pollution measurements of SO₂, O₃, NO_x, particulate sulfates, light scattering, and meteorological measurements including temperature, dew point, and wind speed and direction were made. Twelve-hour integrated samples of size fractioned particles were also obtained using dichotomous samplers and Harvard impactors equipped with an ammonia denuder for subsequent hydrogen ion determination. Particulate samples were analyzed for trace elements by X-ray fluorescence and Neutron Activation, and for organic and elemental carbon by a thermal/optical technique. The measured aerosol was periodically very acidic with observed 12-h averaged H⁺ concentrations in the range < 10–560 nmoles m⁻³. The aerosol H⁺ appeared to represent the net strong acidity after H₂SO₄ reaction with NH₃(g). Average daytime concentrations were higher than night-time for aerosol H⁺, sulfate, fine mass and ozone. Prolonged episodes of atmospheric acidity, sulfate, and ozone were associated with air masses arriving at the measurement site from the west and from the southwest over Lake Erie. Sulfate concentrations measured at the lakeshore camp were more than twice those measured at inland sites during extreme pollution episodes. The concentration gradient observed with onshore flow was potentially due to enhanced deposition near the lakeshore caused by discontinuities in the meteorological fields in this region.     

Chemical characterization of acid precipitation in Albany,New York

Chemical composition of precipitation in Albany, NY from July 1986 to December 1988 has been studied. Mean volume-weighted concentrations (μeq^ℓ−1) were: acidity, 104.0; alkalinity, −63.7; SO₄²⁻, 52.8; NO₃⁻, 29.8; Cl⁻, 5.6; F⁻, 0.50; NH₄⁺, 19.3; Ca²⁺, 6.5; Mg²⁺, 2.8; Na⁺, 3.5; and K⁺, 1.4. Mean pH was 4.2 . Seasonal patterns were pronounced for most species. Concentrations of H⁺, SO₄²⁻, NO₃⁻, NH₄⁺ and Ca²⁺ peaked in the summer and spring. Deposition was related to rainfall amount by a power law relationship in which the exponent of the equation was ∮.6. Wet SO₄²⁻ deposition was 2.35 keq ha⁻¹ over a 30-month period. The SO₄²⁻ and NO₃⁻ deposition rates observed at Albany indicate that transport from midwestern sources have a major influence at this site. On the average, free H⁺ ion concentrations determined from pH measurements accounted for 51% of the measured total acidity. There were unknown species, most likely organic acids, that could contribute to the acidity. Correlation and regression analyses indicated that major anions, SO₄²⁻ and NO₃⁻, were closely associated with H⁺ and NH₄⁺ ions. Factor analysis revealed four common factors which are related to fossil-fuel combustion, sea spray, cement factory and biomass burning.     

Stability of the pH and the contents of ammonium and nitrate in precipitation samples

The changes in the pH and the contents of NH₄⁺, NO₃⁻ and 10 other components including trace elements were studied in precipitation samples for a period of up to 300 days. The concentration of free H⁺ ions is affected after deposition by several processes, the most important being bioconsumption of NH₄⁺ leading to an increase in the H⁺ ion level depending on the length of the sampling interval, the time of year and the way of storing the samples prior to their analysis. It is proposed that, for the purpose of comparing the acidities of precipitation waters and their effects on acidification of the environment, the corrected H⁺ ion concentration (H_c⁺) be calculated from the pH value and the concentrations of NH₄⁺ and NO₃⁻ (H_c⁺ = H⁺+NH₄⁺−NO₃⁻). The H_c⁺ value depends little on the bioconsumption of NH₄⁺ and NO₃⁻ after deposition and thus is not very sensitive to the way of storing the samples, the sampling interval and the time elapsed between deposition and the sample analysis. Dissolution of Fe, Al, Si and some trace elements from the particles scavenged during precipitation was slow in the studied samples; it is advantageous to digest the sample in a microwave oven prior to determination of these elements.