波长色散-X射线荧光光谱法测定PM2.5中23种元素

研究以单元素标准膜为基础，结合NIST SRM 2783颗粒物滤膜标准样品，建立了波长色散-X射线荧光光谱法测定PM_2.5中23种无机元素的测定方法，优化了测试条件，测量一个样品耗时约15 min，计算了各元素的方法检出限。对NIST SRM 2783滤膜标准品在一周内重复测定10次来计算方法的准确度与精密度，测定结果显示大多数元素的测量值在给出的参考值范围内，且测量标准偏差一般在10%以内。对比了石英与聚四氟乙烯材质（Teflon）滤膜的空白值，石英滤膜中Si、Fe、Na、Mg、Al、K、Ca等元素的背景值较高，Teflon滤膜的背景值较低，推荐选用Teflon滤膜作为PM_2.5组分分析采样滤膜。分别用波长色散-X射线荧光光谱法及酸消解-ICP-MS法测定了样品膜中的元素组分，得到的测定结果基本一致。     

大气总悬浮微粒中某些元素的火焰原子吸收分光光度测定法

采用外加百叶箱的国产KB-250空气采样泵,用直径12.5cm国产过氯乙烯滤膜收集20小时大气总悬浮微粒样品,样品滤膜在450℃灰化后用氢氟酸和硝酸硝化、溶解,并用火焰原子吸收法测定其中的K、Na、Ca、Mg、Fe、Zn、Mn、Co、Cu、Ni、Cd、Cr、Pb13种元素。结果表明,该法采集的样品滤膜均匀,前处理方法简便,回收率、精密度均符合要求。     

离子色谱法测定PM_(2.5)中硫酸根离子含量不确定度评议

准确测定大气颗粒物中水溶性组份对分析污染物来源及身体健康具有重要意义。本文采用离子色谱法测定PM2.5中硫酸根离子含量,并对测定的不确定度进行分析。分析过程不确定度来源是样品重复性测量引入不确定度,样品测量准确性引入不确定度和标准曲线的不确定度。应用不确定度评定理论,计算硫酸根离子的合成不确定度。结果表明,滤膜中硫酸根离子本底浓度高低与剪裁滤膜环节是不确定度的主要来源。为了提高分析的准确性,建议使用本底低的滤膜,并取整张滤膜进行分析。     

滤膜在颗粒物无机元素监测中的适用性研究

筛选国内外12个制造商的玻璃纤维、石英、特氟龙、聚丙烯、乙酸纤维、硝酸纤维和混合纤维等7类材质34种滤膜,测定滤膜中的铍、铬、锰、钴、镍、铜、锌、砷、钼、镉、锡、锑、铊和铅等14种元素含量,探讨不同材质滤膜中各元素的质量分数分布,采用大气固定源污染物排放标准中项目限值和分析方法标准中质量控制要求,对铜、锌之外的12种元素进行适用性评价。结果表明:玻璃纤维滤膜比其他材质滤膜中无机元素的质量分数高1～5个数量级,进口玻璃纤维滤膜中铬、镍、砷、镉等4种元素质量分数高于多数国产玻璃纤维滤膜,国产A、H玻璃纤维滤膜中14种元素质量分数相对较低;仅混合纤维滤膜中镉、铅的测定值浓度低于最严标准限值的10%,玻璃纤维滤膜之外的其他材质滤膜均能满足监测其余10种元素的本底需求。     

微波消解体系与聚四氟乙烯滤膜对PM2.5中重金属测定的影响

采用4种微波消解体系对聚四氟乙烯(PTFE)材质滤膜采集的PM2.5样品进行消解,利用电感耦合等离子体质谱(ICP-MS)测定样品中Cr、Mn、Cu、As、Cd 5种重金属元素含量,并计算其空白加标和样品加标回收率,建立了测定PTFE材质滤膜采集的PM2.5样品中重金属元素的最优微波消解体系。结果表明,4种消解体系下,空白加标回收率和样品加标回收率均处于合理范围,分别为95.3%~116.3%和93.3%~118.5%。其中,HNO3放置过夜+H2O2消解体系具有空白值低、测定稳定性强、操作简便、绿色环保、对人体健康危害小等优点,能够满足大批量PM2.5样品中重金属总量的快速、高效、准确分析的要求。     

海洋沉积物中多种重金属的X射线荧光分析法

建立了海洋沉积物中包括砷、铜、铅、锌、镍和总铬在内的多种重金属X射线荧光分析法,测量不需要任何消解前处理过程,可在约1h内测量1个样品中的50余种元素,用该方法分析了8个海洋沉积物标准样品,还与原子荧光光谱法或原子吸收分光光度法比对分析了2个实际样品,结果表明,该方法可信度较高,且具有快速、简便、高效等特点,是一种非破坏性分析方法。     

连续监测中影响总悬浮颗粒物监测质量的因素

在空气环境质量监测中,采用滤膜采样-重量法监测总悬浮颗粒物,监测结果受客观及主观因素的影响较大。因此,在采样和分析过程中必须严格控制各种条件,以提高测量结果的准确性。1　采样1 1　采样流量的影响采样时,采样器的准确度取决于采样流量保持恒定的程度。光化学烟雾、油状颗粒物等均可阻塞滤膜并造成空气流速不匀,使流量迅速下降;浓雾或高湿度空气使滤膜变得太潮,也会使流量明显下降[1]。因此,在能见度低或高湿度天气,可采用分段采样,集中累加,以降低因流量变化对总悬浮颗粒物测量的影响。1 2　气象条件的影响在采样体积与标准体积…     

微波高压络合消解石墨炉原子吸收分光光度法测定环境空气中锑

用有机滤膜采集空气中颗粒物样品,用微波高压络合消解后制成样品溶液。用石墨炉原子吸收分光光度法可确定样品溶液中锑的浓度。该方法具有对有机滤膜和样品消解完全,省时,无损失,灵敏度高,准确度、精密度好等特点。     

水系环境背景值调查中Zn的污染来源

由于水系环境背景值调查研究工作的需要,我们用原子吸收光谱法测定了嘉陵江水系中铜铅锌镉铁钴镍铬锰和钒等十个元素,结果发现,绝大多数元素都能满足环境背景值分析测试质量控制的要求,只有锌出现了溶解态锌(经0.45μ微孔滤膜过滤后过滤水中的锌量)超过总量锌(未经过滤的原水中的锌量)的倒置现象。为了寻找产生倒置的原因,本文从使用的分析方法、存器、滤膜、导水管和环境等各个方面,研究了锌分析结果不正常的原因,通过实验证明,过滤时用的导水管材料不当,和过滤时的环境是污染的主要原因。本文还通过锌等元素的测定,探讨了过滤水样用的微孔滤膜处理方法,方法简单方便,可以避免滤膜和器皿的污染。     

徐州城市表层土壤中重金属的富积、分布特征与环境风险

研究了徐州城市表层土壤的21个样品中30种元素的富集与分布特征。结果表明,与我国土壤元素的背景值(算术平均值)相比,表层土壤中Zn、Cd、As、Hg、Sb、Sn、Ag等元素富集大;Fe、Se、Sc、Ba、Bi、Pb、Cu、Ni、Cr、Mn、Mo、Be、Ti、Al、Ga、Li、Co等元素的富集较小。污染元素的空间分布特征显示了Zn、Cu、Pb、Cd等元素主要与交通运输等扩散污染源相关,而元素As、Sb的空间分布主要与工业污染源(点源)有关。环境风险指数的计算结果表明,表层土壤中重金属污染具有较大的环境风险,其中属于中等环境风险级别以上的样品占近40%,而且高风险区域主要集中在钢铁厂和化机厂等工业区范围内。     

Pentachlorophenol in indoor environments. Does a single measurement of air and dust concentrations represent the contamination?

In order to be able to make a decision, as to whether a room or building has a health-endangering pentachlorophenol (PCP) concentration, usually the PCP concentrations in air and settled dust are measured. The variability of the PCP concentration in indoor air and dust was studied. Air and dust samples were taken from 75 rooms in 30 buildings with suspicion of application of PCP-containing wood preservatives. Sampling was repeated four times within 18 months. Thirty-six rooms were reconstructed within the study; 39 rooms had unchanged contamination status during the study. The four times repeated measurements of PCP concentrations in air and dust in these rooms showed large variations of the measured values. The variability of the results is to a large extent in the same range as the measured values. The observed relative standard deviation of the PCP concentrations in air and dust does not depend on the average PCP concentration detected in the individual rooms.     

利用自动采样滤膜监测PM_(2.5)中铅和镉的可行性

根据PM2.5中重金属监测国标分析方法,从PM2.5采样方法、采样保存条件、滤膜材质性能等方面说明利用空气自动采样滤膜监测PM2.5中铅和镉是可行的;对手工采样(石英滤膜)和Beta射线法自动采样(自动采样滤膜)2种方法,对PM2.5实际样品中铅和镉的结果进行比较,结果显示:自动采样滤膜的空白检出和检出限均满足铅和镉的监测需求,铅和镉的回收率分别为95.2%~107%和91.8%~105%,与手工采样方法相比测得铅和镉的相对误差分别为3.6%~8.4%和1.3%~10.8%,从实践角度进一步证明了利用自动采样滤膜对PM2.5中铅和镉进行监测是可行的。     

恒压氮气隔断连续流动分析法测定水中化学需氧量

为建立恒压氮气隔断连续流动分析法测定水样化学需氧量的分析方法，将连续流动分析法恒流空气隔断改为恒压氮气隔断，优化试剂配方和反应模块，结果表明：恒压氮气隔断法注入氮气的压力是0.06 MPa,仪器稳定时间是20～35 min,持续分析样品时间大于4 h,指标均优于恒流空气隔断法；标准曲线在2.5～40.0 mg/L范围内，相关系数大于0.999,方法检出限为0.44 mg/L,相对标准偏差为0.2%～2.6%,加标回收率在93.8%～103.8%之间，检出限优于恒流空气隔断法，精密度和正确度满足质量控制要求；实样和标样方法比对测定结果相对标准偏差小于5%,结果精密度优于标准的手工法。恒压氮气隔断连续流动分析法适用于大批量低浓度水样化学需氧量的快速检测，对于密度大、黏度大液流恒压氮气隔断具有更好的稳定性、灵敏度和正确度。     

Field measurement of lead in workplace air and paint chip samples by ultrasonic extraction and portable anodic stripping voltammetry

On-site measurement of lead in workplace air filter samples and paint chip samples by ultrasonic extraction and anodic stripping voltammetry (UE-ASV) was evaluated in the field during renovation and remodeling activities in residences having leaded paint. Aerosol and paint samples were collected using standard techniques, and the samples were analyzed on-site for lead content by portable UE-ASV. Lead in sample extracts was subsequently determined by atomic absorption (AA) spectrometry in a fixed-site laboratory. The remaining sample extracts plus undissolved material (air filters or paint particles) were then subjected to hot plate digestion in concentrated nitric acid-30% hydrogen peroxide prior to AA analysis for lead. Field UE-ASV lead data were thereby compared to UE-AA and hot plate digestion-AA results from fixed-site laboratory lead measurement. Determination of lead in air filter samples by UE-ASV (over the range of 5 microg to approximately 800 microg Pb per sample) was extremely well correlated with lead measurement by UE-AA and hot plate digestion-AA procedures. However, a significant negative bias associated with ASV measurement was observed, and this was attributed to a matrix effect. Lead measurement in paint chip samples by UE-ASV (over the range of approximately 10 to approximately 550 microg Pb g(-1)) was well correlated with lead measurement by UE-AA and hot plate digestion-AA procedures. However, correlation and precision were lower for lead measurement in paint samples as compared to aerosol samples, and a negative bias was also observed. Lead measurements by UE-AA were compared to lead determinations by hot plate digestion-AA; these data were highly correlated and demonstrated no significant bias. Thus it was concluded that the ultrasonic extraction procedure performed equivalently to hot plate digestion. It was reasoned that matrix effects due to the preparation and analysis of paint chip particles resulted in greater imprecision as well as negative bias by ASV measurement. Despite significant negative bias in this sample set, UE-ASV offers promise for on-site measurement of lead in samples of interest in occupational and environmental health.     

Ultrasonic extraction and portable anodic stripping voltammetric measurement of lead in paint, dust wipes, soil, and air: an interlaboratory evaluation

Recent studies have demonstrated the utility of ultrasonic extraction (UE), followed by portable anodic stripping voltammetry (ASV), for the on-site determination of lead in environmental and industrial hygiene samples. The aim of this work was to conduct an interlaboratory evaluation of the UE-ASV procedure, with a goal of establishing estimates of method performance based on results from collaborative interlaboratory analysis. In this investigation, performance evaluation materials (PEMs) with characterized lead concentrations were used for interlaboratory testing of the UE-ASV procedure. The UE-ASV protocol examined has been promulgated in the form of two separate national voluntary consensus standards (one for UE and another for electroanalysis, which includes ASV). The PEMs consisted of characterized and homogenized paints, soils, and dusts (the last of which were spiked onto wipes meeting national voluntary consensus standard specifications), and air filter samples (mixed cellulose ester membrane) generated using characterized paints within an aerosol chamber. The lead concentrations within the PEMs were chosen so as to bracket pertinent action levels for lead in the various sample matrices. The interlaboratory evaluation was conducted so as to comply with an applicable national voluntary consensus standard that can be used to estimate the interlaboratory precision of a given analytical test method. Based on the analytical results reported by the participating laboratories, relative standard deviations (RSDs) for repeatability and reproducibility were computed for three different lead contents of the four PEMs. RSDs for repeatability were 0.019-0.100 for paints; 0.030-0.151 for soils; 0.085-0.134 for dust wipes; and 0.095-0.137 for air filters. RSDs for reproducibility were 0.127-0.213 for paints; 0.062-0.162 for soils; 0.085-0.134 for dust wipes; and 0.114-0.220 for air filters. With the exception of one of the air filter samples and one of the paint samples, the precision estimates were within the +/- 20% precision requirement specified in the US Environmental Protection Agency National Lead Laboratory Accreditation Program (NLLAP). The results of this investigation illustrate that the UE-ASV procedure is an effective method for the quantitative measurement of lead in the matrices evaluated in this study.     

土壤氨氮、亚硝酸盐氮、硝酸盐氮的测定试料保存实验

对测定土壤中氨氮、亚硝酸盐氲、硝酸盐氲的试料保存条件和时间进行研究。结果表明，在4℃、避光保存的条件下，试料可以保存7d，而各组份浓度值基本保持不变。其中，氨氮的本底试料值相对标准偏差为2．86％，加标试料值相对标准偏差为2．88％，加标回收率为85．8％～101％；亚硝酸盐氮加标量为0．5μg试料值相对标准偏差为3．55％，加标量为4．0μg试料值相对标准偏差为2．93％；硝酸盐氮与亚硝酸盐氮总量的本底试料值相对标准偏差为7．02％，加标试料值相对标准偏差为4．56％，加标回收率为82．6％～104％。     

Plant Uptake/Bioavailability of Heavy Metals from the Contaminated Soil after Treatment with Humus Soil and Hydroxyapatite

Cellulose nitrate membrane filter was used for the preconcentration-separation of Cu, Co, Cd, Pb and Cr ions. The analyte ions were collected on the membrane filter by the aid of carmine. Then membrane filter was dissolved by using nitric acid. The levels of the analytes in the final solutions were determined by flame atomic absorption spectrometry (FAAS). The analytical parameters including pH, amounts of carmine, sample volumes etc. have been optimized. No influences have been observed from the matrix ions. The detection limits for analytes were in the range of 0.08 μg/l-0.93 μg/l. The validation of the procedure was checked by the analysis of standard reference sediment (GBW 07309). The present method has been successfully applied for the FAAS determinations of analyte ions in real samples including black tea and magnesium salts.     

原子吸收法测定土壤中铅的方法

通过湿法消解土壤样品,利用石墨炉原子吸收分光光度法(GAAS)和火焰原子吸收分光光度法(FAAS)测定不同土壤样品中铅的含量,以验证2种方法的有效性并加以对比。实验结果表明:2种方法均满足土壤中铅含量的测定要求,测定的标准土样含量均在标准值的不确定度范围内,GAAS方法测定结果更接近保证值。二者的相对标准偏差(RSD)值均低于1.5%,FAAS方法的精密度更高,且具有快速简单等优势。     

一种便携式荧光测油仪在海上溢油应急监测中的适用性研究

研究了一种便携式荧光测油仪在海上溢油应急监测中的适用性,并与现行仲裁标准方法进行比较分析。研究表明:该便携式荧光测油仪测定海水中油类样品仅需100 mL水样,平均每个样品所需的前处理时间约340 s,方法检出限为0.003 mg/L,测定下限为0.012 mg/L。测定用标准物质配制的不同浓度海水样品,相对标准偏差为0.08%~0.87%,测定标准样品的相对误差为0.49%~4.50%,实际样品加标回收率为90%~107%。对标准物质配制的海水样品进行检测,与现行仲裁标准方法在0.05水平下无显著性差异。在渤海中部海上监测中,连续6 d测定不同标准样品的相对标准偏差为0.26%~0.83%。研究结果表明,该便携式荧光测油仪适用于现场对油类的定量分析和水质评价。     

Development and validation of methods for environmental monitoring of cyclophosphamide in workplaces

Methods to monitor contamination of workplaces with antineoplastic drugs have been developed and validated. Cyclophosphamide (CP) was used as a model compound as it is one of the most commonly used antineoplastic drugs. A wipe sampling method to detect contamination with CP at surfaces was developed. A personal air sampling method to sample gas and vapour on solid sorbent tubes and particles with filters was also developed. Wipe and filter samples were extracted and sorbent samples were eluted, all with ethyl acetate. The samples were analysed with liquid chromatography tandem mass spectrometry. (2)H(6)-labelled cyclophosphamide was used as an internal standard. The between-day precision was 2-5% for wipe samples, 4-6% for sorbent samples and 3-8% for filter samples. The limit of detection was 0.02 ng CP per sample for the wipe and filter methods and 0.03 ng CP per sample for the solid sorbent method. Wipe sampling on surfaces made of different materials resulted in mean recoveries between 78-106%. The desorption recovery was between 97-102% for the wipe samples, 97% for the sorbent samples and 101% for the filter samples. Samples were stable for up to 2 months at 5 degrees C and -20 degrees C and for about 2 d at room temperature. The developed methods were applied to the measurement of contamination with CP in a hospital pharmacy. Trace amounts of CP, 1.3 and 1.4 ng, were detected on surfaces in the pharmacy.