PM_(2.5)中水溶性离子采样及前处理注意事项的探讨

本文采用四通道采样器,使用Teflon和石英膜对环境空气中的PM2.5样品进行采样,并使用超声振荡-离子色谱法对其中的水溶性离子进行分析。分析结果表明,石英膜和Teflon膜本底结果差异性不大,但石英膜本底离子浓度范围相对较宽。Teflon膜适合于PM2.5质量浓度的测量,石英滤膜更适合于冬季PM2.5水溶性离子的检测分析。     

国内城市大气 PM2.5中重金属污染研究进展*

对PM2.5样品采集和消解,PM2.5中重金属检测方法、来源分析方法以及风险评价常用方法进行了简单介绍,重点介绍了国内主要城市PM2.5样品中重金属污染情况、风险评价情况及研究工作不足之处。     

水质自动采样器的校准方法及不确定度评定

建立水质自动采样器的校准方法。介绍水质自动采样器的工作原理,提出了校准项目与技术指标:单次采样量测量相对误差为±10%,等比例采样量测量相对误差为±15%,时间控制测量相对误差为±0.5%,温度控制测量误差为±2℃,绝缘电阻不低于20 MΩ。对单次采样量测量误差的测量不确定度进行了评定,相对扩展不确定度U=3.0%(k=2)。该校准方法可用于计量技术机构对水质自动采样器的校准,保证测量数据的准确可靠。     

质检总局发布多项仪器校准规范/检定规程

正前不久,质检总局发布《动态压力标准器检定规程》等58个国家计量技术规范,涉及多项仪器校准规范/检定规程:平板电泳仪校准规范、PM2.5质量浓度测量仪校准规范、流式细胞仪校准规范、全自动微生物定量分析仪校准规范、汽     

雾霾之PM2.5的来源、成分、形成及危害

介绍雾霾及PM2.5的基本知识,从化学角度讨论PM2.5的来源、成分、形成和危害;阐述发展PM2.5分析新方法对于掌握其危害,研究其生理影响和找到其源头的重要意义.清洁能源的高效利用,排放物的后处理以及“碳交易”等有希望成为解决雾霾及PM2.5问题的突破口.     

PM_(2.5)中金属元素提取方法的对比研究

对各金属含量已知的国家标准土样经PM2.5悬浮箱再悬浮并用Teflon滤膜和石英纤维滤膜对其进行采集,采用6种方法对滤膜上PM2.5中金属元素Ca,Mg,Na,K进行提取并计算其提取率,将实验室获得的最佳提取方法应用到大气环境以检验提取方法的适用性。结果显示:石英纤维膜上PM2.5中金属元素较Teflon滤膜更易提取;各种酸提法的提取效果优于水提法;HClO4法是Teflon滤膜上PM2.5中金属元素提取率最高的提取方法;除文献法提取Ca外,HF法对石英纤维膜上PM2.5中其它金属元素的提取效果最好;实验室获得的PM2.5中水溶性金属离子的最佳提取方法同样适用于大气环境。     

上海市区大气颗粒物(PM2.5)中铅、镉的分析测定和污染特征研究

以石英超细纤维滤膜采集上海市长宁区的大气颗粒物(PM2.5)样品,采用球磨机将滤膜研磨成细微颗粒,并以0.7％ Triton X-100作为分散剂,制备了稳定均一悬浮液,建立了一种简便、绿色、快速的悬浮液进样-石墨炉原子吸收法测定PM2.5中铅和镉的方法.铅在0.1～75 μg/L范围内,镉在0.2～3 μg/L范围内,校正曲线的线性相关性大于0.998;铅和镉的检出限分别为0.36和0.06 μg/L,相对标准偏差小于5％.采用HF-HN03体系酸消解样品,并与电感耦合等离子体质谱法和石墨炉原子吸收光谱法测试结果对比,验证了方法的准确性.采用本方法对2014年11月～ 2015年5月期间上海市区大气中PM2.5及铅和镉的污染特性进行分析,结果表明,铅和镉的质量浓度随时间变化趋势与PM2.5的质量浓度随时间的变化趋势呈现良好的一致性.     

室内可吸入肺颗粒物PM_(2.5)采集实验与SEM观察

采用自行搭建的大气颗粒物采集平台,对室内可吸入肺颗粒物PM2.5进行了采集实验,并运用扫描电子显微镜分析技术(SEM)对室内PM2.5颗粒物样品进行了形貌观察和分析。实验在同一房间进行,以每天只采集一个PM2.5样品的方式,分别采集了室内不同体积空气中的PM2.5。实验表明:随着抽气体积的增加,可吸入肺颗粒物PM2.5样品的斑点颜色逐渐加深;对于抽气体积在3 m3以上的室内颗粒物样品,肉眼已无法分辨,但SEM可以显著分辨;SEM的分析结果表明,成都市城东龙潭工业园室内可吸入肺颗粒物PM2.5由形貌各异、大小不等的固态颗粒组成,颗粒物轮廓清楚、表面特征明显,粒径在0.01~3μm之间;长时间沉积PM2.5实验显示,室内PM2.5中存在大量不规则片状颗粒物,粒径在1~3μm之间。通过室内可吸入肺颗粒物PM2.5采集实验与SEM观察,可再根据元素分析技术进一步分析室内PM2.5,从而找出室内PM2.5污染物的来源,为制定相应的污染防治措施提供科学依据。     

燃烧源PM2.5凝结洗涤脱除实验研究

利用蒸汽在燃烧源PM2.5表面凝结,促使PM2.5凝结长大,建立一套燃烧源PM2.5凝结洗涤的实验台;考察了颗粒粒径分布、蒸汽添加量、液气比等对两种燃烧源PM2.5凝结洗涤脱除效果的影响。采用电称低压冲击器 (ELPI)在线测试分析燃煤和燃油PM2.5凝结洗涤前后的数浓度和粒径分布特性,并用SEM和XPS对两种不同燃烧源的颗粒进行了形貌和元素组分分析。结果表明,燃煤和燃油产生的PM2.5形貌和组分具有较大的差别,燃煤PM2.5主要为硅铝矿物质,而燃油PM2.5主要为含炭物质;相同条件下,燃煤PM2.5相变脱除效果优于燃油PM2.5;随着蒸汽添加量的增加,两者的脱除效率均升高;随粒径的增大,脱除效率提高;蒸汽添加量为0.08kg/m3时,粒径为0.4μm的燃煤和燃油细颗粒的脱除效率分别81％和72％;此外,适当增加液气比有利于凝结长大含尘液滴的脱除。     

夏普推出PM2.5检测模块

<正>夏普将于2014年2月开始发售PM2.5检测模块DN7C3JA001。这款检测模块具有检测PM2.5以及更大的颗粒物的功能,且检测时间短。目前PM2.5检测仪器是采用数种方法将PM2.5粒子和其它悬浮颗粒物分流,然后使用光传感器测量。仪器结构复杂,需要定期维护,且仪器价格不菲。DN7C3JA001模块将分流器和利用LED的高精度传感器结合并小型化,可以使     

Neutron activation analysis: Still a reference method for air particulate matter measurements

At ITN, PM10 and PM2.5 aerosols were collected on Nuclepore^® polycarbonate filters of 47 mm diameter, using Gent samplers at 15–17 l/min air flux. Filters were analyzed by INAA and PIXE. The availability of certified filters was very scarce, viz.: (1) fly ash embedded in a methyl cellulose 47 mm foil 10 µm thick, BCR CRM128, (2) particle-size reduced air particulate matter (APM) to simulate PM2.5 aerosol matter deposited on a 47 mm polycarbonate filter membrane, NIST SRM 2783. The high price and scarcity of APM standards did not permit their frequent use for analytical quality control. At ITN, to control the filter results' accuracy, the chemical elements potassium, iron and zinc, determined by both techniques, were systematically compared. After a few improvements introduced in INAA, this technique was now considered at ITN as the reference technique in air particulate measurements. Comparison of INAA to PIXE was discussed. Compared to previously reported situation it was concluded that the results were in better agreement for iron and zinc, and potassium values were still biased to the same extent as before.     

Assaying particle-bound polycyclic aromatic hydrocarbons from archived PM2.5 filters

Airborne particulate matter contains numerous organic species, including several polycyclic aromatic hydrocarbons (PAHs) that are known or suspected carcinogens. Existing methods for measuring airborne PAHs are complex and costly, primarily because they are designed to collect both gas-phase and particle-phase PAH constituents. Here, we report an assay for measuring particle-bound PAHs in archived filters from the network of U.S. monitoring stations for particles less than 2.5 microm in diameter (PM2.5), without the need for deploying specialized samplers. PAHs are extracted from Teflon filters with dichloromethane, concentrated, and measured at trace levels using gas chromatography-mass spectrometry. Although PAHs with 3-6 aromatic rings can be assayed, results are only unambiguously accurate for compounds with 5- or 6-rings, due to variable vaporization losses of the more volatile 3- and 4-ring compounds during sampling and/or storage. The method was evaluated for sensitivity, recovery, precision, and agreement of paired air samples, using PM2.5 samplers locally in Chapel Hill, NC. Additionally, three sets of archived samples were analyzed from a study of PM2.5 in the Czech Republic. Levels of some 4-ring and all 5- and 6-ring PAHs in both the local and Czech samples were consistent with published results from investigations employing PAH-specific air samplers. This work strongly suggests that assessment of particle-bound 5- and 6-ring PAHs from archived PM2.5 filters is quantitatively robust. The assay may also be useful for selected 4-ring compounds, notably chrysene and benzo(a)anthracene, if PM2.5 filters are stored under refrigeration.     

Size-fractionated sampling and chemical analysis by total-reflection X-ray fluorescence spectrometry of PMx in ambient air and emissions

PM 10 and PM 2.5 (PMx) have been recently introduced as new air quality standards in the EU (Council Directive 1999/30/EC) for particulate matter. Different estimates and measurements showed that the limit values for PM 10 will be exceeded at different locations in Europe, and thus measures will have to be taken to reduce PMx mass concentrations. Source apportionment has to be carried out, demanding comparable methods for ambient air and emission sampling and chemical analysis. Therefore, a special ambient-air sampler and a specially designed emission sampler have been developed. Total-reflection X-ray fluorescence analysis (TXRF) was used for multi-element analyses as a fast method with low detection limits. For ambient air measurements, a sampling unit was built, impacting particle size classes 10–2.5 μm and 2.5–1.0 μm directly onto TXRF sample carriers. An electrostatic precipitator (ESP) was used as back-up filter to also collect particles <1 μm directly onto the TXRF sample carriers. Air quality is affected by natural and anthropogenic sources, and the emissions of particles <10 μm and <2.5 μm, respectively, have to be determined to quantify their contributions to the so-called coarse (10–2.5 μm) and fine (<2.5 μm) particle modes in ambient air. For this, an in-stack particle sampling system was developed, according to the new ambient air quality standards and in view of subsequent analysis by TXRF. These newly developed samplers, in combination with TXRF analyses, were employed in field campaigns to prove the feasibility and capabilities of the approach. Ambient air data show the quantification of a wide spectrum of elements. From those concentrations, PMx ratios were calculated as an indicator for different sources of elements. Results useful for source apportionment are also the elemental day/night ratios calculated to determine local contributions to PMx mass concentrations. With regard to the emission measurements, results of mass and elemental concentrations obtained in two different processes (steel industry) show that the new PM 10/PM 2.5 cascade impactor and measurements with TXRF give characteristic fingerprints for different sources. Size-fractionated ambient air and emission sampling, together with multi-element analysis, prove to be a useful approach to derive information for source–receptor modeling, a method necessary to set up effective abatement strategies to reduce PMx mass concentrations.     

The certification of a nominal 20 μmol/mol H<Subscript>2</Subscript>S/N<Subscript>2</Subscript> standard reference material using two independent methods

To support federal, state and local regulations on the amount of hydrogen sulfide (H(2)S) released into the atmosphere, the National Institute of Standards and Technology (NIST) has certified standard reference material (SRM) 2731 Hydrogen Sulfide in Nitrogen (nominal amount-of-substance fraction 20 micromol/mol H(2)S). Since it was first produced and certified in 1989, NIST has certified four separate lots of this SRM. In each case, the value assignment of the lot concentration was accomplished by comparison to a permeation tube-generated calibration curve. For the certification of the new lot, two independent methods were used to value-assign the concentration. In addition to the permeation tube method, a second method involving the dynamic dilution of a high-concentration gravimetrically prepared primary standard mixture containing H(2)S/N(2) was also used. Agreement between the two methods was 0.10% and the total uncertainty assigned to the lot concentration was 1.35% (relative).     

A new approach for the determination of sulphur in airborne particles by HR-CS ETAAS

In this work, water and nitric acid extractable sulphur concentrations in PM2.5 fraction of urban aerosols were determined by high-resolution continuum source electrothermal molecular absorption spectrometry using most suitable CS molecular absorption band at 258.056 nm. For this purpose, the PM2.5 airborne particulates were collected on quartz filters using a high-volume sampler (500 L/min) in Istanbul (Turkey) during six months (January–June) of two consecutive years. The instrumental and experimental parameters (pyrolysis temperature, molecule formation temperature and leaching reagents) were optimised. The validity of the method for the sulphur was tested using standard reference material and the results were found to be in the uncertainty limits of the certified value.     

Determination of polycyclic aromatic hydrocarbons from ambient air particulate matter using a cold fiber solid phase microextraction gas chromatography-mass spectrometry method

Polycyclic aromatic hydrocarbons (PAH) from ambient air particulate matter (PM) were analyzed by a new method that utilized direct immersion (DI) and cold fiber (CF) SPME-GC/MS. Experimental design was used to optimize the conditions of extraction by DI-CF-SPME with a 100μm polydimethylsiloxane (PDMS) fiber. The optimal conditions included a 5min equilibration at 70°C time in an ultrasonic bath with an extraction time of 60min. The optimized method was validated by the analysis of a NIST standard reference material (SRM), 1649b urban dust. The results obtained were in good agreement with certified values. PAH recoveries for reference materials were between 88 and 98%, with a relative standard deviation ranging from 5 to 17%. Detection limits (LOD) varied from 0.02 to 1.16ng and the quantification limits (LOQ) varied from 0.05 to 3.86ng. The optimized and validated method was applied to the determination of PAH from real particulate matter (PM10) and total suspended particulate (TPS) samples collected on quartz fiber filters with high volume samplers.     

Application of the chromatographic retention index system for the estimation of the calibration constants of permeation passive samplers with polydimethylsiloxane membranes

The paper presents the results of research on the calibration of permeation passive samplers equipped with polydimethylsiloxane (PDMS) membranes using the physico-chemical properties of the analytes. Strong correlations were found between the calibration constants of the samplers and the linear temperature-programmed retention indices of the analytes determined on columns coated with pure PDMS (r2 = 0.914). These correlations make it possible to estimate the calibration constants for unidentified analytes, which is impossible when using conventional procedures. This, in turn, enables the deployment of permeation passive samplers in the same way in which active samplers are deployed. The reproducibility of the calibration constants determined in different laboratories and retention indices determined using different chromatographic systems was very good, indicating that the calibration constants estimated using this approach should be reproducible as well. The approach proposed should lead to more widespread use of permeation passive samplers.     

A comparison of direct thermal desorption with solvent extraction for gas chromatography-mass spectrometry analysis of semivolatile organic compounds in diesel particulate matter

Direct thermal desorption-gas chromatography-mass spectrometry (DTD-GC-MS) is a technique that is finding application in the characterisation of the semivolatile organic carbon fraction of ambient and combustion source particulate matter (PM) collected on filters. In this study, three DTD-GC-MS methods were assessed and compared to a conventional solvent extraction method for analysis of a mixture of target analytes in solution and of diesel PM collected on quartz filters. The target analytes included n-alkanes, hopanes, steranes and polycyclic aromatic hydrocarbons. This study showed that while the three DTD-GC-MS methods were generally comparable to the solvent extraction method, (1) the choice of calibration strategy and calibration materials has a significant impact on the measured accuracy of a method; (2) very large variations were seen in all methods for the more volatile compounds such as C₁₀ to C₁₃ n-alkanes and naphthalene; (3) accuracy, defined as difference from the known concentration of a liquid sample, ranged from 5% to 32%; (4) precision, defined as the relative standard deviation, ranged from 4% to 16%. The average difference of DTD-GC-MS results from the solvent extraction results for the diesel PM filters ranged from 20% to 40%. This difference was driven by the large number of target analytes present at relatively low concentrations (<25 pg/mm²) and their corresponding higher variability. Differences in performance among the compound classes were noted. Minimum detection limits for the DTD-GC-MS methods were on the order of 0.1 to 1 pg/mm² and were as good as or better than those obtained for the solvent extraction method.     

An investigation of calibration materials for the measurement of metals in ambient particulate matter on filters by LA-ICP-MS

Three different types of simple and low-cost calibration material for the measurement of the metals content of ambient particulate matter (PM) on filters using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) have been compared: cellulose ester filters spiked with multi-element calibration solutions, pellets of compressed ambient particulate matter certified reference material (CRM), and powdered ambient particulate matter CRM adhered to a surface. Elements determined were As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, V and Zn, each at approximate levels of 1000?ng per filter. Blank filters spiked with multi-elemental standards were found to be significantly more reproducible and repeatable than materials based on powdered reference materials. However, a comparison of these spiked filters with real samples of ambient PM showed that the analytical sensitivities obtained per mass of analyte were significantly different. It is concluded that the spiked filters could act as very effective quality control standards correcting, to within 1%, drifts in LA-ICP-MS measurements of up to 10%, or as indirect calibration materials supported by additional measurements using traditional wet chemical techniques.