Pollution characteristics of ambient PM2.5-bound PAHs and NPAHs in a typical winter time period in Taiyuan

The pollution characteristics of ambient fine particulate matter（PM2.5） containing polycyclic aromatic hydrocarbons（PAHs） and nitrated PAHs（NPAHs） in samples collected during a typical winter time period in Taiyuan of China were investigated.The obtained results revealed that the mean mass concentrations of PM2.5,SPAHs（sum of 16 PAHs） and SNPAHs（sum of 3 NPAHs） on PM2.5were161.4 mg/m3,119.8 ng/m3and 0.446 ng/m3,respectively.Diagnostic ratios of PAHs and NPAHs implied that coal consumption might be the main source of the PM2.5pollution.The measured PM2.5mass concentrations,BaP equivalent toxicity（28.632 ng/m3） and individual carcinogenicity index（3.14 10 5） were much higher than those of the recommended safety standards.     

广州市夏、冬季室内外PM2.5中元素组分的特征与来源

通过采集广州市9个居民住宅室内、外的PM2.5样品,测定分析PM2.5中18个元素组分的质量浓度,分析讨论其污染、分布特征并解析其污染来源。经过比较得知,广州市PM2.5中元素污染较严重;不同类型住宅PM2.5中元素浓度存在空间分布特征;大部分元素浓度具有夏季比冬季低的变化特征;室内与室外元素浓度比值介于0.4974～2.0497之间;元素浓度的室内、室外相关拟合结果说明冬季室内空气受室外空气影响比夏季时情况更明显;基于富集因子分析,Se、As、S、Pb、Br、Zn和Cl元素高度富集;Ni、V、Cu元素中等富集,主要来自人为源,而Cr、Sr、K、Mn、Ca和Ti元素不富集,主要来自自然源。     

广州大气细粒子中有机碳、元素碳和水溶性有机碳的分布特征

在广州市中山大学采样点进行了为期1年的大气细粒子(PM2.5)采样,监测分析得到PM2.5及有机碳(OC)、元素碳(EC)和水溶性有机碳(WSOC)等组分的质量浓度,并进行了比较和评价分析。结果表明广州市细粒子碳污染较严重。对OC、EC和WSOC质量浓度的月变化和季节变化特征进行了讨论,并分析了原因。OC、EC浓度相关性好,表明OC、EC来源大部分相同。根据OC/EC比值,估算二次有机碳(SOC)量,结果是SOC占OC的1/3。讨论了SOC和SOC/OC比值的季节分布,结果证明SOC夏季生成比冬季多。     

Assessment of trace elements characteristics and human health risk of exposure to ambient PM2.5 in Hangzhou,China

A method for simultaneously determining the trace elements in particulate matter (PM) (PM2.5) by inductively coupled plasma mass spectrometry was established. The PM2.5-loaded filter samples were digested under the optimised conditions including a mixture of HNO₃–HCl–HF with ultrasonication proceeding at 70°C for 2 h. Recoveries of 90.83–103.33% were achieved for 20 elements (Co, Sr, Ag, Cd, Sb, La, Ce, Sm, W etc.) in NIST standard reference material 1648a (urban PM). PM2.5 samples were collected at urban site in Hangzhou from August 2015 to November 2015. PM2.5 concentrations of 15% sampling days exceeded the daily limitation and the mean concentrations of PM2.5 from August to November reached the 66.4% of the limitation. PM2.5 concentrations in summer were higher than that in autumn. The concentration of Zn was highest, following with Al, Pb, Mn, Cu and As. Significant enrichment was observed in Mn, Zn, Pb, Ag, V, Ni, Cu, As, Se, Hg, Co, Cd and W, which was probably induced by vehicular exhaust, oil and residual fuel combustion and industrial emissions. The daily mass concentrations of PM2.5 and elements fluctuated significantly. Rainfall could significantly reduce the concentration of Ti, Mn, Cu, Zn, As, Se, Hg, Sr, Ag, Cd, Sb, La, Ce, Sm and Pb, and the risk levels of carcinogenic elements and non-carcinogenic elements in rain day were significantly lower (43.7–81.4%) than those in non-rain day. The risk levels of Co, Cd and As could lead to adverse health outcomes through the respiratory system, which should deserve more attention, while the risk levels of Ni and non-carcinogenic elements (Hg, Mn, Cu, Zn, Pb, V) were under average risk acceptance.     

雾过程对大气气溶胶PM10中多环芳烃粒径分布的影响

在雾天气高发期间采集大气气溶胶PM10分级样品,测定了这些样品中的16种优控PAHs.结果表明：雾区近地层大气中PM2.1和PM9.0的平均质量浓度明显增加,雾过程改变了PM2.1的昼、夜浓度变化特征;雾前、雾中与雾后大气PM10中16种优控PAHs主要分布在比表面积大的细粒子上,平均有83.04%分布在Dp <2.1μm的范围,雾中1.1~2.1μm粒子的∑16PAHs浓度明显增加,Dp <0.65μm粒子的∑16PAHs浓度略有降低,说明雾过程对细粒子中∑16PAHs的浓度分布产生明显影响;雾前、雾中与雾后白天时间段,PM10分级粒子的∑16PAHs积聚模态分布出现较大差异,雾中积聚模态峰位置较雾前与雾后向较大粒径偏移;一次连续雾过程中,白天的∑16PAHs积聚模态峰位置随着雾的持续向大粒径方向偏移并停留在1.1~2.1μm;夜间的∑16PAHs积聚模态峰位置没有变化,均在1.1~2.1μm,说明PM10∑16PAHs的粒径分布受雾过程持续时间影响较大.     

智能石墨消解–ICP–MS法测定空气PM2.5中的Pb和Cd

建立电感耦合等离子体质谱(ICP–MS)测定空气PM2.5中的Pb和Cd元素的分析方法。采用连续β射线–DHS PM2.5大气颗粒物浓度监测仪采集空气中的PM2.5,以智能石墨消解PM2.5滤膜样品,ICP–MS测定其中的Pb和Cd元素含量。在优化的仪器条件下,元素Pb和Cd标准曲线的线性相关系数均为0.999 9,检出限分别为0.018,0.52ng/m3,满足HJ 657–2013的要求。Pb和Cd的加标回收率分别为95.8%~101.4%,99.3%~104.9%,测定结果的相对标准偏差分别为4.20%和2.38%(n=6)。对滤膜标准样品进行了测定,测定结果与标准值一致。该方法测定结果准确、可靠,可用于测定空气PM2.5中的Pb和Cd。     

Heavy metal determination in atmospheric particulate matter by Instrumental Neutron Activation Analysis

Instrumental Neutron Activation Analysis (INAA) is employed for its important analytical properties. Fundamentally, INAA is a multi-elemental technique allowing the determination of about 40 elements with a good Limit of Detection. In this paper we applied this nuclear technique to study the element composition in PM10 determining about 30 elements.25 filters were collected in downtown Rome from October 1999 to April 2000 and irradiated at the nuclear reactor Triga Mark II (ENEA-Casaccia Laboratories). The γ-ray measurements have allowed the quali- and quantitative analysis. The element levels in PM10 with the relative correlations have been determined: basically, the concentrations are very low.Furthermore, the enrichment factors of all elements will be reported in order to understand the natural or anthropogenic origins of the particulate matter: some elements may be attributed to long-range transport phenomena from other natural and/or anthropogenic sources.     

Chemical characterization of airborne particulate matter in ambient air of Nagoya, Japan, as studied by the multielement determination with ICP-AES and ICP-MS.

The multielement determination of PM(10) (airborne particulate matter smaller than 10 microm) samples, which was collected by a high volume air sampler at the urban site of Nagoya City, was carried out by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The present analytical method was validated by analyzing urban particulate matter standard reference material of NIST SRM 1648. The analytical data for ca. 30 elements in PM(10) samples collected during a period from 8 September to 9 October, 2003, were obtained in the concentration range from sub-microg g(-1) to several-10 mg g(-1), but the data for 18 elements among ca. 30 elements were available for the characterization of PM(10) samples in ambient air, because of problems caused by the filter blanks. Then, the trends concerning the distributions of diverse elements in PM(10) samples were analyzed based on the enrichment factors and size distribution factors. The lithophile and siderophile elements were distributed more than 50% in coarse particle fraction (>2.1 microm), which was derived mainly from natural sources, such as soils and crustal minerals. On the other hand, chalcophile elements were distributed more than 50% in fine particle fraction (<2.1 microm), which was derived mostly from anthropogenic emission sources. The large enrichment of chalcophile elements in PM(10) samples as well as their mining influence factors (MIFs) suggested their wide use in industrial productions.     

Natural sources and heavy metals

PTS, PM10 and PM2.5 samples have been collected at a rural site of south-east Italy (40 degrees 20' 13" N; 18 degrees 6' 47" E) from June to October, 2004 to investigate natural and anthropogenic contributions on particulate matter and heavy metal mass concentrations. It is shown that sharp-peak particulate-matter concentrations have been recorded during most African dust outbreaks occurred over south-east Italy. In particular, PM10 concentrations exceeding the 24-hour limit value of 50 microg/m3 have been monitored during dust events. Al, Cd, Cr, Cu, Fe, Mn, V, Ni, Pb, and Zn metal concentrations have been evaluated by an inductively coupled plasma atomic emission spectrometer and Al mass concentrations >500 ng/m3 have been observed in PTS and PM10 samples during the advection of African dust particles. Accordingly to geochemical calculations Al, Fe, and Mn, have a significant crustal origin while, Cd, Cu, Pb, and Zn are of anthropogenic origin. Moreover, Fe resulted predominant in the coarse particle fraction, while Ni, Pb, V, and Zn were predominant in the fine particle fraction. It is also shown that Cd, Mn, Ni, Pb, and V concentrations never exceeded guide and/or limit values recommended by the World Health Organization and the European Council Directives.     

Analysis of polycyclic aromatic hydrocarbons in atmospheric particulate samples by microwave‐assisted extraction and liquid chromatography

A methodology based on microwave‐assisted extraction (MAE) and LC with fluorescence detection (FLD) was investigated for the efficient determination of 15 polycyclic aromatic hydrocarbons (PAHs) regarded as priority pollutants by the US Environmental Protection Agency and dibenzo(a,l)pyrene in atmospheric particulate samples. PAHs were successfully extracted from real outdoor particulate matter (PM) samples with recoveries ranging from 81.4 ± 8.8 to 112.0 ± 1.1%, for all the compounds except for naphthalene (62.3 ± 18.0%) and anthracene (67.3 ± 5.7%), under the optimum MAE conditions (30.0 mL of ACN for 20 min at 110°C). No clean‐up steps were necessary prior to LC analysis. LOQs ranging from 0.0054 ng/m³ for benzo(a)anthracene to 0.089 ng/m³ for naphthalene were reached. The validated MAE methodology was applied to the determination of PAHs from a set of real world PM samples collected in Oporto (north of Portugal). The sum of particulate‐bound PAHs in outdoor PM ranged from 2.5 and 28 ng/m³.     

Particulate matter (PM10) from São Carlos-SP (Brazil): spectroanalytical techniques to evaluate and determine chemical elements

Chemical composition of PM10 was studied during the period of 2014–2015 in the city of São Carlos, Brazil (‘Dos Voluntários’ Square). PM10 samples were directly analysed by wavelength dispersive X-ray fluorescence – WD-XRF (Al, Ca, Ce, Cl, Fe, K, Mg, P, S, Si, Ti, V, and Zn), and by laser-induced breakdown spectroscopy – LIBS (Ba, Ca, Fe, K, Mg, Na, Si and Ti) both for qualitative purposes. For quantitative analysis of Al, Ba, Ca, Fe, K, Na, S, and Zn, the analytes were extracted from samples of PM10 collected, in filters of glass fibre, with an extractive acid solution (HNO₃ and HCl) and determined by inductively coupled plasma optical emission spectrometry – ICP OES. Spatial variations of elemental concentrations (ng m^–3) were significantly higher in winter Al (19.0), Ba (13.6), Ca (20.0), Na (27.0), S (37.1), and Zn (9.5), autumn showed the highest concentration of Na (26.4), spring showed the highest concentration of Fe (11.6), K (13.1) and also S (25.3) and summer did not show a high concentration in the comparison between the seasons at the site. Using principal component analysis (PCA), as a data interpretation tool, with the data obtained by the WD-XRF and LIBS it was not possible to obtain a good correlation, but with the data of ICP OES, it was possible to verify correlations between identified and determinate elements, with samples collected in the autumn, winter, spring and summer seasons in the city of São Carlos. These associated analytical techniques were excellent tools in environmental monitoring, through the analysis of PM10 samples, presenting reliable and efficiency strategy, and based on the PCA and the EF equation was possible to draw the profile of the possible origins of these elements in the city.     

Comparative parametric method 5 (PM5) study of trans-stilbene

In this work we report a comparative Austin method 1 (AM1), parametric method 3 (PM3), and parametric method 5 (PM5) studies for trans-stilbene in its ground, excited (singlet and triplet), and ionic (positive and negative polarons and bipolarons) states. We evaluated the accuracy of the recently developed PM5 method. PM5 and AM1 predict a non-planar ground and singlet states for trans-stilbene, while PM3 predicts planar ones, which is in agreement with the available experimental data. In general the PM3 and PM5 bond lengths are superior to AM1 while AM1 bond angles are superior to PM3 and PM5 when compared with available experimental data. The PM5 underestimates the cis–trans isomerization energy and and it is not a quite reliable method for the calculation of relative IP values. The presumed PM5 superior performance against AM1 and PM3 was not observed for the stilbene structures.     

Studies on the metabolism and detectability of the emerging drug of abuse diphenyl‐2‐pyrrolidinemethanol (D2PM) in rat urine using GC‐MS and LC‐HR‐MS/MS

In the last years, the number of new psychoactive substances, so‐called ‘legal highs’, has enormously increased. They are sold via online shops often with inaccurate and false information about the content. The aim of this work was to study the metabolism and the detectability of the drug of abuse diphenyl‐2‐pyrrolidinemethanol (D2PM) in rat urine using gas chromatography‐mass spectrometry and liquid chromatography‐high resolution‐tandem mass spectrometry. Five phase I and two phase II metabolites were identified suggesting hydroxylation at the pyrrolidine and diphenyl part as the main metabolic steps. Assuming similar kinetics, an intake of D2PM should be detectable in human urine mainly via its metabolites. Copyright © 2013 John Wiley & Sons, Ltd.     

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。     

Application of an automatic thermal desorption–gas chromatography–mass spectrometry system for the analysis of polycyclic aromatic hydrocarbons in airborne particulate matter

The application of the thermal desorption (TD) method coupled with gas chromatography–mass spectrometry (GC–MS) to the analysis of aerosol organics has been the focus of many studies in recent years. This technique overcomes the main drawbacks of the solvent extraction approach such as the use of large amounts of toxic organic solvents and long and laborious extraction processes. In this work, the application of an automatic TD–GC–MS instrument for the determination of particle-bound polycyclic aromatic hydrocarbons (PAHs) is evaluated. This device offers the advantage of allowing the analysis of either gaseous or particulate organics without any modification. Once the thermal desorption conditions for PAH extraction were optimised, the method was verified on NIST standard reference material (SRM) 1649a urban dust, showing good linearity, reproducibility and accuracy for all target PAHs. The method has been applied to PM10 and PM2.5 samples collected on quartz fibre filters with low volume samplers, demonstrating its capability to quantify PAHs when only a small amount of sample is available.     

AM1, PM3, and PM5 calculations of the absorption maxima of basic organic dyes

The absorption maxima, λ_max, of various organic dyes such as indigo, azobenzene, phenylamine, hydrazone, anthraquinone, naphthoquinone, and malachite green were calculated using the AM1, PM3, and PM5 semiempirical molecular orbital theories with the configuration interaction singles (CIS) and random phase approximation (RPA) approaches. The calculated λ_max were then compared with the values obtained by CNDO/S, INDO/S, ab initio CIS, and time-dependent density functional theory (TD-DFT). We found that the λ_max values calculated by AM1, PM3, and PM5 were in good correlation with the observed λ_max values. When B3LYP/cc-pVDZ optimized geometries were used, the square of the correlation coefficients between the calculated and observed λ_max, , at the AM1-RPA, PM3-RPA, and PM5-RPA levels were 0.891, 0.897, and 0.927, respectively. In particular, at PM5-RPA//B3LYP/cc-pVDZ was the largest among those obtained from all the other calculations including TD/B3LYP/cc-pVDZ//B3LYP/cc-pVDZ . Accordingly, the standard deviation of the difference between observed and calculated λ_max by the linear regression function at PM5-RPA//B3LYP/cc-pVDZ was the smallest. It was therefore concluded that this method was the most promising for the prediction of λ_max of various dyes among the computational methods studied here. When AM1 optimized geometries were used, at the AM1-RPA, PM3-RPA, and PM5-RPA levels were 0.822, 0.841, and 0.901, respectively, and they were also comparable to that at TD/B3LYP/cc-pVDZ//B3LYP/cc-pVDZ. Therefore, although some calibration efforts may be needed for AM1 geometries, PM5-RPA(CIS)//AM1 may be a second candidate available for the prediction of the absorption maxima of dyes, especially in the case of emphasizing computational cost.     

Chemical characterization of PM10 fractions of urban aerosol

The goal of this investigation was to give an overview about the trace metal and total organic/inorganic carbon (TOC/TIC), water-soluble carbon (WSOC) and polyaromatic hydrocarbons (PAH) concentrations in the PM10 aerosol fraction in Budapest and to monitor monthly changes during the sampling period, whether there is a tendency in the seasonal change of the concentrations. The sampling took place in Budapest, Hungary between September 2004 and August 2007 in an area with high traffic density. For the sampling, a high-volume aerosol sampler equipped with a PM10 head was used. The samples were taken onto quartz fiber filters. Each month, one sample was collected. Sampling time was 96 h, the air intake was 30 m³/h, resulting in 2880 m³ sampled air volume.To measure the metal concentrations two types of sample preparation were used: microwave assisted aqua regia extraction and water extraction by sonication. In both cases, the solutions were analyzed by using a sector field inductively coupled plasma mass spectrometer (SF-ICP-MS). The following 23 elements were investigated: V, Cd, Zn, Cu, Ni, Sb, Sn, Cr, Pt, Pb, Te, Tl, U, Mn, Fe, Co, Ga, Rb, Sr, Mo, Ag, Bi, Li. Comparing the data obtained from the aqua regia extraction to some other cities, the measured trace elements were found in moderate concentration. In the water extract, a significant part of zinc and thallium was found. During the sampling period, no proof of seasonal change in trace element concentrations was found. Trace metal and total organic/inorganic carbon concentrations in Budapest were similar to the concentration data measured in other cities with exception of Mn, Ga, Rb, Cd which are present in higher concentration in Budapest. The TOC content in the PM10 fraction amounted to 30-50%, and its value was the highest during the winter period due to the heating.The yearly average concentration of polyaromatic hydrocarbons was almost constant over the investigated period, but its seasonal change is more than one order of magnitude.     

Determination of polycyclic aromatic hydrocarbons (PAHs) in particulate matter collected with low volume samplers

The determination of polycyclic aromatic hydrocarbons (PAHs) contained in samples of particulate matter (PM), collected with low volume pumps, were carried out with an high sensitivity method that comes from several revisions of a previous method. The present work describes how, by using programmable temperature vaporization (PTV) and a mass selective detector with inert ionic source for the GC-MS analysis and the modifications of microwave-assisted extraction (MAE), the sensitivity of the method can be increased.The PAHs chosen for testing the method are: benzo[a]anthracene (BaA), benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF), benzo[a]pyrene (BaP), indeno[1,2,3-cd]pyrene (Ip) and dibenzo[a,h]anthracene (DbA). They, in fact, belong to that group of substances that are the most harmful for human health for their carcinogenicity.PAHs recoveries for spiked standard solutions at different concentrations were between 95 and 100% with relative standard deviation ranging from 1 to 3%. The revised method was validated using a 1649a urban dust standard reference material (SRM). The results obtained were in good agreement with certified values. The high sensitivity of the method allows to carry out analyses using only a half of the sampled filter (usually 47 mm diameter membranes). In this way, the other half can be used for the characterization of the other components of PM (heavy metals, organic carbon, ions, etc). The last step has been constituted by application of the optimized method on real samples collected in two cities located in Southern Italy (Bari and Taranto).     

Determination of per- and polyfluorinated substances in airborne particulate matter by microwave-assisted extraction and liquid chromatography-tandem mass spectrometry

A sensitive and confirmatory analytical method has been developed for the determination of 12 ionic per- and polyfluorinated alkyl substances (PFAS) in fine airborne particulate matter (PM2.5) at trace levels. The proposed method includes extraction of PM2.5-bound PFAS by microwave-assisted extraction (MAE) followed by centrifugation and injection into the liquid chromatograph coupled to a triple quadrupole tandem mass spectrometry system (LC-MS/MS). The main parameters affecting the performance of MAE were optimised using statistical design of experiments (DoE). Recoveries ranged from 83 to 120% and the method quantification limit (MQL) was 1.4 pg m(-3), when air volumes of 720 m(3) were sampled. This method was successfully applied to 41 samples collected from five stations of the monitoring network of the Valencian Regional Government (Spain) during April-July 2010. Eight out of 12 PFCs investigated were quantified in at least one sample (PFBA, PFPeA, PFHxS, 6:2 FTS, PFOA, PFNA, PFOS and PFDA). The measured concentrations ranged from 1.4 to 34.3 pg m(-3).     

基于高分辨质谱在线观测的2011深圳大运会前后PM_1化学组成与粒径分布

本文利用先进的高分辨飞行时间气溶胶质谱仪（HR-ToF-AMS）于2011年深圳世界大学生运动会前后（2011年8月3日~9月22日）对深圳市区大气亚微米细粒子（PM1）化学成分和粒径分布进行了在线测量.结果表明,整个观测期间PM1质量浓度平均为51.1±32.6gm3,其中有机物占颗粒物总质量的37.9%,硫酸盐为37.1%,铵盐11.9%,黑碳6.6%（由一台单颗粒黑碳光度计（SP2）单独测量）,硝酸盐5.8%,氯化物0.6%.观测期间各成分（除黑碳外）的粒径分布峰值位于真空动力学粒径550nm附近,而有机物在较小粒径范围（100~200nm）仍有较多质量分布,显示出本地一次源的明显贡献.基于高分辨有机质谱计算得到的有机气溶胶的平均元素组成为：碳34.0%、氢53.2%、氧12.0%和氮0.8%（原子个数百分比）,对应的OM/OC（有机物与有机碳质量比）平均值为1.66±0.16.采用正矩阵因子解析（PMF）模型对有机气溶胶高分辨质谱进行因子解析,得到三类有机气溶胶：HOA（还原态有机气溶胶）,SV-OOA（半挥发氧化态有机气溶胶）和LV-OOA（低挥发氧化态有机气溶胶）,分别占有机物总量的31.3%,39.8%和28.9%,说明二次有机气溶胶（以SV-OOA和LV-OOA之和代表）是有机气溶胶的主体部分.结合气团来源分析不同时段PM1化学组成和粒径分布特征表明,大运会召开期间PM1质量浓度水平比整个观测期间的平均值低60.7%,是气团来自洋面等有利气象条件和黄标车限行等污染源控制措施的综合作用结果.