Investigation on the use of chemical mass balance receptor model: Numerical computations

Cheng, M.D. and Hopke, P.K., 1986. Investigation on the use of chemical mass balance receptor model: numerical computations. Chemometrics and Intelligent Laboratory Systems, 1: 33–50.The use of various numerical techniques in the chemical mass balance receptor model leads to different estimations of mass contributions by the identified sources for an ambient air quality data set. Weighted-constrained L₁ (called least absolute deviations in statistics), ordinary weighted least squares, effective variance weighted least squares, and two variants of standard linear programming methods based on the maximized allocation of aerosol mass were studied. The data sets used in this study were the simulated aerosol composition data generated by the National Bureau of Standards for the EPA workshop on mathematical and empirical receptor modeling held at Quail Roost, NC, U.S.A. in 1982. The ensemble reliability of the numerical solutions for these test data sets were evaluated. The weighted-constrained L₁ solutions were found highly stable compared to those from the least-squares methods subject to various complexities of the simulated data sets. The effective variance weighted least squares was found to be ineffective in improving the quality of aerosol mass apportionment by the chemical mass balance model. The results of the standard linear programming methods were insensitive to the lognormal random variations present in the source compositions in Set 3, but gave less precise results than those obtained with the L₁ or least squares methods.     

Improved precision of iTRAQ and TMT quantification by an axial extraction field in an Orbitrap HCD cell

Improving analytical precision is a major goal in quantitative differential proteomics as high precision ensures low numbers of outliers, a source of false positives with regard to quantification. In addition, higher precision increases statistical power, i.e., the probability to detect significant differences. With chemical labeling using isobaric tags for relative and absolute quantitation (iTRAQ) or tandem mass tag (TMT) reagents, quantification is based on the extraction of reporter ions from tandem mass spectrometry (MS/MS) spectra. We compared the performance of two versions of the LTQ Orbitrap higher energy collisional dissociation (HCD) cell with and without an axial electric field with regard to reporter ion quantification. The HCD cell with the axial electric field was designed to push fragment ions into the C-trap and this version is mounted in current Orbitrap XL ETD and Orbitrap Velos instruments. Our goal was to evaluate whether the purported improvement in ion transmission had a measurable impact on the precision of MS/MS based quantification using peptide labeling with isobaric tags. We show that the axial electric field led to an increased percentage of HCD spectra in which the complete set of reporter ions was detected and, even more important, to a reduction in overall variance, i.e., improved analytical precision of the acquired data. Notably, adequate precision of HCD-based quantification was maintained even for low precursor ion intensities of a complex biological sample. These findings may help researchers in their design of quantitative proteomics studies using isobaric tags and establish HCD-based quantification on the LTQ Orbitrap as a highly precise approach in quantitative proteomics.     

Thermal desorption/pyrolysis coupled with photoionization time-of-flight mass spectrometry for the analysis of molecular organic compounds and oligomeric and polymeric fractions in urban particulate matter

Atmospheric aerosols are subject to be responsible for human health effects. In this context, besides mass and number concentration of particles, their chemical composition has gained interest recently. However, knowledge about the organic content of particulate matter is still relatively scarce; i.e., only 10-40% of compounds present in the aerosol are as yet identified. By means of a newly developed measurement technique, thermal desorption/photoionization time-of-flight mass spectrometry (TOFMS), organic species evolved from urban aerosol samples collected at Augsburg, Germany, are analyzed. Thereby, compounds desorbed according to a temperature protocol following procedures for OC/EC analysis (120, 250, and 340 degrees C as desorbing temperatures) are ionized by soft, fragmentationless resonance multiphoton ionization (REMPI) and single photon ionization (SPI), respectively. With REMPI-TOFMS, a large variety of PAH is detectable. A comprehensive analysis is enabled by adding SPI-TOFMS, which gives access to aliphatic and carbonylic hydrocarbons as well as alkanoic acids and esters. Analysis of the data showed a high abundance of phenol and guiacol as well as retene, which are known markers for wood combustion. Similar patterns were found with ash from spruce wood combustion. An increase of volatile substances at 340 degrees C gave rise to the suggestion that these compounds are re-formed by pyrolytic decomposition reactions from oligomeric, polymeric, and polyfunctional oxygenated species. This was corroborated by the investigation of the behavior of cellulose acetate, which exhibited a similar pattern in its SPI-TOFMS spectrum at 340 degrees C as the aerosol. More thorough investigations of urban aerosol and source material with respect to problems such as the mass closure of carbonaceous material, indications for source apportionment, and allotment of organic species on a molecular level to fractions of organic and elemental carbon seem feasible with this measurement method.     

Alternative statistical methods for spectral data processing: applications to laser-induced breakdown spectroscopy of gaseous and aerosol systems

A new spectral data processing scheme based on the standard deviation of collected spectra is compared with the traditional ensemble-averaging of laser-induced breakdown spectroscopy (LIBS)-based spectral data for homogenous (i.e., pure gas phase) systems and with a LIBS-based traditional conditional spectral analysis scheme for non-homogenous (e.g., aerosol system) analyte systems under discrete particle loadings. The range of conditions enables quantitative assessment of the analytical approaches under carefully controlled experimental conditions. In the homogeneous system with gaseous carbon dioxide producing the carbon atomic emission signal, the standard deviation method provided a suitable metric that is directly proportional to the analyte signal and compares favorably with a traditional ensemble averaging scheme. In contrast, the applicability of the standard deviation method for analysis of non-homogenous analyte systems (e.g., aerosol systems) must be carefully considered. It was shown both experimentally and via Monte Carlo simulations that the standard deviation approach can produce an analyte response that is monotonic with analyte concentration up to a point at which the analyte signal starts to transition from a non-homogeneous system to a homogeneous systems (i.e., around a 50% sampling point for aerosol particles). In addition, the standard deviation spectrum is capable of revealing spectral locations of non-homogeneously dispersed analyte species without a priori knowledge.     

Radiative transfer model for aerosols in infrared wavelengths for passive remote sensing applications

A comprehensive analytical radiative transfer model for isothermal aerosols and vapors for passive infrared remote sensing applications (ground-based and airborne sensors) has been developed. The theoretical model illustrates the qualitative difference between an aerosol cloud and a chemical vapor cloud. The model is based on two and two/four stream approximations and includes thermal emission-absorption by the aerosols; scattering of diffused sky radiances incident from all sides on the aerosols (downwelling, upwelling, left, and right); and scattering of aerosol thermal emission. The model uses moderate resolution transmittance ambient atmospheric radiances as boundary conditions and provides analytical expressions for the information on the aerosol cloud that is contained in remote sensing measurements by using thermal contrasts between the aerosols and diffused sky radiances. Simulated measurements of a ground-based sensor viewing Bacillus subtilis var. niger bioaerosols and kaolin aerosols are given and discussed to illustrate the differences between a vapor-only model (i.e., only emission-absorption effects) and a complete model that adds aerosol scattering effects.     

Recent developments in aerosol measurement techniques and the metrological issues

A small error in the aerosol measurements can lead to a considerable influence on our understanding towards its impact on climate. To better simulate aerosol effects on the earth’s radiation budget, the chemical and physical characterizations of aerosol particles with accurate measurements have been a key interest in the aerosol research for last several decades. Recent advances in the chemical characterization of aerosols at bulk and molecular levels, and their physical characterization, such as size distribution, hygroscopicity, and cloud condensation nuclei (CCN) activity have improved our knowledge to better understand the aerosol sources, concentration distributions, atmospheric processing and their potential climate impacts. Apart from the complexity of atmospheric aerosols, because of the limited availability of aerosol certified reference materials, traceability data and measurement protocols, it is still a challenging task to measure the aerosol properties with reduced uncertainty. The recent developments on aerosol analytical techniques (on-line and off-line), which include gas chromatography/flame ionization detector (GC/FID)/mass spectrometry (MS)/isotope ratio mass spectrometry (irMS), ion chromatography (IC), organic carbon/elemental carbon (OC/EC) and water-soluble organic carbon (WSOC) analyzers, and physical measurements using scanning mobility particle sizer (SMPS), hygroscopicity tandem differential mobility analyzer (HTDMA) and cloud condensation nuclei-counter (CCN-C) are discussed with the metrological issues in the measurements. The importance of aerosol metrology is highlighted giving the data obtained from the laboratory studies and aerosol field campaigns.     

A Critical Evaluation of Interlaboratory Data on Total,Elemental, and Isotopic Carbon in the Carbonaceous Particle Reference Material,NIST SRM 1649a

Because of increased interest in the marine and atmospheric sciences in elemental carbon (EC), or black carbon (BC) or soot carbon (SC), and because of the difficulties in analyzing or even defining this pervasive component of particulate carbon, it has become quite important to have appropriate reference materials for intercomparison and quality control. The NIST “urban dust” Standard Reference Material^® SRM 1649a is useful in this respect, in part because it comprises a considerable array of inorganic and organic species, and because it exhibits a large degree of (¹⁴C) isotopic heterogeneity, with biomass carbon source contributions ranging from about 2 % (essentially fossil aliphatic fraction) to about 32 % (polar fraction).A primary purpose of this report is to provide documentation for the new isotopic and chemical particulate carbon data for the most recent (31 Jan. 2001) SRM 1649a Certificate of Analysis. Supporting this is a critical review of underlying international intercomparison data and methodologies, provided by 18 teams of analytical experts from 11 institutions. Key results of the intercomparison are: (1) a new, Certified Value for total carbon (TC) in SRM 1649a; (2) ¹⁴C Reference Values for total carbon and a number of organic species, including for the first time 8 individual PAHs; and (3) elemental carbon (EC) Information Values derived from 13 analytical methods applied to this component. Results for elemental carbon, which comprised a special focus of the intercomparison, were quite diverse, reflecting the confounding of methodological-matrix artifacts, and methods that tended to probe more or less refractory regions of this universal, but ill-defined product of incomplete combustion. Availability of both chemical and ¹⁴C speciation data for SRM 1649a holds great promise for improved analytical insight through comparative analysis (e.g., fossil/biomass partition in EC compared to PAH), and through application of the principle of isotopic mass balance.     

道路旁大气悬浮微粒的理化特性及污染源解析(英文)

旨在探讨道路旁悬浮微粒之理化成分,并解析其可能的污染来源。悬浮微粒采样作业于2003年5月～2004年1月期间进行,悬浮微粒样本采集时间包括春、夏、秋、冬四季的假日与非假日,所采集的悬浮微粒样本经化学成分分析可得水溶性离子成分与金属元素成分,并透过化学质量平衡受体模式及逆轨迹模式进行污染源解析。测量结果显示,假日的大气悬浮微粒PM10浓度高于非假日,而假日与非假日的总悬浮颗粒则无明显变化。此外,道路旁悬浮微粒PM10主要受非交通源的长程传输与当地的交通源所影响,而总悬浮颗粒则主要源自于附近道路的车行及逸散扬尘。另就悬浮微粒化学成分而言,金属元素成分以Ca、Fe、Al最多,水溶性离子成分则主要为SO42-、NO3-、NH4+等二次污染物。受体模式及逆轨迹模式分析结果得知,污染来源主要为交通污染及道路扬尘,然而,亦有相当部分的污染来自上风处的非交通源。     

道路旁大气悬浮微粒之理化特性及污染源解析

旨在探讨道路旁悬浮微粒之理化成分,并解析其可能的污染来源.悬浮微粒采样作业于2003年5月～2004年1月期间进行,悬浮微粒样本采集时间包括春、夏、秋、冬四季的假日与非假日,所采集的悬浮微粒样本经化学成分分析可得水溶性离子成分与金属元素成分,并透过化学质量平衡受体模式及逆轨迹模式进行污染源解析.测量结果显示,假日的大气悬浮微粒PM10浓度高于非假日,而假日与非假目的总悬浮颗粒则无明显变化.此外,道路旁悬浮微粒PM10主要受非交通源的长程传输与当地的交通源所影响,而总悬浮颗粒则主要源自于附近道路的车行及逸散扬尘.另就悬浮微粒化学成分而言,金属元素成分以Ca、Fe、Al最多,水溶性离子成分则主要为SO42-、NO3-、NH4+等二次污染物.受体模式及逆轨迹模式分析结果得知,污染来源主要为交通污染及道路扬尘,然而,亦有相当部分的污染来自上风处的非交通源.     

Automation using robotics in the analysis of SK&F 94836 in plasma

Pearce, J.C., Allan, M.P., O'Connor, S.A. and McDowall, R.D., 1988. Automation using robotics in the analysis of SK&F 94836 in plasma. Chemometrics and Intelligent Laboratory Systems, 3: 315–319.Over the past four years, sensitive and specific assays have been developed in our laboratories for the analysis of a family of positive inotropic agents in plasma. The methods have been based on high-performance liquid chromatography with UV detection, making use of liquid—solid extraction techniques using disposable cassettes of ten mini-extraction cartridges. Samples were prepared off-line prior to on-line elution of the analytes onto the analytical column using an Analytichem Automated Sample Processor (AASP) liquid chromatography module. This paper describes the scheme which we have used to automate the preparation of the AASP cassettes.A system, based on flexible robotics was established and successfully applied to the analysis of SK&F 94836, a positive inotrope with vasodilator activity, in plasma. Comparative results for the accuracy and precision of the assay are presented which show good correlation between the manual and automated approaches. Implementation of such a scheme has the additional benefits of unattended 24 hour operation and improved data integrity. The success of this project supports the use of robotics in the field of bioanalysis.     

南京地区碳气溶胶的数值模拟研究

根据常规的SO2排放源资料以及NOx和HC交通源排放资料,建立了一种估算城市地区黑碳(BC)、有机碳(OC)源排放清单的方法,并利用此方法建立了南京地区碳气溶胶的源排放清单。同时运用NJU-CAQPS模式系统及二次有机气溶胶模式模拟分析了南京地区一次碳气溶胶(BC)、一次有机碳(POC)和二次有机气溶胶(SOC)的浓度分布特征。结果表明:在南京地区,机动车直接排放对城区一次碳气溶胶贡献率达到67.5%,机动车污染已成为主要来源;大气中的碳气溶胶浓度受到交通源(日变化)和气象条件(太阳辐射、温度、大气层结等)的共同影响;OC与BC的质量比冬季高于夏季,平均为2.62;SOC与OC的质量比夏季高于冬季,平均为19.8%。     

Sensitivity of the lidar solution to errors of the aerosol backscatter-to-extinction ratio: influence of a monotonic change in the aerosol extinction coefficient

Unlike other errors in the lidar equation solution for the two-component atmosphere, the error of the measured aerosol extinction coefficient caused by inaccuracies in the assumed aerosol backscatter-to-extinction ratios significantly depends on the aerosol spatial inhomogeneity. In a slightly nonhomogeneous atmosphere, an incorrect value in the assumed aerosol backscatter-to-extinction ratio does not significantly corrupt the measurement result, whereas in an atmosphere with a large monotonic change of the aerosol extinction [e.g., in the lower troposphere], the incorrect value yields a large distortion of the retrieved extinction-coefficient profile. In the latter case, even the far-end solution can produce a large error in the retrieved extinction coefficient. The analytical formulas for the determination of the range errors, obtained for the Klett and the optical-depth solutions, show that these errors significantly depend on the method of the boundary-condition determination. Distortions of the retrieved aerosol extinction profiles are, in general, larger if the assumed aerosol backscatter-to-extinction ratio is underestimated in relation to the real value.     

Source apportionment of PM2.5 in urban area of Hong Kong

A monitoring program for PM(2.5) had been performed at two urban monitoring stations in Hong Kong from November 2000 to February 2001 and June 2001 to August 2001. PM(2.5) samples were collected once every 6 days at PolyU and KT stations with the sampling duration of 24-h. A sum of 25 chemical species in PM(2.5) were determined and selected for receptor models. Enrichment factors relative to earth crust abundances were evaluated and it was noted that most crustal elements including Al, Ti, Mg, Ca and K have small enrichment factors. Correlation and multivariate analysis technique, such as principal components analysis (PCA)/absolute principal components analysis (APCA) and cluster analysis (CA) are used for source apportionment to identify the possible sources of PM(2.5) and to determine their contribution. Six factors at each site were isolated by using PCA/APCA and cluster analysis. Similar sources (crustal matter, automobile emission, diesel emission, secondary aerosols, tire wear, and non-ferrous smelter) are identified by the PCA/APCA and cluster analysis.     

X-Ray Spectrometric Analysis of Noble Metal Dental Alloys

The analysis of noble metal dental alloys for the various constituent elements is a difficult and tedious task by chemical or fire assay procedures. X-ray spectroscopy offered the possibility of increased speed, especially if solid metal samples were employed. This technique was investigated particularly with respect to the analysis of dental alloys having the nominal composition in percent, of gold 72, silver 12, copper 10, platinum 2, palladium 2, and zinc 2. Alloys were prepared by melting the component elements in a high frequency furnace and casting the metal into disk form. Compositions of the castings were determined by chemical analysis. Optimum procedures for casting the sample and for X-ray analysis were established, and analytical curves were developed relating concentrations to measured intensities of the X-ray lines Au L_β, Ag K_α, Cu K_α, Pt L_α, Pd K_α, and Zn K_α. The observed typical coefficients of variation for the method were Au 0.34 percent, Ag 0.44 percent, Cu 2.2 percent, Pt 1.6 percent, Pd 1.2 percent, and Zn 0.72 percent. The results indicate that the method is sufficiently accurate and has marked advantages of speed and simplicity compared to chemical analysis.     

Equivalence of pyrheliometric and monochromatic aerosol optical depths at a single key wavelength

The atmospheric aerosol optical depth (AOD) weighted over the solar spectrum is equal to the monochromatic AOD at a certain wavelength. This key wavelength is ~0.7 mum, which is only slightly influenced by air mass and aerosol content. On the basis of this result, simple relations are proposed to predict monochromatic AOD from pyrheliometric data and vice versa. The accuracy achieved is close to ?0.01 units of AOD at ~0.7 mum, estimated from simultaneous sunphotometer data. The precision required for the estimation of the precipitable water-vapor content is approximately ?0.5 cm.     

Measurements of high-activity sources with a 4πβ-γ coincidence system

A 4πβ-γ coincidence system (IMPECC) working with cumulative dead times is described. The main features of the electronics of that system are presented, and its capability of measuring accurately sources of very high activity is demonstrated experimentally with a set of ⁶⁰Co sources. Results are coherent, and no bias is observed with increasing activities, even for the source of 1.3 MBq which was measured with a relative uncertainty that did not exceed 0.25%. A method derived from selective sampling was also tested successfully with the sources of highest activity.     

Sources of atmospheric pollution: a bibliometric analysis

A bibliometric analysis based on Web of Science was carried out to provide a critical analysis of the literature on atmospheric pollution sources during 2006–2015. The result showed that particulate matter represented the core of this research field, and methods of source apportionment such as positive matrix factorization were the mainstream techniques. Five clusters were identified from the keywords network with central node of particulate matter, traffic, heavy metal, elemental carbon and renewable energy respectively. The hotspots and their relationships were illustrated to describe the characteristics of this research field. The USA and China took the leading position, however, their research emphasis were health effect and characteristics of pollutants respectively. International collaboration was mostly conducted within Asia–Pacific countries, and EU countries. For journals, Atmospheric Environment was most productive during the study period while Environmental Science and Technology had highest impact factor in 2015. This study provides an effective approach to obtain a general knowledge of the atmospheric pollution sources and supports a deeper understanding of research directions in the future.     

A real-time ultrasound time-domain correlation blood flowmeter. II. Performance and experimental verification

For Part I, see ibid., vol.40, no.6, p.768-775 (1993). The performance of a real-time ultrasound time-domain correlation (UTDC) flowmeter employing a high-speed residue number system correlator under various flow conditions for different correlation parameter settings is evaluated. Previous work has incorporated a weighted-averaging scheme to estimate the flow velocity over a wide number of echo signal spacings. The present evaluation indicates that a linear averaging of 50 adjacent echo signal pairs produces equivalent accuracy and precision at real-time processing speed as compared to previous non-real time systems incorporating weighted averaging.     

Radiance reflected from the ocean-atmosphere system: synthesis from individual components of the aerosol size distribution

We describe a method by which the aerosol component of the radiance at the top of the atmosphere (TOA) can be synthesized from the radiances generated by individual components of the aerosol size-refractive-index distribution. The method is exact in the single-scattering approximation. For regimes in which the single-scattering approximation is not valid, the method usually reproduces the aerosol contribution with an error ?2-3% (and only rarely >3-4%) for Sun and viewing angles as large as 80° and 70°, respectively, and for aerosol optical thicknesses as large as 0.50. In the blue, where molecular scattering makes a dominant contribution to the TOA radiance, the percent error in the synthesized total radiance is significantly less than in the synthesized aerosol component and typically will be less than the radiometric calibration uncertainties of Earth-orbiting sensors. When the aerosol is strongly absorbing, the method can fail; however, the potential for failure is easy to anticipate a priori. An obvious application of our technique is to provide a basis for the estimation of aerosol properties with Earth-orbiting sensors, e.g., the Multiangle Imaging Spectroradiometer.     

Investigation of the chemical mixing state of individual Asian dust particles by the combined use of electron probe X-ray microanalysis and Raman microspectrometry

In this work, quantitative electron probe X-ray microanalysis (EPMA) and Raman microspectrometry (RMS) were applied in combination for the first time to characterize the complex internal structure and physicochemical properties of the same ensemble of Asian dust particles. The analytical methodology to obtain the chemical composition, mixing state, and spatial distribution of chemical species within single particles through the combined use of the two techniques is described. Asian dust aerosol particles collected in Incheon, Korea, during a moderate dust storm event were examined to assess the applicability of the methodology to resolve internal mixtures within single particles. Among 92 individual analyzed particles, EPMA and RMS identified 53% of the particles to be internally mixed with two or more chemical species. Information on the spatial distribution of chemical compounds within internally mixed individual particles can be useful for deciphering the particle aging mechanisms and sources. This study demonstrates that the characterization of individual particles, including chemical speciation and mixing state analysis, can be performed more in detail using EPMA and RMS in combination than with the two single-particle techniques alone.