Investigation of different types of filters for atmospheric trace elements analysis by three analytical techniques

Different atmospheric aerosol samples were collected on three types of filters. Disks of both loaded and clean areas of each kind of filter were investigated by XRF, PIXE and Scanning Electron Microscope (SEM) methods. The blank concentration values of the elements Al, Si, P, S, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Br and Pb in the three types of fiters are discussed. It is found that for trace elemental analysis, the Nuclepore membrane filters are the most suitable for sampling. These have much lower blank element concentration values than the glass fibres and ash free filters. It was found also that the PIXE method is a more reliable analytical technique for atmospheric aerosol particles than the other methods.     

Comparison of three methods for trace analysis of polycyclics

Summary Several analytical techniques for the determination of polycyclic aromatic hydrocarbons in air have been evaluated. Two solvents, benzene and cyclohexane, were compared for their efficacy in the preliminary preparation of the air sample. To identify and measure the polycyclics, the techniques of ultraviolet absorption and fluorescence were used. Air sample extracts were analyzed with and without prior Chromatographic separation. A rapid Chromatographic procedure using benzene as elutant was employed for the first time. The extract aliquot or eluate fraction was chromatographed on fully activated alumina using benzene as the eluting solvent. BaP and BkF are eluted from such a column in 30 minutes or less in a total eluate volume of perhaps 50 ml and the two hydrocarbons are determined by fluorescence emission. Work in progress suggests that benzene may be replaced in this application by the less toxic toluene.By any method used the BkF values found were in good agreement. The agreement between the various BaP values was poor, suggesting not all were of equal validity. The highest, and also least accurate, BaP values seem to be associated with the use of benzene as extractant, or ultraviolet absorption as a measuring technique.

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Zusammenfassung Verschiedene Analysenverfahren zur Bestimmung polycyklischer aromatischer Kohlenwasserstoffe in Luft wurden ausgearbeitet. Benzol und Cyklohexan wurden hinsichtlich ihrer Wirksamkeit als Lösungsmittel bei der Vorbereitung der Luftproben verglichen. Zur Identifizierung und Messung der polycyklischen Substanzen wurde die UV-Absorption und die Fluoreszenz herangezogen. Die Luftprobenextrakte wurden mit und ohne vorherige chromatographische Auftrennung analysiert. Bin rasches chromatographisches Verfahren mit Benzol als Elutionsmittel wurde erstmals verwendet. Extraktanteil oder Eluatfraktion wurden auf hochaktivem Aluminiumoxid chromatographiert und mit Benzol eluiert. Benzo(a)perylen (BaP) und Benzo(k)fluoranthen (BkF) werden aus einer solchen Säule in 30 Minuten mit etwa 50 ml eluiert und durch Fluoreszenzmessung bestimmt. Es scheint naheliegend, statt Benzol das weniger toxische Toluol zur Elution zu verwenden. Die nach jeder Methode erhaltenen BkF-Werte stimmen gut überein im Gegensatz zu den BaP-Werten. Die höchsten und gleichzeitig wenigst genauen BaP-Werte treten offenbar auf, wenn Benzol als Extraktionsmittel und UV-Absorption zur Messung verwendet werden.

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Presented at the Anachem Conference, Detroit, Mich., U. S. A., October 11, 1966.     

Comparison of three analytical methods for the determination of trace elements in whole blood

Three different analytical techniques were compared in a study of the role of trace elements in multiple sclerosis. Data for eight elements (Cd, Co, Cr, Cu, Mg, Mn, Pb, Zn) from neutron activation, flame atomic absorption and electrothermal atomic absorption methods were compared and evaluated statistically. No difference (probability less than 0.001) was observed in the elemental values obtained. Comparison of data between suitably different analytical methods gives increased confidence in the results obtained and is of particular value when standard reference materials are not available.     

A sampling and analytical methodology for dental trace element analysis

The role of trace elements in human health and environmental pollution has developed into an extensive field of research. This study describes a sampling and analytical strategy to determine the trace element content of primary (deciduous) teeth and to assess their use in environmental health and nutrition studies. Exfoliated and extracted primary teeth were collected from 21 Ugandan and 27 UK children. The crown and root of the teeth were separated and the former digested and analysed for several elements by inductively coupled plasma mass spectrometry. The influence of country, tooth type, age and gender were statistically investigated in addition to within-person variation. A principal components analysis (PCA) was used to treat the data in a multivariate fashion and facilitated the moderation of outliers. The results demonstrated that country of origin has an important influence on the elemental composition of teeth and that tooth type should be controlled in these types of studies. Given such a restriction, the age and gender of the donor should have no effect and do not need to be controlled. In addition, where country of domicile, age and gender were controlled, the concentrations of most elements within a single tooth type were representative of an individual and therefore may be indicative of health status.     

Comparison of three analytical methods for quality control of clozapine tablets

Three different analytical methods for the quality control of clozapine in commercial formulations were developed and compared: a liquid chromatographic (LC) method with UV detection, a capillary zone electrophoretic (CZE) method, and a linear scan voltammetric (LSV) method. The isocratic LC procedure used a C18 reversed-phase column; the CZE method used an uncoated fused-silica capillary and phosphate buffer containing polyvinylpyrrolidone as the background electrolyte; the LSV method analyzed clozapine solutions with acidic phosphate buffer as the supporting electrolyte. The 3 methods gave similar and satisfactory results, in terms of precision and accuracy. Repeatability and intermediate precision were good (RSD% < 2.2) and accuracy, resulting from recovery studies, was between 98 and 102%. The rapidity of analysis was high for all 3 methods, especially for the LSV.     

Determination of the trace element levels in atmospheric pollutants by neutron activation analysis

An investigation of the potentials of neutron activation analysis for the routine analysis of trace elements present in atmospheric pollutants is discussed. Various techniques including sequential air sampling, multiple neutron irradiation, high resolution γ-ray spectrometry, chemical isolation, high flux neutron irradiation and X-ray spectrometry have been employed to determine the levels of Pb, Al, V, I, Cl, Mn, Cu, Br, Na, La, Mo, Au, Cr, Fe, Ni, Se, Zn, Ag and Co in atmospheric pollutants. The results of the analysis of nearly two hundred samples collected from the Buffalo New York area during 1968–1969 are reported. Presented at the Fourth Annual Conference on Trace Substances in Environmental Health, University of Missouri, Columbia Missouri, USA (June, 1970).     

Nuclear-based methods for the analysis of trace element pollutants in human hair

The trace element composition of human hair is a suitable indicator of exposure to trace element pollutants. During the implementation of an international research programme, coordinated by the IAEA, on the use of nuclear methods for detecting trace element pollutants in hair, much valuable information was collected both on normal levels of trace elements and on increased levels caused by pollution. As a result of reviewing and comparing the data, interesting observations relating to the spread of concentrations were made. Standardized procedures were elaborated for a number of analytical techniques as well as for pre-analytical preparations in the analysis of hair. Paper presented at the Second Meeting on Nuclear Analytical Procedures, Dresden (GDR), 19 to 23 March 1979.     

Development of visual analytical methods for trace determination.

In this paper our recent progress in the field of simple analytical methods is reviewed, with particular focus on the development of rapid, inexpensive, yet sensitive techniques to visualize trace elements of medical, industrial, and environmental importance. Our objective is to solve long-standing practical problems in these fields. We have repeatedly shown that visual perception is remarkably sensitive when used with our new techniques. The applicability of the proposed methods to real samples is also discussed. Making measurements visually is a method free from machinery malfunctions and serves as a simple and sensitive analytical technique, avoiding all of the practical disadvantages associated with sophisticated instrumentation as well as tedious procedures.     

Comparison of trace analytical results obtained with different hollow cathode discharge lamps

Summary Detection limit and sensitivity of trace analysis of powdered samples have been tested using hollow cathod discharge lamps made in our laboratory. We found some special problems for trace analysis with hollow cathode excitation; such problems are the energy tuning and the pressure dependence of spectral lines. Results obtained with improved hollow cathode discharge lamp and with water cooled hollow cathode discharge lamp are compared to each other.

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Vergleich spurenanalytischer, mit verschiedenen Hohlkathodenlampen erzielter, Ergebnisse

Zusammenfassung In Pulveranalysenergebnissen wurde die mit den von uns entwickelten Entladungsröhren erzielten Nachweisgrenzen sowie die Veränderung des Nachweisvermögens geprüft. Es wurde experimentell nachgewiesen, daß bei der Hohlkathodenentladung auch spezielle spurenanalytische Probleme entstehen, wie die Energieabstimmung und die Druckabhängigkeit der Spektrallinien. Die Ergebnisse der modifizierten und die der wassergekühlten Hohlkathodenentladung wurden zusammengestellt und verglichen.

     

Factor analytical approaches for evaluating groundwater trace element chemistry data

The multivariate statistical techniques principal component analysis (PCA), Q-mode factor analysis (QFA), and correspondence analysis (CA) were applied to a dataset containing trace element concentrations in groundwater samples collected from a number of wells located downgradient from the potential nuclear waste repository at Yucca Mountain, Nevada. PCA results reflect the similarities in the concentrations of trace elements in the water samples resulting from different geochemical processes. QFA results reflect similarities in the trace element compositions, whereas CA reflects similarities in the trace elements that are dominant in the waters relative to all other groundwater samples included in the dataset. These differences are mainly due to the ways in which data are preprocessed by each of the three methods.

The highly concentrated, and thus possibly more mature (i.e. older), groundwaters are separated from the more dilute waters using principal component 1 (PC 1). PC 2, as well as dimension 1 of the CA results, describe differences in the trace element chemistry of the groundwaters resulting from the different aquifer materials through which they have flowed. Groundwaters thought to be representative of those flowing through an aquifer composed dominantly of volcanic rocks are characterized by elevated concentrations of Li, Be, Ge, Rb, Cs, and Ba, whereas those associated with an aquifer dominated by carbonate rocks exhibit greater concentrations of Ti, Ni, Sr, Rh, and Bi. PC 3, and to a lesser extent dimension 2 of the CA results, show a strong monotonic relationship with the percentage of As(III) in the groundwater suggesting that these multivariate statistical results reflect, in a qualitative sense, the oxidizing/reducing conditions within the groundwater. Groundwaters that are relatively more reducing exhibit greater concentrations of Mn, Cs, Co, Ba, Rb, and Be, and those that are more oxidizing are characterized by greater concentrations of V, Cr, Ga, As, W, and U.     

Concentration of analytical data as part of data processing in trace element analysis

Summary Statistical data evaluation in trace element analysis was mainly influenced by the Normal Law of Error, which is based on the assumption of a Gaussian normal distribution. Supposing that the analytical error of the trace element concentration is negligibly small compared with its true variations in nature, skew distributions may become more important than normal ones. Often, but not always, the lognormal distribution is a good approximation of the skew distribution. Careful investigation of the type of distribution before starting data evaluation in trace element analysis is still frequently overlooked today.In this Department, data concentration is performed on a routine basis by two programmes ZCH-2 and ZCH-3/1. They include a) investigation of the type of distribution by drawing the histogrammes, probability plot for normal and lognormal distribution as Hazen's straight lines, Kolmogorov-Smirnov- and Cramer- van Mises goodness-of-fit tests as well as skewness and kurtosis. Outliers of the normal distribution can be eliminated b) by t-, Nalimov's r-, Grubb's and Dixon's tests. c) As central values for data location, the arithmetic, geometric, and harmonic means and median are calculated. d) The dispersion around the mean is characterized by variance, standard deviation of a single value as well as the mean, relative coefficient of variation, mean deviation from the arithmetic mean, geometric standard deviation, range and 80% inter-decile range. Confidence intervals are given for the arithmetic mean, geometric mean and median.Typical problems of data concentration are the deviation from the normal distribution, comparison of different mean values, outlier elimination, concentrations below detection limit, homogeneity and heterogeneity of the data sample. They are discussed for examples of data series from one of the author's laboratories, e.g. trace element concentrations in air, lead content in dental calculus, toxic heavy metal leaching from ceramic ware and gamma dose rates from an area of higher natural radioactivity in the Federal Republic of Germany.As a conclusion, it is emphasized that the trace element analyst should overcome the Mystery of the Normal and Quasi-normal Distribution and include skew data distributions and their statistical treatment into his repertoire of routine procedures as well as in his way of thinking.

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Konzentrierung analytischer Daten als Teil der Datenverarbeitung in der Spurenelementanalyse

Zusammenfassung Die statistische Beurteilung von Daten der Spurenelementanalyse war lange Zeit durch das Gesetz der Fehler-Normalverteilung geprägt, welches auf der Annahme einer Gaußschen Normalverteilung beruht. Wird der analytische Fehler der Konzentrationsbestimmung von Spurenelementen vernachlässigbar klein gegenüber den tatsächlichen Schwankungen in der Natur, dann werden schiefe Verteilungen häufig wichtiger als Normalverteilungen. Eine gute Näherung ist oft, allerdings nicht immer, die Lognormalverteilung. Der Spurenanalytiker übersieht häufig auch heute noch, vor Beginn der eigentlichen Datenbeurteilung den Typ der vorliegenden Häufigkeitsverteilung seines Datensatzes zu untersuchen.Die Datenkonzentrierung erfolgt in der hiesigen Zentralabteilung routinemäßig vor allem mit den Programmen ZCH-2 und ZCH-3/1. Darin wird der Typ der Datenverteilung a) durch Zeichnen der Histogramme, Auftragung als Hazens Gerade in Wahrscheinlichkeitskoordinaten für Normal- und Lognormalverteilung, den Kolmogorov-Smirnov- und Cramer-van-Mises-Anpassungstests sowie Schiefe und Wölbung beurteilt. Bei Quasi-Normalverteilungen können b) Ausreißer durch den t-, Nalimovs r-, Grubbs- und Dixon-Test eliminiert werden. Zentralwerte zur Lokalisierung des Datenkollektives sind c) arithmetisches, geometrisches und harmonisches Mittel sowie Median. Die Streuung um die Mittelwerte wird durch d) Varianz, Standardabweichung für Einzelwert sowie Mittel, relativen Variationskoeffizienten, geometrische Standardabweichung, Bereich und 80% Interdezil-Bereich charakterisiert. Zusätzlich werden Vertrauensbereiche für das arithmetische und geometrische Mittel und den Median berechnet.Als typische Probleme der Datenkonzentrierung werden die Abweichungen von der Normalverteilung, ein Vergleich verschiedener Mittelwerte untereinander, die Eliminierung von Ausreißern, die Behandlung von Konzentrationen unterhalb der Nachweisgrenze sowie Homogenität und Heterogenität der Datenkollektive behandelt. Dies wird an Datenreihen aus früheren Untersuchungen eines der Verfasser über Spurenelementkonzentrationen in der Luft, den Bleigehalt in Zahnstein, die Auslaugung toxischer Schwermetalle aus Keramikgeschirr und Gamma-Dosisleistungen aus einem Gebiet der Bundesrepublik mit höherer natürlicher Untergrundradioaktivität erläutert.Als wesentliches Ergebnis soll die Arbeit dazu beitragen, daß der Spurenanalytiker das Mysterium der Normalverteilung überwindet und die Behandlung schiefer Datenverteilungen sowohl in das Repertoire seiner Routineuntersuchungen als auch in sein analytisches Denken aufnimmt. Um einen größeren Kreis von Spurenanalytikern anzusprechen, ist die Darstellung elementar gehalten.

Dedicated to Prof. Dr. E. Blasius, on occasion of his 60th birthday     

Comparison of various liquid chromatographic methods involving UV and atmospheric pressure chemical ionization mass spectrometric detection for the efficient trace analysis of phenylurea herbicides in various types of water samples

The performance of mass spectrometric (MS) detection and UV detection in combination with reversed-phase liquid chromatography without and with the use of coupled column RPLC (LC-LC) has been compared for the trace analysis of phenylurea herbicides in environmental waters. The selected samples of this comparative study originated from an inter-laboratory study. For both detection modes, a 50 mm x 4.6 mm I.D. column and a 100 mm x 4.6 mm I.D. column packed with 3 microm C18 were used as the first (C-1) and second (C-2) column, respectively. Atmospheric pressure chemical ionization mass spectrometry was performed on a magnetic sector instrument. The LC-LC-MS analysis was carried out on-line by means of direct large volume (11.7 ml) injection (LVI). The performance of both on-line (LVI, 4 ml of sample) and off-line LC-LC-UV (244 nm) analysis was investigated. The latter procedure consisted of a solid-phase extraction (SPE) of 250 ml of water sample on a 500 mg C18 cartridge. The comparative study showed that LC-LC-MS is more selective then LC-LC-UV and, in most cases, more sensitive. The LVI-LC-LC-MS approach combines direct quantification and confirmation of most of the analytes down to a level of 0.01 microg/l in water samples in less then 30 min. As regards LC-LC-UV, the off-line method appeared to be a more viable approach in comparison with the on-line procedure. This method allows the screening of phenylurea's in various types of water samples down to a level of at least 0.05 microg/l. On-line analysis with LVI provided marginal sensitivity (limits of detection of about 0.1 microg/l) and selectivity was sometimes less in case of surface water samples. Both the on-line LVI-LC-LC-MS method and the LC-LC-UV method using off-line SPE were validated by analysing a series of real-life reference samples. These samples were part of an inter-laboratory test and contained residues of herbicides ranging from 0.02 to 0.8 microg/l. Beside good correlation between the methods the data agreed very well with the true values of the samples.     

Comparison of atmospheric pressure photoionization and electrospray ionization mass spectrometry for the analysis of UV filters

A comparison was made between the electrospray ionization (ESI) and atmospheric pressure photoionization (APPI) tandem mass spectrometric (MS/MS) responses of eleven ultraviolet (UV) filters. Four of the target compounds were favourably ionized in negative ion mode, and the other seven compounds in positive ion mode. For nine of the compounds APPI generated a similar response to that of ESI, but the APPI signal‐to‐noise (S/N) ratios were 1.3–60 times higher. The two most polar of the UV filter compounds (PBSA and BP‐4) were more efficiently ionized by ESI, offering higher signal intensities and lower detection limits. APPI was, however, less susceptible to ion suppression than ESI when real samples were injected. In order to optimize the APPI conditions different dopant solvents were examined to enhance the efficiency of the photoionization process. Among the evaluated dopants, toluene was selected as the best compromise. At a toluene flow rate of 10% of the solvent flow rates the ionization response increased by a factor of 40–50 over the use of no dopant for the compounds in positive ion mode and by more than 300 for the compounds in negative ion mode. Copyright © 2009 John Wiley & Sons, Ltd.     

Comparison of different types of stationary phases for the analysis of soy isoflavones by HPLC

Nowadays, there are new technologies in high-performance liquid chromatography columns available enabling faster and more efficient separations. In this work, we compared three different types of columns for the analysis of main soy isoflavones. The evaluated columns were a conventional reverse phase particle column, a fused-core particle column, and a monolithic column. The comparison was in terms of chromatographic parameters such as resolution, asymmetry, number of theoretical plates, variability of retention time, and peak width. The lower column pressure was provided by the monolithic column, although lower chromatographic performance was achieved. Conventional and fused-core particle columns presented similar pressure. Results also indicate that direct transfer between particle and monolithic columns is not possible requiring adjustment of conditions and a different method optimization strategy. The best chromatographic performance and separation speed were observed for the fused-core particle column. Also, the effect of sample solvent on the separation and peak shape was evaluated and indicated that monolithic column is the most affected especially when using higher concentrations of acetonitrile or ethanol. Sample solvent that showed the lowest effect on the chromatographic performance of the columns was methanol. Overall evaluation of methanol and acetonitrile as mobile phase for the separation of isoflavones indicated higher chromatographic performance of acetonitrile, although methanol may be an attractive alternative. Using acetonitrile as mobile phase resulted in faster, higher resolution, narrower, and more symmetric peaks than methanol with all columns. It also generated the lower column pressure and flatter pressure profile due to mobile phase changes, and therefore, it presents a higher potential to be explored for the development of faster separation methods.     

Radiometric efficiency of analytical filters at different physical conditions

The radiometric efficiency of three analytical filters AFA-RSP-20, AFA-RMP-20 and AFA-RMV-20 was examined at different air velocities and aerosol number concentrations. An experimental setup had been constructed with 2 m³ radon chamber. Alpha radiometry was used to measure the deposited activities in the filters. Aerosols parameters like number concentration and size distribution are measured continuously with an aerosol diffusion spectrometer (ADS). RMV filter has a stable efficiency ~ 99.8%. The RSP and RMP filters efficiency is depending on the aerosol concentration and air sampling velocity. The effect of an aerosol concentration on the filter efficiency is more obvious than the effect of air velocity.

     

NAA and ICP-MS: A comparison between two methods for trace and ultra-trace element analysis

NAA and ICP-MS are both highly sensitive methods for multi-element trace-and ultra-trace element determination. A comparison between analytical figures of merit of both methods is made. Both methods have specific advantages that put them beyond competition for certain applications. It is concluded that ICP-MS can replace NAA for many routine analyses. NAA remains essential as a highly reliable and accurate reference method.     

Microwave assisted extraction for trace element analysis of plant materials by ICP-AES

Application of microwave assisted extraction for the decomposition and dissolution of plant samples for trace metal determination by ICP-AES was examined. Dried onion, leaves of spinach beet and three reference materials CTA-OTL-1, CTA-VTL-2 and CL-1 were analyzed. Water, EDTA and hydrochloric acid (0.01, 0.10 and 1.0 M, respectively) were used as leaching solutions. The extraction efficiency was investigated by comparison of the results with those obtained after microwave wet digestion. HCl was found to be very suitable for quantitative extraction of B, Ba, Cd, Cu, Mn, Ni, Pb, Sr and Zn from the samples. For reference materials, the measured concentrations are well consistent with the certified values. The use of EDTA led to a complete extraction of B, Cd, Ni, Pb, Sr and Zn. Water was found to be a good leaching solution for boron. For extraction with HCl and EDTA, the RSD values for the concentrations measured were below 8% for most of the elements.     

Comparison of photon activation analysis with other modern analytical methods as tools for the solution of actual analytical problems

A 35 MeV linear electron accelerator is used to investigate how far photon activation analysis can be used within the broad spectrum of analytical methods applied in BAM. The irradiation facilities are described. Examples are given for the application of PAA in the analysis of oxygen in metals and compared with conventional heat extraction and other nuclear analytical methods. It is further shown that PAA is a very useful tool for the analysis of traces of noble metals in Cu compared with other methods. Finally the possibilities of PAA in the field of multielement analysis are demonstrated taking ancient roman potsherds and bronze as examples. The results are compared with those of XRF and AAS. It is concluded that PAA is a valuable tool in the analysis of light elements with at least partly unique possibilities, that it can serve as an independent method for the certification of Reference Materials in many cases and that PAA can be very useful applied for multielement analysis.