Determination of polychlorobiphenyls and polycyclic aromatic hydrocarbons in the atmospheric aerosol of the Venice Lagoon

An analytical method for simultaneous determination of particle-associated and gaseous-phase concentrations of polychlorinated biphenyls (PCB) and polycyclic aromatic hydrocarbons (PAH) in atmospheric aerosol samples obtained by high-volume samplers using polyurethane foam adsorbent (PUF) and quartz fibber filters (QFF) has been investigated. Quality control of the analytical procedure was carried out by blank control and by evaluating limits of detection, recoveries, accuracy, and repeatability. The proposed method was subsequently used to determine PAH and PCB in the gaseous and particulate phases of the aerosols that enter the Venice Lagoon atmosphere. The highest concentrations of PCB and PAH were predominantly in the gaseous phase. In both particulate and gaseous phases the penta-CB congeners dominated total PCB concentrations whereas phenanthrene, fluoranthene, and pyrene dominated the PAH concentrations. Total (gaseous plus particulate) PCB and PAH concentrations were higher at the site directly influenced by the industrial plants but the concentrations in marine aerosol samples were lower by a factor four only and must be taken into consideration when studying the chemical contamination of the Venice Lagoon.     

Zur Frage des Einsatzes ionenspezifischer Elektroden in der Automation

Zusammenfassung Es wurden Untersuchungen mit anionenspezifischen Membranelektroden nach Pungor durchgeführt. Dazu werden Reproduzierbarkeit, Eichfunktion, Einstellzeiten bei auf- und absteigender Konzentration und Querempfindlichkeit im Hinblick auf den Einsatz in automatischen Systemen behandelt. Es wird vorgeschlagen, für die Angabe der Selektivität einen p-Sel analog zum pH zu verwenden, die Behandlung eines Analysensensorsystems wird vorgenommen.

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On the use of ion-specific electrodes in automation

Investigations on anion-specific membrane electrodes are described. Problems of reproducibility, calibration, time-response in respect of in- and decreasing concentrations and sensitivity to interfering ions are demonstrated and discussed with regard to automation. It is proposed to define a p-sel for the selectivity constant analogue to pH and a calculation method for an Analysis-Sensor-System is shown.

     

A variational coupled cluster theory for closed shells using a propagator modification procedure

A general partial summation method for including arbitrary classes of diagrams to all orders in the coupled cluster based size consistent energy functional for closed shell states is developed. Since the various reduced density matrices which appear in the energy functional are essentially the time-independent analogues of the corresponding many body Green functions, it is possible to derive Dyson-like equations for these quantities. By expanding the associated proper self energy parts in terms of the T-amplitudes, one can carry out partial summations in the reduced density matrices and thus in energy. At a higher level, higher order terms in a proper self energy can also be generated by renormalizing the internal propagators in it, and considering only the irreducible self-energy terms.     

Understanding the properties of isospectral points and pairs in graphs: The concept of orthogonal relation

The mathematical property orthogonal relationship is used in proving the fact that isospectrality, isocodality and isocoefficiency of vertices within a graph are all equivalent. The same is true for isospectrality, strict isocodality and strict isocoefficiency of pairs (including edges) within a graph, whereas the weak versions of the latter properties are necessary but not sufficient for isospectrality of pairs. Similarly, necessary and sufficient conditions for isospectrality of vertices and pairs in different graphs are derived. In all these proofs, the concept of orthogonal relation plays a major role in that it allows the use of tools of elementary linear algebra.     

Multielement analysis of NIST proposed SRM 1547 Peach Leaves

The k₀-standardization method of neutron activation analysis was applied for the multielement analysis of the NIST (National Institute of Standards and Technology) proposed Standard Reference Material (SRM) No. 1547 Peach Leaves. At the moment, 50 elements can be determined from a one day irradiation, using the TRIGA Mark II reactor of the Joef Stefan Institute, Ljubljana. Among them, 28 elements were determined quantitatively, and for the remaining 22 elements, less than values were obtained.     

Structural Transformations in Polydisperse Ferrofluids

Real polydisperse ferrofluid is modeled by a bidispersed magnetic colloid composed of large and small particles. It is assumed that the energy of magnetodipole interaction for small particles is much lower and that of large particles is substantially higher than their thermal energy. Therefore, large particles can combine into the chain and droplet aggregates that are present in a sea of small particles. The influence of small particles on the structurization in the ensemble of large particles is studied. It is shown that small particles can either prevent or stimulate these structural transformations depending on the parameters of a medium.     

Zur Literaturdokumentation in der Analytischen Chemie

Zusammenfassung Anhand von 298 Referaten aus Fresenius Z. Anal. Chem. werden systematisch geordnete Listen von Indexbegriffen für die Bereiche Methoden und Anwendungen erstellt und auf diese Referate angewendet. Diese vorläufige Systematik umfaßt 63 und 32 Hauptindexwörter. Den dokumentierten Referaten wurden 815 Schlüsselwörter (Hauptindexwörter) zugeordnet (116 Referate mit 2, 134 Referate mit 3 Hauptindexwörtern, Minimum: 1, Maximum: 5). Für zwei Indexabschnitte, Atomabsorptionsspektrometrie und Geologisches Material, wird die vorgeschlagene Indexierung vorgestellt und mit der bisherigen in Fresenius Z. Anal. Chem. verglichen. Die überschaubare Zahl von 95 Hauptindexwörtern, die erkennbare, einfache Systematik und die Wahlmöglichkeiten von zusätzlichen Nebenindexwörtern sollen zu einer benutzerfreundlichen Dokumentation beitragen, welche hiermit zur Diskussion gestellt wird.

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Literature documentation in analytical chemistryIV. Development of a systematic, easily usable index and documentation system

Summary By means of 298 abstracts from Fresenius Z. Anal. Chem. systematically arranged lists of index terms for the fields methods and applications were compiled and used for these abstracts. This preliminary system contains 63 and 32 first index terms. 815 Key words were allocated to the abstracts (= first index terms): 116 abstracts with 2, 134 abstracts with 3 first index terms, minimum: 1, maximum: 5. For two index sections, l.e. atomic absorption spectrometry and geological materials, the proposed indexing system is presented and compared with the system hitherto used in Fresenius Z. Anal. Chem.. The favourable number of 95 first index words, the obviously simple system and the possibility of selecting additional second index terms should contribute to an easily usable documentation, which is herewith presented for discussion.

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Teil III: Fresenius Z Anal Chem (1982) 312:448–454     

Interplay of Thermochemistry and Structural Chemistry, the Journal and the Discipline, Part 2: Volume 12, 2001

As practiced disciplines, structural chemistry and thermochemistry need not be related. In the current study they are: the entire contents of the journal Structural Chemistry (Vol. 12) for the year 2001 has been reviewed and then each and every article that appeared therein was given a thermochemical commentary, spin or slant.     

The diagram lattice as structural principle A. New aspects for representations and group algebra of the symmetric group B. Definition of classification character,mixing character,statistical order,statistical disorder; A general principle for the time evolution of irreversible processes

It is the aim of this paper to demonstrate the significance of the diagram lattice. This lattice was defined in order to achieve structural insight into the phenomenon of chirality in chemistry. In this context, Theorie der Chiralitätsfunktionen [1] may serve as reference. In the introduction of the present paper a summary of the relevant theorems and definitions is given and a few examples of the diagram lattice are graphically illustrated. Parts A and B can be read independently and presuppose knowledge only of the introduction. Part A is of special interest for mathematicians, Part B and [1] for physicists and chemists.In Part A theorems on the representations of the group _n and certain subgroups of it and on the structure of the group algebra are developed. In Part B the concept classification character with the two complementary aspects of identification and distinction is derived. With the interpretation mixing character the partial order relation gains an interpretation through a mixing process, which can be expressed by a bistochastic matrix. This results in another equivalent definition of the diagram lattice. Interpreted as mixing character of a statistical distribution a diagram represents statistical order and statistical disorder by its row partition and column partition respectively. These concepts and the corresponding lattice structure lead to the hypothesis of growing mixing character as a criterion for the time evolution of isolated systems. The criterion of increasing entropy provides a much weaker condition. A discussion of the master equation leads to a proof of the principle of growing mixing character.[/p]     

Determination of molecular properties by the method of moments

Some precautions needed in the choice of weight functions when calculating wave functions by the method of moments are analysed. It appears that an important criterion for good weight functions is that the difference between the total and the truncated overlaps (both defined in the paper) be high.The method of moments is applied to wave functions involving Hylleraas-type correlation factors using weight functions made up of products of single-particle orbitals. The aim of the calculations is partly to test the criteria for good weight functions, partly a preparation of more extended calculations of a similar type.The new name of the institute is: Computer Application Research and Development Center of the Chemical Industries.     

Chemical algebra. II: Discriminating pairing products

The algebra of stereogenic pairing equlibria is presented in a very general context. Starting from the notions of fuzzy subgroup and conjugacy link, chemical pairing constants between molecular speciesu andv having a skeletal symmetry groupG are formulated as pairing products on aG-Hilbert space. Discriminating pairing productsK are defined by the conditions: K 1 and K = 1 the representative vectors of the paired species areG-equivalent. WhenG has only two elements, the pairing product is always discriminating. For several skeletal symmetries, if the vectors are enantiomorphic (v = u, ² =e, G), thenK is greater than 1 and reaches 1 only ifu is achiral: chirality indexes and general permutational indexes are then defined fromK(u u). The general model is illustrated by some examples.     

Der o-Effekt in den Massenspektren aromatischer Verbindungen

Zusammenfassung Das Massenspektrum des O-Äthylsalicylsäureamides VII b ist von dem seiner m- und p-isomeren Verbindung völlig verschieden und zeigt einen typischen massenspektrometrischen o-Effekt.Die bisher aufgefundenen Verbindungen mit massenspektro-metrischem o-Effekt gehören einem relativ kleinen Kreis von Aromaten mit ganz bestimmten Strukturmerkmalen an. Die Bildung der für den o-Effekt charakteristischen Bruchstücke kann in allen diesen Fällen nach einem vonMcLafferty aufgestellten Mechanismus zwanglos erklärt werden. Verbindung VIIb hätte unter der Voraussetzung, daß eine Entstehung der für den o-Effekt typischen Fragmente nur nach diesem Mechanismus möglich ist, keinen o-Effekt zeigen dürfen.Das Auftreten des o-Effektes im Massenspektrum von VIIb läßt erkennen, daß die Bedingung zur Bildung der für den o-Effekt charakteristischen Bruchstücke lediglich in der Möglichkeit zur Ausbildung stabiler Spaltprodukte zu suchen ist, und daß daher weit mehr Verbindungen einen o-Effekt zeigen sollten als bisher anzunehmen war.Mit 1 Abbildung     

Philosophical aspects of chemometrical strategy in Analytical Chemistry

Summary This paper discusses the philosophical aspects of the three main chemometrical strategies in analytical chemistry: statistical data treatment, optimization and modelling, pattern recognition. It is possible by a more general consideration of these approaches to find a proper place of different philosophical categories such as form and content, induction and deduction, concrete and general in analytical chemistry. The philosophical aspect of the considerations allows a deeper penetration into the theoretical basis of chemical analysis.

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Philosophische Betrachtungen zu chemometrischen Strategien in der Analytischen Chemie

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Presented at the First International Symposium on History and Philosophy in Analytical Chemistry, Vienna, November 22–23, 1985     

An investigation of micro-brownian motions in polydimethylsiloxane by complementary incoherent-neutron-scattering and nuclear-magnetic-resonance experiments below room temperature

Two different experimental methods, neutron scattering and nuclear magnetic resonance are used to investigate the random methyl group and segmental rotational jump motions in polydimethylsiloxane. It is shown that nuclear magnetic relaxation and line width experiments are complementary to incoherent neutron scattering fixed-window experiments, the principle of the fixed-window experiments being discussed in somewhat detail. Satisfactory agreement of these experimental techniques is achieved as to the determination of the two model parameters of the motional processes in question, i. e. the activation energy and the preexponential factor of the Arrhenius ansatz made for the correlation time or jump time, respectively.Contribution partly presented during the meeting of the Macromolecular Club, June 8–10, 1983 in Uppsala, the spring conference of the Deutsche Physikalische Gesellschaft, March 12–17, 1984 in Münster and the Fourth International Seminar on Polymer Physics, October 22–26, 1984 in Eyba (GDR).     

Plutonium in soils, bottom sediments and lichen near peaceful nuclear explosion sites in the Republic of Sakha (Yakutia)

During the 1974–1987 period 12 paceful nuclear explosions were conducted in the Republic of Sakha (Yakutia). For the first time^239,240Pu and²³⁸Pu concentrations were determined in samples of soils, bottom sediments and lichen taken at the Craton-3 and Crystal nuclear explosion sites. At the Craton-3^239,240Pu concentrations in the range 6.2 mBq/g to 5.9 Bq/g samples of soil and^239,240Pu concentrations up to 7.4 Bq/g in samples of lichen were observed.^239,240Pu concentration measurements in bottom sediments of a stream washing out the banking around the borehole of Craton-3 show that plutonium migrates in the direction of the Markha river. At the Crystal site local plutonium concentrations up to 35 Bq/g in soil and 1.8 Bq/g in lichen were observed.     

Determination of total,and bound Se in sera by INAA

In this study we report on the comparison between the total selenium in serum (total Se) with that which is apparently bound to high molecular weight (>12,000 D) species, presumably proteins (bound Se). Nine hundred seventy seven (977) serum samples arising out of a population-based epidemiological study were prepared in duplicate for the determination of total Se by pipeting directly into irradiation vials; and separate duplicate aliquots were dialyzed against DI water for the determination of bound Se. All samples were analyzed by neutron activation analysis via^77mSe (17.4 s). A small dialyzable Se component (6%) (free Se), defined as the difference between the total Se minus the bound Se, was identified.     

Meeting future needs for metrological traceability—a physicist’s view

Abstract Metrological traceability of measurement results provides the comparability needed for reliable measurement in almost every aspect of our daily life, ranging from fundamental science, through health and safety to global trade. From the authors (a physicist) perspective and understanding of recent literature, measurements in chemistry compare the amount of analyte, are often made indirectly, are sometimes not fully traceable to the SI, and metrological traceability is perhaps not always the major concern of the practising analytical chemist. The present article examines which of these views are typically chemical, and which are common to both the physicist and the chemist. Much can be gained by formulating a common understanding of basic concepts of traceability of measurement results in meeting ever-increasing demands for comparability of measurement results in both traditional as well as new areas of technology and societal concern.Based on a lecture given by the author at a mini-symposium Emerging issues in metrology in chemistry organised by the IUPAC Analytical Chemistry Division and IUPAC Working Party for Harmonisation of Quality Assurance at IAEA Headquarters, Vienna, 17th February 2004.     

Preparation and analysis of a river sediment Standard Reference Material for the determination of trace organic constituents

Summary A river sediment Standard Reference Material (SRM) has been prepared and analyzed for determination of the concentrations of trace organic constituents. SRM 1939, Polychlorinated Biphenyls (PCBs) in River Sediment A, has been certified for the concentrations of three PCB congeners using the results obtained from capillary column gas chromatography with electron capture detection (GC-ECD) and from multidimensional (dual column) capillary gas chromatography with mass spectrometric detection (MCGC-MSD). For SRM certification, two independent analytical procedures are usually required. If only one analytical technique is used or if the procedures are not independent, then the concentrations are reported as noncertified or informational values rather than certified values. Noncertified values for 14 additional PCB congeners and five chlorinated pesticides, determined by GC-ECD, are also reported as well as noncertified concentrations for five polycyclic aromatic hydrocarbons (PAHs), determined using gas chromatography with mass spectrometric detection (GC-MSD). SRM 1939 complements SRM 1941, Organics in Marine Sediment, since both materials have 12 PCB congeners, five PAHs and five chlorinated pesticides in common. However, the concentrations differ by an order of magnitude for PAHs, and from one to over two orders of magnitude for the PCB congeners and chlorinated pesticides.     

Certification of a new NIST fly ash standard reference material

In June 1993 the National Institute of Standards and Technology (NIST) released the third version of Constituent Elements in Coal Fly Ash Standard Reference Material (SRM 1633b). This material is intended for quality assurance purposes in evaluating the analytical methods used for the determination of constituent elements in coal fly ash or in materials with similar matrices. It has been certified for 23 major, minor and trace elements using ten different analytical techniques. For an element to be certified in a NIST SRM, its concentration is usually determined by at least two independent analytical techniques. The concentrations of additional 24 elements are provided for information only purposes in the new fly ash. Current plans are to certify the concentrations of a number of rare earths upon completion of additional analytical work now in progress. Homogeneity testing was accomplished using instrumental neutron activation analysis and X-ray fluorescence. This presentation summarizes the preparation of this new material and the analytical results used for certification.     

A canonical ordering of polybenzenes and polymantanes using a prime number factorization technique

The correlation described over twenty years ago by Matula between the prime factorization of integers and the class of alkanes is re-examined with a view to explaining the probable reason why there have, to date, been no major extensions of this idea. By considering the class of alkanes as a one-dimensional one-parameter system, a new perspective on the method is gained that is amenable to extension, but in a different direction than originally anticipated. With this new perspective, the classes of polybenzenes and polymantanes are seen to be the representatives of two- and three-dimensional one-parameter systems, respectively. A nomenclature, comparable to one that Matula used for alkanes, is created that gives a unique canonical name to all possible combinations of either polybenzene or polymantane modules. Such a nomenclature contains a built-in means of positioning the molecule in the field of interest in accordance with arbitrary pre-selected criteria, such as Patterson's rules, and also coding that indicates symmetries inherent in the structure of this molecule.