Characterization of airborne particulates by laser microprobe mass analysis

Summary Laser microprobe mass analysis (LAMMA) was applied to characterize aerosol particles collected and separated from 16m to 0.06m by a low pressure cascade impactor. Positive ion LAMMA spectra showed characteristic molecular peaks such as PbCl⁺, a series of Si₂O⁺–Si₂O₄ ⁺ and NaAl₂Si₂O₂ ⁺–NaAl₂Si₂O₅ ⁺, and TiO⁺ in 0.06–0.12m, 0.5–1m and 4–8m fraction, respectively. In the negative ion LAMMA spectra, it was observed that the fragment peaks of sulfate ions were deficient above 2m and those of nitrate ions were deficient under 2m. LAMMA allows remarkable insights into the chemical nature of aerosol particles.

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Charakterisierung luftgetragener Teilchen durch Laser-Microprobe-Massenspektrometrie

Zusammenfassung Laser-Microprobe-Spektrometrie (LAMMS) wurde zur Analyse atmosphärischen Aerosols herangezogen, welches im Korngrößenbereich zwischen 16m und 0.06m mit einem Niederdruckkaskadenimpaktor fraktioniert gesammelt wurde. Positive LAMMS-Spektren zeigten charakteristische molekulare Peaks, wie etwa PbCl⁺, eine Serie von Si₂O⁺–Si₂O₄ ⁺ und NaAl₂Si₂O₂ ⁺–NaAl₂Si₂O₅ ⁺, sowie TiO⁺ in der 0,06–0,12-m,- 0,5–1–m- bzw. 4–8-m-Fraktion. In den negativen LAMMS-Spektren konnten über 2m keine Fragmentpeaks für Sulfationen, unter 2m. keine für Nitrationen beobachtet werden. LAMMS ermöglicht eine bemerkenswerte Einsicht in die chemische Natur von Aerosolteilchen.

     

Determination of traces of sodium alkylbenzenesulphonate by high-performance liquid chromatography. Application to water

Summary For the trace determination of sodium alkylbenzenesulphonate (ABS) by HPLC the following conditions were employed: Shimadzu ZORBAX SIL Column (5 m, 4.6 mm i.d. x 150 mm) as stationary phase, 0.2% ammoniaethanol (v/v) as mobile phase, UV detector at 225 nm, injection volume 12 l. The chromatograms of ABS were simple and sharp (detection limit of ABS 0.02 g in 12 l of ethanol). The calibration curves of ABS were linear in a concentration range of 0.03 0.3 g in 12 l of ethanol. In the case of linear sodium dodecylbenzenesulphonate positive errors of 1 4% were caused by non-ionic surfactants or laurylsulphate (6 times excess), 10 50% positive errors were caused by 2 6 times excess of household detergents.Standard water samples containing ABS were treated with a weak base anion-exchange resin, the adsorbed ABS were eluted, and then determined either by HPLC or by the methylene blue spectrophotometric method. Recoveries of ABS in water were about 92 107% by HPLC.

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Bestimmung von Spuren Natriumalkylbenzolsulfonat mit Hilfe der HPLC. Anwendung auf Wasser

Zusammenfassung Für die Spurenbestimmung von Natriumalkylbenzolsulfonat (ABS) durch HPLC werden die folgenden Bedingungen empfohlen:Shimadzu ZORBAX SIL (5 m, 4,6 mm x 150 mm) als stationäre Phase, 0,2% Ammoniak/Ethanol als mobile Phase, UV-Detektor bei 225 nm, Injektionsvolumen 12 l. Die erhaltenen Chromatogramme sind einfach und scharf (Nachweisgrenze 0,02 g in 12 ml Ethanol). Die Eichkurven sind im Konzentrationsbereich von 0,03–0,3 g in 12 l Ethanol linear. Im Falle des linearen Natriumdodecylbenzolsulfonats werden bei Anwesenheit von nicht-ionischen oberflächenaktiven Substanzen oder von Laurylsulfat in 6fachem Überschuß positiver Fehler von 1–4% erhalten; bei 2–6fachem Überschuß von Haushaltswaschmitteln ergeben sich positive Fehler von 10–50%.Standard-Wasserproben werden zunächst einer Behandlung mit einem Anionenaustauscher unterzogen, die adsorbierten ABS eluiert und durch HPLC oder nach der Methylenblaumethode analysiert. Wiederfindungsraten liegen bei 92–107%.

     

Certified reference materials (CRM 408 and 409) for quality control of main components (ammonium, calcium, hydronium, magnesium, nitrate, potassium, sodium and sulphate) in simulated rain water

Analyses of rainwater are routinely performed by a number of organisations to monitor the contribution from rainwater to the component occurrences in the environment and the acidification of the environment. To control the quality of such determinations, the Community Bureau of Reference (BCR) has organised a certification campaign to produce two simulated rainwater reference materials (CRM 408, low mineral content and CRM 409, high mineral content). The materials were carefully prepared (addition of pro analysis and supra pure reagents with the mentioned elements to silica-free deionised water) and its homogeneity and long-term stability were verified. The materials were certified for their contents of ammonium (106 mol/kg) (CRM 409), calcium (7.68 and 15.5 mol/kg), chloride (67.3 and 113 mol/kg), hydronium (16.6 and 48.0 mol/kg), magnesium (6.14 and 12.3 mol/kg), nitrate (20.1 and 78.1 mol/kg), potassium (4.25 mol/kg) (CRM 409), sodium (42.0 and 82.9 mol/kg) and sulphate (10.5 and 53.2 mol/kg). Indicative values (not certified) are given for ammonium and potassium in CRM 408. This paper presents the certification work performed, as well as the analytical work for the certification of the contents of relevant species.     

Effect of Surfactants on the Immobilization of 4-(2-Pyridylazo)resorcinol on Silochroms

The effect of cationic surfactants (cetyltrimethylammonium bromide, cetylpyridinium bromide, and tetrabutylammonium perchlorate) and a nonionic surfactant (OP-7) on the conditions of the immobilization of 4-(2-pyridylazo)resorcinol (PAR) on three types of silica gel (Silochrom S-120 (200–350 m), Silochrom S-120 (315–500 m), and Silochrom S-80 (200–350 m)) was studied. It was found that OP-7 does not affect the adsorption of surfactants. The effect of cationic surfactants increases in the order tetrabutylammonium perchlorate < cetyltrimethylammonium bromide < cetylpyridinium bromide. The adsorption activity of silica gels increases in the order Silochrom S-120 (315–500 m) < Silochrom S-80 (200–350 m) < Silochrom S-120 (200–350 m). Cetylpyridinium bromide provides full immobilization of PAR on silica gel Silochrom S-120 (200–350 m) in the pH range 2–9.     

Nickel(II) xanthates with nitrogen heterocycles as bridging ligands

New homopolynuclear nickel(II) xanthate complexes with nitrogen donor heterocycles as bridging ligands have been prepared, namely [Ni(Rxa)2(-L)]n and [Ni2(Rxa)4(-L1)], where R=i-Pr,i-Am; xa=OCS2– L=1,2-bis(4- pyridyl)ethane (bpe), 4,4-dithiodipyridyl (dtp), 1,2-bis(4- pyridyl)ethylene (dpe), 4,4-trimethylene-dipyridine (tmd); L1=2,3-bis(2-pyridyl)pyrazine (bpp), 2,4-bis(5,6- diphenyl-1,2,4-triazine-3-yl)pyridine (bdt), or 2,4,6-tris(2- pyridyl)-1,3,5-triazine (tpt). The compounds have been characterized by elemental analyses, i.r. and electronic spectroscopies, magnetochemical and conductivity measurements. The results show that the [Ni(Rxa)2(-L)]n complexes are linear polymers in which the nitrogen heterocycles bridge between the nickel(II) ions, which are coordinated by four sulfur and two nitrogen atoms and have trans-octahedral geometry. The nearly constant values of the effective magnetic moment (3.36–3.34 eff/B) over the 77–295 K temperature range indicate that exchange interactions are lacking among the paramagnetic centres in the linear structure, [Ni(i-Amxa)2(dpe)]n. The variable- temperature magnetic susceptibilities of the [Ni2(i-Prxa)4(bpp)] (3.00–2.95eff/B per Ni atom), [Ni2(i-Prxa)4(bdt)] (2.72–2.63 eff/B per Ni atom), and [Ni2(i-Amxa)4(tpt)] (2.76–1.87 eff/B per Ni atom) were measured down to liquid nitrogen temperature. In the case of binuclear nickel(II) complexes with bdt or tpt, antiferromagnetic coupling between the nickel(II) ions was detected, giving the exchange integral J=–4.0cm–1 and –29.6cm–1, respectively.     

Determination of oxygen by deuteron-induced PIPPS

Using the 871-keV¹⁶O p/1,0/ prompt -ray, oxygen was determined with a relative precision of ±3.8% at a concentration level of 120 g g^–1. The sensitivity of the method is below 10 g g^–1. 50 nm oxide layers on silicon wafers can be determined with a relative precision of 10%. A chamber for transporting targets sensitive to atmospheric gases and humidity is described.     

Syntheses and structures of chalcogen–molybdenum clusters; [Mo3XSe6{S2P(OEt)2}3]Cl, [Mo3X(SeS)3{S2P(OEt)2}3]I and [Mo3 XSe3{S2P(OEt)2}4(py)] (X=0.65S+0.35Se,py= C5H5N)

The trinuclear Mo cluster [Mo3(3–X)(2–Se2)3{S2P-(OEt)2}3]Cl (X=0.65S+0.35Se) (1) has been synthesised by reacting MoCl3·3H2O with ZnSe and [Me4N][S2P(OEt)2] in an EtOH/HCl medium. Reduction of (1) by Ph3P in the presence of [Me4N]-[S2P(OEt)2] and pyridine gave [Mo3(3–X)(2–Se)3 {S2P(OEt)2}4(py)] (X=0.65S+0.35Se, py=C5H5N) (2). Complex (2) was, in turn, converted into [Mo3(3–X)(2–SeS)3{S2P(OEt)2}3]I (X=0.65S+0.35Se) (3) by treatment with H2S and I2. The structures of complexes (1), (2) and (3) were established by X-ray crystallography.     

Trace and minor elements in four commercial honey brands

Instrumental neutron activation analysis was used to measure the concentrations of 24 elements in four honey brands commercially available in Austin, Texas (USA). The measured elements (and concentration) were: As, (<30 ng/g); Ba, (<2 g/g); Br, (0.24–0.49 g/g); Ce, (<20 ng/g); Co, (9–180 ng/g); Cr, (37–64 ng/g); Cs, (<3–45 ng/g); Fe, (<4–15.9 g/g); Hf, (<3 ng/g); Hg, (1 ng/g); K, (91–230 g/g); La, (<4 ng/g); Na, (20.3–25.3 g/g); Ni, (0.39–0.77 g/g); Rb, (68–340 ng/g); Sb, (13–61 ng/g); Sc, (<0.3–200 ng/g); Se, (<20 ng/g); Sm, (<9 ng/g); Sr, (<2 ng/g); Th, (<4 ng/g); U, (<30 ng/g); Zn, (3.36–4.61 g/g); and Zr, (<0.5–0.84 g/g). The results obtained were compared to the concentration of the same elements in honey produced or commercially available in Turkey, Mexico, El-Salvador, China, Czechoslovakia and Yugoslavia.     

Liquid chromatography of phenolic compounds in natural water using on-line trace enrichment

Summary Two packing materials, C18 and PLRP-S, are studied for on-line trace enrichment of phenolic compounds in water. Various precolumns of different internal diameter are also tested and the addition of an ion-pair reagent to increase retention and thus, breakthrough volumes of phenolic compounds, is studied. Best results are obtained when a PLRP-S precolumn is coupled on-line with a C18 analytical column and DAD detector. Addition of TBA considerably increases breakthrough volumes. In contrast, when a C18 precolumn is used, breakthrough volumes are lower and it is impossible to determine TCP and PCP, under the experimental conditions used, because of interference of other nonpolar compounds in the samples. The performance of the system is evaluated with river and tap water and the preconcentration of 10 ml of sample in a PLRP-S precolumn involves a linear range between 1 g 1^–1 and 20 l^–1 and limits of determination between 0.5 g l^–1 and 1 g l^–1 are obtained.     

Photometric determination of molybdenum in iron and steels using tin(II) chloride in nonaqueous solvent

Summary A new procedure is proposed for the photometric determination of molybdenum in iron and steels using thiocyanate and tin(II) chloride solution [in glycerol-ethannol (31) or in diethylenglycol] as a reducer and extraction with n-butyl acetate. Beer's law is obeyed between 0.2 and 80 g Mo/ml. The minimum photometric error is 3.2%, the molar absorptivity is 15640 at 470 nm and the best concentration range for determination is between 0.6 and 6 g Mo/ml.

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Photometrische Bestimmung von Molybdän in Eisen und Stahl mit Hilfe von Zinn(II)-chlorid in nichtwärigem Medium

Zusammenfassung Das vorgeschlagene Verfahren beruht auf Bildung des Thiocyanatkomplexes unter Verwendung von Zinn(II)-chlorid als Reduktionsmittel [in Glycerin/Äthanol (31) oder Diäthylenglykol]. Als Extraktionsmittel dient n-Butylacetat. Das Beersche Gesetz wird im Bereich 0,2–80 g Mo/l befolgt. Der kleinste photometrische Fehler beträgt 3,2%, die molare Extinktion 15640 bei 470 nm und der optimale Konzentrationsbereich 0,6–6 gMo/l.

Lecture presented at Euroanalysis I Conference, 28. 8. –1. 9. 1972 in Heidelberg, Germany.     

Magnetische Messungen im System Fe—Te

In the binary Fe–Te system six intermediate solid phases exist with varying ranges of homogeneity. With the exception of the high temperature -phase the magnetic behavior of these phases and in some cases the variation of magnetic properties with composition were investigated by susceptibility measurements in the temperature range from 100 to 300 K. Both the -phase (FeTe_1–x ) and the -phase (Fe₅Te₆) follow theCurie—Weiss law and can be designated as antiferromagnetic compounds according to the negativeWeiss constants of –192 K and –314 K, resp. The magnetic moments identify these two phases as high-spin compounds of Fe. The observed increase of the magnetic moments towards the Ferich limit of the -phase is due to the occupation of the octahedral interstices in the anion sublattice by excess iron and it was explained by a simple model. The magnetic moment of the hypothetical equiatomic compounds FeTe, obtained by extrapolation (3.87 _B), as well as the moment of the -phase (3.83 _B) are nearly identical and can be interpreted as being due to the existence of three unpaired 3d-electrons per formula unit. For the Te-rich (Fe_1–x Te)-, (Fe_1–x Te)- and (FeTe₂)-phases the transition metal is supposed to be in the low-spin state. The observedPauli paramagnetism is not temperature independent but decreases with decreasing temperature. Below 100 K FeTe₂ appears to be diamagnetic.

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Mit 7 Abbildungen     

Determination of nitrogen in uranium and uranium-oxide by high-temperature gas-extraction

Summary The reducing fusion gas extraction method has been used for the determination of nitrogen in uranium metal and uranium dioxide reference materials at levels of about 10–15g·g^–1. It has been found that when extracting at temperatures above 2700° C the use of a platinum flux is no longer necessary. Pure nitrogen and nitrogen-helium mixtures were used for calibrating the detection unit in the range of 1.5–670 g. The calibration of the extraction was performed with metallic reference materials in the range of 8–331 g N₂ content.

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Bestimmung von Stickstoff in Uran und Uranoxid durch Hochtemperatur-Gasextraktion

Zusammenfassung Die Gasextraktion aus reduzierender Schmelze wurde zur Stickstoffbestimmung in Uranmetall- und Urandioxid-Referenzmaterialien bei Gehalten von 10–15 g·g^–1 angewendet. Bei Temperaturen über 2700° C ist kein Platinbad mehr erforderlich. Zur Eichung der Detektionseinheit im Bereich von 1,5–670 g wurden reiner Stickstoff oder Stickstoff-Helium-Mischungen benutzt. Zur Eichung der Extraktion wurden metallische Referenzmaterialien mit (8–331g) N₂ eingesetzt.

     

Spectrofluorimetric flow-injection determination of cerium in carbon and low alloy steels

Cerium can be determined spectrofluorimetrically (_em 350 nm, _ex 260 nm) based on the relatively intense native fluorescence of the cerium(III) aquo-ion. The main potential interference in the analysis of steel from iron(III), cerium(IV) and chromium(VI) are removed by use of a carrier solution containing 2.5% w/v hydroxylammonium chloride. The slight residual interference from iron(II) can be corrected by a matrix matching factor linearly related to the amount of iron present. The calibration graphs are linear over the range 0–7 g ml^–1 based on 250 l injection volumes. The sampling rate was 30 h^–1. The relative standard deviation was 2.0% (n=5) at 3 g ml^–1 cerium. The system has been applied to the determination of cerium in carbon or low alloy steels.     

Fällungsanalyse im Mikrogrammbereich: Eine neue Methode

Zusammenfassung Eine neue Methode zur Durchführung gravimetrischer Bestimmungen im Mikrogrammbereich wurde beschrieben; diese beruht im wesentlichen darauf, daß der Niederschlag nicht mehr zusammen mit dem Filter, sondern nach Überführen mit einem geeigneten Lösungsmittel in einem separaten Wägegefäß gewogen wird.Die dazu nötigen Geräte und deren Herstellung wurden beschrieben. Nach dieser Methode wurden folgende Bestimmungen mit zufriedenstellender Richtigkeit durchgeführt: 2,5–25g Al, 5–50g Cu und 5–50g Zn mit Oxin, 2,5–25g Fe(III) und 2,5–25g Ti(IV) mit N-Benzoyl-phenylhydroxylamin, 5–50g Ni und 5–50g Cu mit Salicylaldoxim, 2,5–50g Co(II) und 2,5–50g Fe(III) mit -Nitroso--naphthol sowie 5–50g Chlorid als Silberchlorid.

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Precipitation analysis in the microgram-scale: A new method

Summary A new method for gravimetric determinations in the microgram-scale is described. This method is based on the fact that the precipitate is not weighed together with the filter but is transferred to a separate weighingvessel using a suitable solvent. The necessary simple devices and their use are described. The following determinations were carried out with satisfying accuracy: 2,5–25g Al, 5–50g Cu and 5–50g Zn with Oxine, 2,5–25g Fe and 2,5–25g Ti withN-benzoylphenylhydroxylamine, 5–50g Ni and 5–50g Cu with salicylaldoxime, 2,52–50g Co and 2,5–50g Fe with -nitroso--naphthol and 5–50g chloride as silver chloride.

     

Path of “dry” electrons before localization in liquid hydrocarbons

Conclusions On the basis of measurements of values of in liquid hydrocarbons, it has been shown that the path length before localization of a photoliberated electron increases with increasing mobility of the excess electron, from approximately 40 Å (methylcyclohexane) to 200 Å (isooctane). In a liquid with10^–2 cm²/V·sec (methylcyclohexane, hexane), the localization takes place before or immediately after thermalization of the electron. In a liquid with>10^–1 cm²/V·sec, the electron passes through the main part of its path before localization, being in thermal equilibrium with the medium.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2198–2203, October, 1985.     

Lead determinations in human bone by particle induced X-ray emission (PIXE) and graphite furnace atomic absorption spectrometry (GFAAS)

Chronic lead (Pb) intoxication has been linked to Alzheimer's disease (AD). Lead, like many heavy elements, tends to accumulate in bone. PIXE is a powerful analytical tool which permits the determination of Pb at the g/g level without requiring sample digestion. GFAAS is one of the most sensitive methods for the determination of Pb and is capable of determining ng/g levels in solution. For bone analyses by GFAAS, sample dissolution and a matrix modifier are required. Rib bone samples were analyzed for Pb by PIXE and GFAAS. IAEA Animal Bone (H-5) was used as a secondary standard for Pb with both methods to ensure accuracy. The range of Pb concentrations in human rib bone was 1.4–11.5 g/g for the trabecular surface by PIXE, 1.3–45 g/g for the cortical surface by PIXE, and 1.54–11.75 g/g for whole bone by GFAAS. No significant difference (p>0.05) was found for AD versus control for either surface or for whole bone.     

Fluoridbestimrnung in Wasser und Luft mit ionenselektiven Elektroden

Zusammenfassung Systematische Bestimmungen des Fluoridgehaltes in verschiedenen Wasserproben aus Serbien und in Luftproben aus einigen In-dustriegebieten und aus der Stadt Belgrad wurden durchgeführt. Außerdem wurde der Fluoridgehalt in einigen meistkonsumierten Mineralwässern aus alien Territorien Jugoslawiens geprüft. Etwa 600 Proben wurden analysiert. Die Ergebnisse sollen für die kartographische Erfassung der Verteilung von Fluor im Trinkwasser dienen.

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Determination of fluoride in Yugoslavian air and water with an ion-sensitive electrode

Summary Fluoride has been measured in over 600 samples of air and water with an ion-sensitive electrode. The concentrations found in the air samples were 1.6–l08g/m³ for industrial areas, 1.9–25.6g/m³ for urban areas and 1.1–18.4g/m³ for rural areas. Most of the samples had fluoride levels below 20g/m³3. The concentrations found in water samples were 0.12–0.34g/litre for drinking water and 0.27–5.6g/litre, for mineral waters.

     

Determination of metoprolol in human plasma by column switching high-performance liquid chromatography

Summary Retention characteristics of metoprolol have been studied in reversed phase mode on RP2, RP8 and CN columns. The plots of retention time as a function of the acetonitrile content and of the ionic strength of the mobile phase permitted the choice of the best conditions to separate metoprolol from plasma components by switching of these three types of columns.Human plasma (0.5–1 ml) diluted with water is first injected on a RP2 column (25–40 m particle diameter, prepared by dry packing) and rinsed with water. The sample is then back eluted with acetonitrile-0.022 M acetate buffer (7525, v:v) and switched to a CN column (10 cm long, 5 m particle diameter). The heart cut of the eluate is selected and loaded on a RP8 analytical column (25 cm long, 5 m particle diameter) with acetonitrile-0.088 M acetate buffer (7525, v:v) as mobile phase.Auto-sampler and switching valves are actuated automatically by a computing integrator based on a fixed time schedule. The duration of one cycle is about 30 min, but the last analytical step is about 15 min and represents the time interval between two injections. Metoprolol, its alpha-hydroxy metabolite and the internal standard are detected by fluorescence (_ex= 225 nm; _em > 320 nm).Presented at the 14th International Symposium on Chromatography London, September, 1982