Determination and speciation of minor and trace elements in volcanic exhalations by NAA

Volcanic gases in the temperature range from 269° to 635° were sampled by means of a filter combination, consisting of two activated charcoal filters, a cooler and a condensate trap. Samples of the steam plume were taken additionally to quantify the depletion of the elements after condensation and dilution by the atmosphere. The elements F, Cl, Br, I, As, Sb, Se, Te and Hg were determined by instrumental and radiochemical NAA. The data obtained are compared to literature values and the total amount released is estimated. The concentrations in the condensate are compared to the amounts on the filters, enabling the identification of some of the compounds present in the gases. Objects of the investigation were Stromboli and Vulcano in Southern Italy.     

An automated method for the simultaneous determination of salicylic acid and salicylazoiminopyridine in commercial salicylazosulphapyridine.

A technique for estimating nanogram quantities of mercury in sediment samples is described. Samples are heated at 870°C in an oxygen atmosphere, and the released mercury is collected on a gold-coated glass bead trap. The trap is then heated to 500°C in a helium stream; mercury is swept through a d.c. discharge cell and measured by emission spectrometry. Recoveries of mercury added to sediment samples were quantitative. Comparison of five separate samples by the proposed method and by a conventional cold-vapor atomic absorption technique showed similar results. The proposed method gives linear calibration plots up to 1700 ng Hg; the detection limit is 10 ng Hg, so that the sensitivity is 0.005 ppm for a 2.0-g sample.     

Optimization of the electrothermal vaporization conditions for inductively coupled plasma excitation spectrometry: Selective volatilization versus covolatilization approaches

A new version of the outlet port of a graphite furnace electrothermal vaporizer (upward streaming system) is described, in which the hot sample vapour is mixed with an auxiliary carrier argon stream of ambient temperature. The operation procedures using carrier volatilization of organic liquids as gas phase additives are also outlined. The selective volatilization and transport efficiency for As, Cd, Hg, Pb, Sb, Se and Zn could be increased by applying sodium thiosulfate as chemical modifier to solution samples with controlled nitric acid content. On the other hand, a near simultaneous vaporization of 16 elements using chlorination with CCl₄ vapour at 2100° C could be performed for a multielement analysis. By wetting the auxiliary carrier argon stream, the linearity of the analytical curves was improved (except for chromium), when applying multielement standards. Linear analytical curves could also be obtained in the presence of alkali and alkaline earth metal matrices in multielement standards using halocarbon assisted electrothermal vaporization sample introduction.     

Vapor generation and atom traps: Atomic absorption spectrometry at the ng/L level

Atom-trapping atomic absorption spectrometry is a technique that allows detection at the ng/L level for several analytes such as As, Se, Sb, Pb, Bi, Cd, In, Tl, Te, Sn and Hg. The principle involves generation of volatile species, usually hydrides, trapping these species on the surface of an atom trap held at an optimized temperature and, finally, revolatilizing the analyte species by rapid heating of the trap and transporting them in a carrier gas to a heated quartz tube, as commonly used with hydride generation AAS systems. A transient signal having, in most cases, a full width at half maximum of less than 1 s is obtained. The atom trap may be a quartz surface or a W-coil; the former is heated externally and the latter is heated resistively. Both collection and revolatilization temperatures are optimized. In some cases, the W-coil itself is used as an electrothermal atomizer and a heated quartz tube is then not needed. The evolution of these traps starts with the well-known Watling's slotted quartz tube (SQT), continues with atom trapping SQT and finally reaches the present traps mentioned above. The analytical figures of merit for these traps need to be standardized. Naturally, enhancement is on characteristic concentration, C₀, where the change in characteristic mass, m₀, can be related to trapping efficiency. Novel terms are suggested for E, enhancement factor; such as E_max, maximum enhancement factor; E_t, enhancement for 1.0 minute sampling and E_v, enhancement for 1.0 mL of sample. These figures will allow easy comparison of results from different laboratories as well as different analytes and/or traps.     

Dynamic headspace gas chromatography of volatile compounds in milk

A method is described for investigating volatile compounds in milk. The volatiles are removed from milk by a stream of helium swept at 100 ml/min over the surface of the milk at 70 degrees C. They are trapped on 40 mg of NIOSH charcoal and then desorbed by heat and re-trapped on the front of a chromatographic column of Tenax-GC coated with 1% OV-275, the column being maintained at room temperature during trapping. An amount of 40 mg NIOSH charcoal under these conditions traps over 90% of the total quantity of the lowest boiling compounds swept from the milk, such as acetaldehyde and ethanol, and retains 100% of the total quantity of acetone, propanol and higher boiling compounds from the gas stream. The volume of milk and its temperature affect the ratios of volatiles collected and these factors are useful in increasing the proportion of a volatile of particular interest. The addition of potassium carbonate increases the yield of volatiles from 100 ml aqueous phase but not from 10 ml.     

A recirculating system for concentrating volatile samples

Summary A recirculating system powered by a diaphragm pump which may be readily dismantled for cleaning, is described. The results of operating this system for dynamic headspace sampling in the closed or open mode to load volatiles onto a Tenax trap over a range of temperatures and loading volumes are shown. The system was designed to facilitate the analysis of volatiles in natural products and tested using an equimolar solution of 7 esters of boiling points ranging from 120°C to 299°C. The results showed that compounds in the boiling point range 120–200°C could be loaded onto the trap at 30°C by passing 1–21 of carrier gas through. In order to trap compounds of boiling points approaching 300°C, a temperature of 50–70°C and a loading volume of 2.5–3 1 was necessary. Using the apparatus, human sweat was analysed to show the degree of concentration possible with a natural sample and the variation in the chromatogram profiles of successive trapping from the same sample. Twelve chromatograms from the sweat of two pairs of identical twins were pattern matched to show the high degree of reproducibility possible using this apparatus to trap biological volatiles.     

A study of the reactivity of elemental Cr/Se/Te thin multilayers using X-ray reflectometry, in situ X-ray diffraction and X-ray absorption spectroscopy

The reactivity of [Cr/Se/Te] multilayers under annealing was investigated using X-ray reflectometry, in situ X-ray diffraction, X-ray absorption fine structure (XAFS) measurements and transmission electron microscopy. For all samples, interdiffusion was complete at temperatures between 100 and 300 °C, depending on the repeating tri-layer thickness. A crystalline phase nucleated approximately 20 °C above the temperature where interdiffusion was finished. The first crystalline phase in a binary Cr/Te sample was layered CrTe₃ nucleating at 230 °C. In ternary samples (Se:Te=0.6-1.2), the low-temperature nucleation of such a layered CrQ₃ (Q=Se, Te) phase is suppressed and instead the phase Cr₂Q₃ nucleates first. Interestingly, this phase decomposes around 500 °C into layered CrQ₃. In contrast, binary Cr/Se samples form stable amorphous alloys after interdiffusion and Cr₃Se₄ nucleates around 500 °C as the only crystalline phase. Evaluation of the XAFS data of annealed samples yield Se-Cr distances of 2.568(1) and 2.552(1) Å for Cr₂Q₃ and CrQ₃, respectively. In the latter sample, higher coordination shells around Se are seen accounting for the Se-Te contacts in the structure.     

Loss of selenium in water samples at natural levels during storage

Selenium losses in river, ground, snow-melt and tap water samples, and the recovery of selenite, selenate and selenomethionine added to purified water have been studied. In 1-litre high-density polyethylene bottles, tap, river and snow-melt water samples (at Se concentrations of 44.5–138 ng/l) could be stored at 4 °C for up to 15 days without Se losses. In similar samples stored at room temperature Se losses of 13–25% after 15 days were found, except for groundwater, which showed no Se losses during storage for 13 months at room temperature or at 4 °C. Selenite and selenate added to purified water were recovered without losses after 15 days at 4 °C, while 7.5% of selenomethionine was lost. The stability of different chemical forms of Se during storage followed the order: selenate > selenomethionine > selenite. It is recommended that unacidified water samples should not be kept in polyethylene bottles at room temperature for more than 1 week, nor stored at 4 °C for more than 2 weeks, before analysis for Se.     

Gas-diffusion flow injection determination of Hg(II) with chemiluminescence detection

A gas-diffusion flow injection method for the chemiluminescence detection of Hg(II) based on the luminol-H₂O₂ reaction was developed. The analytical procedure involved the injection of Hg(II) samples and standards into a 1.50 M H₂SO₄ carrier stream, which was subsequently merged with a reagent stream of 0.60% (w/v) SnCl₂ in 1.50 M H₂SO₄ to reduce Hg(II) to metallic Hg. The gas-diffusion cell was thermostated at 85 °C to enhance the vaporisation of metallic Hg. Mercury vapour, transported across the Teflon membrane of the gas-diffusion cell into the acceptor stream containing 1.00 × 10⁻⁴ M KMnO₄ in 0.30 M H₂SO₄, was oxidised back to Hg(II). The acceptor stream was merged with a reagent stream containing 2.50 M H₂O₂ in deionised water and then the combined stream was merged with another reagent stream containing 7.50 × 10⁻³ M luminol in 3.00 M NaOH at a confluence point opposite to the photomultiplier tube of the detection system. The chemiluminescence intensity of the luminol-H₂O₂ reaction was enhanced by the presence of Hg(II) in the acceptor stream. The corresponding increase was related to the original concentration of Hg(II) in the samples and standards. Under optimal conditions, the chemiluminescence gas-diffusion flow injection method was characterised by a linear calibration range between 1 μg L⁻¹ and 100 μg L⁻¹, a detection limit of 0.8 μg L⁻¹ and a sampling rate of 12 samples per hour. It was successfully applied to the determination of mercury in seawater and river samples.     

Competitive reactivities of vinylthiyl radicals thermally generated from haloethylenes and hydrogen sulfide

Acetylene and its derivatives have been used for the first time as “traps” for vinylthiyl radicals generatedin situ from hydrogen sulfide and haloethylenes in gas-phase processes. The competitive reactivity of the vinylthiyl radicals has been studied at 500–570 °C in the presence of two chemical “traps.” The efficiency of chemical “traps” for the vinylthiyl radicals decreases in the following sequence: HC≡CPh > HC≡CH > MeC≡CH > CH₂=CHCl. Acetylene is a more efficient “trap” for the vinylthiyl radicals than 1,2-dichloroethylene, from which they have been generated. The β-phenylvinylthiyl radicals generated during cothermolysis of halostyrene-hydrogen sulfide-acetylene component ternary systems undergo first of all intramolecular ring closure to give benzothiophene, which is a thermodynamically favorable system; the reaction of these radicals with acetylene and its derivatives occurs much more slowly than heterocyclization. Phenylacetylene is a more efficient “trap” than acetylene. α-Phenylvinylthiyl radicals mostly react with acetylene to yield 2-phenylthiophene.     

Die Löslichkeit von Quecksilber in verschiedenen Metallen

Investigations by X-ray analysis proved that V, Nb, Ta, Ti, Zr, Cr, Mo, W, Fe, Ni, Co, Re, Ru, Rh, Os, Ir, Al, Th, and U dissolve only negligible amounts of mercury. The solubility of mercury in platinum up to 250°C is small; at 250°C the solubility increases abruptly to ca. 15.5% and alters little with further temperature increases. The jump at 250°C corresponds to a peritectic reaction in the system Pt–Hg. The data obtained are in good agreement with data in the literature. Manganese dissolves at 500°C ca. 0.3–0.5% Hg; the temperature dependence of the solubility was not examined. Rhenium forms no compounds with Hg, at least at 100–500°C. The metals of the Va and VIa-group of the periodic table do not dissolve any measurable amounts of Zn.

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Evaluation and applications of a gaseous mercuric chloride source

In this study, a diffusion-type device for generating gaseous mercuric chloride (HgCl₂) was systematically evaluated and applied to validate the annular denuder method for sampling gaseous HgCl₂ species in a synthetic gas stream. The results show that it takes at least 48 h for the system to reach a steady-state condition after the diffusion cell reaches the temperature set-point and the carrier gas is activated. The primary Hg species from the source was proven to be HgCl₂. In the temperature range from –5.00 to 11.80 °C, the Hg emission rates from the source vary from 1.8 to 14.2 pg min^–1. It is shown that, under the experimental conditions examined, KCl-coated annular quartz denuders designed for ambient reactive gaseous mercury (RGM) collection could quantitatively collect HgCl₂. It is also demonstrated that the impactors used to remove coarse airborne particulate matter could lead to a loss of up to one third of the HgCl₂ in the gas stream.     

The crystal and molecular structure of bis{μ[(tri-fluoromethyl)selono]manganese tetracarbonyl}

The crystal structure of [(CF₃Se)Mn(CO)₄]₂ has been determined by single crystal X-ray diffraction. The crystals are monoclinic, P2₁/c, a = 6.32, b = 15.35, c = 9.75 Å, β = 108.9°, Z = 2. The molecule possesses a crystallographic centre of symmetry, and is based on a planr [MnSe]₂ unit with four almost equal MnSe bonds (2.50 Å). The principal bonds length and angles are MnMn 3.74, SeSe 3.31 Å ; SeMnSe 83.1°, MnSeMn 96.9°; MnC (mean) 1.83, CO (mean) 1.16, SeC 1.97, CF (mean) 1.31 Å     

A novel analytical system involving hydride generation and gold-coated W-coil trapping atomic absorption spectrometry for selenium determination at ng l level

A novel analytical technique was developed where gaseous hydrogen selenide formed by sodium tetrahydroborate reduction is transported to and trapped on a resistively heated gold-coated W-coil atom trap for in situ preconcentration. Gold coating on W-coil was prepared by using an organic solution of Au. The atom trap is held at 165 °C during the collection stage and is heated up to 675 °C for revolatilization; analyte species formed are transported to an externally heated quartz T-tube where the atomization takes place and the transient signal is obtained. The carrier gas consisted of 112.5 ml min^− 1 Ar with 75 ml min^− 1 H₂ during the collection step and 112.5 ml min^− 1 Ar with 450 ml min^− 1 H₂ in the revolatilization step. The half width of the transient signal obtained is less than 0.5 s. The RSD for the measurements was found to be 3.9% (n = 11) for 0.10 µg l^− 1 Se using peak height measurements.     

Determination of As, Ge, Hg, Pb, Sb, Se and Sn in coal slurries by CVG-ETV-ICP-MS using external or isotopic dilution calibration

A method for the multi-elemental determination of As, Ge, Hg, Pb, Sb, Se and Sn in coal reference materials by slurry sampling chemical vapor generation (CVG) using external calibration and isotopic dilution (ID) calibration and detection by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) is proposed. As, Ge, Sb, Se and Sn were determined using the external calibration, while, Hg, Pb, Se and Sn were determined by isotopic dilution. About 50–250 mg of sample was mixed with an acid solution, containing aqua regia and HCl, in an ultrasonic bath. For the isotopic dilution calibration, the enriched isotopes ²⁰¹Hg, ²⁰⁶Pb, ⁷⁷Se and ¹¹⁹Sn were added to the slurry in an adequate amount in order to produce an altered isotopic ratio close to 1. The vapor produced by the reaction of the sample slurry with the reducing agent was transported to the vaporizer and trapped in a Ir-treated graphite tube at 200 °C, before vaporization at 2100 °C and transportation of the vapor to the plasma. The accuracy of the method was assured by the analysis of four certified reference coal samples, using external calibration with aqueous solutions, prepared in the same medium and subjected to the same CVG and trapping procedure as the slurries and also by isotopic dilution calibration. The obtained concentrations were in agreement with the certified values, using the t-Student test for a confidence level of 95%. The detection limits (3 s; n = 5) of isotopic dilution, in ng g^− 1, were: 0.4 for Hg, 900 for Pb, 0.3 for Se and 0.2 for Sn. For external calibration, the detection limits, in ng g^− 1, were: 1.6 for As, 0.1 for Ge, 0.3 for Sb, 0.9 for Se and 7.5 for Sn. The relative standard deviations generally were lower than 14%, adequate for slurry analysis.     

Eine Apparatur zur Bestimmung von Dampf-Flüssigkeits-Gleichgewichten unter erhöhtem Druck

An apparatus for determination of vapor-liquid-equilibria at elevated pressure is described. For the measurements the static method with mechanical mixing of the phases is used. The apparatus has a working range of +15 to +100°C and 5 to 100 bar. For sampling capillaries and a specially constructed valve are used, whereby gaseous and liquid samples can be lead directly into the carrier-gas stream of a gaschromatograph. The equipment was tested by measurement of equilibrium-data of the binary system Ethane/Propane at +30°C. A consistency test of these experimental data showed agreement with theory within the mean errors of the equipment, which are ±0,05 bar for pressure, ±0,04°C for temperature and ±0,002 for concentration in the molefraction-scale.

     

A Method of Determining the Efficiency of Air Sampling Traps to Collect and Release Volatile Organic Compounds

Abstract

A new method is described that facilitates determining the efficiency of air sampling traps to adsorb and thermally desorb volatile organic compounds. A known volume of a liquid standard of volatile organic compounds is vaporized into an air stream, a fraction of which is collected on an air sampling trap. This trap is subsequently thermally desorbed and analyzed using a GC/FID. The efficiency of the trap to adsorb and thermally desorb each compound tested is calculated.     

Übergangsmetall-Chalkogensysteme, 1. Mitt.: Das System Kobalt-Selen

Zusammenfassung Das Phasendiagramm Co–Se wurde auf Grund der Resultate thermischer und röntgenographischer Untersuchungen aufgestellt. Für die thermischen Analysen wurde eine vollautomatischeDTA-Anlage mit konstanten Heiz- und Kühlgeschwindigkeiten im Bereich von 200 bis 1100 °C konstruiert. Neben der schon früher gefundenen Mischungslücke in kobaltreichen Schmelzen tritt eine weitere Mischungslücke in Schmelzen mit mehr als 70 At %Se oberhalb 952 °C auf. Die B8(NiAs)-Phase Co_1–x Se hat einen kongruenten Schmelzpunkt bei 54,0 At %Se und 1078 °C und eine maximale Phasenbreite von 50,7 At %Se (910 °C) bis 59,0 At %Se (952 °C). Das Eutektikum zwischen Co_1–x Se und -Co liegt bei 44,5 At %Se und 910 °C. CoSe₂ zerfällt peritektisch bei 938 °C in Co_1–x Se und eine Se-reiche Schmelze. Die röntgenographischen Untersuchungen bestätigten die Existenz der drei Verbindungen Co₉Se₈, Co_1–x Se und CoSe₂.

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Transition metal-chalcogen systems, I: The system cobalt-selenium

The Co–Se phase diagram was constructed using results of thermal and X-ray investigations. For the thermal analyses a fully automaticDTA-apparatus for constant heating and cooling rates in the range 200 to 1100 °C was built. In addition to the miscibility gap in liquid cobalt-rich alloys previously reported there exists another miscibility gap in melts with more than 70 at %Se above 952 °C. The B8 (NiAs) phase Co_1–x Se has a congruent melting point at 54,0 at % Se and 1078 °C and a maximal range of homogeneity between 50,7 at %Se (910 °C) and 59,0 at %Se (952 °C). The eutectic between Co_1–x Se and -Co occurs at 44,5 at %Se and 910 °C. CoSe₂ decomposes peritectically at 938 °C into Co_1–x Se and a Se-rich melt. X-ray investigations confirmed the existence of the three compounds Co₉Se₈, Co_1–x Se, and CoSe₂.

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Herrn Prof. Dr.O. Kratky zum 70. Geburtstag gewidmet.     

Choice of procedure conditions for radioimmunoassay of aflatoxin B1 using125I as a marker and dextrancoated charcoal as a separation matrix

Assay conditions for the radioimmunoassay for aflatoxin B₁ using¹²⁵I-radiolabel and dextran-coated charcoal for the separation of free and bound radioligand were optimized. Casein was chosen as the best protecting protein /in contrast with human serum albumin, -globulin and gelatine/. The most suitable incubation conditions are at 4°C for 18 h in darkness, radioligand sorption on the dextrancoated charcoal takes place 30 min at 4°C and the antiserum is diluted in order to reach zero specific binding in the range between 35 and 50%.     

Determination of antimony by using tungsten trap atomic absorption spectrometry

An electrically heated tungsten coil was used as a trap in the determination of antimony. The technique consists of three steps. Initially, SbH₃ is formed by hydride generation procedure; then the analyte species in vapor form are transported to W-coil trap heated at 370 °C. Following the preconcentration step, the trap is heated to 895 °C; analyte species are revolatilized and transported to the flame-heated quartz atom cell where atomization and the formation of signal take place. The experimental parameters were optimized both for trap and no-trap studies. The most important experimental parameters are concentrations of HCl and NaBH₄ solutions, H₂ and Ar gas flow rates, and collection and revolatilization temperatures of W-coil. Accuracy was tested using a certified reference material, waste water EU-L-1. Limit of detection for the system is 16 ng l^− 1 using a sample of 36 ml collected in 4.0 min. Enhancement factor in sensitivity was 17.