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Detlef Günther

Publications and source records attributed to Detlef Günther.

At least 19 recordsLinked to original sources
PubMed2006

Laser ablation inductively coupled plasma mass spectrometry for direct analysis of the spatial distribution of trace elements in metallurgical-grade silicon.

The spatial distribution and concentration of impurities in metallurgical-grade silicon (MG-Si) samples (97-99% w/w Si) were investigated by use of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The spatial resolution (120 mum) and low limits of detection (mg kg(-1)) for quality assurance of such materials were studied in detail. The volume-dependent precision and accuracy of non-matrix-matched calibration for quantification of minor elements, using NIST SRM 610 (silicate standard), indicates that LA-ICP-MS is well suited to rapid process control of such materials. Quantitative results from LA-ICP-MS were compared with previously reported literature data obtained by use of ICP-OES and rf-GD-OES. In particular, the distribution of element impurities and their relationship to their different segregation coefficients in silicon is demonstrated.

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PubMed2006

Evaluation of a pulsed glow discharge time-of-flight mass spectrometer as a detector for gas chromatography and the influence of the glow discharge source parameters on the information volume in chemical speciation analysis.

The figures of merit of a pulsed glow discharge time-of-flight mass spectrometer (GD-TOFMS) as a detector for gas chromatography (GC) analysis were evaluated. The mass resolution for the GD-TOFMS was determined on FWHM in the high mass range (208Pb+) as high as 5,500. Precision of 400 subsequent analyses was calculated on 63Cu+ to be better than 1% RSD with no significant drift over the time of the analysis. Isotope precision based on the 63Cu+/65Cu+ ratio over 400 analyses was 1.5% RSD. The limits of detection for gaseous analytes (toluene in methanol as solvent) were determined to be as low as several hundred ppb or several hundred pg absolute without using any pre-concentration technique. Furthermore, the different GD source parameters like capillary distance, cathode-anode spacing, and GD source pressure with regards to the accessible elemental, structural, and molecular information were evaluated. It was demonstrated that each of these parameters has severe influence on the ratio of elemental, structural, and parent molecular information in chemical speciation analysis.

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PubMed2006

Analyte response in laser ablation inductively coupled plasma mass spectrometry.

The dependence of analyte sensitivity and vaporization efficiency on the operating parameters of an inductively coupled plasma mass spectrometer (ICPMS) was investigated for a wide range of elements in aerosols, produced by laser ablation of silicate glass. The ion signals were recorded for different carrier gas flow rates at different plasma power for two different laser ablation systems and carrier gases. Differences in atomization efficiency and analyte sensitivity are significant for the two gases and the particle size distribution of the aerosol. Vaporization of the aerosol is enhanced when helium is used, which is attributed to a better energy-transfer from the plasma to the central channel of the ICP and a higher diffusion rate of the vaporized material. This minimizes elemental fractionation caused by sequential evaporation and reduces diffusion losses in the ICP. The sensitivity change with carrier gas flow variation is dependent on m/z of the analyte ion and the chemical properties of the element. Elements with high vaporization temperatures reach a maximum at lower gas flow rates than easily vaporized elements. The sensitivity change is furthermore dependent on m/z of the analyte ion, due to the mass dependence of the ion kinetic energies. The mass response curve of the ICPMS is thus not only a result of space charge effects in the ion optics but is also affected by radial diffusion of analyte ions and the mismatch between their kinetic energy after expansion in the vacuum interface and the ion optic settings.

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PubMed2006

Direct determination of tellurium in geological samples by inductively coupled plasma mass spectrometry using ethanol as a matrix modifier.

Direct determination of tellurium in geological samples by inductively coupled plasma mass spectrometry (ICP-MS) is often complicated by its low abundance, poor analytical sensitivity, and the presence of xenon interferences. Therefore, a simplified and rapid method for direct determination of nanogram levels of tellurium in geological samples using ICP-MS by reduction of interferences and improvement of sensitivity was developed. It is impossible to resolve 126Te and 128Te from isotope interferences of Xe even by currently available high-resolution magnetic mass spectrometry due to the extremely small mass difference (0.001-0.002 amu). However, the addition of 4% ethanol was found to suppress the interferences of Xe by a factor of 6 and increases the sensitivity of Te determination in ICP-MS by a factor of 3 relative to the values obtained in conventional 3% (v/v) HNO3 solution at the corresponding optimum operating conditions, respectively. The detection limits of 126Te and 128Te were reduced by a factor of 7.2 and 8.8, respectively, and the limit of quantitation (LOQ) for 126Te in the presence of 4% ethanol was 1.5 ng g(-1) (the LOQ is expressed as the concentration in the solid samples, thereby taking into account the dilution factor of 1000). The agreement between the determined Te concentration values (r = 0.998) in various geological samples (n = 140) by using isotopes of 126Te and 128Te indicates negligible contributions of polyatomic interferences produced by the addition of ethanol at these m/z. The proposed method was successfully applied to the direct determination of nanogram levels of Te in a series of international geological reference materials.

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PubMed2005

The agglomeration state of nanosecond laser-generated aerosol particles entering the ICP.

Fundamental understanding of aerosol formation and particle transport are important aspects of understanding and improving laser-ablation ICP-MS. To obtain more information about particles entering the ICP, laser aerosols generated under different ablation conditions were collected on membrane filters. The particles and agglomerates were then visualised using scanning electron microscope (SEM) imaging. To determine variations between different sample matrices, opaque (USGS BCR-2G) and transparent (NIST SRM 610) glass, CaF(2), and brass (MBH B26) samples were ablated using two different laser wavelengths, 193 and 266 nm. This study showed that the condensed nano-particles ( approximately 10 nm in diameter) formed by laser ablation reach the ICP as micron-sized agglomerates; this is apparent from filters which contain only a few well-separated particles and particle agglomerates. Ablation experiments on different metals and non-metals show that the structure of the agglomerates is matrix-dependent. Laser aerosols generated from silicates and metals form linear agglomerates whereas particle-agglomerates of ablated CaF(2) have cotton-like structures. Amongst other conditions, this study shows that the absorption characteristics of the sample and the laser wavelength determine the production of micron-sized spherical particles formed by liquid droplet ejection.

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PubMed2005

Analytical evidence of amorphous microdomains within nitridosilicate and nitridoaluminosilicate single crystals.

Single crystals of new nitridosilicates and nitridoaluminosilicates with excellent R values in X-ray investigations were analysed quantitatively using 30 to 60 microm single-spot LA-ICP-MS. Significant discrepancies between expected and measured chemical composition could not be explained by the crystallographic data. High spatial resolution analysis using electron probe microanalysis (EPMA, 10 microm) leads to the discovery of inhomogeneities in the crystalline material. The application of standard single-spot LA-ICP-MS with a spatial resolution of 30 to 60 microm is not suitable for the analysis of these crystals as the existing inhomogeneities dominate and alter the determined concentrations. However, owing to the better detection capabilities, a scanning LA-ICP-MS procedure enables a more representative analysis of single crystals of Ca(5)Si(2)Al(2)N(8) than single-spot LA-ICP-MS as a result of a larger sampling volume. It is highly likely that these impurities consist of amorphous, vitreous phases as powder diffraction X-ray data indicates the existence of a significant fraction of an X-ray amorphous material besides crystalline silicates. These microdomains contain less aluminium, silicon and calcium or are nearly free of aluminium, which explains the detected discrepancies in the chemical composition.

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PubMed2005

Potentiometric sensor for the measurement of Cd2+ transport in yeast and plants.

Research on heavy metals, and especially on transport of Cd(2+), has attracted much interest during the past decade. An optimized Cd(2+)-selective electrode for the continuous potentiometric monitoring of Cd(2+) fluxes in biological systems is presented. The selectivity of the electrode for Cd(2+) was further improved, and it now has very good long-term stability. The utility of this simple and inexpensive method is demonstrated by studying the Cd(2+) transport with model organisms, such as the yeast Saccharomyces cerevisiae and Arabidopsis cell cultures, frequently used in plant science. Its lower detection limits in the presence of commonly used growth media for yeast and plant cells are improved by approximately three orders of magnitude and are 10(-10) and 10(-8)M Cd(2+), respectively. Control experiments using atomic absorption spectrophotometry confirm that the decrease in Cd(2+) activities in the cell cultures is indeed due to the uptake of these metal ions by the cells. Both model systems can be easily transformed; therefore, in combination with the new electrode, they are very promising tools for the investigation of any protein of interest that might be involved in Cd(2+) transport.

Arabidopsis↗
PubMed2005

Quantification of aromatic and halogenated hydrocarbons and alcohol mixtures at the elemental, structural, and parent molecular ion level.

The capabilities of a millisecond pulsed glow discharge time-of-flight mass spectrometer for the quantitative analysis of organic molecules were investigated. Mixtures of analytes were separated by gas chromatography, and mass spectra were collected at three different time regimes during the pulse cycle-the prepeak, plateau, and afterpeak time regimes. Elemental information was collected in the prepeak, structural information in the plateau, and molecular ion information in the afterpeak. A sample mixture containing toluene, o-xylene, o-dichlorobenzene, and a binary mixture of methanol and sec-butanol were considered. Calibration curves were constructed for each time regime based on the intensities of the elemental, fragment, and molecular ions. Optimum linearity (r2 = 0.999) was achieved during the plateau time regime, although calibration in the prepeak was also demonstrated, albeit with slightly poorer correlation coefficients (r2 > 0.959). The minimum limits of detection (MDL) were 392, 422, and 557 ng, for toluene, o-xylene, and o-dichlorobenzene, respectively, using a 3-microL injection and a split ratio of 68:1. For the binary alcohol mixture, MDLs of 1.87 and 2.44 microg were determined for methanol and sec-butanol, respectively, based on the intensity of the 16O+ ion during the prepeak and using a split ratio of 58:1.

Alcohols↗
PubMed2005

Development and evaluation of a standard method for the quantitative determination of elements in float glass samples by LA-ICP-MS.

Forensic analysis of glass samples was performed in different laboratories within the NITE-CRIME (Natural Isotopes and Trace Elements in Criminalistics and Environmental Forensics) European Network, using a variety of Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) systems. The main objective of the interlaboratory tests was to cross-validate the different combinations of laser ablation systems with different ICP-MS instruments. A first study using widely available samples, such as the NIST SRM 610 and NIST SRM 612 reference glasses, led to deviations in the determined concentrations for trace elements amongst the laboratories up to 60%. Extensive discussion among the laboratories and the production of new glass reference standards (FGS 1 and FGS 2) established an improved analytical protocol, which was tested on a well-characterized float glass sample (FG 10-1 from the BKA Wiesbaden collection). Subsequently, interlaboratory tests produced improved results for nearly all elements with a deviation of < 10%, demonstrating that LA-ICP-MS can deliver absolute quantitative measurements on major, minor and trace elements in float glass samples for forensic and other purposes.

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PubMed2004

Characterizing ablation and aerosol generation during elemental fractionation on absorption modified lithium tetraborate glasses using LA-ICP-MS.

The influence of sample matrix composition, absorption behavior and laser aerosol particle size distribution on elemental fractionation in laser ablation inductively coupled plasma mass spectrometry was studied for nanosecond laser ablation at a wavelength of 266 nm. To this end, lithium tetraborate glass samples with different iron oxide contents and trace amounts of a group of 11 elements were prepared synthetically. The samples were characterized in terms of optical absorbance, melting points, trace element concentrations and homogeneity. UV/VIS spectra showed that sample absorption rises with increasing Fe2O3 content. Crater depths and time-dependent particle size distributions were measured, and ablated and transported sample volumes were estimated. Furthermore, the laser aerosol was filtered using a particle separation device and transient ICP-MS signals were acquired with and without filtering the aerosol. The results demonstrate that the amount of ablated sample is related to the absorption coefficient of the sample and therefore to the optical penetration depth of the laser beam into the sample. The higher energy densities resulting from the shorter penetration depths result in smaller average particle sizes for highly absorbing samples, which allows more efficient transport to and atomization and excitation of the ablated material within the ICP. The particle size distribution changes continuously with ablation time, and larger particle fractions occur mainly at the beginning of the ablation, which leads to particle-related fractionation processes at the beginning of the transient signal. Exceeding a critical depth to diameter ratio, laser-related elemental fractionation processes occur. Changes in the volatile to non-volatile element intensity ratio after the aerosol is filtered indicate that particle size-related enrichment processes contribute to elemental fractionation.

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PubMed2003

Size-related vaporisation and ionisation of laser-induced glass particles in the inductively coupled plasma.

Ongoing discussions about the origin of elemental fractionation occurring during LA-ICP-MS analysis show that this problem is still far from being well understood. It is becoming accepted that all three possible sources (ablation, transport, excitation) contribute to elemental fractionation. However, experimental data about the vaporisation size limit of different particles in the ICP, as produced in laser ablation, have not been available until now. This information should allow one to determine the signal contributing mass within the ICP and would further clarify demands on suitable laser ablation systems and gas atmospheres in terms of their particle size distribution. The results presented here show a vaporisation size limit of laser induced particles, which was found at particle sizes between 90 nm and 150 nm using an Elan 6000 ICP-MS. Due to the fact that the ICP-MS response was used as evaluation parameter, vaporisation and ionisation limits are not distinguishable. The upper limit was determined by successively removing the larger particles from the aerosol, which was created by ablation of a NIST 610 glass standard at a wavelength of 266 nm, using a recently developed particle separation device. Various particle fractions were separated from the aerosol entering the ICP. The decrease in signal intensity is not proportional to the decrease in volume, indicating that particles above 150 nm in diameter are not completely ionised in the ICP. Due to the limited removal range of the particle separation device, which cannot remove particles smaller than 150 nm, single hole ablations were used to determine the lower vaporisation limit. This is based on measurements showing that larger particles occur dominantly during the first 100 laser pulses only. After this period, the ratio of ICP-MS counts and total particle volume was found to be constant while most of the particles are smaller than 90 nm, indicating complete vaporisation and ionisation of these particles. To describe the influence of different plasma forward powers on the vaporisation limit, the range 1000-1600 W was studied. Results indicate that optimum vaporisation and ionisation occurs at 1300 W. However, an increase of the particle ionisation limit towards larger particles was not observed within the accuracy of this study using the full range of parameters available for optimisation on commonly used ICP-MS instruments.

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PubMed2003

Measurement of isotope ratios on transient signals by MC-ICP-MS.

Precise and accurate isotope ratio measurements are an important task in many applications such as isotope-dilution mass spectrometry, bioavailability studies, or the determination of isotope variations in geological or nuclear samples. The technique of MC-ICP-MS has attracted much attention because it permits the precise measurement of isotope compositions for a wide range of elements combined with excellent detection limits due to high ionisation efficiencies. However, the results are based mainly on measurements using continuous sample introduction. In the present study the determination of isotope ratios on various transient signals with a time duration of 30 to 60 s has been achieved by coupling high-performance liquid chromatography to a multicollector inductively coupled plasma mass spectrometer. In order to investigate the origin of ratio drifts across the transient signals for this hyphenated technique, measurements with the same standard solutions were also carried out using a flow-injection device for sample introduction. As a result of this application it could be concluded that the main source of the bias in the measured isotope ratios is within the ICP-MS instead of fractionation effects on the chromatographic column material. Preliminary studies on short transient signals of gaseous samples (dry plasma) showed a reverse fractionation effect compared with wet plasma conditions (flow injection and HPLC).

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PubMed2003

Climate and the collapse of Maya civilization.

In the anoxic Cariaco Basin of the southern Caribbean, the bulk titanium content of undisturbed sediment reflects variations in riverine input and the hydrological cycle over northern tropical South America. A seasonally resolved record of titanium shows that the collapse of Maya civilization in the Terminal Classic Period occurred during an extended regional dry period, punctuated by more intense multiyear droughts centered at approximately 810, 860, and 910 A.D. These new data suggest that a century-scale decline in rainfall put a general strain on resources in the region, which was then exacerbated by abrupt drought events, contributing to the social stresses that led to the Maya demise.

Archaeology↗
PubMed2003

Elemental fractionation studies in laser ablation inductively coupled plasma mass spectrometry on laser-induced brass aerosols.

Previous investigations on laser-induced aerosols of brass samples showed that preferential vaporization of zinc occurs during the ablation process leading to elemental fractionation and limited possibilities for non matrix matched calibration. In a variety of experiments carried out within this study it is shown that multiple effects are complicating the quantification of brass using IA-ICPMS. It is shown that the ablated copper and zinc is not homogeneously distributed within the laser-produced aerosol. Copper was found enriched up to 100% in particles larger than 100 nm as shown from EDX measurements (electron excited) on individual particles, and zinc was enriched by over 40% in the particles smaller than the lowest measurable particle size (below 100 nm or in the vapor phase). Solution nebulization analysis on digested filter-collected aerosols results in a higher Cu/Zn ratio than the certified value for the brass sample. ESEM pictures with analysis of the electron excited X-rays measured on the filter-collected material support the results showing copper enrichment. However, online LA-ICPMS measurements carried out under the same operating conditions as for filtering show a copper depletion within the ICP, which leads to the conclusion of partial vaporization and ionization of the aerosol particles in the ICP. The larger particles containing more or exclusively copper are not completely ionized. Within this study, three sources of elemental fractionation can be distinguished and described: (A) The ablation process leads to no measurable copper enrichment at the ablation crater rim. (B) Zinc deposition between the ablation site and the aerosol collection on filters leads to an up to 37% higher Cu/Zn ratio on the filter in comparison to the certified value. (C) On-line laser ablation aerosols measured within the ICPMS lead to significantly lower Cu/Zn ratios in comparison to the certified value. (D) Combination of the various studied sources of fractionation can finally lead to an agreement between measured and certified values due to inverse overlapping of various fractionation sources.

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PubMed2003

Detection of metals in proteins by means of polyacrylamide gel electrophoresis and laser ablation-inductively coupled plasma-mass spectrometry: application to selenium.

The capabilities of laser ablation-inductively coupled plasma-mass spectrometry for the detection of trace elements in a gel after gel electrophoresis were systematically studied. Figures of merit, such as limit of detection, linearity, and repeatability, were evaluated for various elements (Li, V, Cr, Mn, Ni, Cu, Zn, As, Se, Mo, Pd, Ag, Cd, Pt, Tl, Pb). Two ablation strategies were followed: single hole drilling, relevant for ablation of spots after two-dimensional (2-D) separations, and ablation with translation, i.e., on a line, relevant for one-dimensional (1-D) separations. This technique was applied to the detection of selenoproteins in red blood cells extracts after a 1-D separation (sodium dodecyl sulfate-polyacrylamide gel electrophoresis) and the detection of selenium-containing proteins in yeast after 2-D electrophoresis (2-DE). The detection procedure was further improved by using the dynamic reaction cell technology, which allowed the removal of the Ar_2(+) interference and hence the use of the most abundant Se isotope, (80)Se. Reaction gases were compared (methane, carbon monoxide, ammonia, oxygen and the combination of argon (collision gas) and hydrogen (reaction gas)). In each instance, the reaction cell parameters were optimized in order to obtain the lowest detection limit for Se (as (80)Se(+), (82)Se(+) or (77)Se(+); and as (80)Se(16)O(+), (82)Se(16)O(+) or (77)Se(16)O(+) with O(2) as the reaction gas). Carbon monoxide was found to offer the best performance. The detection limit with the use of DRC and He as transport gas was 0.07 microg Se g(-1) gel with single hole drilling and 0.15 microg Se g(-1) gel for ablation with translation.

Animals↗
PubMed2002

Niobium-zirconium chronometry and early solar system development.

Niobium-92 (92Nb) decays to zirconium-92 (92Zr) with a half-life of 36 million years and can be used to place constraints on the site of p-process nucleosynthesis and the timing of early solar system processes. Recent results have suggested that the initial 92Nb/93Nb of the solar system was high (>10(-3)). We report Nb-Zr internal isochrons for the ordinary chondrite Estacado (H6) and a clast of the mesosiderite Vaca Muerta, both of which define an initial 92Nb/93Nb ratio of approximately 10(-5). Therefore, the solar system appears to have started with a ratio of <3 x 10(-5), which implies that Earth's initial differentiation need not have been as protracted as recently suggested.

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