Isotope-dilution ICP-MS for trace element determination and speciation: from a reference method to a routine method?

This critical review discusses the conditions under which inductively coupled plasma-isotope dilution mass spectrometry (ICP-IDMS) is suitable as a routine method for trace element and element-speciation analysis. It can, in general, be concluded that ICP-IDMS has high potential for routine analysis of trace elements if the accuracy of results is of predominant analytical importance. Hyphenated techniques with ICP-IDMS suffer both from lack of commercially available isotope-labeled spike compounds for species-specific isotope dilution and from the more complicated system set-up required for species-unspecific ICP-IDMS analysis. Coupling of gas or liquid chromatography with species-specific …

The International Measurement Evaluation Programme (IMEP) IMEP-6: "Trace elements in water"

The sixth round of the International Measurement Evaluation Programme (IMEP) is presented. The programme offers reference values, established by primary methods of measurement, against which participating laboratories can evaluate their performance. The degree of comparability is thus established against the most objective references available at present. In IMEP-6, reference values for total concentrations of 14 trace elements in a synthetic and a natural water were established mainly by isotope dilution mass spectrometry (IDMS). For the majority of the measurands, results traceable to the international system of units (SI) and having expanded uncertainties, U (k=2), of 2% could be establi…

Determination of halogen species of humic substances using HPLC/ICP-MS coupling

A mass spectrometric method for the determination of chlorine, bromine and iodine species of humic substances (HS) has been developed by coupling a HPLC system with ICP-MS. Using size exclusion chromatography, the method was applied to the characterization of natural water samples (ground water, seepage water from soil, brown water) and a sewage water sample. Quantification of iodine/HS species was carried out by the on-line isotope dilution technique, which was not possible for bromine and chlorine species because of mass spectroscopic interferences by using a quadrupole ICP-MS. Characteristic fingerprints of the halogen/HS species, correlated with the corresponding UV chromatogram, were o…

Development of an Isotope Dilution Mass Spectrometric Method for Dimethylthallium Speciation and First Evidence of Its Existence in the Ocean

A sensitive analytical method for the determination of dimethyl thallium (Me2Tl+) in environmental samples by positive thermal ionization isotope dilution mass spectrometry (PTI-IDMS) was developed...

Biomethylation of thallium by bacteria and first determination of biogenic dimethylthallium in the ocean

To investigate a possible biomethylation of thallium, incubation experiments were carried out under aerobic conditions with a sewage sludge and with a mixed bacterial culture isolated from a sewage sludge, as well as under anaerobic conditions with a fresh-water lake sediment, by adding Tl(I) nitrate to these systems. Only in the case of the anaerobic sediment was a significant production of dimethylthallium observed (after three-weeks). Analysing different surface seawater samples and those from a single depth profile down to 4000 m, dimethylthallium was determined above the detection limit of 0.4 ng L−1 in about 20% of all samples, ranging from 0.5 to 3.2 ng l−1. The proportion of dimethy…

Multi-element trace determinations in pure alkaline earth fluoride powders by high-resolution ICP-MS using wet-chemical sample preparation and laser ablation.

Four alternative analytical procedures for the determination of ten important trace impurities (Mg, Cr, Fe, Cu, Zn, Sr, Zr, Cd, Ba, and Pb) in pure alkaline earth fluoride powders were applied using high-resolution inductively coupled plasma mass spectrometry (ICP-MS). Two procedures are based on a wet-chemical microwave digestion with boric acid and quantification by the standard addition technique and isotope dilution mass spectrometry (IDMS), respectively. In addition, analyses are also performed by laser ablation as a direct solid sampling technique applying matrix-matched external calibration as well as isotope dilution of the powdered sample. For most elements good agreement between t…

Determination of Trace Elements and Elemental Species Using Isotope Dilution Inductively Coupled Plasma Mass Spectrometry

Determination of ruthenium in photographic emulsions - Development and comparison of different sample treatments and mass spectrometric methods

Different sample treatment procedures were combined with inductively coupled plasma mass spectrometry (ICP-MS) and negative thermal ionisation mass spectrometry (NTI-MS) for the determination of ruthenium traces in photographic emulsions. Dissolution of the samples in concentrated ammonia solution was used in connection with ICP-MS by external calibration, which has the advantage of a simple sample preparation technique but introduces high amounts of the silver matrix into the mass spectrometer. On the other hand, isotope dilution mass spectrometry (IDMS) with an enriched 99Ru spike solution was applied for ICP-MS and NTI-MS measurements, respectively, in connection with a significant reduc…

Production of methylated mercury and lead by polar macroalgae — A significant natural source for atmospheric heavy metals in clean room compartments

During August and September 1995 samples of different species of macroalgae were collected from the Kongsfjord on Spitsbergen. These macroalgae were cultivated in incubation vessels under polar conditions and the releasing rates of methylated heavy metal compounds for mercury, lead and cadmium were determined. The analysis of monomethyl and dimethyl mercury was carried out by a gas chromatographic system with atomic fluorescence detection after conversion of monomethyl mercury into the volatile methylethyl mercury compound. A differential pulse anodic stripping voltammetric method was used for the determination of trimethyl lead and monomethyl cadmium, respectively. The different species of…

Use of thermal ionization isotope dilution mass spectrometry (TI-IDMS) as an oligo-element method for the determination of photographically relevant trace elements in AgCl emulsions

Thermal ionization isotope dilution mass spectrometry (TI-IDMS) was used as an oligo-element method for the determination of Cr, Cd and Pb in photographic AgCl emulsions. After addition of an appropriate amount of isotopically enriched spikes (53Cr, 116Cd and 206Pb) to the solid samples, the latter were completely dissolved in NH3 solution, permitting isotopic exchange to take place. Thereafter, AgCl was selectively removed by precipitation, whereby ultrasonic treatment was used to enhance the recovery of the elements of interest. Despite the use of concentrated HNO3 and H2O2 during further sample processing, preliminary experiments indicated the presence of a substantial remainder of the o…

Comparative LA-ICP-IDMS determinations of trace elements in powdered samples using laser ablation systems with low and high ablation rates

The results of laser ablation inductively coupled plasma isotope dilution mass spectrometry (LA-ICP-IDMS) with a special laser ablation system with high ablation rates (LINA-Spark-Atomiser), which was constructed for bulk analyses of solid samples, are compared with those obtained by one of the commonly used LA systems (UP213). Using different reference materials for validation it was demonstrated that the accuracy of LA-ICP-IDMS determinations of elements like Fe, Cu, Pb, and Zn by both systems is comparable in the concentration range of 10−2–10−6 g g−1, but the LINA-Spark-Atomiser also provides accurate results in the sub-μg g−1 range. IDMS enables accurate calibration of LA-ICP-MS determ…

Species-Specific GC/ICP-IDMS for Trimethyllead Determinations in Biological and Environmental Samples

An accurate and sensitive species-specific isotope dilution GC/ICPMS method was developed for the determination of trimethyllead (Me3Pb+) in biological and environmental samples. A trimethyllead spike was synthesized from 206Pb-enriched metallic lead by reaction of lead halide with methyllithium and subsequent formation of trimethyllead iodide. The isotopic composition of the spike solution was determined by GC/ICPMS after derivatization with tetraethylborate, and its concentration was determined by reverse isotope dilution analysis. The species-specific GC/ICP-IDMS method was validated by reference material CRM 605 (urban dust) certified for Me3Pb+. The method was also applied to determine…

Isotope dilution mass spectrometry as a calibration method for the analysis of trace elements in powder samples by LA-ICP-MS

The applicability of the isotope dilution (ID) technique for trace element determinations in powdered solid samples by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is demonstrated. LA-ICP-IDMS combines the advantage of the isotope dilution technique as a definitive method with the powerful capability of LA-ICP-MS for a fast and direct multi-element analysis of solid samples. LA-ICP-IDMS therefore allows matrix-matched quantification of element concentrations without any external standard, which is not possible by other calibration strategies used in LA-ICP-MS, up to now. The sample preparation effort is kept minimal and consists of an addition of the corresponding…

Bernd Neidhart (1941 - 2003)

Bromide/bromate speciation by NTI-IDMS and ICP-MS coupled with ion exchange chromatography

Two different mass spectrometric methods, negative thermal ionization isotope dilution mass spectrometry (NTI-IDMS) and inductively coupled plasma mass spectrometry (ICP-MS), off-line and on-line coupled with anion exchange chromatography, have been developed for simultaneous bromide and bromate determinations in water samples. The detection limits of these methods are in the range of 0.03–0.09 μg/L using a 50 mL sample.The results are independent of the content of other anions, which could be demonstrated by the analyses of six mineral waters containing chloride and sulfate of up to 160 mg/L and 1500 mg/L, respectively. Bromide has been analyzed by the NTI-IDMS method in the range of 10–50…

Setting the Scene: Element Determination and its Quality Control in Fractions of Refractory Organic Substances and the Corresponding Original Water Samples

Production of methylated mercury, lead, and cadmium by marine bacteria as a significant natural source for atmospheric heavy metals in polar regions

Abstract Mixed and pure bacterial cultures of polar origin were incubated in model experiments under polar conditions. The releasing rates of monomethyl and dimethyl mercury (MeHg+ and Me2Hg), trimethyl lead (Me3Pb+), and monomethyl cadmium (MeCd+) were determined in dependence on the incubation time. This is the first time that methylation of cadmium by bacteria could be shown. The formation of tetramethyl and dimethyl lead (Me4Pb and Me2Pb2+) was also checked but no release of these methylated compounds was observed. The determination of methylated mercury compounds was carried out by using a purge and trap system after derivatisation of monomethyl mercury into the volatile methylethyl me…

Cr(III)/Cr(VI) speciation in aerosol particles by extractive separation and thermal ionization isotope dilution mass spectrometry

An isotope dilution mass spectrometric (IDMS) method, using the formation of positive thermal ions, was developed for Cr(III) and Cr(VI) speciation in aerosol particles. Cr(III) and Cr(VI) spike species, enriched in 53Cr, were applied for the isotope dilution step. After leaching of filter collected aerosol samples by an alkaline solution at pH 13, species separation was carried out by extraction with a liquid anion exchanger in methyl isobutyl ketone. Cr(VI) in the organic phase was re-extracted into an ammoniacal solution and chromium was then isolated from both fractions of species by electrodeposition. Detection limits of 30 pg/m3 for Cr(III) and of 8 pg/m3 for Cr(VI) were achieved in a…

Characterization of aquatic humic substances and their metal complexes by immobilized metal-chelate affinity chromatography on iron(III)-loaded ion exchangers

The analytical fractionation of aquatic humic substances (HS) by means of immobilized metal-chelate affinity chromatography (IMAC) on metal-loaded chelating ion exchangers is described. The cellulose HYPHAN, loaded with different trivalent ions, and the chelate exchanger Chelex 100, loaded to 90% of its capacity with Fe(III), were used. The cellulose HYPHAN, loaded with 2% Fe(III), resulted in HS distribution coefficients Kd of up to 10(3.7) mL/g at pH 4.0 continuously decreasing down to 10(1.5) at pH 12, which were appropriate for HS fractionation by a pH-depending chromatographic procedure. Similar distribution coefficients Kd were obtained for HS sorption onto Fe(III)-loaded Chelex 100. …

Determination of extremely low (236)U/(238)U isotope ratios in environmental samples by sector-field inductively coupled plasma mass spectrometry using high-efficiency sample introduction.

A method by inductively coupled plasma mass spectrometry (ICP-MS) was developed which allows the measurement of (236)U at concentration ranges down to 3 x 10(-14)g g(-1) and extremely low (236)U/(238)U isotope ratios in soil samples of 10(-7). By using the high-efficiency solution introduction system APEX in connection with a sector-field ICP-MS a sensitivity of more than 5,000 counts fg(-1) uranium was achieved. The use of an aerosol desolvating unit reduced the formation rate of uranium hydride ions UH(+)/U(+) down to a level of 10(-6). An abundance sensitivity of 3 x 10(-7) was observed for (236)U/(238)U isotope ratio measurements at mass resolution 4000. The detection limit for (236)U a…

Determination of Concentration Profiles of Methyl Mercury Compounds in Surface Waters of Polar and other Remote Oceans by GC-AFD

Abstract The concentration of monomethyl mercury (MeHg+) and dimethyl mercury (Me2Hg) was determined in surface sea-water samples of the Antarctic and Arctic Ocean as well as of other remote areas (South Atlantic and South Pacific) during expeditions of the German research vessel “Polarstern”. A purge and trap/gas chromatographic system, equipped with an atomic fluorescence detector (AFD), was used. For the analysis of MeHg+ conversion into the volatile methylethyl mercury by reaction with tetraethyloborate prior to the purging process was carried out. The detection limit for both methylated mercury compounds was 5 pg Hg/L, which allowed their determination in most ocean water samples even …

Buchbesprechung: Guidelines for Achieving High Accuracy in Isotope Dilution Mass Spectrometry (IDMS) Herausgegeben von Mike Sargent, Chris Harrington und Rita Harte

Isotope dilution inductively coupled plasma quadrupole mass spectrometry in connection with a chromatographic separation for ultra trace determinations of platinum group elements (Pt, Pd, Ru, Ir) in environmental samples

An isotope dilution inductively coupled plasma quadrupole mass spectrometric (ID-ICP-QMS) method was developed for the simultaneous determination of the platinum group elements Pt, Pd, Ru, and Ir in environmental samples. Spike solutions, enriched with the isotopes 194Pt, 108Pd, 99Ru, and 191Ir, were used for the isotope dilution step. Interfering elements were eliminated by chromatographic separation using an anion-exchange resin. Samples were dissolved with aqua regia in a high pressure asher. Additional dissolution of possible silicate portions by hydrofluoric acid was usually not necessary. Detection limits of 0.15 ng x g(-1), 0.075 ng x g(-1), and 0.015 ng x g(-1) were achieved for Pt,…

Biomethylation in the Southern Ocean and its contribution to the geochemical cycle of trace elements in Antarctica

Publisher Summary This chapter focuses on biomethylation, which is a chemical process that leads to volatile alkylated compounds of elements, and is the only substantial alkylation process for some heavy metals in the environment. Volatile compounds dissolved in the ocean are transferred into the atmosphere. This is an important mechanism in the geochemical cycle of elements that contributes significantly to the global distribution of individual substances. Most of the methylated compounds are not very stable in the atmosphere because they can decompose. Antarctica and its surrounding polar ocean is one of the few areas on earth that is not directly influenced by anthropogenic sources and, …

Mass spectrometric investigations of the kinetic stability of chromium and copper complexes with humic substances by isotope-labelling experiments

Isotope-labelling exchange experiments were carried out to investigate the kinetic stability of Cr(III) complexes with humic substances (HS). To compare the results with those of an ion, not expected to form kinetically stable HS complexes with respect to its electron configuration, Cu(II) was investigated under the same conditions. HS solutions of different origin were therefore spiked with 53Cr(III) or 65Cu(II) after saturation of HS with chromium and copper of natural isotopic composition. In fractions of metal/HS complexes with different molecular weight, obtained by ultrafiltration and HPLC/ICP-MS using size exclusion chromatography (SEC), respectively, the isotope ratios of chromium a…

Development of an ICP-IDMS method for accurate routine analyses of toxic heavy metals in polyolefins and comparison with results by TI-IDMS

An inductively coupled plasma isotope dilution mass spectrometric (ICP-IDMS) method was developed as a suitable method - with respect to its sensitivity, precision, accuracy, and time-consumption - for the analysis of toxic heavy metal traces (Pb, Cd, Cr, and Hg) in polyolefins. Results for Pb, Cd, and Cr were compared with those obtained by thermal ionization isotope dilution mass spectrometry (TI-IDMS), which was used as a reference method. Because of its high first ionization potential and its high volatility mercury could not be determined by TI-IDMS. A multi-element spike solution, containing isotopically enriched 206Pb, 116Cd, 53Cr, and 201Hg, was used for the isotope dilution step. D…

Book Review: Guidelines for Achieving High Accuracy in Isotope Dilution Mass Spectrometry (IDMS) Edited by Mike Sargent, Chris Harrington and Rita Harte

Producing SI-traceable reference values for Cd, Cr and Pb amount contents in polyethylene samples from the Polymer Elemental Reference Material (PERM) project using isotope dilution mass spectrometry

The present paper describes the certification of the amount content of Cd, Cr and Pb in two different polyethylene materials within the third phase of the Polyethylene Elemental Reference Material (PERM) project. The analytical procedure to establish the reference values for Cd, Cr and Pb amount contents in these materials is based on isotope dilution mass spectrometry used as a primary method of measurement. Cd and Pb were measured with inductively coupled plasma-mass spectrometry and Cr with positive thermal ionization-mass spectrometry. The decomposition of the polymer matrix was carried out using a high pressure asher. Reference values for amount content, traceable to the SI-system, hav…

Development of a species-unspecific isotope dilution GC-ICPMS method for possible routine quantification of sulfur species in petroleum products.

Inductively coupled plasma mass spectrometry (ICPMS) hyphenated with capillary gas chromatography was applied for sulfur multispecies determination in petroleum products by species-unspecific isotope dilution mass spectrometry (IDMS). To guarantee a stable and continuous addition of the spike into the GC-ICPMS system, a special dosing unit was designed and synthesis of a (34)S-labeled dimethyldisulfide spike from (34)S-enriched elemental sulfur in the milligram range was developed. The sample was mixed with an internal standard for spike mass flow calibration. From the mass flow chromatogram obtained by species-unspecific GC-ICP-IDMS, determination of all separated sulfur species and of the…

Development of accurate mass spectrometric routine and reference methods for the determination of trace amounts of iridium and rhodium in photographic emulsions

For the determination of trace amounts of iridium and rhodium in photographic emulsions different sample treatment procedures were coupled with inductively coupled plasma mass spectrometry (ICP-MS) and, for iridium, also with negative thermal ionisation isotope dilution mass spectrometry (NTI-IDMS) and ICP-IDMS. IDMS determinations of iridium were carried out using an enriched 191Ir spike solution. Elimination of the silver matrix was established for both mass spectrometric methods, which prevents corresponding memory effects in the ICP-MS system and is essential for the formation of IrO2 - thermal ions, respectively. For NTI-MS measurements, the gelatine matrix of the emulsion must also be…

2003 European Winter Conference on Plasma Spectrochemistry

Uber 500 Teilnehmer aus 41 Landern besuchten die diesjahrige Winter Conference on Plasma Spectrochemistry, die vom 12.-17. Januar im Kongresshaus von Garmisch-Partenkirchen stattfand. Das wissenschaftliche Programm des Treffens der Spektroskopiker, die mit Plasmamethoden analytische Probleme losen oder entsprechende analytische Geratschaften entwickeln, wurde unter Vorsitz von Klaus G. Heumann, Analytische Chemie der Johannes Gutenberg-Universitat Mainz, zusammengestellt; die Tagungsabteilung der GDCh hatte die technische Organisation ubernommen.

Development of an ICP−IDMS Method for Dissolved Organic Carbon Determinations and Its Application to Chromatographic Fractions of Heavy Metal Complexes with Humic Substances

A sensitive and fast method for direct determinations of dissolved organic carbon (DOC) in bulk samples and in chromatographically separated fractions by inductively coupled plasma isotope dilution mass spectrometry (ICP−IDMS) is developed. A 13C-enriched spike solution of benzoic acid is used for the isotope dilution step. Equal ionization efficiencies are obtained for carbon, independent of the type and molecular weight of the dissolved organic substance, which is the most important precondition for DOC determinations by ICP−IDMS. The detection limits achieved are 0.3 mg L-1 for bulk analyses and 7 × 10-4 μg s-1 for transient signals of chromatographic peaks. The results for different wat…

Biogenic volatile organoiodine and organobromine hydrocarbons in the Atlantic Ocean from 42°N to 72°S

During the cruise ANT X/1 and 2 of the research vessel Polarstern from November 1991 to March 1992, 39 surface water samples of the Atlantic Ocean from 42°N to 72.5°S were collected and analysed for their concentration of volatile iodinated and brominated hydrocarbons. The concentration of chlorophyll-a was used as an indicator for phytoplankton, which is one of the main producers of iodinated and brominated compounds in the ocean. For determination of chlorophyll-a, fluorescence spectroscopy was applied, whereas the measurement of halogenated volatile hydrocarbons was carried out by a purge and trap system with subsequent gas chromatographic separation and detection by an electron capture …

Determination of zirconium traces in polymers by ICP-IDMS - a powerful and fast method for routine testing of zirconium residues in polyolefins

Zirconium trace analyses play an important role for polyolefins produced by modern catalytic processes with zirconium metallocenes. A reliable and fast routine testing method by inductively coupled plasma isotope dilution mass spectrometry (ICP-IDMS) was therefore developed, which allows the determination of zirconium in polymers down to the low ng/g level. With respect to its precision, accuracy, and time-consumption this method is suitable for routine testing of production processes. A spike solution, enriched in the stable isotope 91Zr, was prepared and used for the isotope dilution procedure, which has the advantage of being an internal “one point” calibration method. The polyolefin sam…

Iodine determination in food samples using inductively coupled plasma isotope dilution mass spectrometry.

Two different sample treatment methods are used in connection with inductively coupled plasma isotope dilution mass spectrometry for accurate and precise determinations of iodine traces in food samples. 129I-enriched iodate is applied as a spike compound for the isotope dilution step. Extraction of iodine by tetramethylammonium hydroxide (TMAH) solution at high temperatures in a closed vessel is one of the sample treatment methods. The other one is a complete decomposition of the sample with a mixture of perchloric acid and nitric acid using microwave assistance. By analyzing different certified reference materials (three milk powders with different iodine levels, BCR CRM 63, 150, and 151; …

Metal Complexes of Humic Substances

Determination of heavy metal complexes with humic substances by HPLC/ICP-MS coupling using on-line isotope dilution technique

An isotope dilution mass spectrometric (IDMS) method has been developed for the simultaneous determination of the complexes of 11 heavy metals (Ag, Cd, Cu, Mo, Ni, Pb, Tl, U, W, Zn and Zr) with humic substances (HS) by coupling HPLC with ICP-MS and applying the on-line isotope dilution technique. The HPLC separation was carried out with size exclusion chromatography. This HPLC/ICP-IDMS method was applied to samples from a brown water, ground water, sewage and seepage water as well as for a sample containing isolated fulvic acids. The total contents of heavy metals and of their complexes were analyzed in these samples with detection limits in the range of 5–110 ng/L. The analysis of heavy me…

Spark source mass spectrometric assessment of boron and nitrogen concentrations in crystalline gallium arsenide

The residual or doped element concentration [E] in GaAs measured by SSMS is only accurate with respect to the relative sensitivity coefficient RSCE. For a trace element concentration, the RSCE = [E]SSMS/[E]TRUE is set to unity, if no reference material or method is available to approximate the concentration to the true value. For boron a relative sensitivity coefficient of RSCB = 0.94 ± 0.08 was obtained using TI-IDMS as a reference method. RSCN = 1 is used for nitrogen determinations. A boron and nitrogen detection limit of 4.4 × 1013 cm–3 is achieved. SSMS was used as reference method to calibrate the FTIR factor fE = [E] / Iα due to the integrated local vibrational mode absorption Iα of …

Direct determination of halogens in powdered geological and environmental samples using isotope dilution laser ablation ICP-MS

Abstract Laser ablation inductively coupled plasma isotope dilution mass spectrometry (LA-ICP-IDMS) with a special laser ablation system for bulk analyses (LINA-Spark™-Atomiser) was applied for direct determinations of chlorine, bromine, and iodine in rock and sediment samples. Special attention was focused on possible inter-halogen fractionations and analyte/spike isotope fractionations by using LA-ICP-MS and LA-ICP-IDMS, respectively. A variation of Br/Cl and I/Cl element intensity ratios by a factor of 1.3–3 was observed when changing the nebulizer gas flow rate in the range of 0.84–1.0 L min−1 and the laser power density in the range of 2–10 GW cm−2, respectively. When using an internal…

Transformation of Iodide in Natural and Wastewater Systems by Fixation on Humic Substances

Separation of different fractions of humic substances (HS) by their molecular weight was carried out by size exclusion chromatography (SEC). The fixation of inorganic iodide by HS of these fraction...

Application of isotope-dilution laser ablation ICP-MS for direct determination of Pu concentrations in soils at pg g(-1) levels.

The methods available for determination of environmental contamination by plutonium at ultra-trace levels require labor-consuming sample preparation including matrix removal and plutonium extraction in both nuclear spectroscopy and mass spectrometry. In this work, laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was applied for direct analysis of Pu in soil and sediment samples. Application of a LINA-Spark-Atomizer system (a modified laser ablation system providing high ablation rates) coupled with a sector-field ICP-MS resulted in detection limits as low as 3x10(-13) g g(-1) for Pu isotopes in soil samples containing uranium at a concentration of a few microg g(-1). …

To Professor Dr. Karlheinz Ballschmiter on his 60th birthday

4 th Symposium on Mass Spectrometric Methods for Element Trace Analysis

Structural Investigations: Heavy Metal and Halogen Interactions with Fractions of Refractory Organic Substances Separated by Size-exclusion Chromatography

Validation of Methylmercury Determinations in Aquatic Systems by Alkyl Derivatization Methods for GC Analysis Using ICP-IDMS

Isotope dilution mass spectrometry (IDMS), using an inductively coupled plasma quadrupole mass spectrometer (ICPMS) and a species-specific methylmercury spike was applied to validate the commonly used GC method for methylmercury (MeHg+) determination, which is based on the formation of volatile methylethylmercury by derivatization with NaBEt4. The spike compound, Me201Hg+, was synthesized by reaction of 201Hg-enriched mercury chloride with methylcobalamin. By analyzing different environmental aquatic samples, it was found that in most cases, transformation of MeHg+ into elemental mercury (Hg0) took place. From investigations of synthetic solutions, it could be followed that halide ions are …

Development of an isotope dilution laser ablation ICP-MS method for multi-element determination in crude and fuel oil samples

An inductively coupled plasma isotope dilution mass spectrometric (ICP-IDMS) method with direct introduction of the isotope-diluted sample into the plasma by laser ablation was developed for accurate, sensitive, fast, and simultaneous determination of trace metals in different oil samples. Metallo-organic solutions of isotope spikes (50V, 53Cr, 65Cu, 57Fe, 62Ni, 68Zn, 113Cd, 117Sn, and 206Pb) were prepared from corresponding aqueous stock solutions by using liquid–liquid extraction of complexed metal ions in isobutyl methyl ketone. The isotope-diluted sample was absorbed by a cellulose material, which was fixed in a special PTFE holder for ablation, using a laser system with high ablation r…

Accurate determination of element species by on-line coupling of chromatographic systems with ICP-MS using isotope dilution technique

Abstract The instrumental design for coupling different liquid chromatographic systems such as ion, reversed phase, and size exclusion chromatography as well as capillary gas chromatography, with ICP-MS for the determination of element species is described. For accurate analyses obtaining ‘real time’ concentrations of chromatographic peaks, the isotope dilution mass spectrometric (IDMS) technique is applied. Two different spiking modes are possible, one using species-specific and another one using species-unspecific spike solutions of isotope-enriched labelled compounds. The species-specific mode is only possible for element species well defined in their structure and composition, for examp…

Identification of ground water contaminations by landfills using precise boron isotope ratio measurements with negative thermal ionization mass spectrometry

Precise boron isotope ratio measurements with negative thermal ionization mass spectrometry were used for the identification of ground water contaminations by leakages of landfills. BO 2 - thermal ions were produced to determine the 11 B/ 10 B isotope ratio, which was expressed as δ 11 B value in ‰ normalized to the standard reference material NIST SRM 951. For example, household waste influences the boron isotope ratio by specific components such as washing powder. In the case of one investigated landfill low δ 11 B values correlate well with high boron concentrations in contaminated seepage water samples and vice versa for uncontaminated ground water samples. Possible boron contributions …

Precise isotope ratio measurements as a unique tool in modern analytical chemistry