Investigation of HfO(+) interference in the determination of platinum in a catalytic converter (cordierite) by inductively coupled plasma mass spectrometry.

The determination of Pt in cordierite is subject to strong interference by spectral overlap from HfO(+) ions with all Pt isotopes. Two mathematical correction methods based on the HfO(+)Hf(+) ratio and a method for the chemical separation of Hf based on adsorption chromatography and isotope dilution were investigated to correct for this interference. Flow infection was used to prevent clogging of the cone orifice. To enhance the sensitivity and thus lower the detection limit, thermospray nebulization was used for sample introduction and the method was compared with pneumatic nebulization. In addition, the memory effects were evaulated for both systems. Analysis of artificial solutions (1 ng Pt ml(-1)) yielded results within 3% of the true value. Th Pt content (ca. 50 ng g(-1)) of a cordierite sample, previously exposed to exhaust gases, could be determined with precisions of about 10-25% and the results agreed with earlier determinations by other workers.

Determination of low amounts of platinum in environmental and biological materials using thermospray nebulization inductively coupled plasma-mass spectrometry.

A description is given of the experimental arrangement for thermospray nebulization of discrete liquid samples (100 microl) into an inductively coupled plasma-mass spectrometer (ICP-MS). The determination of ultratrace levels of platinum in environmental and biological materials is described. This method comprises an off-line sample enrichment by adsorptive chromatography, elution with ethanol and subsequent analysis of the evaporated eluate. The quantification of the concentration was performed with isotope dilution. The recovery, precision, accuracy and detection limit of the method are discussed.

Stereoselective pharmacokinetics of oxprenolol and its glucuronides in humans.

OBJECTIVE: To study the pharmacokinetics of R(+)- and S(-)-oxprenolol and their corresponding glucuronide conjugates in healthy subjects. METHODS: An oral dose of 80 mg racemic oxprenolol was given to eight male volunteers. Venous blood samples and urine were collected as a function of time. Oxprenolol enantiomers in plasma and urine were determined by an enantiospecific HPLC method. Oxyprenolol glucuronides in plasma and urine were measured as oxprenolol equivalents after enzymatic hydrolysis. RESULTS: For R-oxprenolol the area under the plasma concentration-time curve was slightly higher (R/S ratio, 1.19) and the oral clearance slightly lower (R/S ratio, 0.84) than those parameters for S-oxprenolol. The free fraction of R-oxprenolol in plasma was 4% higher than that of S-oxprenolol. The intrinsic clearance of S-oxprenolol was 1.5 times larger than that of R-oxprenolol, and a maximum of 3% of the dose was excreted as unchanged enantiomers in the urine. The plasma concentrations of S-oxprenolol glucuronide were more than three times higher than those of R-oxprenolol glucuronide. Twenty-five percent of the dose of the R-enantiomer was excreted in the urine as R-oxprenolol glucuronide; 29% of the S-enantiomer dose was excreted as S-oxprenolol glucuronide. The renal clearance of R-oxprenolol glucuronide was, on average, 172 ml/min, suggesting active tubular secretion. In contrast, the renal clearance of S-oxprenolol glucuronide was only 49 ml/min, which can be explained by the plasma binding of the compound. CONCLUSIONS: Our results show small differences in disposition between R- and S-oxprenolol but a marked difference in disposition between the glucuronides. The difference in plasma concentrations between the oxprenolol glucuronides is mainly attributable to the stereoselectivity of the renal excretion.

Bismuth in human serum: reference interval and concentrations after intake of a therapeutic dose of colloidal bismuth subcitrate.

A sensitive method for the determination of the bismuth concentration in human serum is described. Analyses were carried out by inductively coupled plasma-mass spectrometry (ICP-MS), after a simple dilution of the samples with nitric acid. The detection limit of the applied method is 0.007 microgram/l whereas relative standard deviations varied from 5.7 to 13.6%. Determination of reference values in human serum of healthy adults gave a range from < 0.007 to 0.067 microgram/l (19 persons). Bismuth concentrations in serum were also measured before, during and after the intake of therapeutic doses of colloidal bismuth subcitrate (CBS). About 1.5-2 h after the intake of one tablet of CBS, the bismuth concentration in serum was found to have increased 51-1483 times (two apparently healthy volunteers and six hospitalized patients), showing that the serum bismuth concentrations can increase by several orders of magnitude during the intake of CBS. During the intake of four tablets of CBS per day by two apparently healthy volunteers, bismuth concentrations in serum after an overnight fast were found to be, respectively, 5.56 and 8.1 micrograms/l on day 15 and 4.28 and 13.6 micrograms/l on day 29. After stopping the therapy, the concentration of bismuth in serum slowly returned towards normal over a period of months.

A review of the capabilities of ICP-MS for trace element analysis in body fluids and tissues.

ICP-MS is a powerful analytical technique for the determination of trace and ultra-trace elements in biological materials. Results are given of the analysis of human serum and of several biological reference materials (bovine liver, milk powder, wheat flour and pig kidney). Because concentrations of many trace metals of interest in these materials are low, dilution should be kept as limited as possible, although concentrations of certain concomitant elements (e.g. Na, K) can be high enough to cause significant suppression or enhancement of the ion signal. The result is that the dissolution procedure becomes a critical step in the analysis. Microwave digestion, wet digestion with several acids (HNO3, HClO4, HF) and simple dilution are compared with each other. In addition, three possible approaches to overcome these problems are discussed, namely the internal standardization method, the standard addition method and the isotope dilution method. Furthermore, ICP-MS is also more susceptible than initially expected to isobaric interferences arising from the plasma, the acids used in the sample preparation or the sample itself. These interferences are generally less important above a mass number of 80. Nevertheless, several researchers have investigated the possibility of removing the trace metals from the matrix or of using correction formulae based on the isotopic abundances of the elements. Some of these are evaluated. The need for identifying and quantifying chemical species, not just the elements, is well recognized. One of the reasons why elemental determination may not suffice is that different species of the same element may have a different chemical and toxicological behaviour. Arsenic (As(III), As(V)) and mercury (organomercury) are typical examples.(ABSTRACT TRUNCATED AT 250 WORDS)

Effect of solvent type on the determination of total iodine in milk powder and human serum by inductively coupled plasma mass spectrometry.

A method for the determination of the total iodine content in milk powder and human serum by inductively coupled plasma mass spectrometry is described. It is shown that the oxidation state of the analyte has a strong impact on the analytical performance. If iodine is present as iodide and nitric acid is used for acidification, the observed ion signal is not stable and samples spiked with iodide yield erroneous recoveries up to 750%. Hence, as the iodine in milk powder is present almost exclusively as iodide, destruction of the sample with nitric acid is not suitable. It was found that such an excessive spike recovery does not occur if ammonia solution instead of nitric acid is used as the diluent. The proposed sample preparation was tested by analysing three reference milk powders, namely Certified Reference Materials 150 and 151 Spiked Skim Milk Powder (from the Community Bureau of Reference) and Standard Reference Material 1549 Non-Fat Milk Powder (from the National Institute of Standards and Technology). Good agreement with the certified values was obtained, indicating that no significant errors are introduced. For human serum, samples treated with nitric acid or with ammonia solution gave results that were not significantly different from each other. Results are given for both a 'second-generation' biological reference material, Freeze-Dried Human Serum (University of Ghent), and for sera from healthy individuals.

The use of internal standards in ICP-MS.

Careful study of the matrix effect in ICP-MS showed that, in all cases studied, the magnitude of the signal suppression or enhancement depends in a regular way on the mass number. Hence, accurate correction for non-spectral interferences is only possible using an internal standard with mass number close to that of the analyte element(s). It is also shown that using an internal standard with mass number close to that of the analyte improves the precision. For both cases, the ionization energy of the internal standard seems to be of no or only secondary importance. To obtain optimal precision and accuracy, the internal standard should be selected as close in mass number as possible to that of the analyte element(s). When a number of elements over a considerable mass range are to be determined, several internal standards have to be used.

Determination of strontium in human serum by inductively coupled plasma mass spectrometry and neutron activation analysis: A comparison.

Strontium has been determined in a human serum reference material by ICP-MS and by NAA. By ICP-MS, results for (88)Sr and (86)Sr in both 10- and 5-fold diluted serum were in good agreement. For (88)Sr the precision was better than 3% and the detection limit was 0.05 mug/l. under the conditions used. The results were 25.5 mug/l. in the liquid serum or 0.281 mug/g in the lyophilized reference material. In the NAA the (87m)Sr produced was radiochemically separated by extraction with oxine in chloroform. The precision was about 10% and the detection limit 0.02-0.05 mug/g.

Determination of trace elements in human serum by inductively coupled plasma-mass spectrometry. Comparison with nuclear analytical techniques.

The determination of trace and ultratrace elements in human serum by ICP-MS is described. The accuracy of the method is tested using a "second generation" human serum reference material. Elements determined include Fe, Co, Cu, Zn, Br, Rb, Sr, Mo, and Cs. The method is compared to nuclear analytical methods (NAA, PIXE). Perspectives for the future are also discussed.

Determination of iron, cobalt, copper, zinc, rubidium, molybdenum, and cesium in human serum by inductively coupled plasma mass spectrometry.

A method was developed for the determination of seven trace elements (Fe, Co, Cu, Zn, Rb, Mo, and Cs) in human serum by inductively coupled plasma mass spectrometry (ICP-MS). Sample preparation was kept as limited as possible. As the only sample pretreatment serum samples were diluted with nitric acid and indium was added as an internal standard. The results for iron, cobalt, copper, and zinc were corrected for interferences from polyatomic ions by using a blank solution containing the same concentration of sodium, sulfur, chlorine, and calcium as human serum. For copper and zinc the corrections are small, whereas for iron and cobalt they are important. No interferences occur for the considered isotopes of rubidium, molybdenum, and cesium. In order to test the accuracy and precision of the analytical technique, a "second-generation biological reference material (human serum)" was analyzed. The results obtained by ICP-MS for the seven elements considered showed good agreement with the certified values.