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

Abstract

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 reduction of the matrix by AgCl precipitation. In these cases loss of ruthenium by the AgCl precipitate has no effect on the analytical result. The results of the different methods agreed usually well analysing ruthenium traces in the range of 0.1–10 μg per gram emulsion. The detection limits obtained were 4 ng/g for ICP-IDMS, 20 ng/g for NTI-IDMS, and 15 ng/g for ICP-MS with external calibration. Differences in the results between the different methods could mainly be attributed to sample inhomogeneities. ICP-IDMS with silver matrix reduction by AgCl precipitation is recommended as a routine method, NTI-IDMS with the corresponding sample treatment as a calibration method.