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Liquid chromatography tandem mass spectrometry (LC-MS/MS) is often regarded as a highly reliable methodology for confirmatory testing in analytical toxicology, especially for detection of new psychoactive substances (NPS) by clinical and forensic laboratories. However, false positives still do occur and erroneous reporting can have substantial legal implications. In this study, we investigated into the mechanism behind a clinically implausible, but apparently analytically sound, finding of a NPS (4-hydroxy-N-methyl-N-ethyltryptamine; 4-H