The occurrence: A meaningful parameter to be considered in the validation of multivariate classification-based...

The development of multivariate screening analytical methods in the analytical chemistry field focused particularly on food authentication is growing in recent years, which is evidenced by the increase of scientific publications. Currently there are several guides and technical reports about how -univariate qualitative methods should be properly validated to produce reliable and accurate (fitted-for-purpose) results. Nevertheless, this is not the case when multivariate methods are considered. Aimed at redressing this untenable disadvantage, this paper proposes some guidelines for the validation of multivariate classification-based screening methods. As an application example, the detection of adulteration of virgin olive oil with any other edible vegetal oils is showed. The analytical techniques employed are liquid chromatography coupled to diode array detector (LC-DAD) and gas chromatography coupled to flame ionization detector (GC-FID). For the correct validation of the multivariate screening method a new parameter which never considered before, named occurrence, is accounted. Also, it has been developed two new applicability indicators of the multivariate screening methods: the assignation error index (I_ERROR) and the index saving (I_SAVING) to establish the validation requirements. Then the validation parameters of the methods: precision (or target predictive value), sensitivity, non-target predictive value, specificity and accuracy were estimated. The main conclusion of the work has been the need to take accounts the occurrence value to establish the specific validation requirements to apply the multivariate screening method in a particular scenario.