Air quality assessment regarding metals and metalloids using experimental measurements is expensive and time consuming due to the cost and time required for the analytical determination of the levels of these pollutants. According to the European Union (EU) Air Quality Framework Directive (Directive 2008/50/EC), other alternatives, such as objective estimation techniques, can be considered for ambient air quality assessment in zones and agglomerations where the level of pollutants is below a certain concentration value known as the lower assessment threshold. These conditions occur in urban areas in Cantabria (northern Spain). This work aims to estimate the levels of As, Cd, Ni and Pb in airborne PM 10 at two urban sites in the Cantabria region (Castro Urdiales and Reinosa) using statistical models as objective estimation techniques. These models were developed based on three different approaches: partial least squares regression (PLSR), artificial neural networks (ANNs) and an alternative approach consisting of principal component analysis (PCA) coupled with ANNs (PCA-ANN). Additionally, these models were externally validated using previously unseen data. The results show that the models developed in this work based on PLSR and ANNs fulfil the EU uncertainty requirements for objective estimation techniques and provide an acceptable estimation of the mean values. As a consequence, they could be considered as an alternative to experimental measurements for air quality assessment regarding the aforementioned pollutants in the study areas while saving time and resources.