The aim of this study was to evaluate the contribution of local emission sources to the selected trace metals levels (As, Ni, Cd, Pb, Ti, V, Mn, Cu, Mo and Hg) in urban particulate matter, PM10 and PM2.5, in the Cantabria region (Northern Spain) during the year 2008. PM10 and PM2.5 samples were collected and characterized in an urban sampling site at Santander (Cantabria); additional PM10 samples were collected at a rural site at Los Tojos (50 Km SW) to evaluate both the urban and rural environment. The particulate matter and the metals regulated by the EC air quality directives (Pb, As, Ni and Cd) did not exceed the EC limit or target values in the Cantabria region. The metal concentrations were much lower at the rural site except for Ni. Different techniques were used to analyse the possible sources of the studied metals: enrichment factor, urban impact, wind and pollutant roses and principal component analysis (PCA). A combination of these techniques allowed us to demonstrate that the local emission sources of metals in the particulate matter at Santander city were the most important. Ti, Ni, As and V were identified as the main urban background tracers while Mn and Pb were the main local industrial tracers. The urban background was found to be the major contributor to PM10. The relationship between the emission tracers and the major air pollutants (NO₂, NO, CO, SO₂,O₃ and PM₁₀) was also studied by PCA; a significant relationship between tracers and the major air pollutants was not found, showing a decoupled relationship between major pollutants and metal species in particulate matter.

Mo, Ni, Pb, Ti, V and Zn was investigated in Santander, a Northern Spanish coastal city. Bulk deposition samples were collected monthly for three years using a bottle/funnel device. Taking into account that heavy metals are bioavailable only in their soluble forms, water-soluble and water-insoluble fractions were evaluated separately for element concentration. The fluxes of the studied elements in the bulk deposition exhibited the following order: Zn>Mn>>Cu>Cr>Pb>V>Ni>>As>Mo>Cd. The fluxes of Zn and Mn were more than 10 times higher than those of the other elements, withmaximumvalues of 554.5 and 334.1 µg m-2 day-1, respectively. Low solubilities (below 22%) were found for Cr, Ti and Pb, whereas the highest solubility was found for Zn (78%). With the exception of Cu, all of the studied metals in the water-soluble fraction of the atmospheric deposition showed seasonal dependence, due to the seasonal variability of precipitation. The enrichment factors (EFs) of Cu, Cd and Zn were higher than 100, indicating a clear anthropogenic origin. The EF of Mn (50) was below 100, but an exclusively industrial origin is suggested. Positive Matrix Factorisation (PMF) was used for the source apportionment of the studiedminor and trace elements in the soluble fraction. Four factors were identified from PMF, and their chemical profiles were compared with those calculated from known sources that were previously identified in Santander Bay: two industrial sources, the first of which was characterised by Zn and Mn, which contributes 62.5% of the total deposition flux of the studied elements; a traffic source; and a maritime source. Zinc and Mn are considered to be the most characteristic pollutants of the studied area.The authors are grateful for the financial support from the CTM 2010-16068 project (Spanish Ministry of Science and Innovation)