Despite the various reduction policies that have been implemented across Europe in the past few years, Particulate Matter (PM) exceedances continue to be recorded. Therefore, with the principal aim to clarify the complex association between emissions and fine particles levels, this work evaluates the impact of the anthropogenic contribution to the fine PM chemical profile. The fieldwork was conducted during March in 2008 and 2013 and covers the periods before and during the economic recession. The experimental data were analyzed in parallel with the emissions from the Flexible Emission Inventory for Greece and the Greater Athens Area (FEI-GREGAA). The differentiation of the mass closure results’ and the aerosols’ character is also discussed in combination with the calculated PM_2.5-Air Quality Indexes. The peak in the PM load and the Particulate Organic Matter (POM) component was recorded in 2013, corresponding to the enhancement of the anthropogenic input. Although the monitoring location is traffic-impacted, the sector of heating, from both wood burning and fossil fuel, proved to be the driving force for the configuration of the obtained PM picture. Especially in 2013, its contribution was two times that of traffic. Finally, the low wind speed values led to the deterioration of the air quality, especially for the sensitive groups.