Identification of particulate matter and liquid spills contaminations is essential for many applications, such as forensics, agriculture, security, and environmental protection. For example, toxic industrial compounds deposition in the form of aerosols, or other residual contaminations, pose a secondary, long-lasting health concern due to resuspension and secondary evaporation. This chapter explores several approaches for employing diffuse reflectance spectroscopy in the mid-IR and SWIR to identify particles and films of materials in field conditions. Since the behavior of thin films and particles is more complex compared to absorption spectroscopy of pure compounds, due to the interactions with background materials, the use of physical models combined with statistically-based algorithms for material classification, provides a reliable and practical solution and will be presented.