Raman spectroscopy for detection of ammonium nitrate as an explosive precursor used in improvised explosive devices

Raman spectroscopy was evaluated as a sensor for detection of ammonium nitrate (NH₄NO₃, AN), fuel oil (FO), AN-water solutions, and AN- and FO-soil mixtures deposited on materials such as glass, synthetic fabric, cardboard and electrical tape to simulate field conditions of explosives detection. AN is an inorganic oxidizing salt that is commonly used in fertilizers and mining explosives, however, due to its widespread accessibility, AN-based explosives are also utilized for the manufacture of improvised explosive devices (IED). Pure AN crystals were ground to powder size and deposited on several substrates for Raman analysis, whereas FO was analysed in a quartz cuvette. To simulate field conditions samples of powdered AN, AN-water solutions (0.1% to 10.0% AN w/w), AN-soil (50% to 90% AN w/w) and FO-soil (50% to 75% FO w/w) were prepared and deposited on the clutter materials. Raman spectra were acquired at integration times between 0.1 and 30 s, and 3 replicate Raman measurements were carried out for each sample. The spectral window observed ranged from 300 to 3800 cm^-1. Several characteristic Raman bands were found, namely, at 710 cm^-1 (NO₃^-) and 1040 cm^-1 (NO₃^-) for AN; 1440-1470 cm^-1 (CH) and 2800-3000 cm^-1 (CH) for FO; 3000-3500 cm^-1 (OH) for water; and 615 cm^-1 (CCl), 1254 cm^-1 (CH), 1400 cm^-1 (CH₂) and 1600 cm^-1 (aromatic ring) for polyvinyl chloride (PVC, electrical tape). The effect of the AN concentration and integration time on the total and net Raman intensities, relative standard deviation, signal-to-noise ratio and relative limit of detection was evaluated. The relative limit of detection of AN in water was 0.1% (1 mg/g), and absolute limit of detection was 1.0 μg. The optimum integration time (≈10 s) for the Raman sensor to capture the analyte signals was estimated based on the Raman figures of merit as a function of the integration time.