Supplementary data Analysis of chemical warfare agents by portable Raman spectrometer with both 785 nm and 1064 nm excitation Tomohide Kondoa,b, Ryota Hashimotoa, Yasuhiko Ohruia,b, Ryoji Sekiokaa,b, Taro Nogamic, Fumihito Mutac, Yasuo Seto*a   aNational Reasearch Institute of Police Science, 6-3-1 Kashiwanoha, Kashiwa, Chiba 277-0882, Japan bTokyo Metropolitan Police Department, 2-1-1 Kasumigaseki, Chiyoda-ku, Tokyo 100-8929, Japan cPortable Analyzer Division, Rigaku Corporation, 4-14-4 Sendagaya, Shibuya-ku, Tokyo 151-0051, Japan *Corresponding author. E-mail address: seto@nrips.go.jp (Y. Seto)

Figure legends Fig. S-1. Raman spectra of 2-chloroacetophenone (recrystallized). The Raman spectra of CN in transparent glass vials were measured with 785 nm excitation. Examples of mal-shaped spectra are shown.. Fig. S-2. Raman spectra of reagent-grade 2-chloroacetophenone. The Raman spectra of the reagent-grade CN sample in the transparent glass vials were measured with excitation of 785 nm and 1064 nm. The laser output power was set at 490 mW, and exposure time was 1000 ms. Two examples are shown with 785 nm excitation.   Fig. S-3. Raman spectra of gasoline. The Raman spectra of gasoline (Esso) in transparent glass vials were measured with excitation of 785 nm and 1064 nm, and with the laser output power and exposure time of 490 mW and 1000 ms, respectively. Fig. S-4. Raman spectra of the mixture of tabun and gasoline (Esso). The Raman spectra of pure GA sample, mixtures of GA with gasoline, and gasoline in transparent glass vials were measured with excitation of 785 nm and 1064 nm. The laser output power was set at 490 mW, and exposure time was 1000 ms. The mixing ratio is represented as v/v percentage, and the spectral matching results are shown as HQI values. Fig. S-5. Raman spectra of the mixture of cyclohexylsarin and gasoline (Esso). The Raman spectra of pure GF sample, mixtures of GF with gasoline, and gasoline in transparent glass vials were measured with excitation of 785 nm and 1064 nm. The laser output power was set at 490 mW, and exposure time was 1000 ms. The mixing ratio is represented as v/v percentage, and the spectral matching results are shown as HQI values. Fig. S-6. Raman spectra of the mixture of mustard gas and gasoline (Esso). The Raman spectra of pure HD sample, mixtures of HD with gasoline, and gasoline in transparent glass vials were measured with excitation of 785 nm and 1064 nm. The laser output power was set at 490 mW, and exposure time was 1000 ms. The mixing ratio is represented as v/v percentage, and the spectral matching results are shown as HQI values. Fig. S-7. Raman spectra of the mixture of nitrogen mustard 1 and gasoline (Esso). The Raman spectra of pure HN1 sample, mixtures of HN1 with gasoline, and gasoline in transparent glass vials were measured with excitation of 785 nm and 1064 nm. The laser output power was set at 490 mW, and exposure time was 1000 ms. The mixing ratio is represented as v/v percentage, and the spectral matching results are shown as HQI values. Fig. S-8. Raman spectra of the mixture of chloropicrin and gasoline (Esso). The Raman spectra of pure PS sample, mixtures of PS with gasoline, and gasoline in transparent glass vials were measured with excitation of 785 nm and 1064 nm. The laser output power was set at 490 mW, and exposure time was 1000 ms. The mixing ratio is represented as v/v percentage, and the spectral matching results are shown as HQI values. Fig. S-9. Raman spectra of chloropicrin measured with excitation of 785 nm and 1064 nm in various amber glass containers (thickness: 0.6 mm; 1.56 mm; 2.5 mm). The spectral matching results are shown as HQI values.

Figure S-1 2nd 3rd Raman shift (cm－1) Raman shift (cm－1) Intensity (count) 1597 258 320 419 616 794 848 872 1001 1032 1162 1212 1401 1693 1780 2nd Raman shift (cm－1) Intensity (count) 237 614 792 1001 1032 1160 1210 1400 1596 1699 3rd

Figure S-2 1064 nm 785 nm 1st 785 nm 2nd Raman shift (cm－1) 318 1598 1695 Raman shift (cm－1) Intensity (count) 252 617 795 1001 1030 1165 1211 1400 785 nm 1st 253 1032 321 621 795 1003 1212 1400 1597 1698 Raman shift (cm－1) Intensity (count) 1064 nm Raman shift (cm－1) Intensity (count) 405 615 793 1000 1029 1211 1595 1698 785 nm 2nd

Figure S-3 785 nm 1064 nm Raman shift (cm－1) Raman shift (cm－1) 521 1001 726 792 1030 1211 1381 1449 Raman shift (cm－1) Intensity (count) 785 nm 516 1674 720 893 1005 1032 1208 1300 1377 1453 1613 Raman shift (cm－1) Intensity (count) 1064 nm 616 786 1254 786

Figure S-4 785 nm 1064 nm 100% 50% 100% 40% 50% 30% 30% 20% 0% 0% Raman shift (cm－1) Intensity 100% 50% 40% 30% 0% 785 nm HQI: <50% HQI: 67% HQI: 81% Raman shift (cm－1) Intensity 100% 50% 30% 20% 0% 1064 nm HQI: <50% HQI: 52% HQI: 90%

Figure S-5 1064 nm 785 nm 100% 100% 50% 50% 30% 20% 20% 10% 0% 0% Raman shift (cm－1) Intensity 1064 nm 100% 50% 20% 10% 0% HQI: <50% HQI: 88% HQI: 97% Raman shift (cm－1) Intensity 785 nm 100% 50% 30% 20% 0% HQI: <50% HQI: 77% HQI: 94%

Figure S-6 785 nm 1064 nm 100% 100% 50% 50% 20% 20% 10% 10% 0% 0% Raman shift (cm－1) Intensity 785 nm 100% 50% 20% 10% 0% HQI: <50% HQI: 55% HQI: 96% Raman shift (cm－1) Intensity 1064 nm 100% 50% 20% 10% 0% HQI: <50% HQI: 65% HQI: 97%

Figure S-7 785 nm 1064 nm 100% 100% 50% 50% 30% 30% 20% 20% 0% 0% Raman shift (cm－1) Intensity 785 nm 100% 50% 30% 20% 0% HQI: <50% HQI: 71% HQI: 89% Raman shift (cm－1) Intensity (count) 1064 nm 100% 50% 30% 20% 0% HQI: <50% HQI: 77% HQI: 94%

Figure S-8 785 nm 1064 nm 100% 50% 20% 10% 0% 100% 50% 20% 10% 0% Raman shift (cm－1) Intensity 785 nm 100% 50% 20% 10% 0% HQI: <50% HQI: 77% HQI: 97% Raman shift (cm－1) Intensity 1064 nm 100% 50% 20% 10% 0% HQI: <50% HQI: 83% HQI: 99%

Figure S-9 785 nm 0.6 mm HQI: 99.5% 1064 nm 0.6 mm HQI: 99.6% 785 nm 434 785 nm 0.6 mm HQI: 99.5% 433 1064 nm 0.6 mm HQI: 99.6% 288 Intensity (count) 841 Intensity (count) 840 287 1309 697 1308 707 1348 1606 1608 1348 Raman shift (cm－1) Raman shift (cm－1) 433 785 nm 1.56 mm HQI: 99.5% 434 785 nm 1.56 mm HQI: 97.7% 279 Intensity (count) 280 845 841 Intensity (count) 710 1308 706 1608 1307 1347 1348 1606 Raman shift (cm－1) Raman shift (cm－1) 840 785 nm 2.5 mm HQI: <50% 434 1064 nm 2.5 mm HQI: 78.8% 432 271 280 846 1307 Intensity (count) Intensity (count) Raman shift (cm－1) Raman shift (cm－1)