Analysis of Altoids® Smalls Sugar Free Wintergreen Mints Paul Tschida and Terilyn Lawson University of Alaska Fairbanks, Department of Chemistry and Biochemistry Chemistry 413W Spring 2013

Colors Introduction Methods Plastic Altoids® mints were developed in the early 1800’s and were Methods Dye analysis of the Altoids® was carried out by using a Hewlett- originally marketed as a calmative agent. In 1997, Analysis of the Altoids® plastic wrap Identity of the Altoids® plastic wrap. Packard 8452A Ultraviolet-Visable spectrometer (UV-Vis). The wintergreen-flavored Altoids® were released, followed by the a was carried out using a Nicolet 6700 resulting spectrum was compared to the calibration curves of Blue 1 Percent Similarity Material sugar-free line of wintergreen mints. The goal of this project was Fourier Transform-Infrared 90.08 Polyethylene and Blue 2 to determine the concentration of each in the mint. Spectrometer (FT-IR). The resulting identify and quantify the flavors, colors, plastics and metals used 89.35 Triacontane An image of the mint was captured using ISI-SR-50 Scanning Electron in this consumer product. spectrum was compared to the 89.20 Polyethylene

spectra of various plastic standards, 88.83 Low-density polyethylene Microscope with Backscatter Electrons dectection (SEM-BSE) The table below shows a summary of the ingredients identified along with spectra in the instrument’s 49.02 Low-density polyethylene Blue 1 in the mints and the instruments used in the analysis. Blue 2 library. Ingredient Structure Purpose Instrument Conclusion

Sorbitol is present in the Sweetener NMR mints.

Methyl salicylate is the Natural and Flavor GC-MS and flavoring agent in the Artificial Flavors Additive NMR mints.

Titanium Dioxide Color Present in the mints and in XRF Additive the paint.

The concentration in the SEM-BSE image of the Altoids® mint. Blue 1 Color UV-Vis spectra of Altoids® solution and dye standards. UV-Vis mints is 2.92 +/- 0.002 Additive Comparison of Blue 1 and Blue 2 dye data in the Altoids® mint. ppm. Brilliant Blue (Blue 1) Indigo Carmine (Blue 2) Color The concentration in the λmax (nm) 629 610 Blue 2 UV-Vis Conclusion: The Additive mints is 293 +/- 1.0 ppm. Molar Absorptivity 6 2 1.3 x 10 1.08 x 10 mints contain 2.92 (1/M∙cm) FT-IR spectra of the Altoids® plastic wrap and plastic standards. 6 -4 Sweetener HPLC and ppm Blue 1 and 293 Calibration Equation y = (1.3x10 )x + (2x10 ) y = (108.41)x + (0.0171) Sucralose Below detection limit. 2 Additive NMR Conclusion: The Altoids® plastic wrap is most likely composed of ppm Blue 2. R 1 0.9876 % of Altoids peak 90.28 9.37 References: . (2013). Altoids faq. polyethylene or low-density polyethlylene. [dye] in Altoids® (ppm) 2.92 ± 0.002 293 ± 1.0 References: Hogan, T. A. (2001). Plastics analysis. Midland, MI: Society of Plastics Engineers. Terilyn Lawson (actor) & Paul Tschida (voice-over). (2013). Plastics prep. Available from Youtube.com References: US FDA. (2013, March 03). Overview of food ingredients, additives & colors. Flavors Elemental composition of the Methods Altoids® container.

Gas Chromatography-Mass Spectrometry (GC-MS) headspace Element Concentration analysis was performed on powered mints and flavor standards (wt/wt%) using an Agilent 5975 GC-MS. Fe (Flame AA) 97.3 ± 11.0 Fe (XRF Handheld) 98.76 ± 0.25 An aqueous mint solution and sweetener standards were Cr (XRF Handheld) 0.08 ± 0.03 analyzed by an Agilent 1100 High Performance-Liquid Mn (XRF Handheld) 0.27 ± 0.03 Chromatography (HPLC) instrument with an Evaporative Light Sn (XRF Handheld) 0.68 ± 0.03 Scattering Detector.

Analysis was performed on the mints in deuterated DMSO using a Bruker AV-600 NMR. Metals SEM-BSE Image of the Altoids® container. Methods A small piece of the Altoids® container was digested

with HNO3 and dilute solutions were prepared and analysis was carried out on an Perkin-Elmer 800 Atomic Absorption Spectrometer and an Agilent 7500ce ICP-MS. Results Methyl Saliclyate Analysis of the metal container was carried out using an ISI-SR-50 Scanning Electron Microscope with Energy SEM-EDS elemental analysis spectrum of the Altoids® container. Methyl Saliclyate Dispersive X-Ray Spectroscopy and Backscattered Electrons detection (SEM-EDS, SEM-BSE) Ti Kα

GC-MS chromatograms of Altoids® mints and flavor standards. Mass spectrum of the Altoids® mints, the component is identified as Methyl Salicylate (Wintergreen). A handheld X-Ray Fluorescence (XRG analysis was preformed on the Altoids® container and Altoids® mint Ti Kβ pellet was analyzed with a Pan Alytical Axios XRF. Maltodextrin or Methyl Saliclyate Sorbitol Dextrose? Conclusion: The container is primarily composed of iron, with some titanium in the paint. The mints contains titanium, most likely in the form of titanium Sucrose dioxide. Bulk XRF K energy spectrum of the Altoids® mints. References: Myers, D. (2010). The color of art: Pigment metal, minerals, inert pigments, paint additives and oil paint driers. Clem, D. (2009). Pigments. Acknowledgments HPLC chromatograms of Altoids ® mints and sweetener standards. 1H NMR spectrum of Altoids® mints in d6 -DMSO. Thank you to Dr. Sarah Hayes and Amanda Barker for their patience and continuous help during the semester, Dr. Maciej Sliwinski for his XRF expertise, The mints contain methyl salicylate, sorbitol and possibly maltodextrin or dextrose. Conclusion: Michael Jaramillo for HPLC expertise , Dr. Carl Murphy for his NMR expertise. References: Junginger, S. and Korte, E. (2011). Analyzing synthetic sweeteners in waste water with robust sample preparation. Agilent Technologies. and Advanced Instrumentation Laboratory for use of their instrumentation.