A Fast Efficient Method to Determine the Presence of Nitrosamines in Cosmetics, Personal Care, and Consumer Products

Importance of the Topic

Consumer products such as cosmetics, personal care items, and elastomeric toys may form carcinogenic N-nitrosamines during manufacture or storage. Monitoring these compounds is critical for ensuring product safety, protecting consumer health, and complying with global regulations limiting nitrosamine levels to 50 µg/kg.

Objectives and Scope of the Study

This study presents a rapid LC-MS method for the simultaneous identification and quantitation of eight volatile and non-volatile N-nitrosamines in cosmetics, personal care products, and infant feeding teats. The goals were to achieve quantitation below regulatory thresholds, reduce analysis time, and incorporate RADAR data acquisition for the discovery of unknown contaminants.

Methodology and Instrumentation

Samples were processed by sonic extraction in organic solvent mixtures, followed by cleanup on Oasis HLB SPE cartridges. Separation was accomplished on an ACQUITY UPLC I-Class System with an HSS T3 column using a 9.1 min gradient. Detection employed a Xevo TQ-S micro mass spectrometer in positive APCI mode with optimized MRM transitions. RADAR acquisition enabled simultaneous full-scan data collection. Data control and quantitation were performed using MassLynx with IntelliStart tuning and TargetLynx processing.

Instrumentation Used

• ACQUITY UPLC I-Class System
• ACQUITY UPLC HSS T3 Column (1.7 µm, 2.1×100 mm)
• Xevo TQ-S micro Mass Spectrometer
• MassLynx MS Software with IntelliStart
• TargetLynx Application Manager
• Oasis HLB SPE Cartridges

Key Results and Discussion

Calibration standards from 0.01 to 0.5 ppm exhibited linear responses (R² > 0.99) and matrix effects below 8 %. All eight nitrosamines were baseline resolved at 50 µg/kg in cosmetic matrices. Analysis of shampoo, hand wash, and lipstick detected no nitrosamines; infant feeding teats showed trace levels well below regulatory limits. Spiked recoveries ranged from 98 % to 102 %. RADAR data from aged lipstick samples revealed an unknown peak at m/z 199, tentatively identified as N-nitrosodiphenylamine, demonstrating the method’s capability for untargeted discovery.

Benefits and Practical Applications

• Single LC-MS method for both volatile and non-volatile nitrosamines without derivatization
• Reduced runtime (9.1 min) and solvent consumption
• Sensitivity below regulatory limits (50 µg/kg)
• Enhanced sample throughput and cost efficiency
• Combined targeted quantitation and untargeted screening via RADAR

Future Trends and Opportunities

Future work may expand the analyte panel, apply high-resolution MS to confirm unknowns, integrate automated online SPE, and extend the approach to a broader range of consumer goods for comprehensive safety profiling.

Conclusion

A robust LC-APCI-MS workflow was developed for rapid, sensitive quantitation of eight N-nitrosamines in consumer products. The method meets regulatory requirements, improves throughput, minimizes solvent use, and enables discovery of novel contaminants through RADAR acquisition.

Reference

1. Ashley LM, Halver JE. J Natl Cancer Inst. 1968;41(2):531–552.
2. Barnes JM, Magee PN. Br J Ind Med. 1954;11(3):167–174.
3. Jakszyn P, González CA. World J Gastroenterol. 2006;12(27):4296.
4. Douglass M et al. J Soc Cosmet Chem. 1978;29(9):581–606.
5. Regulation (EC) No 1223/2009. Off J Eur Union. 2009;L342:59–209.
6. Matyska MT, Pesek JJ, Yang L. J Chromatogr A. 2000;887(1):497–503.
7. US FDA, Fed Reg 44. 1979:21365.
8. US FDA, Fed Reg 58. 1983:28288–28292.
9. ASEAN Cosmetics Directive. 2005.
10. Directive 2009/48/EC. Off J Eur Union. 2009;L170:1–37.
11. Ma Q et al. Chin J Anal Chem. 2011;39(8):1201–1207.
12. Flower C et al. Int J Cosmet Sci. 2009;28(1):21–33.
13. Schothorst R, Somers H. Anal Bioanal Chem. 2005;381(3):681–685.
14. Schothorst RC, Stephany RW. Int J Cosmet Sci. 2001;23(2):109–114.
15. Stepanov I et al. J Agric Food Chem. 2002;50(10):2793–2797.
16. Al-Kaseem M et al. Pharmacol Pharm. 2014;5(3):11.
17. Krul CA et al. Food Chem Toxicol. 2004;42(1):51–63.