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Analysis of Primary Aromatic Amines in Cosmetics and Personal Care Products Using the ACQUITY UPLC H-Class System with the ACQUITY QDa Detector and Empower 3 Software

Applications | 2015 | WatersInstrumentation
LC/MS, LC/SQ
Industries
Other
Manufacturer
Waters

Summary

Importance of the topic


Primary aromatic amines (PAAs) are widely used feedstocks in dyes, polymers and pharmaceuticals but pose serious health risks due to their potential carcinogenicity. Regulatory bodies such as the EU Cosmetics Regulation prohibit PAAs in finished consumer products. Accurate, rapid analysis of trace-level PAAs in cosmetics is therefore critical for product safety and compliance.

Study objectives and overview


This work presents a streamlined UPLC-MS workflow for the identification and quantification of 30 PAAs in cosmetics and personal care matrices. By coupling the Waters ACQUITY UPLC H-Class System with the ACQUITY QDa Detector under Empower 3 control, the method aims to reduce analysis time, enhance selectivity and sensitivity, and eliminate labor-intensive sample derivatization.

Methodology and instrumentation


  • Liquid chromatography: BEH C18 column (1.7 µm, 2.1 × 50 mm), 40 °C, 10 min runtime; mobile phases A (water + 0.1% formic acid) and B (methanol + 0.1% formic acid); gradient elution at 0.4 mL/min; 10 µL injection.
  • Mass detection: ACQUITY QDa in ESI+ mode; capillary voltage 0.8 kV; probe 450 °C; Selected Ion Recording for targeted masses.
  • Sample preparation: 0.5 g (solid) or 0.5 mL (liquid) sample with 8 mL water and 2 mL methanol, vortex 2 min, centrifuge, dilute 1:3 with methanol prior to injection.

Main results and discussion


All 30 target PAAs eluted within a 10-minute window with baseline resolution. Mass detection enabled unambiguous peak tracking and co-elution identification compared to UV alone. Calibration was linear from 0.001 to 1.0 µg/mL (0.08–80 mg/kg), and method precision met regulatory requirements. Fortified shampoo, blush and eyeshadow samples showed recoveries between 72% and 104%, demonstrating minimal matrix effects and robust quantification.

Benefits and practical applications


  • High throughput: 10 min analysis per sample without derivatization.
  • Reduced solvent consumption and simplified workflow.
  • Reliable mass confirmation increases confidence in PAA identification.
  • Empower 3 software ensures streamlined data acquisition, processing and reporting.

Future trends and applications


Emerging high-resolution MS detectors will further improve specificity. Automation of sample preparation could increase laboratory throughput. Expanding the PAA panel to include novel impurities and degradation products will support evolving regulatory frameworks. Portable UPLC-MS systems may enable on-site screening in manufacturing environments.

Conclusion


The described UPLC-QDa method delivers a fast, sensitive and cost-effective solution for routine screening of PAAs in cosmetic matrices. It addresses previous limitations in robustness and selectivity, ensuring compliance with safety regulations and protecting consumer health.

References


  1. Benigni R, Passerini L. Carcinogenicity of the aromatic amines: from structure-activity relationships to mechanisms of action and risk assessment. Mutation Research. 2002;511:191–206.
  2. Anirban MP, Cote RJ. Molecular Pathogenesis and Diagnosis of Bladder Cancer. Annu Rev Pathol. 2009;4:501–506.
  3. Ward E, Carpenter A, Markowitz S, et al. Excess Cancers in Workers Exposed to Ortho-Toluidine and Aniline. Natl Cancer Inst. 1991;83(7):501–506.
  4. Regulation (EC) No 1223/2009 of the European Parliament and of the Council on Cosmetic Products. Official Journal of the European Union. 2009;L342:59–209.
  5. Akyuz M, Ata S. Determination of aromatic amines in hair dye and henna samples by ion-pair extraction and GC-MS. J Pharm Biomed Anal. 2008;47:68–74.
  6. Ekladius L, King HK. A colorimetric method for the determination of aliphatic amines in the presence of ammonia. J Chrom A. 2006;1129(1).
  7. Aznar M, Canallas E, Nerin C. Quantitative determination of 22 PAAs by cation-exchange SPE and LC-MS. J Chrom A. 2009;1216:5176–5181.
  8. Zhang Q, Wang C, et al. Determination of aromatic amines from azo dyes by liquid-phase sorbent trapping and thermal desorption-GC-MS. J Sep Sci. 2009;32:2434–2441.

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