Identification of Cigarette Ashes by Direct Analysis in Real Time Mass Spectrometry (DART-MS)

Identification of Cigarette Ashes by Direct Analysis in Real Time Mass Spectrometry (DART-MS)

Xiaokun Duan, Charles C. Liu
ASPEC Technologies Ltd., Beijing, CHINA.

First presented: ASMS, Baltimore USA. June 2025

Overview

This study establishes a Direct Analysis in Real Time Mass Spectrometry (DART-MS) method for rapid identification and classification of cigarette ashes. By analyzing 30 cigarette ash samples and 40 interference ash samples (e.g., pine needles, ginkgo leaves), two pretreatment methods were compared: direct acidification (10% H₃PO₄) and water-acidification. Data acquired using an Agilent 6550 Q-TOF MS in positive ion mode were processed via AnalyzerPro® XD. Volcano plots and PCA revealed distinct chemical markers (e.g., m/z 272.19, 324.27) differentiating cigarette ashes from interference materials. The method demonstrates high specificity and efficiency, offering a novel tool for forensic fire investigations and tobacco quality control.

Introduction

Cigarette ash analysis is critical for identifying fire causes, forensic investigations, and monitoring tobacco product authenticity. Traditional methods for ash characterization are time-consuming and lack specificity. Direct Analysis in Real Time Mass Spectrometry (DART-MS), a rapid and solvent-free technique, enables direct analysis of complex matrices without chromatographic separation. This study pioneers the application of DARTMS for cigarette ash profiling. By comparing two pretreatment protocols and analyzing chemical fingerprints, we aim to: (1) differentiate cigarette ashes from plant-based
interference ashes and (2) classify cigarette types using unique markers. The results highlight DART-MS’s potential as a high-throughput solution for real-world applications.

Material and Methods

I. Cigarette ash samples from 30 commercial brands, and 40 interference ash samples like pine needles, ginkgo leaves, etc. were both sourced from Shenyang Fire Research Institute.

II. A DART Source (IonSense, Saugus, MA, USA) coupled to an Agilent 6550 Q-TOF through a VAPUR Interface (IonSense) was employed with the conditions as follows: helium as working gas, heater temperature at 300℃, rail speed at 0.6 mm·s-1. The pre-treated sample solutions were analyzed by DIP-it module. MS was operated at either positive or negative mode and full scan data were acquired by MassHunter. AnalyzorPro XD software (SpectralWorks, UK) was used for data processing.

III. Both cigarette and interference ash samples were pre-treated with the following method:
10 μg of ash was dissolved in 200 μL of water, vortexed for 30 seconds, and allowed to stand for 30 minutes. The ashes were filtered, then dissolved in 200 μL of 10% phosphoric acid, vortexed, and allowed to stand for 30 minutes.

Results

Conclusions

DART-MS successfully discriminates cigarette ashes from plant-based interference ashes using key markers (I 272.19, 324.27, etc.) and PCA analysis. Water-acidification enhanced sensitivity, extracting 30% more markers than direct acidification. Cigarette-specific ions (e.g. m/z 127.02 for Ash 24; m/z 733–904 for Ash 28) were validated via XIC. This protocol providesa rapid, reliable approach for forensic ash identification and tobacco industry quality assurance.