A liquid chromatography tandem mass spectrometry method for simultaneous analysis of 46 atmospheric particulate-phase persistent organic pollutants and comparison with gas chromatography/mass spectrometry

ABSTRACT

A novel multi-analyte method for the simultaneous determination of 46 compounds of environmental concern, most of them belonging to the category of persistent organic pollutants, was developed using high-performance liquid chromatography and the results were compared to those obtained by gas chromatography. This study was performed in perspective of a cumulative exposure assessment of substances of health concern in environments where high levels, relatively to airborne particulate matter, can be found. The target compounds included polychlorinated biphenyls, brominated flame–retardants and derivatives of polycyclic aromatic hydrocarbons.

The multi-analyte method was evaluated in air particulate matter in terms of reproducibility, linearity, recovery, limits of detection and quantification and matrix effect. The recovery was above 70% for all the analytes, whereas limits of quantification ranged between 23 and 390 pg∙m⁻³ in liquid chromatography and less than ten times in gas chromatography–mass spectrometry.

Matrix effect was generally negligible for both the techniques, except the case of the detection of oxygenated derivatives of polycyclic aromatic hydrocarbons by gas chromatography.

In order to demonstrate the efficacy and to assess the method performances (accuracy and precision), both the techniques were applied to standard reference materials, and the results were compared, discussing their advantages and disadvantages.

The method was finally applied to a real sample of indoor airborne particulate matter with aerodynamic diameter ≤4 μm (PM₄).

We demonstrated that liquid chromatography was the only technique able to analyse the 46 compounds, including thermally degradable ones, with a single chromatographic run without derivatisation steps. On the other hand, gas chromatography still presents higher sensitivity for the detection of some of the investigated compounds. This study can be considered only explorative and further improvements can be expected with new-generation LC-MS instruments (10–100 times more sensitive).

KEYWORDS:

• Persistent organic pollutants
• polychlorinated biphenyls
• brominated flame-retardants
• Oxy-PAHs
• atmospheric particulate matter
• HPLC-MS-MS
• GC-MS

Acknowledgements

This work was supported by ‘Progetto di ricerca Ateneo Sapienza 2016’ and by ‘INAIL/Ricerca Discrezionale /2016-2018/P3O3/UO2.

Disclosure statement

No potential conflict of interest was reported by the authors.

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Funding

This work was supported by the Progetto di ricerca Ateneo Sapienza 2016 [Piccoli progettoi 8A]; INAIL/Ricerca Discrezionale [2016-2018/P3O3/UO2].