Modular Method for the Determination of Polycyclic Aromatic Hydrocarbons in Spices and Dried Herbs by Gas Chromatography–Tandem Mass Spectrometry
This paper describes a method for quantification of the four regulated polycyclic aromatic hydrocarbons (PAHs), (benzo[a]anthracene [BaA], chrysene [CHR], benzo[b]fluoranthene [BbF] and benzo[a]pyrene [BaP]), in the wide matrix group of spices and dried herbs by gas chromatography–tandem mass spectrometry (GC–MS/MS). The design of this method was drawn up using basic material and equipment available in most laboratories and a modular clean-up fitting for each category of this very diverse matrix group. The clean-up strategy consists of dividing this matrix group into three subclasses: regular spices, highly pigmented matrices and complex mix of spices/fatty spices. Depending on the subclass, SPE sorbent is adapted to remove maximum of co-extracts and to obtain clean samples. This method has a limit of quantification of 0.5 μg kg−1 for each PAH and the validation criteria fully satisfied the Commission Regulation (EU) No. 836/2011 (< 0.9 μg kg−1). The quantification performed by isotopic dilution allowed the complete correction of matrix effect and led to very good validation data with a mean recovery close to 100% and a within-laboratory reproducibility below 10% (≤ 22% in Regulation (EU) No. 836/2011) for each PAH and for each matrix group at all concentration levels tested. Furthermore, the method’s performance characteristics have been successfully assessed using a representative certified reference material for each subclass and at a level close to the MRL: 10 μg kg−1 for BaP and 50 μg kg−1 for the sum of the 4 PAHs.
KeywordsPAHs Spices Dried herbs Gas chromatography Mass spectrometry
Philippe Szternfeld is grateful to Julie Broos and Suching Chao for the support provided during the development part of this method.
Philippe Szternfeld is grateful to Dr Martin Kaminski (Federal Office of Consumer Protection and Food Safety, Berlin, Germany) and to Dr Martijn van der Lee (RIKILT, Wageningen, The Netherlands) for providing the curry and spirulina samples.
The authors are grateful for the financial support provided by the Belgian Federal Agency for the Safety of the Food Chain (AFSCA-FAVV).
Compliance with Ethical Standards
Conflict of Interest
Philippe Szternfeld declares that he has no conflict of interest. Jessica Marchi declares that she has no conflict of interest. Svetlana V. Malysheva declares that she has no conflict of interest. Laure Joly declares that she has no conflict of interest.
Human and Animal Studies
This article does not contain any studies with human or animal subjects.
- Anastassiades M, Lehotay SJ, Stajnbaher D, Schenck FJ (2003) Fast and easy multiresidue method employing acetonitrile extraction/partitioning and dispersive solid-phase extraction for the determination of pesticide residues in produce. JAOAC 86:412–431Google Scholar
- European Food Safety Authority (2008) Scientific opinion of the panel on contaminants in the food chain. Polycyclic aromatic hydrocarbons in food. The EFSA J 724:1–114Google Scholar
- Hanot V, Goscinny S, Deridder M (2015) A simple multi-residue method for the determination of pesticides in fruits and vegetables using a methanolic extraction and ultra-high-performance liquid chromatography-tandem mass spectrometry: optimization and extension of scope. J Chromatogr A 1384:53–66CrossRefGoogle Scholar
- Hitzel A, Pöhlmann M, Schwägele F, Speer K, Jira W (2013) Polycyclic aromatic hydrocarbons (PAH) and phenolic substances in meat products smoked with different types of wood and smoking spices. Food Chemistry 139(1-4):955–962Google Scholar
- Provoost L (2010). Analysis of PAH4 on Agilent J&W Select PAH. I. Agilent Technologies (Ed.). Available at https://www.agilent.com/cs/library/applications/SI-02451.pdf (accessed on 20 September 2016)
- SANTE/11813/2017 (2017). Guidance document on analytical quality control and validation procedures for pesticide residues analysis in food and feed. SANTE/11813/2017Google Scholar
- The commission of the European Communities (2011a) Commission regulation (EU) No 835/2011 of 19 August 2011 amending Regulation (EC) No 1881/2006 as regards maximum levels for polycyclic aromatic hydrocarbons in foodstuffs. Off J Eur Union L215:4–7Google Scholar
- The commission of the European Communities (2011c) Commission regulation (EU) No 836/2011 of 19 August 2011 amending Regulation (EC) No 333/2007 laying down the methods of sampling and analysis for the official control of the levels of lead, cadmium, mercury, inorganic tin, 3-MCPD and benzo(a)pyrene in foodstuffs. Off J Eur Union L215:9–16Google Scholar
- The commission of the European Communities (2015) Commission regulation (EU) 2015/1933 of 27 October 2015 amending Regulation (EC) No 1881/2006 as regards maximum levels for polycyclic aromatic hydrocarbons in cocoa fibre, banana chips, food supplements, dried herbs and dried spices. Off J Eur Union L 282:11–13Google Scholar
- Van der Lee M, ten Dam G, van der Weg G, Verheijen P, Wenzl T, Peters R (2015). PAH in food supplements Comparison of measurement strategies. EURL workshop for processing contaminants in food 2015 Google Scholar
- Veyrand B, Brosseaud A, Sarcher L, Varlet V, Monteau F, Marchand P, Andre F, le Bizec B (2007) Innovative method for determination of 19 polycyclic aromatic hydrocarbons in food and oil samples using gas chromatography coupled to tandem mass spectrometry based on an isotope dilution approach. J Chromatogr A 1149:333–344CrossRefGoogle Scholar
- Wenzl T, Johannes H, Schaechtele A, Robouch P, Stroka J (2016) Guidance document on the estimation of LOD and LOQ for measurements in the field of contaminants in feed and food. In: EUR 28099. Publications Office of the European Union, LuxembourgGoogle Scholar
- Ziegenhals K, Jira W, Speer K (2007) Analysis of PAH in foodstuffs with priority in the EU in meat products and spices. Fleischwirtschaft 87:98–103Google Scholar