Abstract
A procedure to evaluate matrix effects was systematized and applied to the analysis of polycyclic aromatic hydrocarbons in roasted coffee and cocoa beans. The analytical method relied on gas chromatography coupled to mass spectrometry with isotope dilution (GC-IDMS). Once the regression assumptions were confirmed, the slopes and intercepts obtained for traditional and matrix-matched calibration curves were compared by the t test, with or without combined variances, depending on the profile of the residual variances. Matrix effects were considered when the slopes and/or intercepts differed significantly. The occurrence of matrix effects diverged for the studied matrices. No matrix effects were detected for roasted coffee using GC-IDMS, whereas significant effects were observed for cocoa beans. An original discussion related to these findings was presented, based on the differences in the chemical compositions of the matrices and the instrumental conditions. These results serve as a warning to current practices in validation of methods that involve IDMS and highlight the importance of the matrix effects evaluation, even when using an isotope dilution approach.
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References
Alonso JIG, Rodríguez-González P (2013) Isotope dilution mass spectrometry. Royal Society of Chemistry, Cambridge
Armitage P, Berry G, Matthews JNS (2002) Statistical methods in medical research. Blackwell Science Ltd., Oxford
Badolato ESG, Martins MS, Pimentel SA, Alaburda J, Kumagai EE, Baptista GG, Rosenthal A (2006) Sistematic study of benzo[a]pyrene in coffee samples. J Braz Chem Soc 17:989–993
Belo RFC, Nunes CM, Santos EV, Augusti DV, Pissinatti R (2012) Single laboratory validation of a SPE method for the determination of PAHs in edible oils by GC-MS. Anal Methods 4:4068–4076
Bordajandi LR, Dabrio M, Ulberth F, Emons H (2008) Optimisation of the GC-MS conditions for the determination of the 15 EU foodstuff priority polycyclic aromatic hydrocarbons. J Sep Sci 31:1769–1778
Bruce P, Minkkinen P, Riekkola ML (1998) Practical method validation: validation sufficient for an analysis method. Mikrochim Acta 128:93–106
Camargo MCR, Toledo MCF (2002) Chá-mate e café como fontes de hidrocarbonetos policíclicos aromáticos (HPAS) na dieta da população de Campinas. Ciênc Tecnol Aliment 22:49–53
Cardone MJ (1986) New technique in chemical assay calculations. 2. Correct solution of the model problem and related concepts. Anal Chem 58:438–445
Caruso MSF, Alaburda J (2008) Hidrocarbonetos policíclicos aromáticos—benzo(a)pireno: uma revisão. Rev Inst Adolfo Lutz 67:1–27
Coelho AV, Franco CMF (2013) Tandem mass spectrometry—molecular characterization. InTech, Rijeka
Cuadros-Rodríguez L, García-Campaña AM, Almansa-López E, Egea-González FJ, Cano LC, Frenich AG, Martínez-Vidal JL (2003) Correction function on biased results due to matrix effects—application to the routine analysis of pesticide residues. Anal Chim Acta 478:281–301
Diletti G, Scortichini G, Scarpone R, Gatti G, Torreti L, Migliorati G (2005) Isotope dilution determination of polycyclic aromatic hydrocarbons in olive pomace oil by gas chromatography–mass spectrometry. J Chromatogr A 1062:247–254
EC (European Commission) (2002) Commission decision no. 2002/657/EC (performance of analytical methods and the interpretation of results). OJ L-221:8–36
EFSA (European Food Safety Authority) (2008) Scientific opinion of the panel on contaminants in the food chain on a request from the European Commission on polycyclic aromatic hydrocarbons in food. The EFSA Journal 724:1–114
Ellison SLR, Thompson M (2008) Standard additions: myth and reality. Analyst 133:992–997
Erney DR, Gillespie AM, Gilvydis DM, Poole CF (1993) Explanation of the matrix-induced chromatographic response enhancement of organophosphorus pesticides during open tubular column gas chromatography with splitless or hot on-column injection and flame photometric detection. J Chromatogr A 638:57–63
EU (European Union) (2011) Commission regulation no. 835/2011/EU (maximum levels for polycyclic aromatic hydrocarbons in foodstuffs). OJ L-215:4–8
Eurachem (2014) Eurachem guide: the fitness for purpose of analytical methods—a laboratory guide to method validation and related topics. In: Magnusson B, Örnemark U (ed) Eurachem Guide: The Fitness for Purpose of Analytical Methods – A Laboratory Guide to Method Validation and Related Topics, 2nd edn. http://www.eurachem.org. Accessed 10 Apr 2015
González FJE, Hernández MET, López EA, Cuadros-Rodríguez L, Vidal JLM (2002) Matrix-effects of vegetable commodities in electron-capture detection applied to pesticide multiresidue analysis. J Chromatogr A 966:155–165
González-Gago A, Brandsma SH, Leonards PEG, de Boer J, Marchante-Gayón JM, Alonso JIG (2011) Determination of ultra-trace levels of priority PBDEs in water samples by isotope dilution GC(ECNI)MS using 81Br-labelled standards. Anal Bioanal Chem 401:2639–2649
Hajšlová J, Čajka T (2007) Gas chromatography-mass spectrometry (GC-MS). In: Picó Y (ed) Food toxicants analysis: techniques, strategies and developments, 1st edn. Elsevier, Amsterdam, pp. 419–471
Hajšlová J, Zrostlíková J (2003) Matrix effects in (ultra) trace analysis of pesticide residues in food and biotic matrices. J Chromatogr A 1000:181–197
Hewavitharana AK (2011) Matrix matching in liquid chromatography–mass spectrometry with stable isotope labelled internal standards—is it necessary? J. Chromatogr A 1218:359–361
Horwitz W (2003) Validation: an invisible component of measurement. AOAC Int, Arlington http://www.aoac.org. Accessed 25 Jan 2005
Lee K, Shin H (2010) Determination of polycyclic aromatic hydrocarbons in commercial roasted coffee beans. Food Sci Biotechnol 16:1435–1440
Li XQ, Yang Z, Zhang QH, Li HM (2014) Evaluation of matrix effect in isotope dilution mass spectrometry based on quantitative analysis of chloramphenicol residues in milk powder. Anal Chim Acta 807:75–83
Pihlström T, Fernández-Alba AR (2013) European Commission, Health & Consumer Protection Directorate-General. Guidance document on analytical quality control and validation procedures for pesticide residues analysis in food and feed (SANCO/12571/2013). http://ec.europa.eu/food/plant/pesticides/guidance_documents/docs/qualcontrol_en.pdf. Accessed 04 July 2014
Pissinatti R, Nunes CM, Souza AG, Junqueira RG, Souza SVC (2015) Simultaneous analysis of 10 polycyclic aromatic hydrocarbons in roasted coffee by isotope dilution gas chromatography-mass spectrometry: optimization, in-house method validation and application to an exploratory study. Food Control 51:140–148
Plaza-Bolaños P, Frenich AG, Martínez Vidal JL (2010) Polycyclic aromatic hydrocarbons in food and beverages. Analytical methods and trends. J Chromatogr A 1217:6303–6326
Rodríguez-González P, Marchante-Gayón JM, Alonso JIG, Sanz-Medel A (2005) Isotope dilution analysis for elemental speciation: a tutorial review. Spectrochim Acta B 60:151–207
Sánchez-Brunete C, Miguel E, Tadeo JL (2007) Analysis of 27 polycyclic aromatic hydrocarbons by matrix solid-phase dispersion and isotope dilution gas chromatography-mass spectrometry in sewage sludge from the Spanish area of Madrid. J Chromatogr A 1148:219–227
Sargent M, Harte R, Harrington C (2002) Guidelines for achieving high accuracy in isotope dilution mass spectrometry (IDMS). Royal Society of Chemistry, Cambridge
SCF (Scientific Committee on Food) (2002) Opinion of the scientific committee on food on the risks to human health of polycyclic aromatic hydrocarbons in food. http://ec.europa.eu/food/fs/sc/scf/out153_en.pdf. Accessed 20 May 2010
Snedecor GW, Cochran WG (1989) Statistical methods. Iowa State University, Ames
Souza SVC, Junqueira RG (2005) A procedure to assess linearity by ordinary least squares method. Anal Chim Acta 552:25–35
Thompson M, Ellison SLR, Wood R (2002) Harmonized guidelines for single-laboratory validation of methods of analysis. Pure Appl Chem 74:835–855
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 1149:333–344
Wang JH, Guo C (2010) Ultrasonication extraction and gel permeation chromatography clean-up for the determination of polycyclic aromatic hydrocarbons in edible oil by an isotope dilution gas chromatography–mass spectrometry. J Chromatogr A 1217:4732–4737
Wenzl T, Simon R, Kleiner J, Anklam E (2006) Analytical methods for polycyclic aromatic hydrocarbons (PAHs) in food and the environment needed for new food legislation in the European Union. Trend Anal Chem 25:716–725
Yarita T, Aoyagi Y, Otake T (2015) Evaluation of the impact of matrix effect on quantification of pesticides in foods by gas chromatography–mass spectrometry using isotope-labeled internal standards. J Chromatogr A 1396:109–116
Yu L, Cao Y, Zhang J, Cui Z, Sun H (2012) Isotope dilution-GC-MS/MS analysis of 16 polycyclic aromatic hydrocarbons in selected medicinal herbs used as health food additives. Food Addit Contam Part A 29:1800–1809
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The authors acknowledge the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) and the CNPq (Proc. 306463/2010-5) for their financial support as well as the Mars Center of Cocoa Science (MCCS) in Brazil for providing the cocoa bean samples.
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Renata França Cassimiro Belo declares that she has no conflict of interest. Rafael Pissinatti declares that he has no conflict of interest. Scheilla Vitorino Carvalho de Souza declares that she has no conflict of interest. Roberto Gonçalves Junqueira declares that he has no conflict of interest.
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Belo, R.F.C., Pissinatti, R., de Souza, S.V.C. et al. Evaluating Matrix Effects in the Analysis of Polycyclic Aromatic Hydrocarbons from Food: Can These Interferences Be Neglected for Isotope Dilution?. Food Anal. Methods 10, 1488–1499 (2017). https://doi.org/10.1007/s12161-016-0706-0
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DOI: https://doi.org/10.1007/s12161-016-0706-0