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PTR-ToF-MS, A Novel, Rapid, High Sensitivity and Non-Invasive Tool to Monitor Volatile Compound Release During Fruit Post-Harvest Storage: The Case Study of Apple Ripening

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Abstract

In the present study, the potential of PTR-ToF-MS for addressing fundamental and technical post-harvest issues was tested on the non-destructive and rapid monitoring of volatile compound evolution in three apple cultivars (‘Golden Delicious’, ‘Braeburn’ and ‘Gold Rush’) during 25 days of post-harvest shelf life ripening. There were more than 800 peaks in the PTR-ToF-MS spectra of apple headspace and many of them were associated with relevant compounds. Besides the ion produced upon proton transfer, we used the ion at mass 28.031 (C2H +4 ) produced by charge transfer from residual O +2 as a monitor for ethylene concentration. ‘Golden Delicious’ apples were characterised by higher ethylene emission rates than ‘Gold Rush’ and ‘Braeburn’, and quantitative comparison has been supported by two segment piecewise linear model fitting. Ester evolution during post-harvest ripening is strongly dependent on endogenous ethylene concentration levels. For ‘Golden Delicious’ and ‘Braeburn’, sesquiterpenes (alpha-farnesene) exhibited a fast response to ethylene emission followed by a rapid decline after the endogenous ethylene maximum peak. Carbonyl compounds displayed a different time evolution as compared to esters and terpenes and did not show any evident relationship with ethylene. Methanol and ethanol concentrations during the entire storage period did not change significantly. We show how multivariate analysis can efficiently handle the large datasets produced by PTR-ToF-MS and that the outcomes obtained are in agreement with the literature. The different volatile compounds could be simultaneously monitored with high time resolution, providing advantages over the more established techniques for the investigation of VOC dynamics in fruit post-harvest storage trials.

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References

  • Aprea, E., Biasioli, F., Märk, T. D., & Gasperi, F. (2007). PTR-MS study of esters in water and water/ethanol solutions: fragmentation patterns and partition coefficients. International Journal of Mass Spectrometry, 262, 114–121.

    Article  CAS  Google Scholar 

  • Barry, C. S., & Giovannoni, J. J. (2007). Ethylene and fruit ripening. Journal of Plant Growth Regulation, 26, 143–159.

    Article  CAS  Google Scholar 

  • Biasioli, F., Gasperi, F., Aprea, E., Colato, L., Boscaini, R., & Märk, T. D. (2003). Fingerprinting mass spectrometry by PTR-MS: heat treatment vs. pressure treatment of red orange juice—A case study. International Journal of Mass Spectrometry, 223–224, 343–353.

    Article  Google Scholar 

  • Biasioli, F., Gasperi, F., Yeretzian, C., & Märk, T. D. (2011a). PTR-MS monitoring of VOCs and BVOCs in food science and technology. TrAC Trends in Analytical Chemistry, 30, 968–977.

    Article  CAS  Google Scholar 

  • Biasioli, F., Yeretzian, C., Märk, T. D., Dewulf, J., & Van Langenhove, H. (2011b). Direct-injection mass spectrometry adds the time dimension to (B)VOC analysis. TrAC Trends in Analytical Chemistry, 30, 1003–1017.

    Article  CAS  Google Scholar 

  • Blake, R. S., Monks, P. S., & Ellis, A. M. (2009). Proton-transfer reaction mass spectrometry. Chemical Reviews, 109, 861–896.

    Article  CAS  Google Scholar 

  • Bleecker, A., & Kende, H. (2000). Ethylene: a gaseous signal molecule in plants. Annual Review of Cell and Developmental Biology, 16, 1–18.

    Article  CAS  Google Scholar 

  • Boschetti, A., Biasioli, F., van Opbergen, M., Warneke, C., Jordan, A., & Holzinger, R. (1999). PTR-MS real time monitoring of the emission of volatile organic compounds during postharvest aging of berryfruit. Postharvest Biology and Technology, 17, 143–151.

    Article  CAS  Google Scholar 

  • Brackmann, A., Streif, J., & Bangerth, F. (1993). Relationship between a reduced aroma production and lipid metabolism of apples after long-term controlled atmosphere storage. Journal of American Society of Horticulture Science, 118, 243–247.

    CAS  Google Scholar 

  • Buhr, K., van Ruth, S., & Delahunty, C. (2002). Analysis of volatile flavour compounds by proton transfer reaction mass spectrometry: Fragmentation patterns and discrimination between isobaric and isomeric compounds. International Journal of Mass Spectrometry, 221(1), 1–7.

    Article  CAS  Google Scholar 

  • Cappellin, L., Biasioli, F., Granitto, P. B., Schuhfried, E., Soukoulis, C., Costa, F., et al. (2011). On data analysis in PTR-TOF-MS: from raw spectra to data mining. Sensors and Actuators B: Chemical, 155, 183–190.

    Article  CAS  Google Scholar 

  • Cappellin, L., Karl, T., Probst, M., Ismailova, O., Winkler, P. M., Soukoulis, C., et al. (2012). On quantitative determination of volatile organic compound concentrations using proton transfer reaction time-of-flight mass spectrometry. Enviromental Science Technology. doi:10.1021/es203985t. In press.

  • Cappellin, L., Probst, M., Limtrakul, J., Biasioli, F., Schuhfried, E., Soukoulis, C., et al. (2010). Proton transfer reaction rate coefficients between H3O + and some sulphur compounds. International Journal of Mass Spectrometry, 295(1–2), 45–48.

    Google Scholar 

  • Costa, F., Sara, S., Van de Weg, W. E., Guerra, W., Cecchinel, M., Dallavia, J., et al. (2005). Role of the genes Md-ACO1 and Md-ACS1 in ethylene production and shelf life of apple (Malus × domestica Borkh). Euphytica, 141, 181–190.

    Article  CAS  Google Scholar 

  • Costa, F., Peace, C. P., Stella, S., Musacchi, S., Bazzani, M., Sansavini, S., et al. (2010). QTL dynamics for fruit firmness and softening around an ethylene dependent polygalacturonase gene in apple (Malus × domestica Borkh.). Journal of Experimental Botany, 61, 3029–3039.

    Article  CAS  Google Scholar 

  • de Vries, H. S. M., Wason, M. A. J., Harren, F. J. M., Woltering, E. J., van der Valk, H. C. P. M., & Reuss, J. (1996). Ethylene and CO2 emission rates and pathways in harvested fruits investigated, in situ, by laser photo deflection and photoacoustic techniques. Postharvest Biology and Technology, 8, 1–10.

    Article  Google Scholar 

  • Defilippi, B. G., Dandekar, A. M., & Kader, A. A. (2004). Impact of suppression of ethylene action or biosynthesis on flavor metabolites in apples (Malus domestica Borkh) fruits. Journal of Agricultural and Food Chemistry, 52, 5694–5701.

    Article  CAS  Google Scholar 

  • Defilippi, B. G., Dandekar, A. M., & Kader, A. A. (2005). Relationship of ethylene biosynthesis to volatile production, related enzymes and precursor availability in apple peel and flesh tissues. Journal of Agricultural and Food Chemistry, 53, 3133–3141.

    Article  CAS  Google Scholar 

  • Dixon, J., & Hewett, E. W. (2000). Factors affecting aroma/flavour volatile concentration: a review. New Zealand Journal of Crop Horticulture, 28, 155–173.

    Article  CAS  Google Scholar 

  • Dunemann, F., Ulrich, D., Malysheva-Otto, L., Weber, W. E., Longhi, S., Velasco, R., et al. (2012). Functional allelic diversity of the apple alcohol acyl-transferase gene MdAAT1 associated with fruit ester volatile contents in apple cultivars. Molecular Breeding, 29, 609–6250.

    Article  CAS  Google Scholar 

  • Echeverria, G., Graell, J., Lopez, M. L., & Lara, I. (2004). Volatile production, quality and aroma related enzyme activities during maturation of ‘Fuji’ apples. Postharvest Biology and Technology, 31, 217–227.

    Article  CAS  Google Scholar 

  • Ennis, C., Reynold, J., Keely, B. J., & Carpenter, L. J. (2005). A hollow cathode proton transfer reaction time of flight mass spectrometer. International Journal of Mass Spectrometry, 247, 72–80.

    Article  CAS  Google Scholar 

  • Fabris, A., Biasioli, F., Granitto, P., Aprea, E., Cappellin, L., Schuhfried, E., et al. (2010). PTR-TOF-MS and data mining methods for rapid characterization of agro-industrial samples: Influence of milk storage conditions on the volatile profile of Trentingrana cheese. Journal of Mass Spectrometry, 45, 1065–1074.

    Article  CAS  Google Scholar 

  • Fellman, J. K., Miller, T. W., Mattinson, D. S., & Mattheis, J. P. (2000). Factors that influence biosynthesis of volatile flavor compounds in apple fruits. Hortscience, 35, 1026–1032.

    CAS  Google Scholar 

  • Gasperi, F., Aprea, E., Biasioli, F., Carlin, S., Endrizzi, I., Pirretti, G., et al. (2009). Effects of supercritical CO2 and N2O pasteurization on the quality of fresh apple juice. Food Chemistry, 115, 129–136.

    Article  CAS  Google Scholar 

  • Giovannoni, J. (2001). Molecular biology of fruit maturation and ripening. Annual Review of Plant Physiology, 52, 725–749.

    Article  CAS  Google Scholar 

  • Golding, J. B., McGlasson, W. B., & Wyllie, S. G. (2001). Relationship between production of ethylene and a-farnesene in apples, and how it is influenced by the timing of diphenylamine treatment. Postharvest Biology and Technology, 21, 225–233.

    Article  CAS  Google Scholar 

  • Granitto, P. M., Biasioli, F., Aprea, E., Mott, D., Furlanello, C., Märk, T. D., et al. (2007). Sensors and Actuators B-Chemical, 121, 379–385.

    Article  CAS  Google Scholar 

  • Harren, F. J. M., Cotti, G., Oomens, J. L., & Hekkert, S. (2006). Photoacoustic spectroscopy in trace gas monitoring. In R. A. Meyers (Ed.), Encyclopaedia of analytical chemistry. Chichester: Wiley.

    Google Scholar 

  • Johnston, J. W., Gunaseelan, K., Pidakala, P., Wang, M., & Schaffer, R. J. (2009). Co-ordination of early and late ripening events in apples is regulated through differential sensitivities to ethylene. Journal of Experimental Botany, 60, 2689–2699.

    Article  CAS  Google Scholar 

  • Jordan, A., Haidacher, S., Hanel, G., Hartungen, E., Herbig, J., & Märk, L. (2009). An online ultra-high sensitivity proton-transfer-reaction mass-spectrometer combined with switchable reagent ion capability (PTR + SRI − MS). International Journal of Mass Spectrometry, 286, 32–38.

    Article  CAS  Google Scholar 

  • Jordan, A., Haidacher, S., Hanel, G., Hartungen, E., Märk, L., Seehauser, H., et al. (2009). A high resolution and high sensitivity proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF-MS). International Journal of Mass Spectrometry, 286, 122–128.

    Article  CAS  Google Scholar 

  • Ju, Z., & Curry, E. A. (2000). Evidence that a-farnesene biosynthesis during fruit ripening is mediated by ethylene regulated gene expression in apples. Postharvest Biology and Technology, 19, 9–16.

    Article  CAS  Google Scholar 

  • Knighton, W. B., Fortner, E. C., Midey, A. J., Viggiano, A. A., Herndon, S. C., Wood, E. C., et al. (2009). HCN detection with a proton transfer reaction mass spectrometer. International Journal of Mass Spectrometry, 283(1–3), 112–121.

    Article  CAS  Google Scholar 

  • Lang, & Hübert, T. (in press). A colour ripeness indicator for apples. Food Bioprocess and Technology. doi: 10.1007/s11947-011-0694-4.

  • Lara, I., Graell, J., Lopez, M. L., & Echeverria, G. (2006). Multivariate analysis of modification in biosynthesis of volatile compounds after CA storage of Fuji apples. Postharvest Biology and Technology, 39, 19–28.

    Article  CAS  Google Scholar 

  • Lindinger, W., Hansel, A., & Jordan, A. (1998). Proton-transfer-reaction mass spectrometry (PTR-MS): on-line monitoring of volatile organic compounds at pptv levels. Chemical Society Reviews, 27, 347–354.

    Article  CAS  Google Scholar 

  • Mattheis, J. P., Buchanan, D. A., & Fellman, J. K. (1998). Volatile compounds emitted by ‘Gala’ apples following dynamic atmosphere storage. Journal of American Society of Horticulture Science, 123, 426–432.

    CAS  Google Scholar 

  • Onishi, M., Inoue, M., Araki, T., Iwabuchi. H., Sagara, Y. (in press). A PTR-MS-based protocol for simulating bread aroma during mastication. Food Bioprocess and Technology. doi: 10.1007/s11947-010-0422-5.

  • Pechous, S. W., & Whitaker, B. D. (2004). Cloning and functional expression of an (E, E)-α-farnesene synthase cDNA from peel tissue of apple fruit. Planta, 219, 84–94.

    Article  CAS  Google Scholar 

  • Rapparini, F., Baraldi, R., & Facini, O. (2001). Seasonal variation of monoterpene emission from Malus domestica and Prunus avium. Phytochemistry, 57, 681–687.

    Article  CAS  Google Scholar 

  • Rowan, D. D., Allen, J. M., Fielder, S., & Hunt, M. B. (1999). Biosynthesis of straight-chain ester volatiles in Red Delicious and Granny Smith apples using deuterium-labelled precursors. Journal of Agricultural and Food Chemistry, 47, 2553–2562.

    Article  CAS  Google Scholar 

  • Schaffer, R. J., Friel, E. N., Souleyre, E. J. F., Bolitho, K., Thodey, K., Ledger, S., et al. (2007). A genomics approach reveals that aroma production in apple is controlled by ethylene predominantly at the final step in each biosynthetic pathway. Plant Physiology, 144, 1899–1912.

    Article  CAS  Google Scholar 

  • Schuhfried, E., Biasioli, F., Aprea, E., Cappellin, L., Soukoulis, C., Ferrigno, A., et al. (2011). PTR-MS measurements and analysis of models for the calculation of Henry's law constants of monosulfides and disulfides. Chemosphere, 83, 311–317.

    Article  CAS  Google Scholar 

  • Song, J., & Bangerth, F. (1996). The effect of harvest date on aroma compound production from ‘Golden Delicious’ apple fruit and relationship to respiration and ethylene production. Postharvest Biology and Technology, 8, 259–269.

    Article  CAS  Google Scholar 

  • Song, J., & Bangerth, F. (2003). Fatty acids as precursors for aroma volatile biosynthesis in pre-climacteric and climacteric apple fruit. Postharvest Biology and Technology, 30(2), 113–121.

    Article  CAS  Google Scholar 

  • Song, J., & Forney, C. F. (2008). Flavour volatile production and regulation in fruit. Canadian Journal of Plant Science, 88, 537–550.

    Article  CAS  Google Scholar 

  • Soukoulis, C., Aprea. E., Biasioli, F., Cappellin, L., Schuhfried, E., Märk, T.D., et al. (in press). PTR-TOF-MS analysis for influence of milk base supplementation on texture and headspace concentration of endogenous volatile compounds in yogurt. Food Bioprocess and Technology. doi:10.1007/s11947-010-0487-1.

  • Tani, A., Hayward, S., & Hewitt, C. N. (2003). Measurement of monoterpenes and related compounds by proton transfer reaction-mass spectrometry (PTR-MS). International Journal of Mass Spectrometry, 223–224, 561–578.

    Article  Google Scholar 

  • Tanimoto, H., Aoki, N., Inamoto, S., Hirokama, J., & Sadamaga, Y. (2007). Development of a PTR-TOF-MS instrument for real-time measurement of volatile organic compounds in air. International Journal of Mass Spectrometry, 263, 1–11.

    Article  CAS  Google Scholar 

  • Wang, A., Yamakake, J., Kudo, H., Wakasa, Y., Hutsuyama, Y., Igarashi, M., et al. (2009). Null mutation of the MdACS3 gene, coding for a ripening-specific 1-aminocyclopropane-1-carboxylate synthase, leads to long shelf life in apple fruit. Plant Physiology, 151, 391–399.

    Article  CAS  Google Scholar 

  • White, P. J. (2002). Recent advances in fruit development and ripening: an overview. Journal of Experimental Botany, 53(377), 1995–2000.

    Article  CAS  Google Scholar 

  • Young, J. C., Chu, C. L., Lu, G., & Zhu, H. (2005). Ester variability in apple varieties as determined by solid-phase microextraction and gas chromatography-mass spectrometry. Journal of Agricultural and Food Chemistry, 52(26), 8086–8093.

    Article  Google Scholar 

  • Zini, E., Biasioli, F., Gasperi, F., Mott, D., Aprea, E., Märk, T. D., et al. (2005). QTL mapping of volatile compounds in ripe apples detected by proton transfer reaction-mass spectrometry. Euphytica, 145, 269–279.

    Article  CAS  Google Scholar 

  • Zhu, Y., & Barritt, B. (2008). Md-ACS1 and Md-ACO1 genotyping of apple (Malus x domestica Borkh.) breeding parents and suitability for marker-assisted selection. Tree Genetics & Genomes, 4(3), 555–562.

    Article  Google Scholar 

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Soukoulis, C., Cappellin, L., Aprea, E. et al. PTR-ToF-MS, A Novel, Rapid, High Sensitivity and Non-Invasive Tool to Monitor Volatile Compound Release During Fruit Post-Harvest Storage: The Case Study of Apple Ripening. Food Bioprocess Technol 6, 2831–2843 (2013). https://doi.org/10.1007/s11947-012-0930-6

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