AQUA 2024

August 26 - 30, 2024

Copenhagen, Denmark

USING PROTON-TRANSFER-REACTION TIME-OF-FLIGHT MASS SPECTROMETRY (PTR-ToF-MS) TO QUANTIFY MICROBIAL OFF-FLAVORS GEOSMIN AND 2-METHYLISOBORNEOL IN WATER: METHOD OPTIMIZATION, PERFORMANCE ASSESSMENT AND COMPARISON WITH ESTABLISHED GC-MS METHODS

Pedro Martínez Noguera*, Sylvester Holt, Raju Podduturi, Wender L.P. Bredie, Jonathan Beauchamp, Mikael A. Petersen

*Department of Food Science, University of Copenhagen (Copenhagen, Denmark)

 Rolighedsvej 26, 1958 Frederiksberg, Denmark

 pedronoguera@food.ku.dk

 



The microbial metabolites geosmin and 2-methylisoborneol (2-MIB) are of significant concern for two key industries worldwide: aquaculture, currently the fastest-growing food production sector, and the drinking water industry [1,4]. These compounds elicit well-known off-flavors that pose a major hurdle for the growth of aquaculture, particularly in recirculated aquaculture systems (RAS), as they greatly hamper fish marketability and thus the economic sustainability of the fish farms [1,2,3]. Their identification and quantification in water has hitherto only been reported using chromatographic methods [5,6,7]. With odor thresholds as low as 5-10 ng/L in water and 0.25 µg/kg in fish [3], robust and highly sensitive methods are necessary for a reliable quantification. Although chromatography offers comprehensive analysis, it is oftentimes slow and tedious. Therefore, the development of more rapid analytical methods to monitor off-flavor  trace levels in both drinking and aquaculture water can be of great benefit for early outbreak detection and product quality monitoring. This study proposes a novel method for quantification of these terpenoids in water based on proton-transfer-reaction mass spectrometry (PTR-MS) . First, the study investigated the fragmentation pattern of both compounds under standard proton-transfer-reaction conditions to determine specific ions suitable for quantification. Second , a static headspace (SH) method was developed after an optimization design  that investigated the effect of three selected variables: temperature (°C), time (min) and NaCl content (g/L) . Finally, optimal and suboptimal PTR-MS-based methods were evaluated from an analytical standpoint (repeatability, linearity, LOD and LOQ)  and their performances were compared with an established GC-MS-based method [8] . Results, on the one hand, show the  typical behaviour  of these two microbial metabolites in H3O+-mediated reactions , dehydration , reported for the first time in PTR-MS studies. On the other hand, a sensitive ( with LOD of 5 ng/L and 10 ng/L for 2-MIB and geosmin respectively) and fast method (10-15 min) for the quantification of these two metabolites in water samples  was successfully developed. This opens the door for further developments in the quick monitoring  of a wider range of contaminants and/or undesired metabolites in aquaculture and drinking water through PTR-MS.

References

1.                        Azaria, S.; van Rijn, J.  Aquacultural Engineering 2018 , 83, 57-64.

2.                        Abd El-Hack, M.E.; El-Saadony, M.T.; Elbestawy, A.R.; Ellakany, H.F.; Abaza, S.S.; Geneedy, A.M.; Salem, H.M.; Taha, A.E.; Swelum, A.A.; Omer, F.A.; et al.  Mar Pollut Bull 2022 , 178, 113579.

3.                        Jones, B.; Rocker, M.M.; Keast, R.S.J.; Callahan, D.L.; Redmond, H.J.; Smullen, R.P.; Francis, D.S.  Reviews in Aquaculture 2022.

4.                        Mustapha, S.; Tijani, J.O.; Ndamitso, M.M.; Abdulkareem, A.S.; Shuaib, D.T.; Mohammed, A.K.  Environ Monit Assess 2021 , 193.

5.                        Podduturi, R.; Petersen, M.A.; Vestergaard, M.; Jorgensen, N.O.G.  Aquaculture 2020 , 514.

6.                        Lindholm-Lehto, P.C.  Environ Sci Pollut Res Int 2022.

7.                        Bristow, R.L.; Haworth-Duff, A.; Young, I.S.; Myers, P.; Hampson, M.R.; Williams, J.; Maher, S.  Sci Rep 2023.