Trace analysis of off-flavor/odor compounds in water using liquid-liquid microextraction coupled with gas chromatography—positive chemical ionization-tandem mass spectrometry

Abstract

A rapid, inexpensive and laboratory friendly method was developed for analysis of off-flavor/odor compounds in fresh and salt water using gas chromatography with chemical ionization-tandem mass spectrometry. Off-flavor/odor compounds included geosmin, 2-methylisoborneol (MIB), 2-isobutyl-3-methyoxypyrazine (IBMP), and 2-isopropyl-3-methoxypyrazine (IPMP). Using this method, a single sample can be extracted within minutes using only 1 mL of organic solvent. The ion transitions for IPMP, IBMP, MIB, and geosmin were 153>121, 167>125, 152>95, and 165>109, respectively. The linearity of this method for analyzing MIB ranged from 4 to 200 ng·L^-1, and from 0.8 to 200 ng·L^-1 for the other analytes. Method recoveries ranged from 97% to 111% and percent relative standard deviations ranged from 3% to 9%, indicating that the method is accurate, precise, and reliable.

Keywords

off-flavor/odor compounds / liquid-liquid microextraction / gas chromatography-tandem mass spectrometry

References

[1] Taylor W D, Losee R F, Torobin M, Izaguirre G, Sass D, Khiari D, Atasi K. Early warning and management of surface water taste-and-odor events. American Water Works Association (AWWA), Denver, CO, USA, 2006

[2] Izaguirre G, Taylor W D. A guide to geosmin- and MIB-producing cyanobacteria in the United States. Water Science and Technology, 2004, 49(9): 19–24

[3] Ma K, Zhang J N, Zhao M, He Y J. Accurate analysis of trace earthy-musty odorants in water by headspace solid phase microextraction gas chromatography-mass spectrometry. Journal of Separation Science, 2012, 35(12): 1494–1501

[4] Parinet J, Rodriguez M J, Serodes J, Proulx F. Automated analysis of geosmin, 2-methyl-isoborneol, 2-isopropyl-3-methoxypyrazine, 2-isobutyl-3-methoxypyrazine and 2,4,6-trichloroanisole in water by SPME-GC-ITDMS/MS. International Journal of Environmental Analytical Chemistry, 2011, 91(6): 505–515

[5] Salemi A, Lacorte S, Bagheri H, Barceló D. Automated trace determination of earthy-musty odorous compounds in water samples by on-line purge-and-trap-gas chromatography-mass spectrometry. Journal of Chromatography. A, 2006, 1136(2): 170–175

[6] Grimm C C, Lloyd S W, Batista R, Zimba P V. Using microwave distillation-solid-phase microextraction—gas chromatography—mass spectrometry for analyzing fish tissue. Journal of Chromatographic Science, 2000, 38(7): 289–296

[7] Grimm C C, Lloyd S W, Zimba P V. Instrumental versus sensory detection of off-flavors in farm-raised channel catfish. Aquaculture (Amsterdam, Netherlands), 2004, 236(1-4): 309–319

[8] Guttman L, van Rijn J. Isolation of bacteria capable of growth with 2-methylisoborneol and geosmin as the sole carbon and energy sources. Applied and Environmental Microbiology, 2012, 78(2): 363–370

[9] Howgate P. Tainting of farmed fish by geosmin and 2-methyl-iso-borneeol: a review of sensory aspects and uptake/depuration. Aquaculture (Amsterdam, Netherlands), 2004, 234(1-4): 155–181

[10] Cortada C, Vidal L, Canals A. Determination of geosmin and 2-methylisoborneol in water and wine samples by ultrasound-assisted dispersive liquid-liquid microextraction coupled to gas chromatography-mass spectrometry. Journal of Chromatography. A, 2011, 1218(1): 17–22

[11] Shin H, Ahn H. Simple, rapid, and sensitive determination of odorous compounds in water by GC-MS. Chromatographia, 2004, 59: 107–113

[12] Hassett A J, Rohwer E R. Analysis of odorous compounds in water by isolation by closed-loop stripping with a multichannel silicone rubber trap followed by gas chromatography-mass spectrometry. Journal of Chromatography. A, 1999, 849(2): 521–528

[13] Zander A K, Pingert P. Membrane-based extraction for detection of tastes and odors in water. Water Research, 1997, 31(2): 301–309

[14] Sung Y H, Li T Y, Huang S D. Analysis of earthy and musty odors in water samples by solid-phase microextraction coupled with gas chromatography/ion trap mass spectrometry. Talanta, 2005, 65(2): 518–524

[15] Van Bramer S E. Introduction to Mass Spectrometry. Widener University, Department of Chemistry, <month>September</month><day>2</day>, 1998. Available online http://www.science.widener.edu/svb/massspec/massspec.pdf

[16] Ma X, Gao N, Chen B, Li Q, Zhang Q, Gu G. Detection of geosmin and 2-methylisoborneol by liquid-liquid extraction-gas chromatograph mass spectrum (LLE-GCMS) and solid phase extraction-gas chromatograph mass spectrum (SPE-GCMS). Frontiers of Environmental Science & Engineering in China, 2007, 1(3): 286–291

[17] Parinet J, Rodriguez M J, Sérodes J B. Modelling geosmin concentrations in three sources of raw water in Quebec, Canada. Environmental Monitoring and Assessment, 2013, 185(1): 95–111

[18] Hsieh W, Hung W, Wang G, Hsieh S, Lin T. Effect of pH on the analysis of 2-MIB and geosmin in Water. Water, Air, and Soil Pollution, 2012, 223(2): 715–721

[19] Zhang L, Hu R, Yang Z. Routine analysis of off-flavor compounds in water at sub-part-per-trillion level by large-volume injection GC/MS with programmable temperature vaporizing inlet. Water Research, 2006, 40(4): 699–709

Acknowledgements

We thank the Florida Department of Agriculture and Consumer Services, Aquaculture Review Council for funding this work (FDACS Contract No. 18491). We thank Mr. Christopher Robinson for technical assistance and matrix sample collection. We also thank the reviewers for their suggestions and critical comments, which greatly improved this manuscript.

RIGHTS & PERMISSIONS

2014 Higher Education Press and Springer-Verlag Berlin Heidelberg