Method Validation for the Trace Analysis of Geosmin and 2-Methylisoborneol in Water by ?Salt-Free? Purge-and-Trap Sampling/GC-MS, Using the Eclipse 4660 Sample Concentrator

Abstract

The Eclipse 4660 purge-and trap sample concentrator, coupled to a gas chromatograph-mass spectrometer, was fully validated for trace analysis of the taste-odorants geosmin (GSM) and 2-methylisoborneol (2-MIB) in the absence of salt or methanol. The procedure involved purging a 25 mL sample volume, at 80°C, for 11 min. Quantitation was done by separation on an HP 5-MS capillary column (30 m × 0.25 mm × 0.25 μm), followed by mass spectrometric detection in the selected ion monitoring (SIM) mode. The method was found to be linear (r2 ≥ 0.995) over the calibration range 0-100 ng/L for both target analytes. The overall accuracy, determined by recovery, was 104.21% ± 19.46 (mean ± SD, range = 65.29-143.13%) for 2-MIB, and 85.24% ± 8.28 (mean ± SD, range = 68.66-101.82%) for GSM. The within-day precision averaged 7.97% for 2-MIB, and 8.77% for GSM. The day-to-day precision was 20.96% for 2-MIB, and 7.52% for GSM. The limit of quantitation (LOQ) was 6 ng/L and 5 ng/L for 2-MIB and GSM; the limit of detection (LOD) was 5 ng/L and 4 ng/L for 2-MIB and GSM respectively. Earlier findings regarding the dehydration of 2-MIB to 2-methyl-2-bornene (2-M-2-B) were confirmed. The average amount of 2-M-2-B formed was 27% (range: 15-50%), with RSD = 33.26%. There is evidence of dehydration of 2-MIB to 2-M-2-B at sample purge temperature of 40°C and higher. The poor day-to-day precision for 2-MIB has been proposed to be due to the inconsistent amount of 2-M-2-B formed. A minimum sample purge temperature of 40°C is required to purge 2-MIB and GSM from water, which can be detected by GC/MS under the purge-and-trap conditions at a concentration of 100 ng/L. The developed method was found to be sensitive, accurate, precise and reproducible for trace analysis of geosmin in water matrices.