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doi:10.1016/j.chroma.2007.12.043 
Copyright © 2007 Elsevier B.V. All rights reserved.
Simultaneous quantification of polar and non-polar volatile organic compounds in water samples by direct aqueous injection-gas chromatography/mass spectrometry
Christoph Aepplia, Michael Berga, 
, 
, Thomas B. Hofstetterb, Rolf Kipfera and René P. Schwarzenbachb
Received 20 August 2007;
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Abstract
A direct aqueous injection-gas chromatography/mass spectrometry (DAI-GC/MS) method for trace analysis of 24 volatile organic compounds (VOCs) in water samples is presented. The method allows for the simultaneous quantification of benzene, toluene, ethyl benzene, and xylenes (BTEX), methyl tert-butyl ether (MTBE), tert-butyl alcohol (TBA), as well as a variety of chlorinated methanes, ethanes, propane, enthenes and benzenes. Applying a liquid film polyethylene glycol or a porous layer open tubular (PLOT) divinylbenzene GC capillary column to separate the water from the VOCs, volumes of 1–10 μL aqueous sample are directly injected into the GC. No enrichment or pretreatment steps are required and sample volumes as low as 100 μL are sufficient for accurate quantification. Method detection limits determined in natural groundwater samples were between 0.07 and 2.8 μg/L and instrument detection limits of <5 pg were achieved for 21 out of the 24 evaluated VOCs. DAI-GC/MS offers both good accuracy and precision (relative standard deviations ≤10%). The versatility of our method is demonstrated for contaminant quantification in drinking water disinfection (advanced oxidation of MTBE) and for VOC concentration measurements in a polluted aquifer. The wide range of detectable compounds and the lack of labor-intensive sample preparation illustrate that the DAI method is robust and easily applicable for the quantification of important organic groundwater contaminants.
Keywords: VOC; Analysis; Groundwater; Environmental aqueous samples; Carbon tetrachloride; Chlorobenzene; Chloroform; 1,2-Dichlorobenzene; 1,4-Dichlorobenzene; 1,2-Dichloroethane; 1,2-Dichloropropane; 1,1,1-Trichloroethane; 1,3-Dichlorobenzene; Trichloroethene; 1,1-Dichloroethene; trans-1,2-Dichloroethene; cis-1,2-Dichloroethene; Perchloroethene; Vinyl chloride; Dichloromethane; Benzene; Toluene; Xylene; Methyl tert-butyl ether (MTBE); tert-Butyl alcohol (TBA)
Article Outline
- 1. Introduction
- 2. Experimental
- 2.1. Chemicals
- 2.2. Preparation of standard solutions
- 2.3. Field sampling and sample preparation
- 2.4. DAI-GC/MS analysis
- 2.5. Determination of absolute and relative recoveries, method detection limits (MDLs) and instrument detection limits (IDLs)
- 3. Results and discussion
- 3.1. Chromatographic separation
- 3.2. Injection volumes
- 3.3. Calibration, recoveries, precision and detection limits
- 3.4. Vacuum in ion source
- 3.5. Use of a PLOT column for improved sensitivity of late-eluting compounds
- 3.6. Application to environmental and laboratory samples
- 4. Conclusions
- Acknowledgements
- References
