Comparison of peak integration methods for the determination of enantiomeric fraction in environmental samples

被引:34
作者
Asher, Brian J. [1 ]
D'Agostino, Lisa A. [1 ]
Way, Jenilee D. [1 ]
Wong, Charles S. [1 ,2 ,3 ]
Harynuk, James J. [1 ]
机构
[1] Univ Alberta, Dept Chem, Edmonton, AB T6G 2G2, Canada
[2] Univ Winnipeg, Environm Studies Program, Winnipeg, MB R3B 2E9, Canada
[3] Univ Winnipeg, Dept Chem, Richardson Coll Environm, Winnipeg, MB R3B 2E9, Canada
基金
加拿大自然科学与工程研究理事会;
关键词
Chiral separations; Deconvolution; Enantiomeric fraction; EF; Integration; POLYCHLORINATED BIPHENYL ATROPISOMERS; 2-DIMENSIONAL GAS-CHROMATOGRAPHY; MASS-TRANSFER KINETICS; OVERLAPPED PEAKS; ORGANOCHLORINE COMPOUNDS; CHIRAL SIGNATURES; FOOD-WEB; RATIOS; DECONVOLUTION; SEPARATION;
D O I
10.1016/j.chemosphere.2009.01.041
中图分类号
X [环境科学、安全科学];
学科分类号
08 ; 0830 ;
摘要
Enantiomeric fractions (EFs) are used extensively in environmental pollutant research because of the insights on biochemical weathering available from quantifying enantiomeric composition. While this analysis is powerful, it can also be subject to significant error, depending on how chromatographic peaks are integrated. Two methods of integration, the common valley drop method (VDM) and the deconvolution method (DIM) were compared using both instrumental and simulated chromatograms to assess their performance when integrating pairs of enantiomers. The effect of peak parameters such as true EF, peak resolution, signal-to-noise ratio, and asymmetry were also investigated. The VDM biased Us by up to +6% to -4% (relative to the 0-1 EF scale) for symmetric peaks, and as low as -20% for asymmetric peaks. For both instrumental and simulated data, biases tended to increase with decreasing resolution and more extreme (nonracemic) EFs. In contrast, the DM produced biases that were less than 1% in most cases, including at very low resolutions. Estimates from previously published studies based on EF, such as biotransformation rate and source apportionment, could be dramatically affected by small errors in EF. Our results suggest that a deconvolution-based integration method is preferable for the handling of enantiomer compositions. Caution is also advised when comparing published studies on chiral environmental pollutants as most do not specify how chromatographic data is processed. (C) 2009 Elsevier Ltd. All rights reserved.
引用
收藏
页码:1042 / 1048
页数:7
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