Evaluation of Conditions of Comprehensive Two-Dimensional Gas Chromatography That Yield a Near-Theoretical Maximum in Peak Capacity Gain

Author(s): Matthew S. Klee1, Jack Cochran2, Mark Merrick3, Leonid M. Blumberg4

  1. XO Associates LLC
  2. Restek Corporation
  3. LECO
  4. Advachrom

Published By: Journal of Chromatography A

Year of Publication: 2015

Link: http://www.sciencedirect.com/science/article/pii/S0021967315000771


The peak capacity gain (Gn) of a GCxGC system is the ratio of the system peak capacity to that of an optimized one-dimensional GC analysis lasting the same time and providing the same detection limit. A near-theoretical maximum in Gn has been experimentally demonstrated in GCxGC-TOF based on a 60 m x 0.25 mm primary column. It was found that Gn was close to 9 compared to the theoretical maximum of about 11 for this system. A six-sigma peak capacity of 4500 was obtained during an 80 min heating ramp from 50 °C to 320 °C. Using peak deconvolution, 2242 individual peaks were determined in a Las Vegas runoff water sample. This is the first definitive experimental demonstration known to us of an order-of-magnitude Gn. The key factors enabling this gain were: relatively sharp (about 20 ms at half height) reinjection pulses into the secondary column, relatively long (60 m) primary column, the same diameters in primary and secondary columns, relatively low retention factor at the end of the secondary analysis (k ≅ 5 instead of 15, optimal for ideal conditions), optimum flow rate in both columns, and helium (rather than hydrogen) used as the carrier gas. The latter, while making the analysis 65% longer than if using H2, was a better match to the reinjection bandwidth and cycle time.



Determination of Emerging Contaminants in Wastewater Utilizing Comprehensive Two-Dimensional Gas-Chromatography Coupled with Time-of-Flight Mass Spectrometry

Author(s): Sarah Prebihalo1, Adrienne Brockman1, Jack Cochran1,2, Frank L. Dorman1,3

1. Pennsylvania State University, Forensic Science Program
2. Restek Corporation
3. Pennsylvania State University, Department of Biochemistry and Molecular Biology

Published By: Journal of Chromatography A

Year of Publication: 2015

Link: www.sciencedirect.com/science/article/pii/S0021967315014132

Abstract: An analytical method for identification of emerging contaminants of concern, such as pesticides and organohalogens has been developed and utilized for true discovery-based analysis. In order to achieve the level of sensitivity and selectivity necessary for detecting compounds in complex samples, comprehensive gas chromatography coupled with time-of-flight mass spectrometry (GCxGC-TOFMS) was utilized to analyze wastewater samples obtained from the Pennsylvania State University wastewater treatment facility (WWTF). Determination of emerging contaminants through a process of combining samples which represent “normal background” and comparing this to new samples was developed. Results show the presence of halogenated benzotriazoles in wastewater samples as well as soil samples from Pennsylvania State University agricultural fields. The trace levels of chlorinated benzotriazoles observed in the monitoring wells present on the property indicate likely environmental degradation of the chlorinated benzotriazoles. Preliminary investigation of environmental fate of the substituted benzotriazoles indicates their likely degradation into phenol; an Environmental Protection Agency (USEPA) priority pollutant.