Dynamic thermal gradient gas chromatography.

The use of negative axial thermal gradients in gas chromatography (TGGC) has intrigued chromatographers since the early 1950s because of the dramatic narrowing of analyte bands and concomitant raised expectations for improving resolving power. However, technical difficulties experienced in construction of TGGC instrumentation and control of the temperature along the column have made its implementation and, hence, detailed study difficult. In this work, we describe a TGGC system capable of rapidly producing and varying thermal gradient profiles by simultaneous use of resistive heating and convective cooling. Heating and cooling rates as high as 1200 and 2500°C/min, respectively, allowed the creation of dynamic temperature gradients. The separation characteristics of TGGC with dynamically changing temperature gradients are demonstrated. A gradient velocity of 2.22cm/s provided repetitive separations every 45s, and injection band widths of 45s duration were transformed into approximately 1-s peak widths. Peak tailing for basic compounds was nearly eliminated. Dynamic TGGC allows unique control over separations, oftentimes improving resolution and detection signal-to-noise. Thermally controlled elution in TGGC holds great promise for performing smart separations in which the separation time window is most efficiently utilized, and optimized separations can be quickly achieved. Rapid adjustment of relative compound elution can be used to greatly reduce GC method development time.

Peak sweeping and gating using thermal gradient gas chromatography.

When axial temperature gradients are applied in gas chromatography (GC), i.e., "thermal gradient GC" (TGGC), the temperature changes both in time and position, T(t,L), along the column, allowing unique control of the movement and elution of sample components. One method of performing TGGC involves introducing a sample into a column with a preset decreasing temperature gradient along its length, waiting for a short time until the sample separates along the gradient, and then raising the temperature to sweep all of the compounds out of the column and into the detector (i.e., "peak sweeping"). This method of operation is demonstrated here using a simple laboratory apparatus based on simultaneous resistive heating and convective cooling. An experimental comparison between isothermal GC (ITGC), temperature programmed GC (TPGC) and TGGC shows that TGGC is essentially equivalent in performance to TPGC operation when using the same column length (peak capacity production rate of 106, 381 and 469 min(-1), respectively); however, narrower peaks and higher signal-to-noise are achieved in TGGC. Furthermore, TGGC helps to minimize band broadening and peak tailing that arise from column adsorption and less than perfect sample injection. The low thermal mass of the TGGC system allows rapid column heating (4000°C/min) and cooling (3500°C/min) for selective separation (i.e., "peak gating") of compounds in a mixture without sacrificing the resolution of earlier or later eluting compounds.

Hand-portable gas chromatograph-toroidal ion trap mass spectrometer (GC-TMS) for detection of hazardous compounds.

A novel gas chromatograph-mass spectrometer (GC-MS) based on a miniature toroidal ion trap mass analyzer (TMS) and a low thermal mass GC is described. The TMS system has an effective mass/charge (m/z) range of 50-442 with mass resolution at full-width half-maximum (FWHM) of 0.55 at m/z 91 and 0.80 at m/z 222. A solid-phase microextraction (SPME) fiber mounted in a simple syringe-style holder is used for sample collection and introduction into a specially designed low thermal mass GC injection port. This portable GC-TMS system weighs <13 kg (28 lb), including batteries and helium carrier gas cartridge, and is totally self-contained within dimensions of 47 x 36 x 18 cm (18.5 x 14 x 7 in.). System start-up takes about 3 min and sample analysis with library matching typically takes about 5 min, including time for column cool-down. Peak power consumption during sample analysis is about 80 W. Battery power and helium supply cartridges allow 50 and 100 consecutive analyses, respectively. Both can be easily replaced. An on-board library of target analytes is used to provide detection and identification of chemical compounds based on their characteristic retention times and mass spectra. The GC-TMS can detect 200 pg of methyl salicylate on-column. n-Butylbenzene and naphthalene can be detected at a concentration of 100 ppt in water from solid-phase microextraction (SPME) analysis of the headspace. The GC-TMS system has been designed to easily make measurements in a variety of complex and harsh environments.