Non-radioactive electron capture detector based on soft X-ray ionization for gas chromatography - A possible replacement for radioactive detectors.

In this paper, we present a new electron capture detector based on a compact X-ray tube (X-ECD) for electron generation by soft X-ray radiation instead of using a radioactive source. ECDs are commonly used in many laboratories as standard GC detectors since their invention in the 1950s, especially for highly sensitive detection of halogenated substances, pesticides or other environmental pollutants. However, due to unsatisfactory alternatives, many ECDs are still used with radioactive ß-emitters, which is difficult and expensive in most applications today due to legal restrictions. The new X-ECD contains a small X-ray tube for generating free electrons by ionizing the carrier gas like in radioactive ECDs. Thus, no additional dopants or special gases are required. The X-ECD has limits of detection in the pptv range and shows linearity over a wide concentration range. Furthermore, the used X-ray tube shows good long-term stability. So far, we have operated the X-ray tube continuously for about one year without notable degradation. However, in case of future degradation, the X-ECD can still be operated with the same sensitivity by simple adjusting the set point current in constant current mode. This makes calibration robust against possible degradation of the X-ray tube. In combination with a conventional gas chromatograph, the X-ECD is able to detect halogenated hydrocarbons and even low volatile pesticides without any peak distortion such as tailing. Thereby a minimum detectability in the upper fg/µL range for Lindane was reached, which is similar when compared to radioactive ECDs.

Ultrasensitive Ion Source for Drift Tube Ion Mobility Spectrometers Combining Optimized Sample Gas Flow with Both Chemical Ionization and Direct Ionization.

Efficient ionization of analyte molecules is a crucial step for the outstanding sensitivity of ion mobility spectrometers (IMS) used for trace gas detection. Here, we present a new ion source that combines the previously published extended field switching ion shutter with two switchable ionization sources and an optimized sample gas flow that leads to a focused laminar stream through the reaction region of the ion source. The X-ray ionization source allows for chemical gas phase ionization of analyte molecules, while the UV ionization source allows for direct ionization of analyte molecules. The optimized sample gas flow not only allows for quickly washing out analyte molecules from the reaction region but also has improved sensitivity by a factor of about 5 for protonated monomers, 20 for proton-bound dimers, and over 100 for the proton-bound trimer of 1-octanol. The resulting limits of detection using chemical X-ray ionization are in the subpptv-range for protonated monomers and in the low pptv-range for proton-bound dimers, while the limits of detection using direct UV ionization are in the subppbv-range. Especially, a direct comparison between chemical and direct ionization of ketones using this ultrasensitive ion source reveals a stepwise conversion from directly ionized monomers to proton-bound dimers via protonated monomers during direct UV ionization.

Improving Ion Mobility Spectrometer Sensitivity through the Extended Field Switching Ion Shutter.

Field switching ion shutters allow generating short ion packets with high ion densities by first ionizing for several milliseconds in a field-free ionization region and then quickly pushing the entire ion population out into the drift region. Thus, they are an excellent choice for compact ion mobility spectrometers with both high resolving power and low limits of detection. Here, we present an improved setup, named the extended field switching ion shutter. By generating a second field-free region between the ionization region and the drift region, shielding of the ionization region is significantly improved, even when using grids with higher optical transparency to improve ion transmission into the drift region. Furthermore, it is shown that under certain conditions, ion transmission through multiple grids in series can even surpass transmission through a single grid of the same transparency. For the studied ions, the signal intensity at low concentrations increases by approximately a factor of 7 to 9 for protonated monomers, 10 to 14 for proton-bound dimers, and 25 for the proton-bound 1-octanol trimer compared to the classical field switching shutter. However, due to the nonlinear response for ions containing multiple analyte molecules, the limits of detection improve only by a factor of 3 to 4 for proton-bound dimers and 3 for the proton-bound 1-octanol trimer. Nevertheless, this still leads to single-digit pptv limits of detection for protonated monomers and hundred pptv limits of detection for proton-bound dimers measured for a series of ketones. However, for the most intense peaks such as the reactant ion peak, a significant loss of resolving power by a factor of up to 1.4 was observed due to Coulomb repulsion.