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.

Non-radioactive electron source with nanosecond pulse modulation for atmospheric pressure chemical ionization.

Ion mobility spectrometers (IMSs) are well-known instruments for fast and ultrasensitive trace gas detection. In recent years, we introduced a compact nonradioactive electron source providing a defined current of free electrons with high kinetic energy at atmospheric pressure for initiating a chemical gas phase ionization of the analytes identical to radioactive sources. Besides its nonradioactivity, one major advantage of this electron source is its controlled electron emission current even in pulsed mode. By optimizing the geometric parameters and developing faster control electronics, we now achieve electron pulses with extremely short pulse widths down to 23 ns. This allows us to kinetically control the formation of reactants and analyte ions by chemical gas phase ionization (e.g., reducing discrimination processes caused by competing ionization), enhancing the analytical performance of the IMS. However, this paper concentrates on the pulsed electron source. For its characterization, we developed a measurement setup, which allows the detection of nanosecond electron pulses with amplitudes of only a few nanoamperes. Furthermore, we investigated the spatial ion distribution in the ionization region depending on several operating parameters, such as the kinetic electron energy or the ionization time.

Non-radioactive electron capture detector for gas chromatography - A possible replacement for radioactive detectors.

With detection limits in the low ppbv-range, electron capture detectors (ECD) are the most sensitive GC-detectors available for electron affine compounds, such as pesticides or chlorofluorocarbons. The working principle is based on the generation of free electrons at atmospheric pressure, which are usually emitted from a radioactive Ni-63 source. However, the use of radioactive materials leads to regulatory restrictions regarding purchase, operation and disposal. Recently, we introduced a novel ECD based on a non-radioactive electron source, achieving comparable detection limits, e.g. 1 ppbv (6 ng/l) for 1,1,2-trichloroethane. However, the linear range was still below that of radioactive ECDs. In addition, the detector volume was too large to be used as a GC detector. We now present an improved version of this non-radioactive ECD with significantly increased linear range of 6.5∙103 for 1,1,2-trichloroethane by implementing pulsed operation using a newly developed, autonomous control electronics. In addition, the detector volume is reduced to 100 µl, leading to faster response times, less memory effects and thus less peak broadening. The improved ECD with non-radioactive electron source reaches similar analytical performance compared to commercially available radioactive ECDs and thus can be used as a possible replacement of radioactive ECDs.

Ion mobility spectrometer with orthogonal X-Ray source for increased sensitivity.

Ion mobility spectrometers (IMS) are compact devices for extremely sensitive detection of proton and electron affine volatile compounds down to low pptv concentrations within less than a second. The measuring principle requires ionization of the target analyte. Most IMS employ radioactive electron sources, such as 63Ni or 3H. These radioactive materials suffer from legal restrictions limiting the fields of application. Furthermore, the electron emission has a predetermined intensity and cannot be controlled or disabled. In a previous work, we replaced the axially mounted 3H source of our ion mobility spectrometer with a commercially available X-ray source operated at low acceleration voltage of 4.5 kV to be applicable in most application without legal restrictions. However, the high penetration depth of the radiation together with the statistical behavior of the X-ray ionization process led to an increase of Fano noise and thus a limited signal-to-noise ratio. Therefore, the X-ray source is now mounted orthogonal to the drift tube in order to avoid Fano noise. Here, we compare the analytical performance of this orthogonal setup with the axially mounted X-ray source. The noise level is significantly reduced. This improves the signal-to-noise ratio from 700 with the axially placed source to more than 3000 with the orthogonally placed source, while the resolving power still remains at R = 100. Furthermore, typical limits of detection for some model substances in the low pptv range in positive and negative ion mode are given.