Apparatus and method for static gas mass spectrometry

Patent metadata

Field	Value
Publication number	US-10192729-B2
Application number	US-201715612146-A
Country	US
Kind code	B2
Filing date	Jun 2, 2017
Priority date	Jun 6, 2016
Publication date	Jan 29, 2019
Grant date	Jan 29, 2019

Abstract

A method of static gas mass spectrometry is provided. The method includes the steps of: introducing a sample gas comprising two or more isotopes to be analyzed into a static vacuum mass spectrometer at a time, t 0 ; operating an electron impact ionization source of the mass spectrometer with a first electron energy below the ionization potential of the sample gas for a first period of time that is following t 0 until a time t 1 ; and operating the electron impact ionization source with a second electron energy at least as high as the ionization potential of the sample gas for a second period of time that is after time t 1 . The first time period from t 0 to t 1 is a period corresponding to a period taken for the isotopes of the sample gas to equilibrate in the mass spectrometer. A constant ion source temperature is preferably maintained. Also provided is a static gas mass spectrometer.

First claim

The invention claimed is:

1. A method of static gas mass spectrometry comprising the steps of:
introducing a sample gas comprising two or more isotopes to be analyzed into a static vacuum mass spectrometer at a time, t 0 ;
operating an electron impact ionization source of the mass spectrometer with a first electron energy below the ionization potential of the sample gas for a first period of time that is following t 0 until a time t 1 , wherein the first time period from t 0 to t 1 is set based on a previous determination of an equilibration period taken for the isotopes of the sample gas to equilibrate in the mass spectrometer; and
operating the electron impact ionization source with a second electron energy at least as high as the ionization potential of the sample gas for a second period of time that is after time t 1 ;
wherein isotope ratio measurements are taken by the spectrometer during the second period but not during the first period.

2. The method of claim 1 further comprising regulating a filament heating current of a filament of the electron impact ionization source so as to keep the temperature of the ionization source substantially the same during the first period and the second period.

3. The method of claim 1 further comprising the step of mass analyzing the two or more isotopes in the mass spectrometer beginning with the second period of time.

4. The method of claim 3 wherein the step of mass analyzing comprises determining at least one isotope ratio of the sample gas.

5. The method of claim 4 wherein the mass analyzing comprises, for each of two or more isotopes, measuring the intensity of the isotope over time; performing a best fit of each measured isotope intensity with time, extrapolating each best fit to a time zero when the second electron energy is raised at least as high as the ionization potential of the sample gas, and calculating a ratio of the extrapolated time zero isotope intensities of two isotopes to give an isotope ratio of the sample gas.

6. The method of claim 1 wherein the sample gas is a noble gas.

7. The method of claim 1 wherein the first time period from t 0 to t 1 is not significantly longer than a time for the sample gas to equilibrate in the mass spectrometer.

8. The method of claim 1 wherein the first time period is at least 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 5, 5.5, 6, 6.5, 7, 8, 9, 10, 11, 12, 13, 14 or 15 minutes.

9. The method of claim 1 wherein the first electron energy of the ionization source is lower than the ionization potential by at least 2 eV, 4 eV, 6 eV, 8 eV, 10 eV, or 12 eV.

10. The method of claim 1 wherein the first electron energy of the ionization source is about 10 eV.

11. The method of claim 1 wherein the second electron energy of the ionization source is higher than the ionization potential of the sample gas by at least 10 eV, or 20 eV, or 30 eV, or 40 eV, or 50 eV, or 60 eV, or 70 eV.

12. The method of claim 1 wherein the second electron energy of the ionization source is about 80 eV.

13. The method of claim 1 wherein the second electron energy is at least 2×, or 3×, or 4×, or 5×, or 6×, or 7×, or 8×, or 9×, or 10× the first electron energy.

14. A static gas mass spectrometer comprising:
an electron impact ionization source for receiving a sample gas comprising two or more isotopes and ionising the sample gas,
a controller to control the electron impact ionization source,
a mass analyzer for mass analyzing the generated ions,
an ion detector for detecting ions that have been mass analyzed, and
at least one pump for generating a vacuum in the mass spectrometer, which can be isolated from the mass spectrometer before a sample gas is received by the ionization source,
wherein the ionization source is operable with a first electron energy below the ionization potential of the sample gas for a first period of time following a sample gas introduction into the ion source at time t 0 until a time t 1 ; and operable with a second electron energy at least as high as the ionization potential of the sample gas for a second period of time that is after time t 1 , wherein the controller controls the electron energy of the ionization source and sets the first time period from t 0 to t 1 based on a previous determination of an equilibration period taken for the isotopes of the sample gas to equilibrate in the mass spectrometer.

15. The static gas mass spectrometer of claim 14 wherein the first time period from t 0 to t 1 is not significantly longer than a time for the sample gas to equilibrate in the mass spectrometer.

16. The static gas mass spectrometer of claim 14 wherein the vacuum is an ultra high vacuum, the mass analyzer is a magnetic sector mass analyzer and the ion detector is a multicollector.

17. The static gas mass spectrometer of claim 14 further comprising a temperature monitor to measure the temperature of a filament of the electron impact ionization source and provide a feedback signal to control a filament current supplied to the filament so as to maintain substantially constant filament temperature during the first and second periods.

Assignees

• Thermo Fisher Scient Bremen Gmbh

Inventors

• Schwieters Johannes
• Hamilton Dougal

Classifications

• H01J49/0422

  for gaseous samples (interfaces to gas chromatographs G01N30/7206) · CPC title

• H01J49/147 Primary

  with electrons, e.g. electron impact ionisation, electron attachment (H01J49/145 takes precedence) · CPC title

• G01N27/62 Primary

  by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode · CPC title

• H01J49/0468

  with means for heating or cooling the sample · CPC title

• H01J49/24

  Vacuum systems, e.g. maintaining desired pressures · CPC title