Gas inlet system for isotope ratio spectrometer

• US 10,408,747 B2
• Filed: 10/17/2018
• Issued: 09/10/2019
• Est. Priority Date: 11/08/2013
• Status: Active Grant

• Current Assignee: Thermo Fisher Scientific (Bremen) GmbH (Thermo Fisher Scientific Incorporated)
• Original Assignee: Thermo Fisher Scientific (Bremen) GmbH (Thermo Fisher Scientific Incorporated)
• Inventors: Schlueter, Hans-Juergen, Schwieters, Johannes, Wapelhorst, Eric, Krummen, Michael
• Primary Examiner(s): Maskell, Michael
• Application Number:
  US16/163,436
• Publication Number:
  US 20190086328A1
• Time in Patent Office: 328 Days
• Field of Search: 250281, 250282, 250288
• CPC Class Codes: G01N 2030/8411 Intermediate storage of effluent, including condensation on surface
• CPC Class Codes: G01N 21/11 Filling or emptying of cuvettes
• CPC Class Codes: G01N 21/31 Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry G01N21/72 takes precedence
• CPC Class Codes: G01N 21/3504 for analysing gases, e.g. multi-gas analysis
• CPC Class Codes: G01N 30/7206 interfaced to gas chromatograph interfaces in general for introducing or extracting samples to be analysed with specially adapted mass spectrometer, see H01J49/04
• CPC Class Codes: G01N 30/84 Preparation of the fraction to be distributed
• CPC Class Codes: H01J 49/0422 for gaseous samples interfaces to gas chromatographs G01N30/7206

Abstract

A gas inlet system for an isotope ratio spectrometer and a method for coupling analyte gas to an isotope ratio spectrometer are disclosed. A variable volume reservoir is located between a supply of analyte gas and a spectrometer. The reservoir'"'"'s internal volume is controllably adjusted at a pre-determined rate to generate a defined flow of analyte gas or mixture to or from the reservoir. Analyte gas and carrier gas are taken up by the reservoir on increasing the reservoir'"'"'s internal volume and then expelled from the reservoir to the spectrometer on decreasing the reservoir'"'"'s internal volume. An open split can be used together with the reservoir to facilitate splitting away and hence dilution of analyte within the reservoir. A method for cleaning the gas inlet system is provided, which involves flushing the system with carrier gas.

Claims

1. A method of coupling an analyte gas to an isotope ratio spectrometer, comprising:

supplying a first analyte gas to a variable volume reservoir of a gas inlet system;

expanding the variable volume reservoir so as to take up the first analyte gas into the reservoir;

expelling, by compressing the variable volume reservoir, the first analyte gas, or a first analyte mixture containing the first analyte gas, from the reservoir at a controlled flow rate, by controllably adjusting the volume inside the variable volume reservoir at a predetermined rate;

directing a flow of the said first analyte gas or first analyte mixture to the spectrometer at the controlled flow rate; and

selectively supplying a carrier gas to the spectrometer and/or to the variable volume reservoir;

wherein the reservoir is expanded at a rate faster than the rate of supply of the first analyte gas so as to create a vacuum within the reservoir and thereby to suck in substantially all of the first analyte gas supplied by a first analyte gas supply during a sample uptake period wherein a part of the carrier gas passes to the variable volume reservoir so as to dilute the concentration of the first analyte gas in the reservoir.

2. The method of claim 1, wherein at least a part of the carrier gas passes to an open split located upstream of the spectrometer and/or the variable volume reservoir.

6. The method of claim 1, comprising determining the concentration of the first analyte gas within the variable volume reservoir by:

connecting the variable volume reservoir to an opening once the first analyte gas has been taken up into the reservoir;

decreasing the volume of the reservoir to a known amount by expelling a part of the contents of the reservoir to the opening; and

determining the concentration of the first analyte gas using the spectrometer.

7. The method of claim 1, further comprising:

isolating the variable volume reservoir from the spectrometer and from a supply of the first analyte gas, once the reservoir has taken up first analyte gas through expansion of the reservoir;

compressing the volume of the reservoir following the said isolation of the reservoir, until the pressure of the gas within the reservoir reaches a chosen pressure; and

connecting the variable volume reservoir to the spectrometer for expulsion of at least a part of the contents of the reservoir thereto.

8. The method of claim 1, further comprising:

determining an optimum equilibrium flow into the spectrometer.

14. The method of claim 1, comprising determining the concentration of the first analyte gas within the variable volume reservoir by:

connecting the variable volume reservoir to an opening once the first analyte gas has been taken up into the reservoir;

decreasing the volume of the reservoir to a known amount by expelling a part of the contents of the reservoir to the opening; and

determining the concentration of the first analyte gas using the spectrometer.

15. The method of claim 14, wherein the opening is a second open split, the method further comprising:

isolating the variable volume reservoir from the spectrometer whist the volume of the reservoir is being decreased to the known amount, and

connecting the variable volume reservoir to the spectrometer subsequently.

16. The method of claim 1, further comprising:

isolating the variable volume reservoir from the spectrometer and from a supply of the first analyte gas, once the reservoir has taken up first analyte gas through expansion of the reservoir;

compressing the volume of the reservoir following the said isolation of the reservoir, until the pressure of the gas within the reservoir reaches a chosen pressure; and

connecting the variable volume reservoir to the spectrometer for expulsion of at least a part of the contents of the reservoir thereto.

17. The method of claim 1, further comprising:

supplying the first analyte gas to the variable volume reservoir as a series of gas pulses.

18. The method of claim 17, further comprising:

capturing substantially all of the first analyte gas in one or more gas pulses arriving at the reservoir.

19. The method of claim 17, further comprising:

capturing only a part of the first analyte gas in one or more gas pulses arriving at the reservoir.

20. The method of claim 1, further comprising:

storing a sample in a sample holder, forcing the sample out of the sample holder by flushing carrier gas into the sample holder, so as to generate the said first analyte gas, entrained with carrier gas, for supply to the variable volume reservoir.

21. The method of claim 1, comprising injecting a sample into a gas chromatograph;

and

oxidizing the sample gas eluted from the gas chromatograph, so as to produce a supply of the first analyte gas.

22. The method of claim 1, further comprising flushing the gas inlet system with a carrier gas by:

(a) isolating the variable volume reservoir from a supply of first analyte gas;

(b) connecting the reservoir to a carrier gas supply line that selectively supplies carrier gas from a carrier gas supply to the spectrometer;

(c) expelling the contents of the reservoir to the carrier gas supply line by compression of the reservoir; and

(d) expanding the reservoir with the first analyte gas supply still isolated, so as to draw carrier gas from the carrier gas supply line into the reservoir.

3. A method of coupling an analyte gas to an isotope ratio spectrometer, comprising:

supplying a first analyte gas to a variable volume reservoir of a gas inlet system;

expanding the variable volume reservoir so as to take up the first analyte gas into the reservoir;

expelling, by compressing the variable volume reservoir, the first analyte gas, or a first analyte mixture containing the first analyte gas, from the reservoir at a controlled flow rate, by controllably adjusting the volume inside the variable volume reservoir at a predetermined rate;

directing a flow of the said first analyte gas or first analyte mixture to the spectrometer at the controlled flow rate, wherein at least a part of the carrier gas passes to an open split located upstream of the spectrometer and/or the variable volume reservoir;

diluting the first analyte gas once the variable volume reservoir has taken it up by;

isolating the variable volume reservoir from a supply of the first analyte gas;

compressing the reservoir by a known amount so as to expel a proportion of the first analyte gas to the spectrometer and to expel the remaining portion of the first analyte gas to the open split;

subsequently expanding again the variable volume reservoir to or by a predetermined amount, at a speed which is smaller than the difference between the uptake of the spectrometer and the carrier gas flow, so as to cause carrier gas to be drawn into the variable volume reservoir and to dilute the first analyte gas therein;

wherein the predetermined amount of expansion of the reservoir is selected on the basis of the subsequently desired dilution/concentration of the first analyte gas.

4. A method of coupling an analyte gas to an isotope ratio spectrometer, comprising:

supplying a first analyte gas to a variable volume reservoir of a gas inlet system;

expanding the variable volume reservoir so as to take up the first analyte gas into the reservoir;

expelling, by compressing the variable volume reservoir, the first analyte gas, or a first analyte mixture containing the first analyte gas, from the reservoir at a controlled flow rate, by controllably adjusting the volume inside the variable volume reservoir at a predetermined rate;

directing a flow of the said first analyte gas or first analyte mixture to the spectrometer at the controlled flow rate, wherein at least a part of the carrier gas passes to an open split located upstream of the spectrometer and/or the variable volume reservoir;

wherein the reservoir is expanded at a rate slower than the rate of supply of the first analyte gas so as to create a vacuum within the reservoir and thereby to suck a part, but not all, of the first analyte gas being supplied by a first analyte gas supply during a sample uptake period.

5. The method of claim 4, further comprising determining the first analyte gas concentration within the variable volume reservoir when the first analyte gas concentration is present therein.

9. The method of claim 4, wherein at least a portion of the first analyte gas not sucked into the variable volume reservoir is sucked into the spectrometer.

10. The method of claim 4, wherein the open split receives a flow of first analyte gas from the first analyte gas supply in excess of the sum of the input flow rate of the first analyte gas into the variable volume reservoir and the input flow rate of the laser analyzer.

11. The method of claim 4, further comprising determining the first analyte gas concentration within the variable volume reservoir when the first analyte gas concentration is present therein.

12. The method of claim 11, wherein the step of determining the first analyte gas concentration comprises calculating the concentration based upon measurement or inference of flow rates and volumes within the gas inlet system.

13. The method of claim 11, wherein the step of determining the first analyte gas concentration comprises inferring the concentration of the gas within the reservoir based upon the concentration of the first analyte gas which does not enter the variable volume reservoir as it is expanded.