Method and apparatus for concentrating samples for analysis

• US 6,952,945 B2
• Filed: 01/25/2001
• Issued: 10/11/2005
• Est. Priority Date: 01/25/2000
• Status: Active Grant

• Current Assignee: State Of Oregon Acting By And Through The State Board Of Higher Education On Behalf Of Portland State University
• Original Assignee: State Of Oregon Acting By And Through The State Board Of Higher Education On Behalf Of Portland State University
• Inventors: O'Brien, Robert
• Primary Examiner(s): Williams, Hezron
• Assistant Examiner(s): FRANK, RODNEY T
• Application Number:
  US09/770,942
• Publication Number:
  US 20030015019A1
• Time in Patent Office: 1,720 Days
• Field of Search: 73/233.5, 73/232, 73/234, 738/648.3, 210/634, 342/90, 356/73, 435/1.3, 436/89, 702/24
• US Class Current: 73/23.35
• CPC Class Codes: G01N 1/2202 involving separation of sample components during sampling
• CPC Class Codes: G01N 1/24 Suction devices G01N1/22 - G01N1/2294 take precedence
• CPC Class Codes: G01N 1/40 Concentrating samples
• CPC Class Codes: G01N 2001/2223 aerosol sampling devices
• CPC Class Codes: G01N 2001/4027 evaporation leaving a concentrated sample
• CPC Class Codes: G01N 2015/0046 in gas, e.g. smoke
• CPC Class Codes: G01N 2015/0092 Monitoring flocculation or agglomeration
• CPC Class Codes: G01N 2030/025 Gas chromatography
• CPC Class Codes: G01N 2030/328 valves, e.g. check valves of pumps
• CPC Class Codes: G01N 2030/625 by measuring reference material, e.g. carrier without sample
• CPC Class Codes: G01N 2030/626 calibration, baseline
• CPC Class Codes: G01N 30/06 Preparation
• CPC Class Codes: G01N 30/22 in high pressure liquid systems
• CPC Class Codes: G01N 30/32 of pressure or speed G01N30/36 takes precedence
• CPC Class Codes: G01N 30/78 using more than one detector
• CPC Class Codes: G01N 30/8606 Integration
• CPC Class Codes: G01N 30/8641 Baseline

Abstract

A method for analyzing a gas sample is described. The method comprises providing a gas sample, increasing pressure applied to the gas sample to compress the sample to a smaller volume and provide a pneumatically focused gas sample, and analyzing the pneumatically focused gas sample using any of a variety of analytical techniques. Pneumatic Focusing generally means increasing the pressure of the sample, column or cell to a pressure of from about 100 psi to about 15,000 psi, more typically from about 200 psi to about 2,000 psi. Examples including gas chromatography and absorption spectroscopy are illustrated herein. Numerous other examples could be given. The method is well suited for analyzing gaseous samples, such as ambient air samples, both continuously, and remotely, using computer control. Continuously sampling ambient air provides a method for real-time monitoring of air quality. Continuous monitoring allows for pollutant exposure and allows for the identification of emission sources. The method is also well suited for analysis of breath exhalations from respiring organisms useful in metabolic studies or disease diagnosis.

Claims

1. A method for analyzing a gas sample, comprising:

providing a gas sample or converting a sample to a gas sample;

increasing pressure applied to the sample to compress the sample to a smaller volume and provide a pneumatically focused gas sample; and

analyzing the pneumatically focused gas sample by gas chromatography.

2. The method according to claim 1 where the sample is pneumatically focused concurrently with or prior to reaching a separatory column.

3. The method according to claim 1 where increasing the pressure to pneumatically focus the gas sample comprises increasing the pressure of the sample to a pressure of from about 100 psi to about 15,000 psi.

4. The method according to claim 1 where increasing the pressure to pneumatically focus the gas sample comprises increasing the pressure of the sample to a pressure of from about 200 psi to about 2,000 psi.

5. The method according to claim 1 where increasing the pressure to pneumatically focus the gas sample comprises increasing the pressure of the sample to a pressure of from about 300 psi to about 700 psi.

6. The method according to claim 1 where increasing the pressure to pneumatically focus the gas sample is accomplished using a gas selected from the group consisting of hydrogen, helium, nitrogen, argon, carbon dioxide, air, or mixtures thereof.

7. The method according to claim 1 where increasing the pressure to pneumatically focus the gas sample is accomplished using a focusing carrier gas containing an internal standard.

8. The method according to claim 1 where methane in the sample is used as an internal standard.

9. The method according to claim 1 where the gas sample is pneumatically focused using a carrier gas or a compressor at a first pressure and further comprising rapidly decreasing or increasing pressure between a first and second pressure.

10. The method according to claim 1 where analyzing the pneumatically focused sample comprises cooling a head portion of the column prior to injecting the pneumatically focused sample onto the column.

11. The method according to claim 1 where analyzing the pneumatically focused sample comprises heating the column subsequent to injecting the pneumatically focused sample onto the column.

12. The method according to claim 1 where analyzing the pneumatically focused sample includes eluting a pneumatically focused sample with a first carrier gas, and then eluting the column with a second carrier gas.

13. The method according to claim 1 and further comprising continuously analyzing pneumatically focused samples.

14. The method according to claim 1 and further comprising averaging individual chromatograms of pneumatically focused samples.

15. The method according to claim 14 where peak locations determined from the average are used to integrate peak areas in individual chromatograms contributing to the average.

16. The method according to claim 1 where analytes from the pneumatically focused sample are determined by a detector selected from the consisting of FID, IR, FTIR, NDIR, ECD, TCD NPD, FPD, UV/Visibie detector and combinations thereof.

17. The method according to claim 1 where the pneumatically focused sample is parallel or serially injected onto plural parallel or serial separatory columns.

18. The method according to claim 17 where the pneumatically focused sample is analyzed by 2-dimensional chromatography.

19. The method according to claim 17 where the pneumatically focused sample is analyzed by comprehensive chromatography.

20. The method of claim 1 where the providing the sample, the increasing pressure on the sample, and the analyzing the sample are automated.

21. The method according to claim 20 where the providing the sample, the increasing pressure on the sample, and the analyzing the sample are computer controlled.

22. The method according to claim 1 where portions of the pneumatically focused sample are fed to separate columns upstream of separate, plural detectors.

23. The method according to claim 22 where the detectors are connected in series.

24. The method according to claim 22 where the plural detector are connected in parallel.

25. The method according to claim 1 where the pneumatically focused sample is fed to plural separatory columns.

26. The method according to claim 25 where the separatory columns are connected in parallel.

27. The method according to claim 1 where the gas sample is provided as a pre-stored gaseous sample.

28. The method according to claim 1 where the gas sample includes a material selected from the group of air toxics, VOCs, OVOCs, metabolites, anesthetics, and combinations thereof.

29. The method according to claim 1 where the gas sample is collected at a boundary of a site for fence-line monitoring of analytes.

30. The method according to claim 1 where providing the gaseous sample comprises providing the sample to a column within a period of less than one minute.

31. The method according to claim 30 and providing the sample to a column within a period of less than about 1 second.

32. The method according to claim 31 and providing the sample to a column within a period of less than about 1 millisecond.

33. The method according to claim 1 and further comprising determining the directional distribution of pollution sources.

34. The method according to claim 1 and further comprising using a Gaussian Plume model to determine source location, emission rate, or both.

35. The method according to claim 1 and further comprising determining analyte source location by triangulation.

36. The method according to claim 1 and further comprising removing materials from the gaseous sample prior to pneumatically focusing the sample.

37. The method according to claim 36 where materials removed from the sample are selected from the group consisting of water vapor, aerosols, ozone, NO₂, and combinations thereof.

38. The method according to claim 36 where the materials are removed by filtering, absorption, vortexing, and combinations thereof.

39. The method according to claim 1 further comprising condensing water vapor in the gaseous sample by pneumatic focusing.

40. The method according to claim 39 where the condensed water vapor is removed prior to analyzing the gaseous sample using an analytical device.

41. The method according to claim 40 where the condensed water vapor contains water-soluble analytes, and such water-soluble analytes are collected for continuous or discontinuous subsequent analysis.

42. The method according to claim 7 where methane is added to the focusing-carrier gas.

43. The method according to claim 1 where the pneumatically focused sample is separated into aqueous and gaseous components which are separately analyzed.

44. The method according to claim 1 where the pneumatically focused sample

is a gas;

and

is subsequently cryogenically liquefied.

45. The method according to claim 1 wherein pneumatic focusing is used to make eddy correlation measurements to quantify fluxes.

46. The method according to claim 4 where increasing the pressure to pneumatically focus the gas sample comprises increasing the pressure of the sample to a pressure of from about 300 psi to about 1,500 psi.

47. The method according to claim 1 where portions of the pneumatically focused sample are fed to separate columns upstream of a single detector.

48. The method according to claim 47 where the separate columns are connected in parallel.

49. The method according to claim 1 where analyzing the pneumatically focused gas sample by gas chromatography comprises analyzing the sample using a packed capillary column.

50. The method according to claim 2 where the separatory column comprises a packed capillary column.

51. The method according to claim 17 where at least one of the columns comprises a packed capillary column.

52. The method according to claim 22 where at least one of the separate columns comprises a packed capillary column.

53. The method according to claim 25 where at least one of the separatory columns comprises a packed capillary column.

54. The method according to claim 26 where at least one of the separatory columns comprises a packed capillary column.

55. The method according to claim 47 where at least one of the separate columns comprises a packed capillary column.

63. The method according to claim 1 further comprising controlling a flow rate of a carrier gas through a gas chromatographic column using a valve downstream of the column.

64. The method according to claim 1 further comprising controlling a flow rate of a carrier gas through a gas chromatographic column using a valve downstream of a detector.

65. The method according to claim 1 where the gas sample is an air sample.

66. The method according to claim 1 where the gas sample is a breath sample.

67. The method according to claim 1 where providing a gas sample comprises continuously providing an air sample for pollution analysis.

68. The method according to claim 1 where providing a gas sample comprises continuously providing a breath sample for analysis.

69. The method according to claim 1 where the gas sample is an exhalation from a respiratory organism.

70. The method according to claim 1 where the sample is a water sample.

56. A method for analyzing VOCs, comprising:

compressing a gas sample comprising VOCS, to a smaller volume in a sample collection tube by increasing pressure applied to the sample using a carrier-pneumatic focusing gas to provide a pneumatically focused sample;

separating VOC components of the pneumatically focused sample on a gas chromatographic column; and

detecting the separated VOC components to provide an analysis of the VOC content of the sample.

57. The method according to claim 56 where increasing pressure applied to the sample comprises increasing the pressure to a pressure of about 100 psi to about 15,000 psi.

58. The method according to claim 57 where increasing pressure applied to the sample comprises increasing the pressure to a pressure of about 200 psi to about 2,000 psi.

59. The method according to claim 56 where the gas chromatographic column comprises a packed capillary column.

60. The method according to claim 56 where detecting the separated VOC components comprises detecting the components using an FID detector.

61. The method according to claim 56 where the method is automated.

62. The method according to claim 61 where the method is computer controlled.