Selective detection with high speed gas chromatography

• US 5,099,743 A
• Filed: 07/08/1987
• Issued: 03/31/1992
• Est. Priority Date: 07/08/1987
• Status: Expired due to Term

• Current Assignee: Thermedics Incorporated 470 Wildwood Street Woburn Massachusetts
• Original Assignee: Thermedics, Inc. (Thermo Fisher Scientific Incorporated)
• Inventors: Rounbehler, David P., Lieb, David P., Hainsworth, Eugenie
• Primary Examiner(s): Nelson, Peter A.
• Application Number:
  US07/081,917
• Time in Patent Office: 1,728 Days
• Field of Search: 436/155-159, 73/1 G, 73/23.4, 73/28, 73/35, 73/167, 86/50
• US Class Current: 86/50
• CPC Class Codes: G01N 1/02 Devices for withdrawing samples sampling of foundation soil E02D1/04; collecting or conveying radioactive samples G01T7/00, e.g. G01T7/02, G01T7/08
• CPC Class Codes: G01N 1/2214 by sorption
• CPC Class Codes: G01N 1/2226 Sampling from a closed space, e.g. food package, head space
• CPC Class Codes: G01N 1/28 Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Qmounting specimens on microscopic slides G02B21/34; means for supporting the objects or the materials to be analysed in electron microscopes H01J37/20 ; laboratory gas handling apparatus B01L5/00
• CPC Class Codes: G01N 1/40 Concentrating samples
• CPC Class Codes: G01N 2001/022 sampling for security purposes, e.g. contraband, warfare agents
• CPC Class Codes: G01N 2001/028 Sampling from a surface, swabbing, vaporising
• CPC Class Codes: G01N 2030/025 Gas chromatography
• CPC Class Codes: G01N 2030/065 using different phases to separate parts of sample
• CPC Class Codes: G01N 2030/085 using absorbing precolumn
• CPC Class Codes: G01N 2030/121 cooling; cold traps
• CPC Class Codes: G01N 2030/122 cryogenic focusing
• CPC Class Codes: G01N 2030/123 using more than one trap
• CPC Class Codes: G01N 2030/125 pyrolising
• CPC Class Codes: G01N 2030/126 evaporating sample
• CPC Class Codes: G01N 2030/143 selective absorption
• CPC Class Codes: G01N 2030/167 on-column injection
• CPC Class Codes: G01N 2030/3007 same temperature for whole column
• CPC Class Codes: G01N 2030/3046 temperature control of column inlet
• CPC Class Codes: G01N 2030/3053 using resistive heating
• CPC Class Codes: G01N 2030/3061 : column or associated structural member used as heater
• CPC Class Codes: G01N 2030/3069 : electrical resistance used to determine control temperature
• CPC Class Codes: G01N 2030/3076 : using specially adapted T(t) profile
• CPC Class Codes: G01N 2030/3084 : ovens
• CPC Class Codes: G01N 2030/626 : calibration, baseline
• CPC Class Codes: G01N 2030/642 : photoionisation detectors
• CPC Class Codes: G01N 2030/8405 : using pyrolysis
• CPC Class Codes: G01N 21/76 : Chemiluminescence; Bioluminescence
• CPC Class Codes: G01N 30/08 : using an enricher
• CPC Class Codes: G01N 30/12 : by evaporation
• CPC Class Codes: G01N 30/14 : by elimination of some components
• CPC Class Codes: G01N 30/40 : using back flushing
• CPC Class Codes: G01N 30/461 : with serial coupling of separation columns
• CPC Class Codes: G01N 30/62 : Detectors specially adapted therefor
• CPC Class Codes: G01N 30/72 : Mass spectrometers mass spectrometers per se H01J49/00
• CPC Class Codes: G01N 30/84 : Preparation of the fraction to be distributed
• CPC Class Codes: G01N 33/0057 : for warfare agents or explosives properties of explosives G01N33/227
• CPC Class Codes: G01V 9/007 : by detecting gases or particles representative of underground layers at or near the surface analysing earth materials G01N33/24; analysing gases per se G01N

Abstract

A highly selective, sensitive, fast detection system and method are disclosed for detecting vapors of specific compounds in air. Vapors emanating from compounds such as explosives, or stripped from surfaces using heat and suction from a hand-held sample gun, are collected on surfaces coated with gas chromatograph (GC) material which trap explosives vapors but repel nitric oxide, then are desorbed and concentrated in one or more cold spot concentrators. A high speed gas chromatograph (GC) separates the vapors, after which specific vapors are decomposed in two pyrolyzers arranged in parallel and the resulting nitric oxide is detected. A low temperature pyrolyzer with silver produces NO from nitramines or nitrite esters; a high temperature pyrolyzer decomposes all explosives vapors to permit detection of the remaining explosives. Also disclosed is a series arrangement of pyrolyzers and gas chromatographs and an NO detector to time-shift detection of certain vapors and facilitate very fast GC analyses. The use of hydrogen as a carrier gas, plus unique collectors and concentrators, high speed heaters, NO detectors, and very fast, temperature-programmable GC'"'"'s enhance selectivity, sensitivity and speed of detection.

Claims

1. Gas chromatographic (GC) apparatus for rapidly analyzing samples, said apparatus operable to selectively detect specific organic compounds such as explosives in said samples in a time interval of less than about thirty seconds, comprising:

a GC tube having a capillary column of inner diameter less than about 0.5 mm, the inner wall of said column having a coating of thickness 0.1-5 microns of an organic material operable to selectively retain and timewise-separate vapors of said specific compounds in said sample;

means for rapidly injecting into said column a sample containing vapors of compounds to be analyzed and hydrogen as a carrier gas;

a heater for maintaining the temperature of said column at an elevated level less than the decomposition temperature of said vapors;

means connected to the output of said column for decomposing said vapors following their passage through said column, so as to produce a specific gas; and

means for detecting said specific gas produced by said decomposition means.

2. Apparatus as in claim 1 wherein said coating of the column is a silicone polymer.

3. Apparatus as in claim 2 wherein said coating of the column is a material selected from the group consisting of polymerized methyl silicone and polymerized methyl/phenyl silicone.

4. Apparatus as in claim 1 wherein said decomposition means includes a tube operable to heat vapors of specific nitrogen-containing compounds to produce nitric oxide as said specific gas.

5. Apparatus as in claim 4 wherein said means for detecting said specific gas is a nitric oxide detector including a reaction chamber, means for supplying ozone to said reaction chamber to react with nitric oxide received from said decomposition means, and means for detecting radiation at selected wavelengths produced by the reaction between ozone and nitric oxide.

6. Apparatus as in claim 1 wherein said means for rapidly injecting a sample into said column includes a concentration tube with a coating for trapping and concentrating vapors of specific nitrogen-containing compounds and means for flash-heating said concentration tube to release vapors of said nitrogen-containing compounds into a flow of hydrogen gas without decomposing said compounds.

7. Apparatus as in claim 1 wherein said column has a length of about five meters or less.

8. Apparatus as in claim 1 wherein said coating of the analytical column has a thickness in the range of about 1 to 2 microns.

9. Gas chromatographic (GC) apparatus for very rapidly analyzing samples, said apparatus operable to selectively detect specific organic compounds such as explosives in said sample in a time interval of less than about five seconds, comprising:

a GC tube having a capillary column of length less than ten feet, the inner wall of said column having a coating of thickness 0.1-5 microns of an organic material operable to selectively retain vapors of said specific compounds in said sample;

means for very rapidly injecting into said column a sample containing vapors of compounds to be analyzed and hydrogen as a carrier gas;

a metal tube enclosing, and closely fitting over the outer diameter of, said column of the GC tube;

means for very rapidly heating said metal tube to release said vapors from the coating of said column for outflow from the column in timewise-separated flow;

means connected to the output of said column for decomposing said vapors following their passage through said column, so as to produce a specific gas; and

means for detecting said specific gas produced by said decomposition means.

10. Apparatus as in claim 9 wherein said coating of the column is a silicone polymer.

11. Apparatus as in claim 9 wherein said decomposition means includes a tube operable to heat vapors of specific nitrogen-containing compounds to produce nitric oxide as said specific gas.

12. Apparatus as in claim 11 wherein said means for detecting said specific gas is a nitric oxide detector including a reaction chamber, means for supplying ozone to said reaction chamber to react with nitric oxide received from said decomposition means, and means for detecting radiation at selected wavelengths produced by the reaction between ozone and nitric oxide.

13. Apparatus as in claim 11 wherein said means for very rapidly injecting a sample into said column includes a concentration tube with a coating for trapping and concentrating vapors of specific nitrogen-containing compounds and means for flash-heating said concentration tube to release vapors of said nitrogen-containing compounds into a flow of hydrogen gas without decomposing said compounds.

14. A method of performing a gas chromatographic (GC) analysis on a sample to selectively detect specific organic compounds in said sample in a time interval of less than about thirty seconds comprising:

injecting a sample containing vapors of said specific compounds and hydrogen into a capillary column of a heated GC tube of inner diameter less than about 0.5 mm and containing a inner coating 0.1-5 microns thick of an organic material operable to selectively retain and timewise-separate said vapors in their passage through said column;

decomposing said vapors emerging from said column while maintaining said timewise separation, to produce a specific gas; and

detecting said specific gas produced in said decomposition step.

15. A method as in claim 14 wherein said injection step comprises flash-heating a tube containing a coating in which said vapors are trapped and, while flash-heating said tube, passing hydrogen through said tube.

16. A method as in claim 14 wherein said organic compounds are nitrogen-containing compounds and said decomposition step comprises heating said decomposition step said vapors to produce nitric oxide.

17. A method of performing a gas chromatographic (GC) analysis on a sample to selectively detect specific organic compounds in said sample in a time interval of less than about five seconds comprising:

very rapidly injecting a sample containing vapors of said specific compounds and hydrogen into a capillary column of a GC tube of inner diameter less than about 0.5 mm and containing an inner coating 0.1-5 microns thick of an organic material operable to selectively retain and timewise-separate said vapors in their passage through said column;

very rapidly heating said tube to release said vapors from the inner coating of said column for outflow from the column in timewise-separated flow;

decomposing said vapors emerging from said column, while maintaining said timewise separation, to produce a specific gas; and

detecting said specific gas produced in said decomposition step.

18. A method as in claim 17 wherein said injection step comprises flash-heating a tube containing a coating in which said vapors are trapped and, flash-heating said tube, while passing hydrogen through said tube.

19. A method as in claim 17 wherein said organic compounds are nitrogen-containing compounds and said decomposition step comprises heating said vapors to produce nitric oxide.