Method and apparatus for measuring stable isotopes

Abstract

Spectroscopic measurements of stable isotopes are performed using a tunable lead salt diode laser. The design of the system is based upon the optimization of isotopic spectral lines from two different path lengths in an absorption cell using a single gaseous sample. A short path cell to measure the more abundant species and a long path cell to measure the less abundant species are used. A micrometer adjustment of a path length is used for equalizing spectral line intensities to obtain a measure of isotope enrichment or of absolute isotopic concentration.

The embodiment of the invention in which an exclusive property or privilege is claimed are defined as follows: 
     
       1. The method of measuring different concentrations of isotopes in a sample comprising the steps of; transmitting monochromatic radiation through the sample in at least two different path lengths, which comprise at least one short path length and at least one long path length, and sweeping the radiation frequency over absorption lines of the isotopes being measured,   detecting the intensities of spectral lines in the different paths to measure more abundant isotopes in the short path lengths and less abundant isotopes in the long path lengths,   adjusting the relative path lengths to obtain a non-saturated spectral line intensity for each isotope being measured, measuring the relative path lengths and determining the concentrations of the isotopes from the relative path lengths and the detected spectral line intensities.   
     
     
       2. The method of measuring different concentrations of stable isotopes in a gaseous sample comprising the steps of; transmitting monochromatic radiation through the sample in at least two different path lengths, which comprise at least one short path length and at least one long path length, and   sweeping the radiation frequency over absorption lines of the isotopes being measured,   detecting the intensities of spectral lines in the different paths to measure more abundant isotopes in the short path lengths and less abundant isotopes in the long path lengths,   adjusting at least one path length to equalize the detected intensities, measuring the relative path lengths, and   determining the concentrations of the isotopes from the relative path lengths and/or the detected spectral line intensities.   
     
     
       3. The method of measuring different concentrations of stable isotopes in a gaseous sample comprising the steps of; introducing a reference gas into a cell,   transmitting monochromatic radiation through the reference gas in at least two different path lengths, which comprise at least one short path length and at least one long path length, and sweeping the radiation frequency over absorption lines of the isotopes being measured,   detecting the intensities of spectral lines in the different paths to measure more abundant isotopes in the short path lengths and less abundant isotopes in the long path lengths,   equalizing the detected intensities, removing the reference gas from the cell introducing the sample gas into the cell,   repeating the transmitting the detecting steps, and adjusting the length of at least one of the paths to equalize the detected intensities for the sample gas, so that the amount of the adjustment represents the isotope enrichment in the sample.   
     
     
       4. Apparatus for measuring different concentrations of stable isotopes in a gaseous sample comprising; a tunable source of monochromatic radiation for scanning radiation through a frequency band,   a sample cell arrangement having at least two optical paths through the same sample, the paths having different lengths in a ratio generally corresponding to the inverse ratio of the isotope concentrations,   means for transmitting radiation from the source through the paths,   detector means for sensing the spectral line intensity of each of isotope,   means for adjusting at least one path length by measured amounts to adjust the line intensity of the corresponding path, and   circuitry responsive to the detector means for determining isotope concentration from the path lengths and/or the respective line intensities.   
     
     
       5. Apparatus for measuring isotope enrichment in different concentrations of stable in a gaseous sample comprising; a tunable source of monochromatic radiation for scanning the frequency through a band,   a sample cell arrangement having at least two optical paths through the same sample, the paths having different lengths in a ratio generally corresponding to the inverse ratio of a isotope concentrations,   means for transmitting radiation from the source through the paths,   detector means for measuring the spectral line intensity of an isotope in each path, and   means for adjusting the relative path lengths by measured amounts to equalize the measured line intensities, so that the amount of adjustment for a sample gas relative to a reference gas is a measure of isotope enrichment.   
     
     
       6. Apparatus for measuring different concentrations of stable isotopes in a gaseous sample comprising; a tunable source of monochromatic radiation for scanning radiation through a frequency band,   a sample cell arrangement having at least two optical paths through the same sample, the paths having different lengths in ratio generally corresponding to the inverse ratio of the isotope concentrations,   means for transmitting radiation from the source through the paths,   detector means for measuring the spectral line intensity of each isotope,   means for adjusting at least one of the path lengths for equalizing the line intensities, and   circuitry responsive to the detector means for comparing the line intensities for indicating equality of line intensities for different path lengths.   
     
     
       7. Apparatus for measuring different concentrations of stable isotopes in a gaseous sample comprising; a tunable source of monochromatic radiation for scanning radiation through a frequency band,   a sample cell arrangement having at least two optical paths through the same sample, the paths having different lengths in a ratio generally corresponding to the inverse ratio of the isotope concentrations,   means for transmitting radiation from the source through the paths,   detector means for measuring the spectral line intensity of each isotope, and   micrometer adjustment means for precisely adjusting at least one of the path lengths for varying the line intensities, so that isotope concentrations can be accurately determined from measured path lengths and line intensities.   
     
     
       8. The method of measuring the isotopic ratio of different concentrations of stable isotopes in a gaseous sample comprising the steps of; transmitting monochromatic radiation through at least two different length paths in the absence of gas, detecting the transmitted radiation in each path and electronically equalizing the .[.detectected.]. .Iadd.detected .Iaddend.signals,   admitting sample gas into the paths,   transmitting the radiation through the paths and sweeping the radiation frequency over absorption lines of the isotopes being measured,   detecting the intensities of spectral lines in the different paths to measure more abundant isotopes in short path lengths and less abundant isotopes in long path lengths,   adjusting at least one path length to equalize the detected intensities, measuring the relative path lengths and   calculating the absolute isotopic ratio from the relative path lengths, the absorption coefficients and the Beer-Lambert law. .Iadd.   
     
     
       9.  The method of measuring different concentrations of isotopes in a sample comprising the steps of: transmitting monochromatic radiation through the sample in at least two different path lengths, which comprise at least one short path length and at least one long path length, and sweeping the radiation frequency to an absorption line for each isotopic specie being measured; detecting the intensities of spectral lines in the different paths to measure more abundant isotopes in the short path lengths and less abundant isotopes in the long path lengths;   adjusting the relative path lengths to obtain a non-saturated spectral line intensity for each isotope being measured, measuring the relative path lengths, and determining the concentrations of the isotopes from the relative path lengths and the detected spectral line intensities. .Iaddend. .Iadd.10. The method of measuring different concentrations of stable isotopic species in a gaseous sample comprising the steps of:   transmitting monochromatic radiation through the sample in at least two different path lengths, which comprise at least one short path length and at least one long path length, and sweeping the radiation frequency to an absorption line for each isotopic specie being measured;   detecting the intensities of spectral lines in the different paths to measure more abundant isotopic species in the short path lengths and less abundant isotopic species in the long path lengths;   adjusting at least one path length to equalize the detected line intensities for each isotopic specie being measured, measuring the relative path lengths; and   determining the ratio of the concentrations of the isotopic species from the relative path lengths and/or the detected spectral line intensities.   
     
     
        .Iaddend. .Iadd.11.  The method of measuring different concentrations of stable isotopic species in a gaseous sample comprising the steps of: introducing a reference gas into a cell;   transmitting monochromatic radiation through the cell in at least two different path lengths, which comprise at least one short path length and at least one long path length, and sweeping the radiation frequency to an absorption line for each isotopic specie being measured;   detecting the intensities of spectral lines in the different paths to measure more abundant isotopic species in the short path lengths and less abundant isotopic species in the long path lengths;   equalizing the detected intensities, removing the reference gas from the cell, introducing the sample gas into the cell;   repeating the transmitting and detecting steps; and   adjusting the length of at least one of the paths to equalize the detected intensities for the sample gas, so that the amount of the adjustment represents the enrichment of an isotopic species in the sample. .Iaddend.   
     
     
        .Iadd.12.  Apparatus for measuring different concentrations of stable isotopes in a gaseous sample comprising: a sweeping source of monochromatic radiation for tuning the radiation frequency to an absorption line for each isotopic specie being measured;   a sample cell arrangement having at least two optical paths through the same sample, the paths having different lengths in a ratio generally corresponding to the inverse ratio of the isotope concentrations;   means for transmitting radiation from the source through the paths;   detector means for sensing the absorption line intensity of each isotope;   means for adjusting at least one path length by measured amounts to adjust the line intensity of the corresponding path; and   circuitry responsive to the detector means for determining isotope ratios from the path lengths and/or the respective line intensities. .Iaddend.   
     
     
        .Iadd.13.  Apparatus for measuring isotope enrichment in different concentrations of stable isotopes in a gaseous sample comprising: a sweeping source of monochromatic radiation for tuning the radiation frequency to an absorption line for each isotopic specie being measured;   a sample cell arrangement having at least two optical paths through the same sample, the paths having different lengths in a ratio generally corresponding to the inverse ratio of the isotope concentrations;   means for transmitting radiation from the source through the paths;   detector means for sensing the absorption line intensity of each isotope; and   means for adjusting the relative path lengths by measured amounts to equalize the sensed line intensities, so that the amount of adjustment for a sample gas relative to a reference gas is a measure of isotope   
     
     
        enrichment. .Iaddend. .Iadd.14.  Apparatus for measuring the ratio of concentrations of stable isotopes in a gaseous sample comprising: a sweeping source of monochromatic radiation for tuning the radiation frequency to an absorption line for each isotopic specie being measured;   a sample cell arrangement having at least two optical paths through the same sample, the paths having different lengths in a ratio generally corresponding to the inverse ratio of the isotope concentrations;   means for transmitting radiation from the source through the paths;   detector means for sensing the absorption line intensity of each isotope;   means for adjusting at least one path length for equalizing the line intensity of each isotope; and   circuitry responsive to the detector means for comparing the line intensities for indicating equality of line intensities for different path   
     
     
        lengths. .Iaddend. .Iadd.15.  Apparatus for measuring different concentrations of stable isotopes in a gaseous sample comprising: a sweeping source of monochromatic radiation for tuning the radiation frequency to an absorption line for each isotopic specie being measured;   a sample cell arrangement having at least two optical paths through the same sample, the paths having different lengths in a ratio generally corresponding to the inverse ratio of the isotope concentrations;   means for transmitting radiation from the source through the paths;   detector means for sensing the absorption line intensity of each isotope; and   micrometer adjustment means for precisely adjusting at least one path length for varying the line intensity of the corresponding paths, so that isotope ratios can be accurately determined from measured path lengths and line intensities. .Iaddend. .Iadd.16. The method of measuring the isotopic ratio of different concentrations of stable isotopes in a gaseous sample comprising the steps of:   transmitting monochromatic radiation through at least two different length paths in the absence of gas, detecting the transmitted radiation in each path and electronically equalizing the detected signals;   admitting sample gas into the paths;   transmitting the radiation through the paths and sweeping the radiation frequency to an absorption line for the isotopic specie being measured;   detecting the intensities of spectral lines in the different paths to measure more abundant isotopes in short path lengths and less abundant isotopes in long path lengths;   adjusting at least one path length to equalize the detected intensities, measuring the relative path lengths; and   calculating the absolute isotopic ratio from the relative path lengths, the   
     
     
        absorption coefficients and the Beer-Lambert law. .Iaddend. .Iadd.17.  The method of evaluating a process in a system containing material amenable to isotope enrichment by measuring relative spectral absorption lines of isotopic species comprising the steps of: treating the system with a substance enriched with a tracer isotope;   after such treatment, collecting a gaseous sample of material from the system;   transmitting monochromatic radiation in at least two paths through the gaseous sample, the paths having different lengths to provide a non-saturated line intensity for each isotopic specie being measured, and sweeping the radiation frequency to an absorption line or each measured specie; and   detecting the intensity of a spectral line for each measured isotopic specie in the sample, and determining the enrichment value of the tracer isotopic specie in the sample from the paths lengths and/or the detected   
     
     
        spectral line intensities. .Iaddend. .Iadd.18.  The method of evaluating a process in a system containing material amenable to isotope enrichment by measuring relative spectral absorption lines of isotopic species comprising the steps of: treating the system with a substance enriched with a tracer isotope;   after such treatment, collecting a gaseous sample of material from the system;   transmitting monochromatic radiation in at least two paths through the gaseous sample, the paths having different lengths to provide a non-saturated line intensity for each isotopic specie being measured, and sweeping the radiation frequency to an absorption line for each measured specie;   adjusting the relative path lengths to equalize the detected intensities;   measuring the relative path lengths; and   detecting the intensity of a spectral line for each measured isotopic specie i the sample, and determining the enrichment value of the tracer isotopic specie in the sample from the path lengths and/or the detected   
     
     
        spectral line intensities. .Iaddend. .Iadd.19.  The method of evaluating a biological function in a subject by a stable isotope tracer comprising the steps of: administering to the subject an isotopic tracer enriched substance which is eventually expired in the form of isotopically enriched gas;   after such administration, collecting a breath sample from the subject;   transmitting monochromatic radiation in at least two paths through the sample, the paths having different lengths to provide a non-saturated line intensity for each isotopic specie being measured, and sweeping the radiation frequency to an absorption line for each specie; and   detecting the intensity of a spectral line for each measured isotopic specie in the sample, and determining the enrichment value of the tracer isotopic specie in the sample from the path lengths and the detected   
     
     
        spectral line intensities. .Iaddend. .Iadd.20.  The method of evaluating a biological function in a subject by a stable isotope tracer comprising the steps of: administering to the subject an isotopic tracer substance enriched with carbon-13 which is eventually expired in the form of a gas isotopically enriched with carbon-13;   after such administration, collecting a breath sample containing carbon dioxide enriched with carbon-13 as the tracer isotopic specie;   transmitting monochromatic radiation in at least two paths through the sample, the paths having different lengths to provide a non-saturated line intensity for each isotopic specie being measured, and sweeping the radiation frequency to an absorption line for each specie; and   detecting the intensity of a spectral line for each measured isotopic specie in the sample, and determining the enrichment value of the tracer isotopic specie in the sample from the path lengths and the detected spectral line intensities. .Iaddend. .Iadd.21. The method of evaluating a biological function in a subject by a stable isotope tracer comprising the steps of:   administering to the subject an isotopic tracer substance enriched with a low abundance isotope of carbon which is eventually expired in the form of an isotopically enriched gas;   after such administration, collecting a breath sample containing carbon monoxide as the tracer isotopic specie from the subject;   transmitting monochromatic radiation in at least two paths through the sample, the paths having different lengths to provide a non-saturated line intensity for each isotopic specie being measured, and sweeping the radiation frequency to an absorption line for each specie; and   detecting the intensity of a spectral line for each measured isotopic specie in the sample, and determining the enrichment value of the tracer isotopic specie in the sample from the path lengths and the detected   
     
     
        spectral line intensities. .Iaddend. .Iadd.22.  The method of evaluating a biological function in a subject by a stable isotopic tracer comprising the steps of: administering to the subject an isotopic tracer substance enriched with carbon-13 which is eventually expired in the form of isotopically enriched gas;   after such administration, collecting a breath sample containing carbon dioxide enriched with carbon-13 as the tracer isotopic specie from the subject;   transmitting monochromatic radiation in at least two paths through the sample, the paths having different lengths to provide a non-saturated line intensity for each isotopic specie being measured, and sweeping the radiation frequency to an absorption line for each specie; and   detecting the intensity of a spectral line for each measured isotopic specie in the sample, and determining the enrichment value of the tracer isotopic specie in the sample from the path lengths and the detected   
     
     
        spectral line intensities. .Iaddend. .Iadd.23.  The method of evaluating a biological function in a subject by a stable isotope tracer comprising the steps of: administering to the subject a substance enriched with oxygen-18 which is eventually deposited in the tissue of the subject;   processing such tissue to produce a gaseous sample containing carbon monoxide enriched with the oxygen-18;   transmitting monochromatic radiation in two paths through the sample, the paths having different lengths to provide non-saturated line intensities for the oxygen-18 enriched specie and another isotopic specie being measured, and sweeping the radiation frequency to an absorption line for each measured specie; and   detecting the intensity of a spectral line for each measured specie in the sample, and determining the enrichment value of the enriched CO specie in the sample from the path lengths and the detected spectral line intensities. .Iaddend.