Spectroscopic quantification of extremely rare molecular species in the presence of interfering optical absorption
Optical spectrometer apparatus, systems, and methods for analysis of carbon-14 including a resonant optical cavity configured to accept a sample gas including carbon-14, an optical source configured to deliver optical radiation to the resonant optical cavity, an optical detector configured to detect optical radiation emitted from the resonant cavity and to provide a detector signal; and a processor configured to compute a carbon-14 concentration from the detector signal, wherein computing the carbon-14 concentration from the detector signal includes fitting a spectroscopic model to a measured spectrogram, wherein the spectroscopic model accounts for contributions from one or more interfering species that spectroscopically interfere with carbon-14.
1. An optical spectrometer for analysis of carbon-14, the optical spectrometer comprising:
a resonant optical cavity configured to accept a sample gas including carbon-14;
an optical source configured to deliver optical radiation to the resonant optical cavity;
an optical detector configured to detect optical radiation emitted from the resonant cavity and to provide a detector signal; and
a processor configured to compute a carbon-14 concentration from the detector signal;
wherein computing the carbon-14 concentration from the detector signal includes fitting a spectroscopic model to a measured spectrogram;
wherein the spectroscopic model accounts for contributions from one or more interfering species that spectroscopically interfere with carbon-14.
2. The optical spectrometer of claim 1 , wherein the interfering species have greater concentration in the sample gas than the concentration of carbon-14 in the sample gas.
3. The optical spectrometer of claim 1 , wherein carbon-14 has an abundance of 1000 parts per trillion or less in the sample gas, and wherein the carbon-14 concentration in the sample gas is quantified with a precision of 10% of the abundance or better.
4. The optical spectrometer of claim 1 , wherein the optical spectrometer is further configured to reduce spectroscopic interference by operating at a sample gas temperature between about −12° C. and about 0° C.
5. The optical spectrometer of claim 1 , wherein the optical spectrometer is further configured to reduce spectroscopic interference by operating at a sample gas pressure of about 75 Torr or less.
6. The optical spectrometer of claim 1 , wherein the optical spectrometer is further configured to reduce spectroscopic interference by processing and/or purifying an input sample gas to deliver a processed sample gas to the resonant optical cavity.
7. The optical spectrometer of claim 6 , wherein the processing the input sample gas comprises a method selected from the group consisting of: chromatography, passage through species selective membranes, passage through a cold trap, and combustion in a combustion reactor.
8. The optical spectrometer of claim 7 , wherein the processing the input sample gas comprises reducing concentrations of one or more interfering species selected from the group consisting of: N 2 O, CO, CO 2 , H 2 O, O 3 , CH 4 , and all stable isotopes thereof.
9. The optical spectrometer of claim 1 , wherein the interfering species include one or more species chemically distinct from a carbon-14 containing species being measured.
10. The optical spectrometer of claim 1 , wherein the interfering species include one or more isotopologues distinct from a carbon-14 containing isotopologue being measured.
11. The optical spectrometer of claim 1 , further comprising a sample preparation unit configured to convert a biological sample to the sample gas.
12. The optical spectrometer of claim 11 , wherein the sample preparation unit comprises a combustion chamber having carbon dioxide as the relevant species in the sample gas.
13. The optical spectrometer of claim 11 , wherein the sample preparation unit comprises a reduction chamber having carbon monoxide as the relevant species in the sample gas.
14. The optical spectrometer of claim 11 , wherein the sample preparation unit comprises a chemical reactor having methane as the relevant species in the sample gas.
15. The optical spectrometer of claim 1 , wherein the optical spectrometer is further configured to compensate for spectroscopic interference by determining concentrations of one or more of the interfering species via one or more auxiliary concentration measurements and using results from the auxiliary concentration measurements when fitting the spectroscopic model.
16. The optical spectrometer of claim 1 , wherein a time constant for an exponential decay in time is determined from the detector signal.
17. The optical spectrometer of claim 16 , wherein the time constant is used to determine an absorbance of the sample gas.
18. The optical spectrometer of claim 1 , wherein the detector signal is analyzed to provide separate linear absorbance and saturated absorbance terms.