Spectroscopic quantification of extremely rare molecular species in the presence of interfering optical absorption

Patent metadata

Field	Value
Publication number	US-2016011101-A1
Application number	US-201514714658-A
Country	US
Kind code	A1
Filing date	May 18, 2015
Priority date	Jul 14, 2014
Publication date	Jan 14, 2016
Grant date	—

Abstract

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.

First claim

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 the rare species 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.

19 . A cavity ring-down biological accelerator mass spectrometer apparatus for analyzing a sample, comprising:
a light source that produces a light beam wherein said light source can be turned off, a sample cavity, a wavelength monitor and optical train that monitors said light beam and mode matches said light beam to said cavity, a system for directing the sample into said sample cavity, a system for directing said light beam into said sample cavity, a multiplicity of mirrors in said cavity that cause said light beam to make a multiplicity of passes in said cavity and interact with the sample wherein said multiplicity of mirrors are positioned in said cavity to provide a cavity length for said light beam, a cavity length adjustment system for adjusting said cavity length, and a detector connected to said cavity wherein when said light source is turned off said detector detects exponentially decaying light intensity from said light beam in said cavity for analyzing the sample.

20 . The cavity ring-down biological accelerator mass spectrometer apparatus of claim 19 wherein said cavity length adjustment system for adjusting said cavity length is a piezoelectric crystal.

21 . The cavity ring-down biological accelerator mass spectrometer apparatus of claim 19 wherein said cavity has a cavity wall and said multiplicity of mirrors are positioned on said cavity wall in said cavity to provide a cavity length for said light beam and further comprising a cavity length adjustment system between said cavity wall and at least one of said mirrors for adjusting said cavity length.

22 . The cavity ring-down biological accelerator mass spectrometer apparatus of claim 19 wherein said cavity length adjustment system for adjusting said cavity length is a piezoelectric crystal.

23 . A method of quantifying the amount of 14 C derived from a biochemical sample containing 14 C and 12 C using cavity ring down spectroscopy, comprising the steps of:
using a light source to direct a light beam into a sample cavity, monitoring said light beam and mode matching said light beam to said cavity, introducing the sample containing 14 C and 12 C into said cavity, using a multiplicity of mirrors to direct said light beam in said cavity to make a multiplicity of passes in said cavity and interact with the sample containing 14 C and 12 C, and turning the light source off and detecting the exponentially decaying light intensity from said light beam in said cavity for measuring the amounts of 14 C and 12 C and quantifying the amount of 14 C derived from the biochemical sample.

24 . The method of quantifying the amount of 14 C derived from a biochemical sample containing 14 C and 12 C using cavity ring down spectroscopy of claim 23 wherein said step of detecting the exponentially decaying light intensity from said light beam in said cavity for measuring the amounts of 14 C and 12 C and quantifying the amount of 14 C derived from the biochemical sample includes computing a carbon-14 concentration from a detector signal by fitting a spectroscopic model to a measured spectrogram wherein the spectroscopic model accounts for contributions from one or more interfering species that spectroscopically

Assignees

• L Livermore Nat Security Llc
• Picarro Inc

Inventors

• Ognibene Ted
• Bench Graham
• Mccartt Alan Daniel
• Turteltaub Kenneth
• Rella Chris W
• Tan Sze
• Hoffnagle John A
• Saad Nabil
• Crosson Eric

Classifications

• G01J3/42

  Absorption spectrometry; Double beam spectrometry; Flicker spectrometry; Reflection spectrometry (beam switching arrangements G01J3/08) · CPC title

• H01J49/0086

  Accelerator mass spectrometers · CPC title

• G01N21/3103 Primary

  Atomic absorption analysis · CPC title

• G01N2201/0612

  Laser diodes · CPC title

• H01J49/0495

  Vacuum locks; Valves (valves per se F16K) · CPC title