Mass spectrometry method

1. A method of quantitating isotopomers of a hydrogen-containing compound, comprising the steps of:

a) creating a calibration table of ratio of masses for standard isotopomers using a mass spectrometer;

b) relating in an equation the ratio of observed mass distributions of standard isotopomers to the relative amounts of each isotopomer in a sample; and

c) applying the equation to the ratio of masses identified in the sample to quantitate the relative amount of each isotopomer of the hydrogen-containing compound;

wherein the equation is:

Y=g(X,A), wherein Y=(f m/z=(m/z)i )n, wherein f m/z=(m/z)i is the observed fractional mass spectral mass spectrum peak area for peak with mass to charge ratio m/z i and n is the total number of significant peaks in the mass spectrum; i is the number of charge to mass ratios m/z; and

g(X,A) is a function that relates the measured fractional m/s peak areas to the actual isotopomer fractions in the sample; wherein A is a parameter that can be determined by fitting function g(X,A) to calibration data; and X=(f CH×Dy )m, wherein f CH×Dy is the actual fraction of a given isotopomer with x hydrogen atoms and y deuterium atoms and m is the total number of isotopomers considered.

2. The method of claim 1 , wherein the isotopomer contains one or more deuterium atoms.

3. The method of claim 1 , further comprising:

a. contacting a hydrogen-deficient compound with a solution comprising deuterium oxide (D 2 O); and

b. quantitating the relative amounts of each isotopomer of a product compound according to claim 1 in order to measure the amount of deuterium incorporation into the hydrogen-containing compound.

4. The method of claim 1 , further comprising

a. contacting a hydrogen-deficient compound with a solution comprising D 2 ; and

b. quantitating the relative amounts of each isotopomer of a product compound according to claim 1 in order to measure the amount of deuterium incorporation into the hydrogen-containing compound.

5. The method of claim 1 , wherein the isotopomers of the compound comprise 0, 1, 2, 3, 4 or more deuterium atoms.

6. The method of claim 1 , wherein the compound comprises 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 or more hydrogen atoms.

7. The method of claim 1 , wherein the compound is a linear, cyclic or branched compound.

8. The method of claim 1 , wherein the compound is a hydrocarbon.

9. The method of claim 8 , wherein the hydrocarbon is an alkane, an alkene, or an aromatic compound.

10. The method of claim 9 , wherein the alkane is methane, ethane, propane, n-butane, 2-methylbutane, isobutane, cyclobutane, pentane, isopentane (2-methylbutane), neopentane (2,2-dimethylpropane), cyclopentane, hexane, 3-methylhexane, heptane, octane, nonane, decane, hexadecane, or iso-octane, or the like.

11. The method of claim 9 , wherein the alkene is ethylene, butene, butadiene, pentene, hexene, polyethylene, polypropylene, or polybutadiene.

12. The method of claim 9 , wherein the aromatic compound is benzene or a derivative thereof, furan, pyridine, toluene, benzoic acid, naphthalene, anthracene, tetracene, pentacene, phenanthrene, triphenylene, or a polyaromatic hydrocarbon (PAH).

13. The method of claim 12 , wherein the PAH is naphthalene, tetracene, phenanthrene, Benzy[a]pyrene, anthracene, chrysene, pentacene, acenaphthene, acenaphthylene, phenanthrene, fluorene, fluoranthene, benzo(a)anthracene, pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene, dibenz[a,h]anthracene, benzo[g,h,i]perylene, or indeno[1,2,3-cd]pyrene.

14. The method of claim 9 , wherein the aromatic compound comprises from 1 to about 50 rings.

15. The method of claim 9 , wherein the aromatic compound is up to a C 100 compound.

16. The method of claim 3 or 4 , wherein the hydrogen-deficient compound is part of a mixture of compounds found in a hydrocarbon material.

17. The method of claim 16 , wherein the hydrocarbon material is coal, gasoline, oil, jet fuel, or diesel.

18. The method of claim 1 , wherein the hydrogen-containing compound is an alcohol, a lipid, or a carbohydrate.

19. The method of claim 18 , wherein the alcohol is methanol, ethanol, butanol, propanol, iso-propanol, iso-butanol, 3-methylbutanol, or 2-methylbutanol.

20. The method of claim 1 , wherein the hydrogen-containing compound is methane and

X=(f CH×Dy )m, wherein f CH×Dy is the actual fraction of a given isotopomer with x hydrogen atoms and y deuterium atoms and m is the total number of isotopomers considered.

21. The method of claim 20 , wherein the function g(X,A) is estimated using calibration data with mixtures of known isotopomer fractions.

22. The method of claim 20 , wherein the function g(X,A)=A, where A is a matrix estimated from calibration data using multivariate linear multiple regression.

23. The method of claim 20 , wherein the function g(X,A) is a nonlinear function and parameter A is estimated from calibration data using nonlinear multivariate multiple regression.

24. The method of claim 20 , wherein the relationship between Y and X is inverted to determine the actual isotopomer fractions given the mass spectrometry peak areas in a test sample as X=g −1 (Y) denotes the inverse function of g(X).

25. The method of claim 24 , wherein g −1 =A −1 is a matrix inverse of matrix A.

26. The method of claim 25 , wherein A −1 is approximated by the pseudoinverse A* of the matrix A in order to obtain a best fit solution to X in a least squares sense.

27. The method of claim 20 , wherein the matrix equation comprises Y=AX, wherein:

a) Y=(f m/z=20 , f m/z=19 , f m/z=18 , f m/z=17 , f m/z=16 );

b) X=(f CH4 , f CH3D , f CH2D2 , f CHD3 , f CD4 ); and

c) A=a matrix that relates the measured fractions related to the actual fractions.

28. The method of claim 1 , wherein the hydrogen-containing compound is ethane (C 2 H 6 ) and the matrix equation comprises Y=g(X,A), wherein:

a) Y=(f m/z=30 , f m/z=31 , f m/z=32 , f m/z=33 , f m/z=34 , f m/z=35 , f m/z=36 f m/z=37 );

b) X=(f C2H6 , f C2H5D , f C2H4D2 , f C2H3D3 , f C2H2D4 , f C2HD5 , f C2D6 ); and

c) g(X,A)= a function with parameters A that relates the measured fraction related to the actual fractions.

29. The method of claim 1 , wherein the hydrogen-containing compound is benzene (C 6 H 6 ) and the matrix equation comprises Y=g(X,A), wherein:

a) Y=(f m/z=78 , f m/z=79 , f m/z=80 , f m/z=81 , f m/z=82 , f m/z=83 , f m/z=84 );

b) X=(f C6H6 , f C6H5D , f C6H4D2 , f C6H3D3 , f C6H2D4 , f C6HD5 , f C6D6 ); and

c) g(X,A)= a function with parameters A that relates the measured fractions related to the actual fractions.

30. The method of claim 1 , wherein the hydrogen-containing compound is naphthalene (C 10 H 8 ) the matrix equation comprises Y=g(X,A), wherein:

a) (f m/z=128 , f m/z=129 , f m/z=130 , f m/z=131 , f m/z=132 , f m/z=133 f m/z=134 , f m/z=135 , f m/z=136 ,);

b) X=(f C10H8 , f C10H7D , f C10H6D2 , f C10H5D3 , f C10H4D4 , f C10H3D5 , f C2H2D6 , f C2HD7 , f C2D8 ); and

c) g(X,A)= a function with parameters A that relates the measured fractions related to the actual fractions.

31. The method of claim 1 , wherein the equation is computed with a general use computer.