Abstract

A novel diode laser spectrometer was developed using dual-wavelength multiplexing, ensuring ideal conditions for high-precision and simultaneous measurements of the 2H/1H, 17O/16O, and 18O/16O isotope ratios in water. A 1.4-µm diode laser probed a H16OH / HO2H line pair near 7198 cm-1, while a similar laser observed H16OH, H17OH, and H18OH ro-vibrational lines around 7183 cm-1, or a H16OH / H18OH line pair near 7200 cm-1. The 1-σ standard deviation is 0.2‰ for 18O/16O, and 0.5‰ for the 2H/1H and 17O/16O isotope ratios. Preliminary experiments with repeated injections of a natural abundance sample point to an accuracy of about 1‰ for all three isotope ratios in natural samples.

© 2003 Optical Society of America

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References

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Anal. Chem.

E. R. Th. Kerstel, R. van Trigt, N. Dam, J. Reuss, and H. A. J. Meijer, �??Simultaneous determination of the 2H/1H, 17O/16O, and 18O/16O isotope abundance ratios in water by means of laser spectrometry,�?? Anal. Chem. 71, 5297-5303 (1999).
[CrossRef] [PubMed]

Ann. Glaciol.

R. van Trigt, H. A. J. Meijer, A. E. Sveinbjornsdottir, S. J. Johnsen, and E. R. Th. Kerstel, �?? Measuring stable isotopes of hydrogen and oxygen in ice: the Bølling transition in the Dye�??3 (south Greenland) ice core,�?? Ann. Glaciol. 35, 125-130 (2002).
[CrossRef]

Appl. Opt.

Appl. Phys. B

L. Gianfrani, P. De Natale, and G. De Natale, �??Remote sensing of volcanic gases with a DFB-laser-based fiber spectrometer,�?? Appl. Phys. B 70, 467-470 (2000).

I. Linnerud, P. Kaspersen, and T. Jaeger, �??Gas monitoring in the process industry using diode laser spectroscopy,�?? Appl. Phys. B 67, 297-305 (1998).
[CrossRef]

J. Appl. Physiol.

R. van Trigt, E. R. Th. Kerstel, R. E. M. Neubert, H. A. J. Meijer, M. McLean, and G. H. Visser, �??Validation of the doubly labeled water method in japanese quail at different water fluxes,�?? J. Appl. Physiol. 93, 2147-2154 (2002).
[PubMed]

Opt. Lett.

Rev. Sci. Instr.

G. Gagliardi, R. Restieri, G. De Biasio, P. De Natale, F. Cotrufo, and L. Gianfrani, �??Quantitative diode laser absorption spectroscopy near 2 m with high precision measurements of CO2 concentration,�?? Rev. Sci. Instr. 72, 4228-4233 (2001).
[CrossRef]

Spectrochim. Acta

E. R. Th. Kerstel, G. Gagliardi, L. Gianfrani, H. A. J. Meijer, R. van Trigt, and R. Ramaker, �??Determination of the 2H/1H, 17O/16O, and 18O/16O isotope ratios in water by means of tunable diode laser spectroscopy at 1.39 m,�?? Spectrochim. Acta 58, 2389-2396 (2002).
[CrossRef]

Other

R. A. Toth: private communication (2000).

E. R. Th. Kerstel: Isotope Ratio Infrared Spectrometry, in Handbook of Stable Isotope Analytical Techniques, ed. P.A. de Groot, Elsevier, accepted for publication.

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Figures (4)

Fig. 1.
Fig. 1.

Sketch of the experimental setup. OI stands for optical isolator, LIA for lock-in amplifier, and DL for diode laser.

Fig. 2.
Fig. 2.

Examples of absorption spectra observed in this work in two different spectral windows. The first includes H18OH, H16OH, and H17OH lines around 7183.7 cm-1, while the second shows HO2H and H16OH lines at 7197.95 and 7197.55 cm-1, respectively.

Fig. 3.
Fig. 3.

Short and long term reproducibility in the δ2H determination, using DL2. The statistical analysis of the values reported in the upper plot yielded a mean value of 1.08‰ and a 1-σ standard deviation of 0.46‰. For the values in the lower part of the figure, we found a mean value of 1.09‰ and a standard deviation of 0.84‰. “Label” refers to a single measurement of 160 s.

Fig. 4.
Fig. 4.

Examples of δ18O and δ17O measurements by means of DL2. The short-term reproducibility was found to be 0.2‰, 0.5‰, and 0.1‰, respectively for the data set plot in a), b), and c).

Tables (3)

Tables Icon

Table 1. List of the absorption lines observed in this work. Line positions and assignments were taken from Refs. [1416]. The temperature coefficients were evaluated at 296 K

Tables Icon

Table 2. Examples of δ2H determinations at 7198 cm-1, by means of DL2. Set dimension is the number of remaining measurements after removal of outliers from the original 20 or 30 measurements (see text).

Tables Icon

Table 3. Examples of δ18O and δ17O determinations at 7183 cm-1, by means of DL1.

Equations (2)

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S ( T ) = S ( T 0 ) ( T 0 T ) 3 2 exp [ hc E ' k ( 1 T 1 T 0 ) ] .
δ 18 O = ( n 18 n 16 ) sample ( n 18 n 16 ) reference 1 = ( n 18 ) sample ( n 18 ) reference ( n 16 ) sample ( n 16 ) reference 1 ,

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