References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-8-5263-2008

Long-term field performance of a tunable diode laser absorption spectrometer for analysis of carbon isotopes of CO2 in forest air

Schaeffer

S. M.

¹ ⁶ Miller

J. B.

² ³ Vaughn

B. H.

⁴ White

J. W. C.

⁴ Bowling

D. R.

¹ ⁵

Department of Biology, University of Utah, Salt Lake City, UT 84112, USA

National Oceanic and Atmospheric Administration, Earth System Research Laboratory, Boulder, CO 80305, USA

Cooperative Institute for Research in Environmental Science, University of Colorado, Boulder, CO 80309, USA

Institute for Arctic and Alpine Research, University of Colorado, Boulder, CO 80302, USA

Stable Isotope Ratio Facility of Environmental Research, University of Utah, Salt Lake City, UT 84112, USA

now at: Department of Ecology, Evolution, and Marine Biology, University of California, Santa Barbara, CA 93106, USA

05 09 2008

8 17 5263 5277

This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

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Tunable diode laser absorption spectrometry (TDLAS) is gaining in popularity for measuring the mole fraction [CO2] and stable isotopic composition (δ13C) of carbon dioxide (CO2) in air in studies of biosphere-atmosphere gas exchange. Here we present a detailed examination of the performance of a commercially-available TDLAS located in a high-altitude subalpine coniferous forest (the Niwot Ridge AmeriFlux site), providing the first multi-year analysis of TDLAS instrument performance for measuring CO2 isotopes in the field. Air was sampled from five to nine vertical locations in and above the forest canopy every ten minutes for 2.4 years. A variety of methods were used to assess instrument performance. Measurement of two compressed air cylinders that were in place over the entire study establish the long-term field precision of 0.2 μmol mol−1 for [CO2] and 0.35&permil; for δ13C, but after fixing several problems the isotope precision improved to 0.2\permil (over the last several months). The TDLAS provided detail on variability of δ13C of atmospheric CO2 that was not represented in weekly flask samples, as well as information regarding the influence of large-scale (regional) seasonal cycle and local forest processes on [CO2] and δ13C of CO2. There were also clear growing season and winter differences in the relative contributions of photosynthesis and respiration on the [CO2] and δ13C of forest air.

References 1

Allison, C. E. and Francey, R. J.: Verifying Southern Hemisphere trends in atmospheric carbon dioxide stable isotopes, J. Geophys. Res., 112, D21304, doi:10.1029/2006JD007345, 2007.

Alstad, K. P., Lai, C.-T., Flanagan, L. B., and Ehleringer, J. R.: Environmental controls on the carbon isotope composition of ecosystem-respired CO2 in contrasting forest ecosystems in Canada and the USA, Tree Physiol., 27, 1361–1374, 2007.

Bakwin, P. S., Tans, P. P., White, J. W. C., and Andres, R. J.: Determination of the isotopic ($^13$C/$^12$C) discrimination by terrestrial biology from a global network of observations, Global Biogeochem. Cy., 12, 555–562, 1998.

Barbour, M. M., Farquhar, G. D., Hanson, D. T., Bickford, C. P., Powers, H., and McDowell, N. G.: A new measurement technique reveals temporal variation in $\delta ^18$O of leaf-respired CO2, Plant Cell Environ., 30, 456–468, 2007a.

Barbour, M. M., McDowell, N. G., Tcherkez, G., Bickford, C. P., and Hanson, D. T.: A new measurement technique reveals rapid post-illumination changes in the carbon isotope composition of leaf-respired CO2, Plant Cell Environ., 30, 469–482, 2007b.

Becker, J. F., Sauke, T. B., and Loewenstein, M.: Stable isotope analysis using tunable diode laser spectroscopy, Appl. Optics, 31, 1921–1927, 1992.

Bowling, D. R., Sargent, S. D., Tanner, B. D., and Ehleringer, J. R.: Tunable diode laser absorption spectroscopy for stable isotope studies of ecosystem-atmosphere CO2 exchange, Agr. Forest Meteorol., 118, 1–19, 2003.

Bowling, D. R., Burns, S. P., Conway, T. J., Monson, R. K., and White, J. W. C.: Extensive observations of CO2 carbon isotope content in and above a high-elevation subalpine forest, Global Biogeochem. Cy., 19, GB3023, doi:10.1029/2004GB002394, 2005.

Bowling, D. R., Pataki, D. E., and Randerson, J. T.: Carbon isotopes in terrestrial ecosystem pools and CO2 fluxes, New Phytol., 178, 24–40, 2008.

Brand, W. A.: High Precision Isotope Ratio Monitoring Techniques in Mass Spectrometry, J. Mass Spectrom., 31, 225–235, 1996.

Ciais, P., Tans, P. P., White, J. W. C., Trolier, M., Francey, R. J., Berry, J. A., Randall, D. R., Sellers, P. J., Collatz, J. G., and Schimel, D. S.: Partitioning of ocean and land uptake of CO2 as inferred by $\delta ^13$C measurements from the NOAA Climate Monitoring and Diagnostics Laboratory Global Air Sampling Network, J. Geophys. Res., 100, 5051–5070, 1995.

Craig, H.: Isotopic standards for carbon and oxygen and correction factors for mass-spectrometric analysis of carbon dioxide, Geochim. Cosmochim. Ac., 12, 133–149, 1957.

Crosson, E. R., Ricci, K. N., Richman, B. A., Chilese, F. C., Owano, T. G., Provencal, R. A., Todd, M. W., Glasser, J., Kachanov, A. A., Paldus, B. A., Spence, T. G., and Zare, R. N.: Stable isotope ratios using cavity ring-down spectroscopy: Determination of $^13$C/$^12$C for carbon dioxide in human breath, Anal. Chem., 74, 2003–2007, 2002.

Esler, M. B., Griffith, D. W. T., Wilson, S. R., and Steele, L. P.: Precision trace gas analysis by FT-IR spectroscopy. 2. The $^13$C/$^12$C isotope ratio of CO2, Anal. Chem., 72, 216–221, 2000.

Farquhar, G. D., Ehleringer, J. R., and Hubick, K. T.: Carbon isotope discrimination and photosynthesis, Annu. Rev. Plant Phys., 40, 503–537, 1989.

Fisher, R., Lowry, D., Wilkin, O., Sriskantharajah, S., and Nisbet, E. G.: High-precision, automated stable isotope analysis of atmospheric methane and carbon dioxide using continuous-flow isotope-ratio mass spectrometry, Rapid Commun. Mass Sp., 20, 200–208, 2006.

Francey, R. J., Tans, P. P., Allison, C. E., Enting, I. G., White, J. W. C., and Trolier, M.: Changes in oceanic and terrestrial carbon uptake since 1982, Nature, 373, 326–330, 1995.

Francey, R. J., Allison, C. E., Etheridge, D. M., Trudinger, C. M., Enting, I. G., Leuenberger, M., Langenfelds, R. L., Michel, E., and Steele, L. P.: A 1000-year high precision record of $\delta ^13$C in atmospheric CO2, Tellus, 51B, 170–193, 1999.

Griffis, T. J., Baker, J. M., Sargent, S. D., Tanner, B. D., and Zhang, J.: Measuring field-scale isotopic CO2 fluxes with tunable diode laser absorption spectroscopy and micrometeorological techniques, Agr. Forest Meteorol., 124, 15–29, 2004.

Griffis, T. J., Baker, J. M., and Zhang, J.: Seasonal dynamics and partitioning of isotopic CO2 exchange in a C3/C4 managed ecosystem, Agr. Forest Meteorol., 132, 1–19, 2005a.

Griffis, T. J., Lee, X., Baker, J. M., Sargent, S. D., and King, J. Y.: Feasibility of quantifying ecosystem-atmosphere C$^18$O$^16$O exchange using laser spectroscopy and the flux-gradient method, Agr. Forest Meteorol., 135, 44–60, 2005b.

Griffis, T. J., Zhang, J., Baker, J. M., Kljun, N., and Billmark, K.: Determining carbon isotope signatures from micrometeorological measurements: Implications for studying biosphere-atmosphere exchange processes, Bound.-Lay. Meteorol., 123, 295–316, 2007.

Griffith, D. W. T., Toon, G. C., Sen, B., Blavier, J. F., and Toth, R. A.: Vertical profiles of nitrous oxide isotopomer fractionation measured in the stratosphere, Geophys. Res. Lett., 27, 2485–2488, 2000.

Gulluk, T., Wagner, H. E., and Slemr, F.: A high-frequency modulated tunable diode laser absorption spectrometer for measurements of CO2, CH4, N2O, and CO in air samples of a few cm3, Rev. Sci. Instrum., 68, 230–239, 1997.

Hoefs, J.: Stable Isotope Geochemistry, Springer, Berlin, 201 pp., 1997.

Keeling, C. D., Whorf, T. P., Wahlen, M., and van der Plicht, J.: Interannual extremes in the rate of rise of atmospheric carbon dioxide since 1980, Nature, 375, 666–670, 1995.

Knohl, A.: Carbon dioxide exchange and isotopic signature ($^13$C) of an unmanaged 250 year-old deciduous forest, PhD dissertation, FS Universitat Jena, Germany, 2003.

Knohl, A. and Buchmann, N.: Partitioning the net CO2 flux of a deciduous forest into respiration and assimilation using stable carbon isotopes, Global Biogeochem. Cy., 19, GB4008, doi:10.1029/2004GB002301, 2005.

Knohl, A., Werner, R. A., Brand, W. A., and Buchmann, N.: Short-term variations in $\delta ^13$C of ecosystem respiration reveals link between assimilation and respiration in a deciduous forest, Oecologia, 142, 70–82, 2005.

Lai, C.-T., Ehleringer, J. R., Schauer, A. J., Tans, P. P., Hollinger, D. Y., Paw U, K. T., Munger, J. W., and Wofsy, S. C.: Canopy-scale $\delta ^13$C of photosynthetic and respiratory CO2 fluxes: observations in forest biomes across the United States, Glob. Change Biol., 11, 633–643, 2005.

Lai, C. T., Ehleringer, J. R., Tans, P., Wofsy, S. C., Urbanski, S. P., and Hollinger, D. Y.: Estimating photosynthetic $^13$C discrimination in terrestrial CO2 exchange from canopy to regional scales, Global Biogeochem. Cy., 18, GB1041, doi:10.1029/2003GB002148, 2004.

Lai, C. T., Riley, W., Owensby, C., Ham, J., Schauer, A., and Ehleringer, J. R.: Seasonal and interannual variations of carbon and oxygen isotopes of respired CO2 in a tallgrass prairie: Measurements and modeling results from 3 years with contrasting water availability, J. Geophys. Res.-Atmos., 111, D08S06, doi:10.1029/2005JD006436, 2006.

Lee, X., Sargent, S., Smith, R., and Tanner, B.: In situ measurement of the water vapor $^18$O/$^16$O isotope ratio for atmospheric and ecological applications, J. Atmos. Ocean. Tech., 22, 555–565, 2005.

Masarie, K. A., Langenfelds, R. L., Allison, C. E., Conway, T. J., Dlugokencky, E. J., Francey, R. J., Novelli, P. C., Steele, L. P., Tans, P. P., Vaughn, B., and White, J. W. C.: NOAA/CSIRO Flask Air Intercomparison Experiment: A strategy for directly assessing consistency among atmospheric measurements made by independent laboratories, J. Geophys. Res.-Atmos., 106, 20 445–20 464, 2001.

McManus, J. B., Nelson, D. D., Shorter, J. H., Jimenez, R., Herndon, S., Saleska, S., and Zahniser, M.: A high precision pulsed quantum cascade laser spectrometer for measurements of stable isotopes of carbon dioxide, J. Mod. Optic., 52, 2309–2321, 2005.

Monson, R. K., Turnipseed, A. A., Sparks, J. P., Harley, P. C., Scott-Denton, L. E., Sparks, K., and Huxman, T. E.: Carbon sequestration in a high-elevation, subalpine forest, Glob. Change Biol., 8, 459–478, 2002.

Monson, R. K., Burns, S. P., Williams, M. W., Delany, A. C., Weintraub, M., and Lipson, D. A.: The contribution of beneath-snow soil respiration to total ecosystem respiration in a high-elevation, subalpine forest, Global Biogeochem. Cy., 20, GB3030, doi:10.1029/2005GB002684, 2006.

Mortazavi, B., Chanton, J. P., Prater, J. L., Oishi, A. C., Oren, R., and Katul, G.: Temporal variability in $^13$C of respired CO2 in a pine and a hardwood forest subject to similar climatic conditions, Oecologia, 142, 57–69, 2005.

Mortazavi, B., Chanton, J. P., and Smith, M. C.: Influence of $^13$C-enriched foliage respired CO2 on $\delta ^13$C of ecosystem-respired CO2, Global Biogeochem. Cy., 20, GB3029, doi:10.1029/2005GB002650, 2006.

Murnick, D. E. and Peer, B. J.: Laser-based analysis of carbon isotope ratios, Science, 263, 945–947, 1994.

Murnick, D. E. and Okil, J. O.: Use of the optogalvanic effect (OGE) for isotope ratio spectrometry of $^13$CO2 and $^14$CO2, Isot. Environ. Healt. S., 41, 363–371, 2005.

Ogee, J., Peylin, P., Ciais, P., Bariac, T., Brunet, Y., Berbigier, P., Roche, C., Richard, P., Bardoux, G., and Bonnefond, J.-M.: Partitioning net ecosystem carbon exchange into net assimilation and respiration using $^13$CO2 measurements: A cost-effective sampling strategy, Global Biogeochem. Cy., 17, 1070, doi:10.1029/2002GB001995, 2003.

Pataki, D. E., Ehleringer, J. R., Flanagan, L. B., Yakir, D., Bowling, D. R., Still, C. J., Buchmann, N., Kaplan, J. O., and Berry, J. A.: The application and interpretation of Keeling plots in terrestrial carbon cycle research, Global Biogeochem. Cy., 17, 1022, doi:10.1029/2001GB001850, 2003.

Pataki, D. E., Bowling, D. R., Ehleringer, J. R., and Zobitz, J. M.: High resolution atmospheric monitoring of urban carbon dioxide sources, Geophys. Res. Lett., 33, L03813, doi:10.1029/2005GL024822, 2006.

Provencal, R., Gupta, M., Owano, T. G., Baer, D. S., Ricci, K. N., O'Keefe, A., and Podolske, J. R.: Cavity-enhanced quantum-cascade laser-based instrument for carbon monoxide measurements, Appl. Optics, 44, 6712–6717, 2005.

Sacks, W. J., Schimel, D. S., and Monson, R. K.: Coupling between carbon cycling and climate in a high-elevation, subalpine forest: a model-data fusion analysis, Oecologia, 151, 54–68, 2007.

Saleska, S. R., Shorter, J. H., Herndon, S., Jimenez, R., McManus, B., Munger, J. W., Nelson, D. D., and Zahniser, M. S.: What are the instrumentation requirements for measuring the isotopic composition of net ecosystem exchange of CO2 using eddy covariance methods?, Isot. Environ. Healt. S., 42, 115–133, 2006.

Schaeffer, S. M., Anderson, D. E., Burns, S. P., Monson, R. K., Sun, J., and Bowling, D. R.: Canopy structure and atmospheric flows in relation to the $\delta ^13$C of respired CO2 in a subalpine coniferous forest, Agr. Forest Meteorol., 148, 592–605, 2008.

Schauer, A. J., Lott, M. J., Cook, C. S., and Ehleringer, J. R.: An automated system for stable isotope and concentration analyses of CO2 from small atmospheric samples, Rapid Commun. Mass Sp., 19, 359–362, 2005.

Scholze, M., Kaplan, J. O., Knorr, W., and Heimann, M.: Climate and interannual variability of the atmosphere-biosphere $^13$CO2 flux, Geophys. Res. Lett., 30, 1097, doi:10.1029/2002GL015631, 2003.

Tans, P. P., Bakwin, P. S., and Guenther, D. W.: A feasible global carbon cycle observing system: a plan to decipher today's carbon cycle based on observations, Glob. Change Biol., 2, 309–318, 2005.

Trolier, M., White, J. W. C., Tans, P. P., Masarie, K. A., and Gemery, P. A.: Monitoring the isotopic composition of atmospheric CO2: Measurements from the NOAA Global Air Sampling Network, J. Geophys. Res.-Atmos., 101, 25 897–25 916, 1996.

Turnipseed, A. A., Blanken, P. D., Anderson, D. E., and Monson, R. K.: Energy budget above a high-elevation subalpine forest in complex topography, Agr. Forest Meteorol., 110, 177–201, 2002.

Vaughn, B. H., Ferretti, D. F., Miller, J., and White, J. W. C.: Stable isotope measurements of atmospheric CO2 and CH4, in: Handbook of Stable Isotope Analytical Techniques, edited by: de Groot, P. A., Elsiever, Amsterdam, 272–304, 2004.

Wahl, E. H., Fidric, B., Rella, C. W., Koulikov, S., Kharlamov, B., Tan, S., Kachanov, A. A., Richman, B. A., Crosson, E. R., Paldus, B. A., Kalaskar, S., and Bowling, D. R.: Applications of cavity ring-down spectroscopy to high precision isotope ratio measurement of $^13$C/$^12$C in carbon dioxide, Isot. Environ. Healt. S., 42, 21–35, 2006.

Webster, C. R., Flesch, G. J., Scott, D. C., Swanson, J. E., May, R. D., Woodward, W. S., Gmachl, C., Capasso, F., Sivco, D. L., Baillargeon, J. N., Hutchinson, A. L., and Cho, A. Y.: Quantum-cascade laser measurements of stratospheric methane and nitrous oxide, Appl. Optics, 40, 321–326, 2001.

Weidmann, D., Wysocki, G., Oppenheimer, C., and Tittel, F. K.: Development of a compact quantum cascade laser spectrometer for field measurements of CO2 isotopes, Appl. Phys. B-Lasers O., 80, 255–260, 2005.

Zhang, J., Griffis, T. J., and Baker, J. M.: Using continuous stable isotope measurements to partition net ecosystem CO2 exchange, Plant Cell Environ., 29, 483–496, 2006.

Zhang, Q. L. and Li, W.-J.: A calibrated measurement of the atomic weight of carbon, Chinese Sci. Bull., 35, 290–296, 1990.