<?xml version="1.0" encoding="utf-8" standalone="no"?>
<!DOCTYPE article SYSTEM "http://www.atmos-meas-tech-discuss.net/inc/amtd/copernicus.dtd">
<article language="en">
	<journal>
		<journal_title>Atmospheric Measurement Techniques Discussions</journal_title>
		<journal_url>www.atmos-meas-tech-discuss.net</journal_url>
		<eissn>1867-8610</eissn>
		<volume_number>2</volume_number>
		<issue_number>4</issue_number>
		<publication_year>2009</publication_year>
	</journal>
	<doi>10.5194/amtd-2-2055-2009</doi>
	<article_url>http://www.atmos-meas-tech-discuss.net/2/2055/2009/</article_url>
	<abstract_html>http://www.atmos-meas-tech-discuss.net/2/2055/2009/amtd-2-2055-2009.html</abstract_html>
	<fulltext_pdf>http://www.atmos-meas-tech-discuss.net/2/2055/2009/amtd-2-2055-2009.pdf</fulltext_pdf>
	<start_page>2055</start_page>
	<end_page>2085</end_page>
	<publication_date>2009-08-28</publication_date>
	<article_title content_type="html">Water vapor &amp;delta;&lt;sup&gt;2&lt;/sup&gt;H and &amp;delta;&lt;sup&gt;18&lt;/sup&gt;O  measurements using off-axis integrated cavity output spectroscopy</article_title>
	<authors>
		<author numeration="1" affiliations="1">
			<name>P. Sturm</name>
			<email>patrick.sturm@ipw.agrl.ethz.ch</email>
		</author>
		<author numeration="2" affiliations="1">
			<name>A. Knohl</name>
		</author>
	</authors>
	<affiliations>
		<affiliation numeration="1" content_type="html">Institute of Plant Sciences, ETH Zürich, Universitätsstrasse 2, 8092 Zürich, Switzerland</affiliation>
	</affiliations>
	<abstract content_type="html">We present a detailed assessment of a commercially available water vapor
isotope analyzer (WVIA, Los Gatos Research, Inc.) for simultaneous in-situ
measurements of &amp;delta;&lt;sup&gt;2&lt;/sup&gt;H and &amp;delta;&lt;sup&gt;18&lt;/sup&gt;O in water vapor. This method, based on off-axis
integrated cavity output spectroscopy, is an alternative to the conventional
water trap/isotope ratio mass spectrometry (IRMS) techniques. We evaluate the
analyzer in terms of precision, memory effects, concentration dependence,
temperature sensitivity and long-term stability. A calibration system based
on ink jet technology is used to characterize the performance and to
calibrate the analyzer. Our results show that the precision at an averaging
time of 15 s is 0.16&amp;permil; for &amp;delta;&lt;sup&gt;2&lt;/sup&gt;H and 0.08&amp;permil; for &amp;delta;&lt;sup&gt;18&lt;/sup&gt;O. The isotope
ratios are strongly dependent on the water mixing ratio of the air. Taking
into account this concentration dependence as well as the temperature
sensitivity of the instrument we obtained a long-term stability of the water
isotope measurements of 0.38&amp;permil; for &amp;delta;&lt;sup&gt;2&lt;/sup&gt;H and 0.25&amp;permil; for &amp;delta;&lt;sup&gt;18&lt;/sup&gt;O. The
accuracy of the WVIA was further assessed by comparative measurements using
IRMS and a dew point generator indicating a linear response in isotopic
composition and H&lt;sub&gt;2&lt;/sub&gt;O concentrations. The WVIA combined with a calibration
system provides accurate high resolution water vapor isotope measurements and
opens new possibilities for hydrological and ecological applications.</abstract>
	<references>
		<reference numeration="1" content_type="text"> Andersen, K., Azuma, N., Barnola, J., Bigler, M., Biscaye, P., Caillon, N., Chappellaz, J., Clausen, H., Dahl-Jensen, D., Fischer, H., et~al.: High-resolution record of Northern Hemisphere climate extending into the last interglacial period, Nature, 431, 147–151, 2004. </reference>
		<reference numeration="2" content_type="text"> Angert, A., Lee, J., and Yakir, D.: Seasonal variations in the isotopic composition of near-surface water vapour in the eastern Mediterranean, Tellus B, 60, 674–684, doi:10.1111/j.1600-0889.2008.00357.x, 2008. </reference>
		<reference numeration="3" content_type="text"> Baer, D., Paul, J., Gupta, M., and O&apos;Keefe, A.: Sensitive absorption measurements in the near-infrared region using off-axis integrated-cavity-output spectroscopy, Appl. Phys. B-Lasers O., 75, 261–265, doi:10.1007/s00340-002-0971-z, 2002. </reference>
		<reference numeration="4" content_type="text"> Barbour, M.: Stable oxygen isotope composition of plant tissue: a review, Funct. Plant Biol., 34, 83–94, doi:10.1071/FP06228, 2007. </reference>
		<reference numeration="5" content_type="text"> Brand, W A., Geilmann, H., Crosson, E R., and Rella, C W.: Cavity ring-down spectroscopy versus high-temperature conversion isotope ratio mass spectrometry and a case study on $\delta^2$H and $\delta^18$O of pure water samples and alcohol/water mixtures, Rapid Commun. Mass Sp., 23, 1879–1884, doi:10.1002/rcm.4083, 2009. </reference>
		<reference numeration="6" content_type="text"> Buck, A.: New equations for computing vapor pressure and enhancement factor, J. Appl. Meteorol., 20, 1527–1532, 1981. </reference>
		<reference numeration="7" content_type="text"> Coplen, T., Wildman, J., and Chen, J.: Improvements in the gaseous hydrogen-water equilibration technique for hydrogen isotope-ratio analysis, Anal. Chem., 63, 910–912, 1991. </reference>
		<reference numeration="8" content_type="text"> Epstein, S. and Mayeda, T.: Variation of O$^18$ content of waters from natural sources, Geochim. Cosmochim. Ac., 4, 213–224, doi:10.1016/0016-7037(53)90051-9, 1953. </reference>
		<reference numeration="9" content_type="text"> Farquhar, G., Cernusak, L., and Barnes, B.: Heavy Water Fractionation during Transpiration, Plant Physiol., 143, 11–18, doi:10.1104/pp.106.093278, 2007. </reference>
		<reference numeration="10" content_type="text"> Gat, J.: Oxygen and hydrogen isotopes in the hydrologic cycle, Annu. Rev. Earth Pl. Sc., 24, 225–262, 1996. </reference>
		<reference numeration="11" content_type="text"> Gehre, M., Geilmann, H., Richter, J., Werner, R., and Brand, W.: Continuous flow &lt;sup&gt;2&lt;/sup&gt;H/$^1$H and $^18$O/$^16$O analysis of water samples with dual inlet precision, Rapid Commun. Mass Sp., 18, 2650–2660, doi:10.1002/rcm.1672, 2004. </reference>
		<reference numeration="12" content_type="text"> Gianfrani, L., Gagliardi, G., van Burgel, M., and Kerstel, E.: Isotope analysis of water by means of near infrared dual-wavelength diode laser spectroscopy, Opt. Express, 11, 1566–1576, 2003. </reference>
		<reference numeration="13" content_type="text"> Gonfiantini, R.: Standards for stable isotope measurements in natural compounds, Nature, 271, 534–536, 1978. </reference>
		<reference numeration="14" content_type="text"> Gupta, P., Noone, D., Galewsky, J., Sweeney, C., and Vaughn, B. H.: Demonstration of high-precision continuous measurements of water vapor isotopologues in laboratory and remote field deployments using wavelength-scanned cavity ring-down spectroscopy (WS-CRDS) technology, Rapid Commun. Mass Sp., 23, 2534–2542, doi:10.1002/rcm.4100, 2009. </reference>
		<reference numeration="15" content_type="text"> Han, L., Groning, M., Aggarwal, P., and Helliker, B.: Reliable determination of oxygen and hydrogen isotope ratios in atmospheric water vapour adsorbed on 3A molecular sieve, Rapid Commun. Mass Sp., 20, 3612–3618, doi:10.1002/rcm.2772, 2006. </reference>
		<reference numeration="16" content_type="text"> Iannone, R Q., Romanini, D., Kassi, S., Meijer, H A., and Kerstel, E. R T.: A microdrop generator for the calibration of a water vapor isotope ratio spectrometer, J. Atmos. Ocean. Tech., 26, 1275–1288, doi:10.1175/2008JTECHA1218.1, 2009. </reference>
		<reference numeration="17" content_type="text"> Kerstel, E., van Trigt, R., Dam, N., Reuss, J., and Meijer, H.: Simultaneous determination of the &lt;sup&gt;2&lt;/sup&gt;H/$^1$H, $^17$O/$^16$O, and $^18$O/$^16$O isotope abundance ratios in water by means of laser spectrometry, Anal. Chem., 71, 5297–5303, 1999. </reference>
		<reference numeration="18" content_type="text"> Kerstel, E., Gagliardi, G., Gianfrani, L., Meijer, H., van Trigt, R., and Ramaker, R.: Determination of the &lt;sup&gt;2&lt;/sup&gt;H/$^1$H, $^17$O/$^16$O, and $^18$O/$^16$O isotope ratios in water by means of tunable diode laser spectroscopy at 1.39 μm, Spectrochim. Acta A, 58, 2389–2396, 2002. </reference>
		<reference numeration="19" content_type="text"> Kerstel, E., Iannone, R., Chenevier, M., Kassi, S., Jost, H., and Romanini, D.: A water isotope (&lt;sup&gt;2&lt;/sup&gt;H, $^17$O, and $^18$O) spectrometer based on optical feedback cavity-enhanced absorption for in situ airborne applications, Appl. Phys. B-Lasers O., 85, 397–406, doi:10.1007/s00340-006-2356-1, 2006. </reference>
		<reference numeration="20" content_type="text"> 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. </reference>
		<reference numeration="21" content_type="text"> Lis, G., Wassenaar, L I., and Hendry, M J.: High-Precision Laser Spectroscopy D/H and $^18$O/$^16$O Measurements of Microliter Natural Water Samples, Anal. Chem., 80, 287–293, doi:10.1021/ac701716q, 2008. </reference>
		<reference numeration="22" content_type="text"> Majoube, M.: Fractionnement en oxygène-18 et en deutérium entre l&apos;eau et sa vapeur, J. Chim. Phys., 68, 1423–1436, 1971. </reference>
		<reference numeration="23" content_type="text"> Rothman, L., Jacquemart, D., Barbe, A., Chris~Benner, D., Birk, M., Brown, L., Carleer, M., Chackerian, C., Chance, K., Coudert, L., et~al.: The HITRAN 2004 molecular spectroscopic database, J. Quant. Spectrosc. Ra., 96, 139–204, doi:10.1016/j.jqsrt.2004.10.008, 2005. </reference>
		<reference numeration="24" content_type="text"> Uemura, R., Matsui, Y., Yoshimura, K., Motoyama, H., and Yoshida, N.: Evidence of deuterium excess in water vapor as an indicator of ocean surface conditions, J. Geophys. Res., 113, D19114, doi:10.1029/2008JD010209, 2008. </reference>
		<reference numeration="25" content_type="text"> Wang, L., Caylor, K., and Dragoni, D.: On the calibration of continuous, high-precision $\delta^18$O and $\delta^2$H measurements using an off-axis integrated cavity output spectrometer, Rapid Commun. Mass Sp., 23, 530–536, doi:10.1002/rcm.3905, 2009. </reference>
		<reference numeration="26" content_type="text"> Wen, X., Sun, X., Zhang, S., Yu, G., Sargent, S., and Lee, X.: Continuous measurement of water vapor D/H and $^18$O/$^16$O isotope ratios in the atmosphere, J. Hydrol., 349, 489–500, doi:10.1016/j.jhydrol.2007.11.021, 2008. </reference>
		<reference numeration="27" content_type="text"> Werle, P., Mücke, R., and Slemr, F.: The limits of signal averaging in atmospheric trace-gas monitoring by tunable diode-laser absorption spectroscopy (TDLAS), Appl. Phys. B-Lasers O., 57, 131–139, 1993. </reference>
	</references>
</article>

