Tracing water in coastal wetland soils and trees using laser spectroscopy: Errors in cryogenic vacuum distillation

Yu-Hsin Hsueh, Brandon L. Edwards, Richard F. Keim

School of Renewable Natural Resources, Louisiana State University, Baton Rouge, LA, USA

wetland hydrology requires greater experimental precision than in some other cases because of fluctuations of water table and mixture of subsurface water occur frequently. In a forested wetland of the Mississippi River delta, we used isotopes in sapwood water to distinguish Taxodium distichum water use among sources in hummocks and swales. METHOD Cryogenic vacuum distillation (CVD, Fig 1, [9]) was to extract water from soil and wood samples. Several controlled tests were used to test efficiency, accuracy, and precision of this modified system; following analysis used a liquid water isotope analyzer (LWIA) from Los Gatos Research Inc. Fig 1. CVD system
10 0 -10 2H() -20 -30 -40 -50 -60 50% 40% 30% 20% 10% Fraction remaining, F (%) 0%
T=110 C

INTRODUCTION Application of water isotopes as tracers in coastal

OBJECTIVES

1. To address the systematic error from CVD, observed deviation (product reactant) derived from incomplete extraction was compared with theoretical values (Fig. 2 and Eq. 1, [4], where F as fraction of water remaining in the extraction side; alpha as the fractionation factor at target temperature) 2. To test efficacy of extraction from wood, we soaked sapwood core specimens in deionized water, then completed extractions. (Fig. 3) 3. To test whether activated carboncommonly used to reduce volatile organic carbon VOCscaused fractionation by adding activated carbon 10- 40% by mass to deionized water and analyzing after three days. (Fig. 4)
Table 1. Comparison of CVD extraction studies
-1 -3 -5 -7 -9 -11 -13 -15 0 20 40 60 1 0 -1 -2 -3 -4 -5 -6 -7 -8 Authors Ingraham and Shadel (1992) Aragus-Aragus et al. (1995) West et al. (2006) Koeniger et al. (2011) Schmidt et al., (2012) This study Extraction method CVD CVD CVD CVD CVD CVD Isotope analyzer IRMS IRMS IRIS IRMS IRMS IRIS IRMS IRIS Sample type Loamy soil Clayey soil Clayey soil Tree core (Picea abies) Twig (beech, oak, pine) Tree core (Taxodium distichum) Standard deviation 18O 2H 11.0 1.80 3.0 0.30 0.69 0.15 4.7 0.63 0.5 0.22 2.5 0.38

2H

2 1 0 -1 -2 18O() -3 -4 -5 Rayleigh distillation -6 -7 -8 50%

T=25 C

Activated carbon

18O
2H()

T=110 C

T=25 C

Percent of activated carbon (%) in relative to the total weight of sample

Rayleigh distillation

contributed by activated carbon in deionized water.

Figure 4. Deviation of 2H and 18O

Rewetted wood
0% 2 0 -2 -4 -6 -8 -10 -12 () 18O

40% 30% 20% 10% Fraction remaining, F (%)

2H

50% 40% 30% 20% 10% 0% Figure 2. Deviation of 2H and 18O contributed by incomplete extraction References Fraction remaining, F (%) (triangles); error bars show internal error ranges for the LGR-LWIA as 2H and 18O Figure 3. Deviation of experimentally estimated in our lab. Rayleigh distillation curves (dash lines) were contributed and blank test on rewetted derived from under open and evaporating system in which water phase changes wood. between vapor-liquid-solid (Eq 1).
1. 2. 3. 4. 5. 6. 7. 8. 9.

18O()

offset for 18O, but at a lower slope for 2H (Fig.2). Error from applying activated carbon in deionized water was negligible (Fig 4). The greatest error was in extraction from wood, in which there was an average deviation in 2H - 9.2 but no identifiable deviation in 18O (Fig 3). This large deviation in 2H may come from mass error or memory effect in wood [5]. Yet comparing to other studies over the standard deviation, such errors are rather unpredictable (Table 1). In summary, systematic errors in CVD were smaller than theoretical fractionation and also less than variation in natural waters of this coastal swamp. Errors can be reduced under extraction efficiency greater than 90% and high temperature, but an empirical, systematic or species specific correction for fractionation of 2H may be appropriate.
Aragus-Aragus, L., Rozanski, K., Gonfiantini, R., & Louvat, D. (1995). Isotope effects accompanying vacuum extraction of soil water for stable isotope analyses. Journal of Hydrology, 168, 159171. Barbour, M. M., Andrews, T. J., & Farquhar, G. D. (2001). Correlations between oxygen isotope ratios of wood constituents of Quercus and Pinus samples from around the world. Australian Journal of Plant Physiology, 28(5), 335348. Brand, W. A., Geilmann, H., Crosson, E. R., & Rella, C. W. (2009). Cavity ring-down spectroscopy versus high-temperature conversion isotope ratio mass spectrometry; a case study on 2 H and 18 O of pure water samples and alcohol/water mixtures. Rapid Communications in Mass Spectrometry, 23(12), 18791884. doi:10.1002/rcm.4083 Horita, J., & Wesolowski, D. J. (1994). Liquid-vapor fractionation of oxygen and hydrogen isotopes of water from the freezing to the critical temperature. Geochimica et Cosmochimica Acta, 58(16), 34253437. doi:10.1016/0016-7037(94)90096-5 Koeniger, P., Marshall, J. D., Link, T., & Mulch, A. (2011). An inexpensive, fast, and reliable method for vacuum extraction of soil and plant water for stable isotope analyses by mass spectrometry: Vacuum extraction of soil and plant water for stable isotope analyses. Rapid Communications in Mass Spectrometry, 25(20), 30413048. doi:10.1002/rcm.5198 Schmidt, M., Maseyk, K., Lett, C., Biron, P., Richard, P., Bariac, T., & Seibt, U. (2012). Reducing and correcting for contamination of ecosystem water stable isotopes measured by isotope ratio infrared spectroscopy: Organic contaminants in water samples affecting 18O and 2H in CRDS. Rapid Communications in Mass Spectrometry, 26(2), 141153. doi:10.1002/rcm.5317 Schultz, N. M., Griffis, T. J., Lee, X., & Baker, J. M. (2011). Identification and correction of spectral contamination in 2H/1H and 18O/16O measured in leaf, stem, and soil water: Correction of 2H/1H and 18O/16O in plant and soil water using IRIS. Rapid Communications in Mass Spectrometry, 25(21), 3360 3368. doi:10.1002/rcm.5236 West, A. G., Goldsmith, G. R., Brooks, P. D., & Dawson, T. E. (2010). Discrepancies between isotope ratio infrared spectroscopy and isotope ratio mass spectrometry for the stable isotope analysis of plant and soil waters. Rapid Communications in Mass Spectrometry, 24(14). doi:10.1002/rcm.4597 West, A. G., Patrickson, S. J., & Ehleringer, J. R. (2006). Water extraction times for plant and soil materials used in stable isotope analysis. Rapid Communications in Mass Spectrometry, 20(8), 13171321. doi:10.1002/rcm.2456

Results of liquid water extractions showed deviation following the theoretical slope at an

Contact: yhsueh1@tigers.lsu.edu