Improved Methods for High Precision Isotope-Ratio Infrared Laser
Spectroscopy of Ecohydrological Waters with Organic Contaminants
Abstract
Applications of high-precision isotope analysis of ecohydrological water
samples such as soil and plant waters with infrared (IR) laser
spectrometry have been hampered by spectral interferences of volatile
organic compounds. In this study, three methods were tested to remove
methanol (MeOH) and/or ethanol (EtOH) added to water for δ
2H, δ 18O, and
17O-excess analysis with Picarro L2140-i: Micro
Combustion Module (MCM), pre-treatment with solid-phase extraction
(SPE), and pre-treatment with simple MeOH/EtOH combustion (SMEC) method.
The Picarro MCM was not able to combust the alcohols of high
concentrations. Hydrophilic-Lipophilic Balanced (HLB) SPE could adsorb
MeOH/EtOH at low concentrations (e.g., 0.1% EtOH). However, its
adsorption capacity could be readily exhausted, and adsorbed water on
the SPE adsorbents co-elutes and mix with a sample water. The SMEC can
successfully combust highly concentrated waters (0.5% MeOH and 1%
EtOH) at 450-500°C, but the alcohol combustion and oxygen isotope
exchange with added O 2 could significantly increase δ
18O values (up to 6-7‰) and decrease
17O-excess (up to 110 per meg) in the presence of a
catalyst. A strategy of combining the two methods is proposed for
high-precision isotope analysis of organic contaminated samples:
post-analysis corrections of Picarro MCM data (δ 2H
and δ 18O) and pre-treatment with SMEC method (δ
2H and 17O-excess). Overall accuracy
and precision are ≤3 and ≤2 ‰ (δ 2H), ≤0.2 and ≤0.3‰
(δ 18O), and ≤20 and ≤47 per meg (
17O-excess), respectively.