Efficient collection and preparation of methane from low concentration waters for natural abundance radiocarbon analysis

K. J. Sparrow; J. D. Kessler
2017 | Limnol Oceanogr Methods

Freshwater and marine environments constitute the largest global reservoirs of the greenhouse gas methane (CH4) and natural abundance radiocarbon measurements (14C-CH4) can allow for high confidence interpretations about CH4 dynamics operating in these environments. Collecting sufficient amounts of CH4 sample for a standard, high precision 14C-accelerator mass spectrometry (AMS) analysis (∼ 200 μg carbon (C)) was previously unfeasible when sampling from low CH4 concentration waters, such as much of the surface ocean (∼ 2 nM), which would require collecting the CH4 from 8500 L of seawater. The method described here involves pumping 20,000–40,000 L of seawater up from depth through a dissolved gas extraction system, which enables the collection of a sample composed of 100s of L of gas in less than 4 h on station. The large volume extracted gas sample is compressed into a 1.7 L cylinder for transport from the ship to the home laboratory. The home laboratory preparation of each sample to a CH4-derived carbon dioxide aliquot for 14C-AMS analysis is carried out in 3 h on a flow-through vacuum line that simultaneously prepares aliquots for stable isotope analyses (δ13C-CH4 and δ2H-CH4). The total process blank of the method is small (5.0 μg CH4-C) and composes 1.2% of the average collected and prepared sample (424 ± 163 μg, from a recent campaign; n = 16). The 14C-CH4 blanks prepared on the vacuum line have acceptably low 14C content (0.23 ± 0.07 percent Modern Carbon (pMC); n = 7) relative to the 14C-dead (0 pMC) CH4 from which they are prepared.

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