Continuous In Situ Measurement of Dissolved Methane in Lake Kivu Using a Membrane Inlet Laser Spectrometer

We report the first high resolution continuous profile of dissolved methane in the shallow water of Lake Kivu, Rwanda. The measurements were performed using an in situ dissolved gas sensor, called Sub-Ocean, based on a patented, membrane based extraction technique coupled with a highly sensitive optical spectrometer. The sensor was originally designed for ocean settings, but both the spectrometer and the extraction system were modified to extend the dynamical range up to six orders of magnitude with respect to the original prototype (from nmol L−1 to mmol L−1 detection) to fit the range of concentrations at lake Kivu. The accuracy of the instrument was estimated to ±22 % (2 s) from the standard deviation of eight profiles at 80 m of depth, corresponding to ±112 μBar of CH4 in water or ±160 nmol L−1 at 25 °C and 1 atm. The instrument was able to continuously measure the top 150 m of water depth within only 25 min. The maximum observed mixing ratio of CH4 in the gas phase concentration was 77 % at 150 m depth, which at this depth and thermal condition of the lake corresponds to 3.5 mmol L−1. At deeper depth, dissolved CH4 concentrations were too large for the methane absorption spectrum to be correctly retrieved. Results were in good agreement with discrete in situ measurements conducted with the commercial HydroC sensor. The fast profiling feature will be highly profitable for future monitoring of the lake, while the spectrometer could be replaced with a less sensitive analytical technique possibly including simultaneous detection of dissolved CO2 and which would allow to measure at higher concentrations of CH4.