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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 6 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 % (2σ) from the standard deviation of eight profiles at 80 m depth, corresponding to ±0.112 mbar of CH4 in water or ±160 nmol L -1 at 25 ∘ C and 1 atm. The instrument was able to continuously profile the top 150 m of the water column within only 25 min. The maximum observed mixing ratio of CH4 in the gas phase concentration was 77 %, which at 150 m depth and under thermal conditions of the lake corresponds to 3.5 mmol L -1. Deeper down, dissolved CH4 concentrations were too large for the methane absorption spectrum to be correctly retrieved. Results are in good agreement with discrete in situ measurements conducted with the commercial HydroC® sensor. This fast-profiling feature is highly useful for studying the transport, production and consumption of CH4 and other dissolved gases in aquatic systems. While the sensor is well adapted for investigating most environments with a concentration of CH4 up to a few millimoles per liter, in the future the spectrometer could be replaced with a less sensitive analytical technique possibly including simultaneous detection of dissolved CO2 and total dissolved gas pressure, for exploring settings with very high concentrations of CH4 such as the bottom waters of Lake Kivu. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Methane (CH4) in marine sediments has the potential to contribute to changes in the ocean and climate system. Physical and biochemical processes that are difficult to quantify with current standard methods such as acoustic surveys and discrete sampling govern the distribution of dissolved CH4 in oceans and lakes. Detailed observations of aquatic CH4 concentrations are required for a better understanding of CH4 dynamics in the water column, how it can affect lake and ocean acidification, the chemosynthetic ecosystem, and mixing ratios of atmospheric climate gases. Here we present pioneering high-resolution in situ measurements of dissolved CH4 throughout the water column over a 400 m deep CH4 seepage area at the continental slope west of Svalbard. A new fast-response underwater membrane-inlet laser spectrometer sensor demonstrates technological advances and breakthroughs for ocean measurements. We reveal decametre-scale variations in dissolved CH4 concentrations over the CH4 seepage zone. Previous studies could not resolve such heterogeneity in the area, assumed a smoother distribution, and therefore lacked both details on and insights into ongoing processes. We show good repeatability of the instrument measurements, which are also in agreement with discrete sampling. New numerical models, based on acoustically evidenced free gas emissions from the seafloor, support the observed heterogeneity and CH4 inventory. We identified sources of CH4 , undetectable with echo sounder, and rapid diffusion of dissolved CH4 away from the sources. Results from the continuous ocean laser-spectrometer measurements, supported by modelling, improve our understanding of CH4 fluxes and related physical processes over Arctic CH4 degassing regions. [ABSTRACT FROM AUTHOR]

Methane (CH4) in marine sediments has the potential to contribute to changes in the ocean- and climate system. Physical and biochemical processes that are difficult to quantify with current standard methods such as acoustic surveys and discrete sampling govern the distribution of dissolved CH4 in oceans and lakes. Detailed observations of aquatic CH4 concentrations are required for a better understanding of CH4 dynamics in the water column, how it can affect lake- and ocean acidification, the chemosynthetic ecosystem, and mixing ratios of atmospheric climate gases. Here we present pioneering high-resolution in-situ measurements of dissolved CH4 throughout the water column over a 400 m deep CH4 seepage area at the continental slope west of Svalbard. A new fast-response under-water membrane-inlet laser spectrometer sensor demonstrates technological advances and breakthroughs for ocean measurements. We reveal decametre-scale variations of dissolved CH4 concentrations over the CH4 seepage zone. Previous studies could not resolve such heterogeneity in the area, assumed smoother distribution and therefore lacked both details and insights to ongoing processes. We show good repeatability of the instrument measurements, which are also in agreement with discrete sampling. New numerical models, based on acoustically evidenced free gas emissions from the seafloor, support the observed heterogeneity and CH4 inventory. We identified sources of CH4, undetectable with echosounder, and rapid diffusion of dissolved CH4 away from the sources. Results from the continuous ocean laser-spectrometer measurements, supported by modelling, improve our understanding of CH4 fluxes and related physical processes over Arctic CH4 degassing regions. [ABSTRACT FROM AUTHOR]

Simultaneous measurement of C2H6 and CH4 concentrations, and of the δ13C-CH4 isotope ratio is demonstrated using a cavity enhanced absorption spectroscopy technique in the mid-IR region. The spectrometer is compact and has been designed for field operation. It relies on optical-feedback assisted injection of 3.3-μm radiation from an Interband Cascade Laser (ICL) into a V-shaped high-finesse optical cavity. A minimum absorption coefficient of 2.8×10−9cm−1 is obtained in a single scan (0.1s) over 0.7cm−1. Precisions of 3ppbv, 11ppbv, and 0.08‰ for C2H6, CH4, and δ13C-CH4, respectively, are achieved after 400s of integration time. Laboratory calibrations and tests of performance are reported here. They show the potential for the spectrometer to be embedded in a sensor probe for in situ measurements in ocean waters, which could have important applications for the understanding of the source and fate of hydrocarbons from the seabed and in the water column. [ABSTRACT FROM AUTHOR]