Improved Membrane Inlet Mass Spectrometer Method for Measuring Dissolved Methane Concentration and Methane Production Rate in a Large Shallow Lake

Natural water bodies, such as lakes, rivers, and oceans, are important sources of atmospheric methane (CH4). Therefore, quantitative and accurate determination of the dissolved CH4 concentration in water is of great significance for studying CH4 emissions and providing an in-depth understanding of the carbon cycle. Headspace gas chromatography (HGC) is the traditional method for measuring CH4 in water. Despite its long success, it has a lot of problems in use, such as complex pretreatment and a long measurement time, and it is not suitable for the CH4 determination of a large number of samples. In view of these shortcomings, a more convenient and efficient method based on membrane inlet mass spectrometry (MIMS) for quantitative measurements of the dissolved CH4 concentration in water was established. In our study, the standard curves showed that the method had high accuracy, both at low and high CH4 concentrations. After a laboratory test, to evaluate the sensitivity of this method, samples were collected from a large shallow lake (Lake Taihu). Both the HGC method and MIMS method were used to determine the dissolved CH4 to compare these two methods. The small difference in CH4 concentration obtained from the MIMS and HGC methods and the significant correlation between the CH4 concentrations derived from the MIMS method with those derived from the HGC method showed that the MIMS method could replace the HGC method in the determination of dissolved CH4 in natural waters. In addition, we also measured the sediment CH4 production rates in three different areas of Lake Taihu using a laboratory incubation experiment. During the experiment, significant CH4 accumulations were observed, indicating that sediment CH4 production was an important source of dissolved CH4 in the water column. Our study concluded that the MIMS method was sufficient and a better alternative than the HGC method owing to its capacity to measure a broad range of values plus the fact that it was relatively easy to use with less manipulation of the samples.

Dissolved CH₄ coupled to photosynthetic picoeukaryotes in oxic waters and to cumulative chlorophyll <i>a</i> in anoxic waters of reservoirs

Methane (CH4) emissions from reservoirs are responsible for most of the atmospheric climatic forcing of these aquatic ecosystems, comparable to emissions from paddies or biomass burning. Primarily, CH4 is produced during the anaerobic mineralization of organic carbon in anoxic sediments by methanogenic archaea. However, the origin of the recurrent and ubiquitous CH4 supersaturation in oxic waters (i.e., the methane paradox) is still controversial. Here, we determined the dissolved CH4 concentration in the water column of 12 reservoirs during summer stratification and winter mixing to explore CH4 sources in oxic waters. Reservoir sizes ranged from 1.18 to 26.13 km2. We found that dissolved CH4 in the water column varied by up to 4 orders of magnitude (0.02–213.64 µmol L−1), and all oxic depths were consistently supersaturated in both periods. Phytoplanktonic sources appear to determine the concentration of CH4 in these reservoirs primarily. In anoxic waters, the depth-cumulative chlorophyll a concentration, a proxy for the phytoplanktonic biomass exported to sediments, was correlated to CH4 concentration. In oxic waters, the photosynthetic picoeukaryotes' abundance was significantly correlated to the dissolved CH4 concentration during both the stratification and the mixing. The mean depth of the reservoirs, as a surrogate of the vertical CH4 transport from sediment to the oxic waters, also contributed notably to the CH4 concentration in oxic waters. Our findings suggest that photosynthetic picoeukaryotes can play a significant role in determining CH4 concentration in oxic waters, although their role as CH4 sources to explain the methane paradox has been poorly explored.

A Fast-response automated gas equilibrator (FaRAGE) for continuous in situ measurement of methane dissolved in water

Biogenic methane (CH4) emissions from inland waters contribute substantially to global warming. In aquatic systems, CH4 dissolved in freshwater lakes and reservoirs is highly heterogeneous both in space and time. To better understand the biological and physical processes that affect sources and sinks of CH4 in lakes and reservoirs, dissolved CH4 needs to be measured with a highest temporal resolution. To achieve this goal, we developed the Fast-Response Automated Gas Equilibrator (FaRAGE) for real-time in situ measurement of dissolved CH4 concentration at the water surface and in the water column. FaRAGE can achieve an exceptionally short response time (t95 % = 12 s when including the response time of the gas analyzer) while retaining an equilibration ratio of 63 % and a measurement accuracy of 0.5 %. An equilibration ratio as high as 91.8 % can be reached at the cost of a slightly increased response time (16 s). The FaRAGE is capable of continuously measuring dissolved CH4 concentrations in the nM-to-mM (10−9–10−3 mol L−1) range with a detection limit of sub-nM (10−10 mol L−1), when coupled with a cavity ring-down greenhouse gas analyzer (Picarro GasScouter). It enables the possibility of mapping dissolved CH4 concentration in a quasi three-dimensional manner in lakes. The FaRAGE is simple to operate, inexpensive, and suitable for continuous monitoring with a strong tolerance to suspended particles. The easy adaptability to other gas analyzers such as Ultra-portable Los Gatos and stable isotopic gas analyzer (Picarro G2132-i) also provides the potential for many further applications, e.g. measuring dissolved 13δC-CH4 and CO2.

Dissolved CH₄ coupled to Photosynthetic Picoeukaryotes in Oxic Waters and Cumulative Chlorophyll-a in Anoxia

CH4 emissions from reservoirs are responsible for the majority of the atmospheric climatic forcing of these aquatic ecosystems, comparable to emissions from paddies or biomass burning. Primarily, CH4 is produced during the anaerobic mineralization of organic carbon in the anoxic sediments by methanogenic archaea. However, the origin of the recurrent and ubiquitous CH4 supersaturation in oxic waters (i.e., methane paradox) is still controversial. Here, we determined the dissolved CH4 concentration in the water column of twelve reservoirs during the summer stratification and the winter mixing. We obtained that the dissolved CH4 concentration varied up to four orders of magnitude (0.02–213.64 μM), and all depths were consistently supersaturated (710–7082234 %) in both periods. Phytoplanktonic sources of carbon appear to determine the concentration of CH4 in the reservoirs. In the anoxic waters, the depth-cumulative chlorophyll-a concentration, a proxy for the total phytoplanktonic biomass exported to sediments, determined the CH4 concentration. In the oxic waters, the photosynthetic picoeukaryotes abundance significantly determined the dissolved CH4 concentration both during the stratification and the mixing. The mean depth of the reservoirs, as a surrogate of the CH4 transport from sediment to the oxic waters, also contributed in shallow systems. Our findings suggest that photosynthetic picoeukaryotes can have a significant role in determining the CH4 concentration in oxic waters and, in comparison to cyanobacteria, have been poorly explored as CH4 sources.