Improved Method for the Quantification of Methane Concentrations in Unconsolidated Lake Sediments.

There is conclusive evidence that the methods most commonly used to sample methane (CH4) dissolved in the pore water of lake sediments produce results that are likely to be affected by gas loss or gas exchange with the atmosphere. To determine the in situ amount of CH4 per unit mass of pore water in sediments, we developed and validated a new method that combines techniques developed for noble-gas analysis in pore waters with a standard headspace technique to quantify the CH4 present in the pore space in dissolved and gaseous form. The method was tested at two sites: Lake Lungern, where CH4 concentrations were close to saturation; and Lake Rotsee, where CH4 concentrations are known to exceed saturation and where CH4 bubble formation and gas ebullition are commonly observed. We demonstrate that the new method, in contrast to the available methods, more reliably captures the total amount of CH4 per unit mass of pore water consisting of both dissolved and free CH4 (i.e., gas bubbles) in the pore space of the sediment.

Conquering the outdoors with on-site mass spectrometry.

In recent years, mass spectrometers with a membrane inlet separating gases from water for final analysis have been used successfully for the on-site quantification of dissolved gases in surface waters. In 'classical' membrane inlet mass spectrometers (MIMS), the membrane directly separates the water from the high-vacuum environment of the mass spectrometer. The gas equilibrium MIMS (GE-MIMS) that is described in this review, however, makes use of an intermediate pressure reduction stage after the membrane inlet. Hence, the gas concentrations after the membrane are at steady state, near solubility equilibrium with the water to be analyzed. This setup has several advantages over classical MIMS, which enable autonomous and continuous in-field operation. The GE-MIMS can be used to acquire noble gas concentration time series (NGTS). Noble gases are useful tracers for physical gas exchange and transport in groundwater and other aqueous systems. Hence NGTS enable the temporal dynamics of physical gas exchange and transport in groundwater and other aqueous systems to be investigated. To determine the O2 turnover that has occurred in groundwater since recharge, both the O2 concentration in situ and the total input of O2 to the groundwater since recharge is needed. Determination of the latter is only possible if the relevant physical exchange and transport mechanisms can be quantified. In particular, gas exchange between soil air and groundwater often significantly affects groundwater O2 concentrations. Determination of O2 turnover in groundwater therefore requires a combined analysis of O2 and noble gas concentrations.

Application of the gas tracer method for measuring oxygen transfer rates in subsurface flow constructed wetlands.

The oxygen transfer rate (OTR) has a significant impact on the design, optimal operation and modelling of constructed wetlands treating wastewater. Oxygen consumption is very fast in wetlands and the OTR cannot be determined using an oxygen mass balance. This problem is circumvented in this study by applying the gas tracer method. Experiments were conducted in an unplanted gravel bed (dimensions L x W x d 125 x 50 x 35 cm filled with a 30-cm layer of 10-11-mm gravel) and a planted horizontal subsurface flow constructed wetland (HSSFCW) (L x W x d 110 x 70 x 38 cm filled with a 30-cm layer of 3.5-mm gravel with Phragmites australis). Tap water saturated with propane as gas tracer (pure or commercial cooking gas, depending on the test) was used. The mass transfer ratio between oxygen and commercial propane gas was quite constant and averaged R = 1.03, which is slightly lower than the value of R = 1.39 that is usually reported for pure propane. The OTR ranged from 0.31 to 5.04 g O(2) m(-2) d(-1) in the unplanted gravel bed and from 0.3 to 3.2 g O(2) m(-2) d(-1) in the HSSFCW, depending on the hydraulic retention time (HRT). The results of this study suggest that the OTR in HSSFCW is very low for the oxygen demand of standard wastewater and the OTR calculations based on mass balances and theoretical stoichiometric considerations overestimate OTR values by a factor that ranges from 10 to 100. The gas tracer method is a promising tool for determining OTR in constructed wetlands, with commercial gas proving to be a viable low-cost alternative for determining OTR.