Changes in the storage and sink of carbon dioxide in subsurface atmospheres controlled by climate-driven processes: the case of the Ojo Guareña karst system

A comprehensive environmental monitoring program was conducted in the Ojo Guareña cave system (Spain), one of the longest cave systems in Europe, to assess the magnitude of the spatiotemporal changes in carbon dioxide gas (CO2) in the cave–soil–atmosphere profile. The key climate-driven processes involved in gas exchange, primarily gas diffusion and cave ventilation due to advective forces, were characterized. The spatial distributions of both processes were described through measurements of CO2 and its carbon isotopic signal (δ13C[CO2]) from exterior, soil and cave air samples analyzed by cavity ring-down spectroscopy (CRDS). The trigger mechanisms of air advection (temperature or air density differences or barometric imbalances) were controlled by continuous logging systems. Radon monitoring was also used to characterize the changing airflow that results in a predictable seasonal or daily pattern of CO2 concentrations and its carbon isotopic signal. Large daily oscillations of CO2 levels, ranging from 680 to 1900 ppm day−1 on average, were registered during the daily oscillations of the exterior air temperature around the cave air temperature. These daily variations in CO2 concentration were unobservable once the outside air temperature was continuously below the cave temperature and a prevailing advective-renewal of cave air was established, such that the daily-averaged concentrations of CO2 reached minimum values close to atmospheric background. The daily pulses of CO2 and other tracer gases such as radon (222Rn) were smoothed in the inner cave locations, where fluctuation of both gases was primarily correlated with medium-term changes in air pressure. A pooled analysis of these data provided evidence that atmospheric air that is inhaled into dynamically ventilated caves can then return to the lower troposphere as CO2-rich cave air.

Ordered mesoporous titanium oxide for thin film microbatteries with enhanced lithium storage

A 3D mesoporous TiO2 material with well-developed mesostructure is prepared in the form of a binder-free thin (100 nm) film and studied as potential candidate for the negative electrode in lithium microbatteries. By appropriate thermal treatments, the selected crystal structure (anatase, rutile, or amorphous), and micro-/mesostructure of the materials was obtained. The effects of voltage window and prelithiation treatment improved first cycle reversibility up to 86% and capacity retention of 90% over 100 cycles. After a prolonged intercalation of lithium ions in ordered mesoporous TiO2 appeared small particles assigned to Li2Ti2O4 with cubic structure as observed from ex-situ TEM micrographs. This study highlights the flexibility of the potential window to which the electrode can operate. Maximum capacity values over 100 cycles of 470 μA h cm−2 μm−1 and 177 μA h cm−2 μm−1 are obtained for voltage ranges of 0.1–2.6 V and 1.0–2.6 V, respectively. The observed values are between 6 and 2 times higher than those obtained for films with 600 nm (80 μA h cm−2 μm−1) and 900 nm (92 μA h cm−2 μm−1) lengths. This indicates that 100 nm thin TiO2 films with high accessibility show finite-length type diffusion which is interesting for this particular application.