Climate change-driven shifts in streamflow timing have been documented for western North America and are expected to continue with increased warming. These changes will likely have the greatest implications on already short and overcommitted water supplies in the region. This study investigated changes in western North American streamflow timing over the 1948-2008 period, including the very recent warm decade not previously considered, through (i) trends in streamflow timing measures, (ii) two second-order linear models applied simultaneously over the region to test for the acceleration of these changes, and (iii) changes in runoff regimes. Basins were categorized by the percentage of snowmelt-derived runoff to enable the comparison of groups of streams with similar runoff characteristics and to quantify shifts in snowmelt-dominated regimes. Results indicate that streamflow has continued to shift to earlier in the water year, most notably for those basins with the largest snowmelt runoff component. However, an acceleration of these streamflow timing changes for the recent warm decades is not clearly indicated. Most coastal rain-dominated and some interior basins have experienced later timing. The timing changes are connected to area-wide warmer temperatures, especially in March and January, and to precipitation shifts that bear subregional signatures. Notably, a set of the most vulnerable basins has experienced runoff regime changes, such that basins that were snowmelt dominated at the beginning of the observational period shifted to mostly rain dominated in later years. These most vulnerable regions for regime shifts are in the California Sierra Nevada, eastern Washington, Idaho, and northeastern New Mexico. Snowmelt regime changes may indicate that the time available for adaptation of water supply systems to climatic changes in vulnerable regions are shorter than previously recognized.

Piezoelectric crystals like langasite (La 3 Ga 5 SiO 14 , LGS) and gallium orthophosphate (GaPO 4 ) exhibit piezoelectrically excited bulk acoustic waves at temperatures of up to at least 1450 • C and 900 • C, respectively. Consequently, resonant sensors based on those materials enable new sensing approaches. Thereby, resonant high-temperature microbalances are of particular interest. They correlate very small mass changes during film deposition onto resonators or gas composition-dependent stoichiometry changes of thin films already deposited onto the resonators with the resonance frequency shift of such devices. Consequently, the objective of the work is to review the high-temperature properties, the operation limits and the measurement principles of such resonators. The electromechanical properties of high-temperature bulk acoustic wave resonators such as mechanical stiffness, piezoelectric and dielectric constant, effective viscosity and electrical conductivity are described using a one-dimensional physical model and determined accurately up to temperatures as close as possible to their ultimate limit. Insights from defect chemical models are correlated with the electromechanical properties of the resonators. Thereby, crucial properties for stable operation as a sensor under harsh conditions are identified to be the formation of oxygen vacancies and the bulk conductivity. Operation limits concerning temperature, oxygen partial pressure and water vapor pressure are given. Further, application-relevant aspects such as temperature coefficients, temperature compensation and mass sensitivity are evaluated. In addition, approximations are introduced which make the exact model handy for routine data evaluation. An equivalent electrical circuit for high-temperature resonator devices is derived based on the one-dimensional physical model. Low-and high-temperature approximations are introduced. Thereby, the structure of the equivalent circuit corresponds to the Butterworth-van Dyke equivalent circuit extended by a finite bulk resistance. Assignments of the lumped elements to the physical properties are given. Finally, an application example demonstrates the capabilities of high-temperature stable piezoelectric resonators. The simultaneous determination of mechanical and electrical properties of thin sensor films by resonant sensors enables the detection of CO in hydrogen-containing atmospheres.

Conventional piezoelectric materials such as quartz are widely used as high precision transducers and sensors based on bulk acoustic waves. However, their operation temperature is limited by the intrinsic materials properties to about 500 • C. High-temperature applications are feasible by applying materials that retain their piezoelectric properties up to higher temperatures. Here, langasite (La 3 Ga 5 SiO 14 ) and compounds of the langasite family are the most promising candidates, since they are shown to exhibit bulk acoustic waves up to at least 1400 • C. The mass sensitivity of langasite resonators at elevated temperatures is about as high as that of quartz at room temperature. Factors limiting potential use of those crystals include excessive conductive and viscous losses, deviations from stoichiometry and chemical instability. Therefore, the objective of this work is to identify the related microscopic mechanisms, to correlate electromechanical properties and defect chemistry and to improve the stability of the materials by e.g. appropriate dopants.Further application examples such as resonant gas sensors are given to demonstrate the capabilities of hightemperature stable piezoelectric materials. The electromechanical properties of langasite are determined and described by a one-dimensional physical model. Key properties relevant for stable operation of resonators are found to be shear modulus, density, electrical conductivity and effective viscosity. In order to quantify their impact on frequency and damping, a general-H. Fritze (B)

Langasite (La3Ga5SiO14) and related compounds are promising candidates for high-temperature piezoelectric applications. To determine the stable operation of langasite as a high-temperature bulk acoustic wave (BAW) resonator, we characterized electrical conductivity [σel=1.56×exp(−1.07 eV/kT)S/cm] and oxygen diffusivity [DoxT=5×10−5 exp(−1.45 eV/kT)cm2/s] up to elevated temperatures. Langasite was successfully operated up to 900 °C as a BAW resonator with an average mass sensitivity of about 0.17 μg Hz−1 cm−2. This enables, in principle, high-temperature monitoring of deposition rates and thermogravimetry with high sensitivity.

Bulk ceria-zirconia solid solutions (Ce1−xZrxO2−δ, CZO) are highly suited for application as oxygen storage materials in automotive three-way catalytic converters (TWC) due to the high levels of achievable oxygen non-stoichiometry δ. In thin film CZO, the oxygen storage properties are expected to be further enhanced. The present study addresses this aspect. CZO thin films with 0 ≤ x ≤ 1 were investigated. A unique nano-thermogravimetric method for thin films that is based on the resonant nanobalance approach for high-temperature characterization of oxygen non-stoichiometry in CZO was implemented. The high-temperature electrical conductivity and the non-stoichiometry δ of CZO were measured under oxygen partial pressures pO2 in the range of 10−24–0.2 bar. Markedly enhanced reducibility and electronic conductivity of CeO2-ZrO2 as compared to CeO2−δ and ZrO2 were observed. A comparison of temperature- and pO2-dependences of the non-stoichiometry of thin films with literature data for bulk Ce1−xZrxO2−δ shows enhanced reducibility in the former. The maximum conductivity was found for Ce0.8Zr0.2O2−δ, whereas Ce0.5Zr0.5O2-δ showed the highest non-stoichiometry, yielding δ = 0.16 at 900 °C and pO2 of 10−14 bar. The defect interactions in Ce1−xZrxO2−δ are analyzed in the framework of defect models for ceria and zirconia.