Towards SI-traceable Isotope Ratios of Greenhouse Gases

<p>The emission of greenhouse gases and the resulting global warming is one of the most important and challenging issues of the 21<sup>st</sup> century. Carbon dioxide is one of the major contributors to the greenhouse effect and its atmospheric abundance has growing constantly since the beginning of the industrialization. The isotope ratios n(<sup>13</sup>C)/n(<sup>12</sup>C) and n(<sup>18</sup>O)/n(<sup>16</sup>O) are important tools for studying the impact of anthropogenic CO<sub>2</sub>. Usually, isotopic compositions of CO<sub>2</sub> are reported as δ-values, that express isotope ratios relative to an artifact based on a fossil calcite called VPDB. This relative VPDB scale was necessary, since absolute and SI-traceable isotope ratios of CO<sub>2</sub> are currently not available, neither by isotope ratio mass spectrometry (IRMS) nor by optical isotope ratio spectroscopy (OIRS). In this study we present a potential way of deriving absolute carbon and oxygen isotope ratios of carbon dioxide via IRMS based on the gravimetric mixture approach. Besides practical improvements like an air buoyancy correction scheme for masses of gases, we show first results applying our method which demonstrate its feasibility, limitations, and achievable uncertainties. Also, we show the mathematics behind our approach and discuss further improvements and applications. Furthermore, we show how these absolute ratios can be used in field applications by OIRS methods including a new approach on OIRS uncertainty assessments according to the GUM. For this contribution we report on our recent results within in the European metrology research projects SIRS (16ENV06). and STELLAR (19ENV05).</p>

Partial differentiation of air density in mass metrology

There are four major uncertainty components to be considered when performing mass comparisons. They are uncertainties of weighing process, reference weight used, air buoyancy, and mass comparator. The systematic effect of air buoyancy can be greatly reduced if the air density and the densities of the test and reference weights are known. This paper will emphasis on the uncertainty due to air buoyancy correction only. To calculate the uncertainty of air density correction, partial derivatives of temperature, barometric pressure and humidity must be performed. In this paper, two methods for partial differentiation of air density components are discussed.

Experimental research on mass determination of non-metal weights

With the revision of the definition of the kilogram, more and more weights made of non-metal material, such as silicon spheres and PM 2.5 film, need to be determined with high accuracy. As conventional mass is commonly used in mass metrology, this paper discusses the mass-measuring process for silicon and PM 2.5 film. Electrostatic eliminators are used to eliminate the electrostatic effects of non-metal material to improve the stability of mass measurement. Due to the big difference of weights’ densities, the air buoyancy correction and its uncertainty evaluation are also conducted.

Footprint-weighted tile approach for a spruce forest and a nearby patchy clearing using the ACASA model

The ACASA (Advanced Canopy–Atmosphere–Soil Algorithm) model, with a higher-order closure for tall vegetation, has already been successfully tested and validated for homogeneous spruce forests. The aim of this paper is to test the model using a footprint-weighted tile approach for a clearing with a heterogeneous structure of the underlying surface. The comparison with flux data shows a good agreement with a footprint-aggregated tile approach of the model. However, the results of a comparison with a tile approach on the basis of the mean land use classification of the clearing is not significantly different. It is assumed that the footprint model is not accurate enough to separate small-scale heterogeneities. All measured fluxes are corrected by forcing the energy balance closure of the test data either by maintaining the measured Bowen ratio or by the attribution of the residual depending on the fractions of sensible and latent heat flux to the buoyancy flux. The comparison with the model, in which the energy balance is closed, shows that the buoyancy correction for Bowen ratios >1.5 better fits the measured data. For lower Bowen ratios, the correction probably lies between the two methods, but the amount of available data was too small to make a conclusion. With an assumption of similarity between water and carbon dioxide fluxes, no correction of the net ecosystem exchange is necessary for Bowen ratios >1.5.

Application of the ACASA model for a spruce forest and a nearby patchy clearing

The ACASA (Advanced Canopy-Atmosphere-Soil Algorithm) model, with a higher order closure for tall vegetation, has already been successfully tested and validated for spruce forests. The aim of this paper is the further application for a clearing with a heterogeneous structure of the underlying surface. The comparison with flux data shows a good agreement with a footprint aggregated tile approach of the model. However, the results of a comparison with a tile approach on the basis of the mean land use classification of the clearing is not significantly different. It is assumed that the footprint model is not accurate enough to separate small scale heterogeneities. All measured fluxes are corrected for energy balance closure with a Bowen ratio and a buoyancy flux correction method. The comparison with the model – where the energy balance is closed – shows that the buoyancy correction for Bowen ratios > 1.5 better fits the measured data. For lower Bowen ratios, the correction probably lies between both methods, but the amount of available data was too small to make a conclusion. With an assumption of a similarity between water and carbon dioxide fluxes, no correction of the net ecosystem exchange is necessary for Bowen ratios > 1.5.

Development of Moving Particle Simulation Method for Multiliquid-Layer Sloshing

The mixed oil and gas including water and sand are extracted from well to offshore structure. This mixed fluid must be separated for subsequent processes by using wash tanks or separators. To design such a system, a proper numerical-prediction tool for multiphase fluids is required. In this regard, a new moving particle simulation (MPS) method is developed to simulate multiliquid-layer sloshing problems. The new MPS method for multifluid system includes extra search methods for interface particles, boundary conditions for interfaces, buoyancy-correction model, and surface-tension model for interface particles. The new particle interaction models are verified through comparisons with published numerical and experimental data. In particular, the multiliquid MPS method is verified against Molin et al’s (2012) experiment with three liquid layers. In case of excitation frequency close to one of the internal-layer resonances, the internal interface motions can be much greater than top free-surface motions. The verified multiliquid MPS program is subsequently used for more nonlinear cases including multichromatic multimodal motions with larger amplitudes, from which various nonlinear features, such as internal breaking and more particle detachment, can be observed. For the nonlinear case, the differences between with and without buoyancy-correction and surface-tension models are also demonstrated.