Influence of Pressure on the Composition of Gaseous Reference Materials.

We have shown that the amount fraction of carbon dioxide in a nitrogen or synthetic air matrix stored in cylinders increases as the pressure of the gas mixture reduces, while the amount fraction of methane remains unchanged. Our measurements show the initial amount fraction of carbon dioxide to be lower than the gravimetric value after preparation, which we attribute to the adsorption of a proportion of the molecules to active sites on the internal surface of the cylinder and the valve. As the mixture is consumed, the pressure in the cylinder reduces and the amount fraction of the component is observed to increase. The effect is less pronounced in the presence of water vapor. More dramatic effects have been observed for hydrogen chloride. These findings have significant implications for the preparation of high accuracy gaseous reference materials with unprecedented uncertainties which underpin a broad range of requirements, in particular atmospheric monitoring of high impact greenhouse gases.

Improvements to standard methodologies for the analytical determination of metals in stationary-source emissions samples.

Deficiencies with the current European reference method for the analysis using inductively couple plasma-mass spectrometry of metals in samples from stationary emissions sources are presented based on experimental data obtained from real samples. The effect of these deficiencies on the quality and accuracy of data is highlighted with biases of up to 40% being observed in real samples. Suggestions to improve the performance of the standard method are presented. In particular, the beneficial effect of using a drift correction procedure to account for the decrease in instrument sensitivity observed during an analytical measurement series is demonstrated. It is shown that this corrective procedure results in substantial improvements to the accuracy of data produced.