Step Change in Improving the Accuracy of Nitrous Oxide Reference Materials for Underpinning Atmospheric Composition Measurements.

We have employed a new approach to quantify the amount fraction of nitrous oxide in a synthetic air matrix gas used to prepare high-accuracy reference materials of the same component. Until now, this was the largest contributor to the measurement uncertainty of nitrous oxide in air reference materials at atmospheric amount fractions (∼330 nmol mol-1), as identified in a recent international comparison. A novel preconcentration method has resulted in a measurement of 363 pmol mol-1 of nitrous oxide in a synthetic air matrix gas with an expanded uncertainty of 27 pmol mol-1. This represents a significant breakthrough as using these developments with an optimized dilution hierarchy (to minimize the gravimetric uncertainty) promises to result in SI traceable reference materials with expanded uncertainties as low as 0.032% relative (k = 2). This supports the World Meteorological Organization-Global Atmosphere Watch network compatibility goal for underpinning atmospheric observations.

Boreas: A Sample Preparation-Coupled Laser Spectrometer System for Simultaneous High-Precision In Situ Analysis of δ13C and δ2H from Ambient Air Methane.

We present a new instrument, "Boreas", a cryogen-free methane (CH4) preconcentration system coupled to a dual-laser spectrometer for making simultaneous measurements of δ13C(CH4) and δ2H(CH4) in ambient air. Excluding isotope ratio scale uncertainty, we estimate a typical standard measurement uncertainty for an ambient air sample of 0.07‰ for δ13C(CH4) and 0.9‰ for δ2H(CH4), which are the lowest reported for a laser spectroscopy-based system and comparable to isotope ratio mass spectrometry. We trap CH4 (∼1.9 µmol mol-1) from ∼5 L of air onto the front end of a packed column, subsequently separating CH4 from interferences using a controlled temperature ramp with nitrogen (N2) as the carrier gas, before eluting CH4 at ∼550 µmol mol-1. This processed sample is then delivered to an infrared laser spectrometer for measuring the amount fractions of 12CH4, 13CH4, and 12CH3D isotopologues. We calibrate the instrument using a set of gravimetrically prepared amount fraction primary reference materials directly into the laser spectrometer that span a range of 500-626 µmol mol-1 (CH4 in N2) made from a single pure CH4 source that has been isotopically characterized for δ13C(CH4) by IRMS. Under the principle of identical treatment, a compressed ambient air sample is used as a working standard and measured between air samples, from which a final calibrated isotope ratio is calculated. Finally, we make automated measurements of both δ13C(CH4) and δ2H(CH4) in over 200 ambient air samples and demonstrate the application of Boreas for deployment to atmospheric monitoring sites.

Breakthrough in Negating the Impact of Adsorption in Gas Reference Materials.

We have shown that an exchange dilution preparation method reduces the impact of surface adsorption of the target component in high-pressure gas mixtures used for underpinning measurements of amount-of-substance fraction. Gas mixtures are diluted in the same cylinder by releasing an aliquot of the parent mixture. Additional matrix gas is then added to the cylinder. This differs from conventional methods where dilutions are achieved by transferring the parent mixture to another cylinder, which then stores the final reference material. The benefit of this revolutionary approach is that losses due to adsorption to the walls of the cylinder and the valve are reduced as the parent mixture pacifies the surface with only a negligible relative change in amount-of-substance fraction. This development allows for preparation of gas reference materials with unprecedented uncertainties beyond the existing state of the art. It has significant implications for the preparation of high accuracy gas reference materials which underpin a broad range of requirements, particularly in atmospheric monitoring of carbon dioxide, where understanding the adsorption effects is the major obstacle to advancing the measurement science. It has the potential to remove the reliance on proprietary surface pretreatments as the method provides an in situ and consistent alternative.

Synthetic Zero Air Reference Material for High Accuracy Greenhouse Gas Measurements.

The purity analysis of zero air is a significant contributor to the uncertainty in preparing reference materials of high impact greenhouse gases, limiting progress toward coherent and comparable measurements required to assess climate trends. We have produced a commutable synthetic zero air reference material with an oxygen, nitrogen, and argon matrix closely matching atmospheric composition. This is the critical step in preventing systematic biases from pressure broadening effects when using these reference materials to calibrate instruments based on optical spectroscopy. The amount fractions of carbon dioxide, methane, and carbon monoxide, which are present as minor impurities in the zero air reference material, have been accurately quantified using a novel dilution device that can generate gas mixtures of these components at trace amount fractions. These developments will have a significant impact on advancing the state of the art in high accuracy reference materials and for baseline calibration of spectroscopic instrumentation.

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.

Large-area functionalized CVD graphene for work function matched transparent electrodes.

The efficiency of flexible photovoltaic and organic light emitting devices is heavily dependent on the availability of flexible and transparent conductors with at least a similar workfunction to that of Indium Tin Oxide. Here we present the first study of the work function of large area (up to 9 cm(2)) FeCl3 intercalated graphene grown by chemical vapour deposition on Nickel, and demonstrate values as large as 5.1 eV. Upon intercalation, a charge density per graphene layer of 5 ⋅ 10(13) ± 5 ⋅ 10(12) cm(-2) is attained, making this material an attractive platform for the study of plasmonic excitations in the infrared wavelength spectrum of interest to the telecommunication industry. Finally, we demonstrate the potential of this material for flexible electronics in a transparent circuit on a polyethylene naphthalate substrate.