Abstract. The need for a unifying scale anchor for isotopes of CO2 in air was brought to light at the 11th WMO/IAEA Meeting of Experts on Carbon Dioxide in Tokyo 2001. During discussions about persistent discrepancies in isotope measurements between the worlds leading laboratories, it was concluded that a unifying scale anchor for Vienna Pee Dee Belemnite (VPDB) of CO2 in air was desperately needed. Ten years later, at the 2011 Meeting of Experts on Carbon Dioxide in Wellington, it was recommended that the Jena Reference Air Set (JRAS) become the official scale anchor for isotope measurements of CO2 in air (Brailsford, 2012). The source of CO2 used for JRAS is two calcites. After releasing CO2 by reaction with phosphoric acid, the gases are mixed into CO2-free air. This procedure ensures both isotopic stability and longevity of the CO2. That the reference CO2 is generated from calcites and supplied as an air mixture is unique to JRAS. This is made to ensure that any measurement bias arising from the extraction procedure is eliminated. As every laboratory has its own procedure for extracting the CO2, this is of paramount importance if the local scales are to be unified with a common anchor. For a period of four years, JRAS has been evaluated through the IMECC1 program, which made it possible to distribute sets of JRAS gases to 13 laboratories worldwide. A summary of data from the six laboratories that have reported the full set of results is given here along with a description of the production and maintenance of the JRAS scale anchors. 1 IMECC refers to the EU project "Infrastructure for Measurements of the European Carbon Cycle" (http://imecc.ipsl.jussieu.fr/).

For anchoring CO(2) isotopic measurements on the δ(18)O(VPD-CO2) scale, the primary reference material (NBS 19 calcite) needs to be digested using concentrated ortho-phosphoric acid. During this procedure, great care must be taken to ensure that the isotopic composition of the liberated gas is accurate. Apart from controlling the reaction temperature to ±0.1 °C, the potential for oxygen isotope exchange between the produced CO(2) and water must be kept to a minimum. The water is usually assumed to reside on the walls in the headspace of the reaction vessel. We demonstrate here that a large fraction of the exchange may also occur with water inside the acid. Our results indicate that both exchange reactions have a significant impact on the results and may have largely been responsible for scale inconsistencies between laboratories in the past. The extent of CO(2)/H(2)O oxygen exchange depends on the concentration (amount of free water) in the acid. For acids with a nominal H(3)PO(4) mass fraction of less than 102%, oxygen isotope exchange can create a substantial isotopic bias during high-precision measurements with the degree of the alteration being proportional to the effective isotopic contrast between the acid and the CO(2) released from the calcite. Water evaporating from the acid at 25 °C has a δ(18)O value of -34.5‰ relative to the isotopic composition of the whole acid. This large fractionation is likely to occur in two steps; by exchange with phosphate, water inside the acid is decreased in oxygen-18 relative to the bulk acid by ∼ -22‰. This water is then fractionated further during evaporation. Oxygen exchange with both water inside the acid and water condensate in the headspace can contribute to the measured isotopic signature depending on the experimental parameters. The system employed for this study has been specifically designed to minimize oxygen exchange with water. However, the amount of altered CO(2) for a 95% H(3)PO(4) at 25 °C still accounts for about 3% of the total CO(2) produced from a 40 mg calcite sample, resulting in a δ(18) O range of about 0.8‰ when varying the δ(18)O value of the acid by 25‰. Least biased results for NBS19-CO(2) were obtained for an acid with a δ(18)O value close to +23‰ vs. VSMOW. In contrast, commercial acids from several sources had an average δ(18)O value of +13‰, amounting to a 10‰ offset from the optimal value. This observation suggests that the well-known scale incompatibilities between laboratories could arise from this difference with measurements that may have suffered systematically from non-optimal acid-δ(18)O values, thus producing variable offsets, depending on the experimental details. As a remedy, we suggest that the δ(18)O of phosphoric acid reacted with calcites for establishing a δ(18)O scale anchor be adjusted, and this should reduce the variability of the δ(18)O of CO(2) evolved in acid digestion to less than ±0.05‰. The adjustment should be made by taking into account the difference in δ(18)O between the calcite-CO(2) and the acid, with a target d...

The system has been in routine operation at the MPI-BGC since 2012. Consistency of the data and compatibility with results from other laboratories at a high precision level are of utmost importance. A high sample throughput and reliability of operation are important achievements of the presented system to cope with the large number of air samples to be analyzed. Copyright © 2016 John Wiley & Sons, Ltd.

The thickness of solution layers adsorbed onto rotating glass plates designed for use on an oceanic glass plate sampler was investigated in laboratory experiments using optical techniques. Using the Beer‐Lambert Law, light attenuation measurements were used to calculate the thickness of adsorbed solution layers on a rotating glass disk with and without salt and surfactants. The observations have shown that the adsorbed film thickness can vary between 80 and 40 µm for glass rotation speeds between 4 and 16 cm s−1, depending on salinity and surfactant concentrations. For example, the thickness of a film of water with 40 ppt of salt and 5 cm s−1 rotation speed was in the range of 80 µm. The adsorbed layer thickness increases with increasing salt concentration and with increasing concentrations of surface active substances. These results are comparable to results obtained by vertically dipping a glass plate and determining film thickness from the collected volume of water. Because the glass disk rotational speed significantly influences the thickness of the adsorbed solution layer, it is important that the speed is maintained at a value for which the adsorbed thickness has been calibrated. At typical oceanic salinities, the dependence of the adsorbed film thickness on rotation speed was limited. However, even small changes in surface active substances resulted in significant thickness changes.

The need for a unifying scale anchor for isotopes of CO₂ in air was brought to light at the WMO CO₂ Experts Meeting in Tokyo 2001. During discussions about persistent discrepancies in isotope measurements between the worlds leading laboratories it was concluded that a unifying scale anchor for VPDB of CO₂ in air was desperately needed. Now, 10 yr later, the 2011 CO₂-Experts-Meeting in Wellington has decided that the Jena Reference Air Set or JRAS is recommended as official scale anchor for isotope measurements of CO₂ in air.

The JRAS gases consist of reference CO₂ mixed into CO₂ free air. To safeguard both stability and longevity of the CO₂, it is directly generated from two solid reference calcites. That the reference CO₂ is supplied in air is unique to JRAS. This is made to ensure that any measurement bias arising from the extraction procedure is eliminated. As every lab has its own procedure for extracting the CO₂ this is of paramount importance if the local scales are to be unified.

For a period of four years, JRAS has been evaluated through the IMECC program, which made it possible to distribute sets of JRAS gases to 11 laboratories worldwide. A summary of the results is reported here along with a description of the production and maintenance of the JRAS scale anchors