• Energy Research

Abstract. The International Halocarbons in Air Comparison Experiment (IHALACE) was conducted to document relationships between calibration scales among various laboratories that measure atmospheric greenhouse and ozone depleting gases. This study included trace gases such as chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs), as well as nitrous oxide, methane, sulfur hexafluoride, very short-lived halocompounds, and carbonyl sulfide. Many of these gases are present in the unpolluted atmosphere at pmol mol−1 (parts per trillion) or nmol mol−1 (parts per billion) levels. Six stainless steel cylinders containing natural and modified natural air samples were circulated among 19 laboratories. Results from this experiment reveal relatively good agreement (within a few percent) among commonly used calibration scales. Scale relationships for some gases, such as CFC-12 and CCl4, were found to be consistent with those derived from estimates of global mean mole fractions, while others, such as halon-1211 and CH3Br, revealed discrepancies. The transfer of calibration scales among laboratories was problematic in many cases, meaning that measurements tied to a particular scale may not, in fact, be compatible. Large scale transfer errors were observed for CH3CCl3 (10–100%) and CCl4 (2–30%), while much smaller scale transfer errors (< 1%) were observed for halon-1211, HCFC-22, and HCFC-142b. These results reveal substantial improvements in calibration over previous comparisons. However, there is room for improvement in communication and coordination of calibration activities with respect to the measurement of halogenated and related trace gases.

Molecular hydrogen (H2) is the second most abundant trace gas in the atmosphere after methane (CH4). In the troposphere, the D/H ratio of H2 is enriched by 120 per thousand relative to the world's oceans. This cannot be explained by the sources of H2 for which the D/H ratio has been measured to date (for example, fossil fuels and biomass burning). But the isotopic composition of H2 from its single largest source--the photochemical oxidation of methane--has yet to be determined. Here we show that the D/H ratio of stratospheric H2 develops enrichments greater than 440 per thousand, the most extreme D/H enrichment observed in a terrestrial material. We estimate the D/H ratio of H2 produced from CH4 in the stratosphere, where production is isolated from the influences of non-photochemical sources and sinks, showing that the chain of reactions producing H2 from CH4 concentrates D in the product H2. This enrichment, which we estimate is similar on a global average in the troposphere, contributes substantially to the D/H ratio of tropospheric H2.

Elevated carbon monoxide (CO) mixing ratios in excess of those derived from emissions inventories have been observed in plumes from one gas- and coal-fired power plant and three of four lignite coal-fired electric utility power plants observed in east and central Texas. Observations of elevated CO on days characterized by differing wind directions show that CO emissions from the lignite plants were relatively constant over time and cannot be ascribed to separate sources adjacent to the power plants. These three plants were found to be emitting CO at rates 22 to 34 times those tabulated in State and Federal emissions inventories. Elevated CO emissions from the gas- and coal-fired plant were highly variable on time scales of hours to days, in one case changing by a factor of 8 within an hour. Three other fossil-fueled power plants, including one lignite-fired plant observed during this study, did not emit substantial amounts of CO, suggesting that a combination of plant operating conditions and the use of lignite coal may contribute to the enhanced emissions. Observed elevated CO emissions from the three lignite plants, if representative of average operating conditions, represent an additional 30% of the annual total CO emissions from point sources for the state of Texas.