Brad Hall

Oceanic consumption of CH3CCl3: Implications for tropospheric OH

Strong and extensive negative saturation anomalies for CH3CCl3 were observed in the mid-Pacific Ocean during the spring of 1990. Anomalies were largest at the equator, where upwelling and biological activity were greatest, but present virtually everywhere in our sampling range of 15°S to 20°N. The mean saturation anomaly for all of our data, corrected for physical effects, was −11.0%, implying that the ocean is a significant sink for CH3CCl3. The loss rate to maintain this anomaly is supported roughly by known hydrolysis rates, but contributions from other processes cannot be ruled out at this time. If hydrolysis and mixing are the only processes removing CH3CCl3 from seawater, then about 6% of atmospheric CH3CCl3 is removed by consumption in the oceans. Our data show that losses to the ocean most probably would range from 5 to 11% of the CH3CCl3 removed from the atmosphere. This range translates to a partial residence time of 59–128 years for atmospheric CH3CCl3 relative to oceanic consumption. Although these data indicate that the ocean is not an overwhelmingly large sink, its neglect does represent a systematic error in the calculation of tropospheric OH concentration from CH3CCl3 production, growth, and distribution in the atmosphere.

An unexpected and persistent increase in global emissions of ozone-depleting CFC-11

The Montreal Protocol was designed to protect the stratospheric ozone layer by enabling reductions in the abundance of ozone-depleting substances such as chlorofluorocarbons (CFCs) in the atmosphere1–3. The reduction in the atmospheric concentration of trichlorofluoromethane (CFC-11) has made the second-largest contribution to the decline in the total atmospheric concentration of ozone-depleting chlorine since the 1990s1. However, CFC-11 still contributes one-quarter of all chlorine reaching the stratosphere, and a timely recovery of the stratospheric ozone layer depends on a sustained decline in CFC-11 concentrations1. Here we show that the rate of decline of atmospheric CFC-11 concentrations observed at remote measurement sites was constant from 2002 to 2012, and then slowed by about 50 per cent after 2012. The observed slowdown in the decline of CFC-11 concentration was concurrent with a 50 per cent increase in the mean concentration difference observed between the Northern and Southern Hemispheres, and also with the emergence of strong correlations at the Mauna Loa Observatory between concentrations of CFC-11 and other chemicals associated with anthropogenic emissions. A simple model analysis of our findings suggests an increase in CFC-11 emissions of 13 ± 5 gigagrams per year (25 ± 13 per cent) since 2012, despite reported production being close to zero4 since 2006. Our three-dimensional model simulations confirm the increase in CFC-11 emissions, but indicate that this increase may have been as much as 50 per cent smaller as a result of changes in stratospheric processes or dynamics. The increase in emission of CFC-11 appears unrelated to past production; this suggests unreported new production, which is inconsistent with the Montreal Protocol agreement to phase out global CFC production by 2010.Atmospheric CFC-11 concentrations have been declining less rapidly since 2012; evidence suggests that this finding is explained by an increase in the emission of CFC-11during these years.

Final report on international comparison CCQM-K68: Nitrous oxide in synthetic air

Nitrous oxide (N2O) is one of six greenhouse gases that are regulated by the Kyoto Protocol and has a Global Warming Potential (GWP) that is 296 times that of carbon dioxide. Global levels of nitrous oxide have increased at a rate of 0.25%/yr (0.8 ppb/yr) during the last ten years. In order to monitor levels of nitrous oxide in the atmosphere, it is necessary to use measurement standards with demonstrated equivalence at the highest level of accuracy. This report describes the results of a key comparison of standard gas mixtures of nitrous oxide in synthetic air at an amount fraction of 320 nmol/mol. This key comparison is part of the programme of the Gas Analysis Working Group (GAWG) of the CCQM to demonstrate the equivalence of the standards and measurement capabilities of the NMIs for greenhouse gases. It will support the development of measurement capability at the NMIs for nitrous oxide with uncertainties within the target set by the Global Atmospheric Watch (GAW) programme of the WMO for its global monitoring networks. Main text. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (MRA).

International comparison CCQM-K82: methane in air at ambient level (1800 to 2200) nmol/mol

The CCQM-K82 comparison was designed to evaluate the degrees of equivalence of NMI capabilities for methane in air primary reference mixtures in the range (1800 to 2200) nmol/mol. The balance gas for the standards was either scrubbed dry real air or synthetic air. CH4 in air standards have been produced by a number of laboratories for many years, with more recent developments focused on standards at atmospheric measurement concentrations and aimed at obtaining agreement between independently produced standards. A comparison of the differences in primary gas standards for methane in air was previously performed in 2003 (CCQM-P41 Greenhouse gases. 1 and 2) with a standard deviation of results around the reference value of 30 nmol/mol and 10 nmol/mol for a more limited set of standards. This can be contrasted with the level of agreement required from field laboratories routinely measuring atmospheric methane levels, set by Data Quality Objectives (DQO) established by the World Meteorological Organization (WMO) to reflect the scientifically desirable level of compatibility for CH4 measurements at the global scale, currently set at 2 nmol/mol (1 sigma). The measurements of this key comparison took place from May 2012 to June 2012. Eight laboratories took part in this comparison coordinated by the BIPM and NIST. Key comparison reference values were calculated based on Cavity Ring Down Spectroscopy Measurements performed at the BIPM, combined with participants gravimetric values to identify a consistent set of standards. Regression analysis allowed predicted values for each standard to be calculated which acted as the KCRVs. In this comparison reported standard uncertainties by participants ranged from 0.50 nmol/mol to 2.4 nmol/mol and the uncertainties of individual KCRVs ranged from 0.68 nmol/mol to 0.71 nmol/mol. The standard deviation of the ensemble of standards about the KCRV value was 1.70 nmol/mol. This represents a greater than tenfold improvement in the level of compatibility of methane in air standards compared to that demonstrated in 2003. Further improvements in the compatibility of standards will require improved methods and uncertainties for the measurement of trace level methane in balance gases. Main text. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).