Grab samples for nonmethane hydrocarbons (NMHCs) were collected from three sites: daily at Alert, Northwest Territories (82.5° N, 62.3° W) from January 21 to April 19, daily at an ice floe 150 km north of Alert from April 9 to 25, and on an aerial survey conducted in April over the Arctic archipelago. Insitu measurements of n‐butane and i‐pentane were also made hourly at Alert from April 2 to April 15. During the dark period (January to March), C2‐C6 hydrocarbon concentrations correlated with those of methane. Concentrations declined gradually from January to April, consistent with removal by HO radicals. On the other hand, during low‐ozone periods in April an additional decrease in NMHC concentrations and change in distribution were observed. Concentration changes of alkanes were correlated to Cl atom reaction rate constants. Acetylene displayed a greater change in concentration than predicted from chlorine kinetics, possibly indicating additional removal by Br atoms. The Br atom concentration derived from the depletion of acetylene can account for the low‐ozone concentrations periodically observed at Alert. The estimated Cl atom concentration is too small to be a significant loss mechanism for ozone. Thus the data from Alert and the ice floe site provide evidence for Cl and Br atom chemistry during the ozone depletion episodes observed at polar sunrise.

Abstract.A new analytical inversion method has been developed to determine the regional and global emissions of long-lived atmospheric trace gases. It exploits in situ measurement data from three global networks and builds on backward simulations with a Lagrangian particle dispersion model. The emission information is extracted from the observed concentration increases over a baseline that is itself objectively determined by the inversion algorithm. The method was applied to two hydrofluorocarbons (HFC-134a, HFC-152a) and a hydrochlorofluorocarbon for the period January 2005 until March 2007. Detailed sensitivity studies with synthetic as well as with real measurement data were done to quantify the influence on the results of the a priori emissions and their uncertainties as well as of the observation and model errors. It was found that the global a posteriori emissions of HFC-134a, HFC-152a and HCFC-22 all increased from 2005 to 2006. Large increases (21%, 16%, 18%, respectively) from 2005 to 2006 were found for China, whereas the emission changes in North America (−9%, 23%, 17%, respectively) and Europe (11%, 11%, −4%, respectively) were mostly smaller and less systematic. For Europe, the a posteriori emissions of HFC-134a and HFC-152a were Correspondence to: A. Stohl (ast@nilu.no) slightly higher than the a priori emissions reported to the United Nations Framework Convention on Climate Change (UNFCCC). For HCFC-22, the a posteriori emissions for Europe were substantially (by almost a factor 2) higher than the a priori emissions used, which were based on HCFC consumption data reported to the United Nations Environment Programme (UNEP). Combined with the reported strongly decreasing HCFC consumption in Europe, this suggests a substantial time lag between the reported time of the HCFC-22 consumption and the actual time of the HCFC-22 emission. Conversely, in China where HCFC consumption is increasing rapidly according to the UNEP data, the a posteriori emissions are only about 40% of the a priori emissions. This reveals a substantial storage of HCFC-22 and potential for future emissions in China. Deficiencies in the geographical distribution of stations measuring halocarbons in relation to estimating regional emissions are also discussed in the paper.

[1] We used laser-induced fluorescence to measure the concentrations of OH and HO 2 radicals in central Tokyo during two intensive campaigns (IMPACT IVand IMPACT L) in January-February and July-August 2004. The estimated detection limit for the 10-min data was 1.3 Â 10 5 cm À3 for the nighttime and 5.2 Â 10 5 cm À3 for the daytime. The median values of the daytime peak concentrations of HO 2 were 1.1 and 5.7 pptv for the winter and summer periods, respectively, while the values for OH were 1.5 Â 10 6 and 6.3 Â 10 6 cm À3 . High HO 2 mixing ratios (>50 pptv) were observed on a day in summer when O 3 mixing ratios exceeded 100 ppbv. The average nighttime concentrations of HO 2 were 0.7 and 2.6 pptv for the winter and summer periods, respectively, while the values for OH were 1.8 Â 10 5 and 3.7 Â 10 5 cm À3 . A photochemical box model constrained by ancillary observations was able to reproduce daytime OH concentrations reasonably well for both periods, although daytime HO 2 concentrations were underestimated in winter and overestimated in summer. Increasing the wintertime hydrocarbon concentrations in the model led to an increase in daytime HO 2 concentrations, thereby showing better agreement with observations; however, the model continued to underestimate HO 2 concentrations at high NO mixing ratios. This underestimate was most pronounced in the mornings of both periods and during the daytime in winter. We studied processes that are capable of explaining this discrepancy, including unknown reactions of HNO 4 or an unidentified HO x source that is linearly scalable to the NO mixing ratio. The important processes in terms of producing radicals were the olefin + O 3 reactions in the nighttime of both periods and during the daytime in winter, the photolysis of carbonyls in the daytime for both periods, and the photolysis of HONO during the daytime in winter (using measured HONO concentrations) and during mornings in summer (using estimated HONO concentrations).

Abstract. We present the organization, instrumentation, datasets, data interpretation, modeling, and accomplishments of the multinational global atmospheric measurement program AGAGE (Advanced Global Atmospheric Gases Experiment). AGAGE is distinguished by its capability to measure globally, at high frequency, and at multiple sites all the important species in the Montreal Protocol and all the important non-carbon-dioxide (non-CO2) gases assessed by the Intergovernmental Panel on Climate Change (CO2 is also measured at several sites). The scientific objectives of AGAGE are important in furthering our understanding of global chemical and climatic phenomena. They are the following: (1) to accurately measure the temporal and spatial distributions of anthropogenic gases that contribute the majority of reactive halogen to the stratosphere and/or are strong infrared absorbers (chlorocarbons, chlorofluorocarbons – CFCs, bromocarbons, hydrochlorofluorocarbons – HCFCs, hydrofluorocarbons – HFCs and polyfluorinated compounds (perfluorocarbons – PFCs), nitrogen trifluoride – NF3, sulfuryl fluoride – SO2F2, and sulfur hexafluoride – SF6) and use these measurements to determine the global rates of their emission and/or destruction (i.e., lifetimes); (2) to accurately measure the global distributions and temporal behaviors and determine the sources and sinks of non-CO2 biogenic–anthropogenic gases important to climate change and/or ozone depletion (methane – CH4, nitrous oxide – N2O, carbon monoxide – CO, molecular hydrogen – H2, methyl chloride – CH3Cl, and methyl bromide – CH3Br); (3) to identify new long-lived greenhouse and ozone-depleting gases (e.g., SO2F2, NF3, heavy PFCs (C4F10, C5F12, C6F14, C7F16, and C8F18) and hydrofluoroolefins (HFOs; e.g., CH2 = CFCF3) have been identified in AGAGE), initiate the real-time monitoring of these new gases, and reconstruct their past histories from AGAGE, air archive, and firn air measurements; (4) to determine the average concentrations and trends of tropospheric hydroxyl radicals (OH) from the rates of destruction of atmospheric trichloroethane (CH3CCl3), HFCs, and HCFCs and estimates of their emissions; (5) to determine from atmospheric observations and estimates of their destruction rates the magnitudes and distributions by region of surface sources and sinks of all measured gases; (6) to provide accurate data on the global accumulation of many of these trace gases that are used to test the synoptic-, regional-, and global-scale circulations predicted by three-dimensional models; and (7) to provide global and regional measurements of methane, carbon monoxide, and molecular hydrogen and estimates of hydroxyl levels to test primary atmospheric oxidation pathways at midlatitudes and the tropics. Network Information and Data Repository: http://agage.mit.edu/data or http://cdiac.ess-dive.lbl.gov/ndps/alegage.html (https://doi.org/10.3334/CDIAC/atg.db1001).

Volatile halogenated organic compounds containing bromine and iodine, which are naturally produced in the ocean, are involved in ozone depletion in both the troposphere and stratosphere. Three prominent compounds transporting large amounts of marine halogens into the atmosphere are bromoform (CHBr₃), dibromomethane (CH₂Br₂) and methyl iodide (CH₃I). The input of marine halogens to the stratosphere has been estimated from observations and modelling studies using low-resolution oceanic emission scenarios derived from top-down approaches. In order to improve emission inventory estimates, we calculate data-based high resolution global sea-to-air flux estimates of these compounds from surface observations within the HalOcAt (Halocarbons in the Ocean and Atmosphere) database (https://halocat.geomar.de/). Global maps of marine and atmospheric surface concentrations are derived from the data which are divided into coastal, shelf and open ocean regions. Considering physical and biogeochemical characteristics of ocean and atmosphere, the open ocean water and atmosphere data are classified into 21 regions. The available data are interpolated onto a 1°×1° grid while missing grid values are interpolated with latitudinal and longitudinal dependent regression techniques reflecting the compounds' distributions. With the generated surface concentration climatologies for the ocean and atmosphere, global sea-to-air concentration gradients and sea-to-air fluxes are calculated. Based on these calculations we estimate a total global flux of 1.5/2.5 Gmol Br yr⁻¹ for CHBr₃, 0.78/0.98 Gmol Br yr⁻¹ for CH₂Br₂ and 1.24/1.45 Gmol Br yr⁻¹ for CH₃I (robust fit/ordinary least squares regression techniques). Contrary to recent studies, negative fluxes occur in each sea-to-air flux climatology, mainly in the Arctic and Antarctic regions. "Hot spots" for global polybromomethane emissions are located in the equatorial region, whereas methyl iodide emissions are enhanced in the subtropical gyre regions. Inter-annual and seasonal variation is contained within our flux calculations for all three compounds. Compared to earlier studies, our global fluxes are at the lower end of estimates, especially for bromoform. An under-representation of coastal emissions and of extreme events in our estimate might explain the mismatch between our bottom-up emission estimate and top-down approaches