Ozone and carbon monoxide observations over open oceans on R/V?iMirai/i from 67°?S to 75°?N during 2012 to 2017: testing global chemical reanalysis in terms of Arctic processes, low ozone levels at low latitudes, and pollution transport

摘要

Constraints from ozone ( Osub3/sub ) observations over oceans are needed in addition to those from terrestrial regions to fully understand global tropospheric chemistry and its impact on the climate. Here, we provide a large data set of ozone and carbon monoxide?(CO) levels observed (for 11?666 and 10?681?h, respectively) over oceans. The data set is derived from observations made during 24 research cruise legs of R/V?Mirai during 2012 to 2017, in the Southern, Indian, Pacific, and Arctic oceans, covering the region from 67 sup°/sup S to 75 sup°/sup N. The data are suitable for critical evaluation of the over-ocean distribution of ozone derived from global atmospheric chemistry models. We first give an overview of the statistics in the data set and highlight key features in terms of geographical distribution and air mass type. We then use the data set to evaluate ozone mixing ratio fields from the tropospheric chemistry reanalysis version 2 (TCR-2), produced by assimilating a suite of satellite observations of multiple species into a global atmospheric chemistry model, namely CHASER. For long-range transport of polluted air masses from continents to the oceans, during which the effects of forest fires and fossil fuel combustion were recognized, TCR-2 gave an excellent performance in reproducing the observed temporal variations and photochemical buildup of Osub3/sub when assessed from ΔOsub3/sub∕ΔCO ratios. For clean marine conditions with low and stable CO mixing ratios, two focused analyses were performed. The first was in the Arctic (?70 sup°/sup N) in September every year from 2013 to 2016; TCR-2 underpredicted Osub3/sub levels by 6.7?ppbv (21?%) on average. The observed vertical profiles from Osub3/sub soundings from R/V?Mirai during September 2014 had less steep vertical gradients at low altitudes (?850?hPa) than those obtained by TCR-2. This suggests the possibility of a more efficient descent of the Osub3/sub -rich air from above than assumed in the models. For TCR-2 (CHASER), dry deposition on the Arctic ocean surface might also have been overestimated. In the second analysis, over the western Pacific equatorial region (125–165 sup°/sup E, 10 sup°/sup S to 25 sup°/sup N), the observed Osub3/sub level more frequently decreased to less than 10?ppbv in comparison to that obtained with TCR-2 and also those obtained in most of the Atmospheric Chemistry Climate Model Intercomparison Project (ACCMIP) model runs for the decade from 2000. These results imply loss processes that are unaccounted for in the models. We found that the model's positive bias positively correlated with the daytime residence times of air masses over a particular grid, namely 165–180 sup°/sup E and 15–30 sup°/sup N; an additional loss rate of 0.25?ppbv?h sup?1/sup in the grid best explained the gap. Halogen chemistry, which is commonly omitted from currently used models, might be active in this region and could have contributed to additional losses. Our open data set covering wide ocean regions is complementary to the Tropospheric Ozone Assessment Report data set, which basically comprises ground-based observations and enables a fully global study of the behavior of Osub3/sub .