Validating the reported random errors of ACE‐FTS measurements

In order to validate the reported precision of space‐based atmospheric composition measurements, validation studies often focus on measurements in the tropical stratosphere, where natural variability is weak. The scatter in tropical measurements can then be used as an upper limit on single‐profile measurement precision. Here we introduce a method of quantifying the scatter of tropical measurements which aims to minimize the effects of short‐term atmospheric variability while maintaining large enough sample sizes that the results can be taken as representative of the full data set. We apply this technique to measurements of O3, HNO3, CO, H2O, NO, NO2, N2O, CH4, CCl2F2, and CCl3F produced by the Atmospheric Chemistry Experiment–Fourier Transform Spectrometer (ACE‐FTS). Tropical scatter in the ACE‐FTS retrievals is found to be consistent with the reported random errors (RREs) for H2O and CO at altitudes above 20 km, validating the RREs for these measurements. Tropical scatter in measurements of NO, NO2, CCl2F2, and CCl3F is roughly consistent with the RREs as long as the effect of outliers in the data set is reduced through the use of robust statistics. The scatter in measurements of O3, HNO3, CH4, and N2O in the stratosphere, while larger than the RREs, is shown to be consistent with the variability simulated in the Canadian Middle Atmosphere Model. This result implies that, for these species, stratospheric measurement scatter is dominated by natural variability, not random error, which provides added confidence in the scientific value of single‐profile measurements.

Seasonal persistence of northern low- and middle-latitude anomalies of ozone and other trace gases in the upper stratosphere

Analysis of observed ozone profiles in Northern Hemisphere low and middle latitudes reveals the seasonal persistence of ozone anomalies in both the lower and upper stratosphere. Principal component analysis is used to detect that above 16 hPa the persistence is strongest in the latitude band 15–45°N, while below 16 hPa the strongest persistence is found over 45–60°N. In both cases, ozone anomalies persist through the entire year from November to October. The persistence of ozone anomalies in the lower stratosphere is presumably related to the wintertime ozone buildup with subsequent photochemical relaxation through summer, as previously found for total ozone. The persistence in the upper stratosphere is more surprising, given the short lifetime of Ox at these altitudes. It is hypothesized that this “seasonal memory” in the upper stratospheric ozone anomalies arises from the seasonal persistence of transport-induced wintertime NOy anomalies, which then perturb the ozone chemistry throughout the rest of the year. This hypothesis is confirmed by analysis of observations of NO2, NOx, and various long-lived trace gases in the upper stratosphere, which are found to exhibit the same seasonal persistence. Previous studies have attributed much of the year-to-year variability in wintertime extratropical upper stratospheric ozone to the Quasi-Biennial Oscillation (QBO) through transport-induced NOy (and hence NO2) anomalies but have not identified any statistical connection between the QBO and summertime ozone variability. Our results imply that through this “seasonal memory,” the QBO has an asynchronous effect on ozone in the low to midlatitude upper stratosphere during summer and early autumn.

The interaction of iron pyrite with oxygen, nitrogen and nitrogen oxides: a first-principles study

Sulphide materials, in particular MoS2, have recently received great attention from the surface science community due to their extraordinary catalytic properties. Interestingly, the chemical activity of iron pyrite (FeS2) (the most common sulphide mineral on Earth), and in particular its potential for catalytic applications, has not been investigated so thoroughly. In this study, we use density functional theory (DFT) to investigate the surface interactions of fundamental atmospheric components such as oxygen and nitrogen, and we have explored the adsorption and dissociation of nitrogen monoxide (NO) and nitrogen dioxide (NO2) on the FeS2(100) surface. Our results show that both those environmentally important NOx species chemisorb on the surface Fe sites, while the S sites are basically unreactive for all the molecular species considered in this study and even prevent NO2 adsorption onto one of the non-equivalent Fe–Fe bridge sites of the (1 1)–FeS2(100) surface. From the calculated high barrier for NO and NO2 direct dissociation on this surface, we can deduce that both nitrogen oxides species are adsorbed molecularly on pyrite surfaces.

Spatio-temporal variations of ozone and nitrogen dioxide concentrations under urban trees and in a nearby open area

The evergreen Quercus ilex L. is one of the most common trees in Italian urban environments and is considered effective in the uptake of particulate and gaseous atmospheric pollutants. However, the few available estimates on O3 and NO2 removal by urban Q. ilex originate from model-based studies (which indicate NO2/O3 removal capacity of Q. ilex) and not from direct measurements of air pollutant concentrations. Thus, in the urban area of Siena (central Italy) we began long-term monitoring of O3/NO2 concentrations using passive samplers at a distance of 1, 5, 10 m from a busy road, under the canopies of Q. ilex and in a nearby open-field. Measurements performed in the period June 2011-October 2013 showed always a greater decrease of NO2 concentrations under the Q. ilex canopy than in the open-field transect. Conversely, a decrease of average O3 concentrations under the tree canopy was found only in autumn after the typical Mediterranean post-summer rainfalls. Our results indicate that interactions between O3/NO2 concentrations and trees in Mediterranean urban ecosystems are affected by temporal variations in climatic conditions. We argue therefore that the direct measurement of atmospheric pollutant concentrations should be chosen to describe local changes of aerial pollution.