Anna E. Jones

Speciation and rate of photochemical NO and NO2 production in Antarctic snow

Measurements were made of NO and NO2, in controlled experiments to investigate their production from snow. Throughout a diurnal cycle, measurements were made of ambient air and air from inside a snowblock. Enhanced concentrations of NO and NO2 (up to 15 pptv and 32 pptv respectively) were measured inside the snowblock. The production rate inside the block varied with intensity of incident radiation, and reached a maximum of 1.1×106 molecs/cm³/s for NO and 2.1 × 106 molecs/cm³/s for NO2. A second experiment, in which the snowblock was alternately exposed to sunlight and then shaded, confirmed that the diurnal production was driven by photochemistry rather than some other diurnally varying factor. Concentrations of nitrate in the snowblock did not change as a result of 50 hours of experiments, confirming that if nitrate is the source reservoir, it can not be rapidly depleted. Snowpack production may contribute significantly to NOx concentrations in the Antarctic lower troposphere.

Measurements of NOx emissions from the Antarctic snowpack

It has been shown that NOx is produced photochemically within the snowpack of polar regions. If emitted to the atmosphere, this process could be a major source of NOx in remote snowcovered regions. We report here on measurements made at the German Antarctic station, Neumayer, during austral summer 1999, aimed at detecting and quantifying emissions of NOx from the surface snow. Gradients of NOx measured, and fluxes calculated using local meteorology measurements. On the 2 days of flux measurements, the derived fluxes showed continual release from the snow surface, varying between ∼0 and 3 × 108 molecs/cm²/s. When not subject to turbulence, the variation was coincident with the uv diurnal cycle, suggesting rapid release once photochemically produced. Scaling the diurnal average of Feb. 7th (1.3 × 108 molecs/cm²/s) suggests an annual emission over Antarctica of the order 0.0076TgN.

The impact of the mixing properties within the Antarctic stratospheric vortex on ozone loss in spring

Calculations of equivalent length from an artificial advected tracer provide new insight into the isentropic transport processes occurring within the Antarctic stratospheric vortex. These calculations show two distinct regions of approximately equal area: a strongly mixed vortex core and a broad ring of weakly mixed air extending out to the vortex boundary. This broad ring of vortex air remains isolated from the core between late winter and midspring. Satellite measurements of stratospheric H2O confirm that the isolation lasts until at least mid-October. A three-dimensional chemical transport model simulation of the Antarctic ozone hole quantifies the ozone loss within this ring and demonstrates its isolation. In contrast to the vortex core, ozone loss in the weakly mixed broad ring is not complete. The reasons are twofold. First, warmer temperatures in the broad ring prevent continuous polar stratospheric cloud (PSC) formation and the associated chemical processing (i.e., the conversion of unreactive chlorine into reactive forms). Second, the isolation prevents ozone-rich air from the broad ring mixing with chemically processed air from the vortex core. If the stratosphere continues to cool, this will lead to increased PSC formation and more complete chemical processing in the broad ring. Despite the expected decline in halocarbons, sensitivity studies suggest that this mechanism will lead to enhanced ozone loss in the weakly mixed region, delaying the future recovery of the ozone hole.

Validation of Ground-Based Visible Measurements of Total Ozone by Comparison with Dobson and Brewer Spectrophotometers

Comparisons of total column ozone measurements from Dobson, Brewer and SAOZ instruments are presented for the period 1990 to 1995 at seven stations covering the mid- and the high northern latitudes, as well as the Antarctic region. The main purpose of these comparisons is to assess, by reference to the well established Dobson network, the accuracy of the zenith-sky visible spectroscopy for the measurement of total ozone. The strengths and present limitations of this latter technique are investigated. As a general result, the different instruments are found to agree within a few percent at all stations, the best agreement being obtained at mid-latitudes. On average, for the mid-latitudes, SAOZ O3 measurements are approximately 2% higher than Dobson ones, with a scatter of about 5%. At higher latitudes, both scatter and systematic deviation tend to increase. In all cases, the relative differences between SAOZ and Dobson or Brewer column ozone are characterised by a significant seasonal signal, the amplitude of which increases from about 2.5% at mid-latitude to a maximum of 7.5% at Faraday, Antarctica. Although it introduces a significant contribution to the seasonality at high latitude, the temperature sensitivity of the O3 absorption coefficients of the Dobson and Brewer instruments is shown to be too small to account for the observed SAOZ/Dobson differences. Except for Faraday, these differences can however be largely reduced if SAOZ AMFs are calculated with realistic climatological profiles of ozone, pressure and temperature. Other sources of uncertainties that might affect the comparison are investigated. Evidence is found that the differences in the air masses sampled by the SAOZ and the other instruments contribute significantly to the scatter, and the impact of the tropospheric clouds on SAOZ measurements is displayed.

A role for newly forming sea ice in springtime polar tropospheric ozone loss? Observational evidence from Halley station, Antarctica

Since March 2003, measurements of surface ozone have been made at the British Antarctic Survey Clean Air Sector Laboratory (CASLab) at Halley station in coastal Antarctica. Detailed measurements of boundary layer meteorology, as well as standard meteorological parameters, are also measured at the CASLab. Combining these data allows us to probe the transport pathway of air masses during ozone depletion events (ODEs). ODEs were observed at Halley on several occasions during Antarctic spring 2003. On some occasions, extremely rapid loss of ozone was observed (loss of 16 ppbv in 1 min on one occasion), which was associated with regional-scale transport. For each such event during 2003, the air mass originated in the southern Weddell Sea, an area of vigorous sea-ice production. On other occasions the development of the event and its recovery were strongly associated with the build-up and decline of a stable boundary layer. In these cases, air masses had had recent contact with a nearby open water lead where sea-ice production is known to occur. The data presented here are entirely consistent with the idea that halogens responsible for ozone loss are derived during new sea-ice formation from an associated surface such as brine slush or frost flowers.

Biodiversity of air-borne microorganisms at Halley station Antarctica

A study of air-borne microbial biodiversity over an isolated scientific research station on an ice-shelf in continental Antarctica was undertaken to establish the potential source of microbial colonists. The study aimed to assess: (1) whether microorganisms were likely to have a local (research station) or distant (marine or terrestrial) origin, (2) the effect of changes in sea ice extent on microbial biodiversity and (3) the potential human impact on the environment. Air samples were taken above Halley Research Station during the austral summer and austral winter over a 2-week period. Overall, a low microbial biodiversity was detected, which included many sequence replicates. No significant patterns were detected in the aerial biodiversity between the austral summer and the austral winter. In common with other environmental studies, particularly in the polar regions, many of the sequences obtained were from as yet uncultivated organisms. Very few marine sequences were detected irrespective of the distance to open water, and around one-third of sequences detected were similar to those identified in human studies, though both of these might reflect prevailing wind conditions. The detected aerial microorganisms were markedly different from those obtained in earlier studies over the Antarctic Peninsula in the maritime Antarctic.

Seasonality of reactive nitrogen oxides (NOy) at Neumayer Station, Antarctica

Abstract. NO, NOy (total reactive nitrogen oxides), gaseous HNO3 and particulate nitrate (p-NO3-) were measured at Neumayer Station from February 1999 to January 2000. We found a mean NOy mixing ratio of 46±29 pptv, with significantly higher values between February and the end of May (58±35 pptv). Between February and November, the (HNO3+p-NO3-)/NOy ratio was extremely low (around 0.22) and in contrast to NOy the seasonality of p-nitrate and HNO3 showed a distinct maximum in November and December, respectively. Trajectory analyses and radioisotope measurements (7Be, 10Be, 210Pb, and 222Rn) indicated that the upper troposphere or stratosphere was the main source region of the observed NOy with a negligible contribution of ground-level sources at northward continents. Frequent maxima of NOy mixing ratios up to 100 pptv are generally associated with air mass transport from the free troposphere of continental Antarctica, while air masses with the lowest NOy mixing ratios were typically advected from the marine boundary layer. Due to the highly variable (HNO3+p-NO3-)/NOy ratio and different seasonality of (HNO3+p-NO3-) and NOy, nitrate concentrations in firn caused by deposition of HNO3 and p-nitrate are most probably not directly connected with the atmospheric budget of reac-tive nitrogen oxides. Consequently, there is no straightforward way to derive the total reactive nitrogen content of the paleo-atmosphere from ice nitrate records.

OH and halogen atom influence on the variability of non-methane hydrocarbons in the Antarctic Boundary Layer

Ozone measurements from Measurements of OZone and wAter vapour by aIrbus in-service airCraft (MOZAIC) have been assimilated into the global chemical transport model ofMétéo France known as Mod`ele de Chimie Atmosphérique `a Grande Echelle (MOCAGE). The assimilation makes improvements to the free model simulations of ozone in the upper troposphere and lower stratosphere, which are generally overestimated in the tropical region and underestimated in mid-latitudes. The tropical–subtropical gradient of ozone is also improved following assimilation and comparison with vertical profiles from ozonesondes suggests that the assimilation leads to a better representation of the vertical gradient around the tropopause.We use the assimilated fields to calculate a value for the flux of ozone across the tropopause. The net flux of ozone from stratosphere to troposphere is found to be 451 Tg yr-1 before assimilation and 383 Tg yr-1 after assimilation. The downward flux of ozone in the mid-latitudes exhibits an annual cycle with maximum flux occurring in early spring and minimum flux in autumn.

Reconciling the changes in atmospheric methane sources and sinks between the Last Glacial Maximum and the pre-industrial era

We know from the ice record that the concentration of atmospheric methane, [CH4], at the Last Glacial Maximum (LGM) was roughly half that in the pre-industrial era (PI), buthow much of the difference was source-driven, and how much was sink-driven, remains uncertain. Recent developments include: a higher estimate of the LGM-PI change in methane emissions from wetlands―the dominant, natural methane source; and the possible recycling of OH consumed in isoprene oxidation―the principal methane sink. Here, in view of these developments, we use an atmospheric chemistry-transport model to re-examine the main factors affecting OH during this period: changes in air temperature and emissions of non-methane volatile organic compounds from vegetation. We find that their net effect was negligible(with and without an OH recycling mechanism), implyingthe change in [CH4] was almost entirely source driven―a conclusion that, though subject to significant uncertainties,can be reconciled with recent methane source estimates.

Sea salt as an ice core proxy for past sea ice extent: a process-based model study

Sea ice is a reflection of, and a feedback on, the Earths climate. We explore here, using a global atmospheric chemistry-transport model, the use of sea salt in Antarctic ice cores to obtain continuous long-term, regionally integrated records of past sea ice extent, synchronous with ice core records of climate. The model includes the production, transport, and deposition of sea salt aerosol from the open ocean and “blowing snow” on sea ice. Under current climate conditions, we find that meteorology, not sea ice extent, is the dominant control on the atmospheric concentration of sea salt reaching coastal and continental Antarctic sites on interannual timescales. However, through a series of idealized sensitivity experiments, we demonstrate that sea salt has potential as a proxy for larger changes in sea ice extent (e.g., glacial-interglacial). Treating much of the sea ice under glacial conditions as a source of salty blowing snow, we demonstrate that the increase in sea ice extent alone (without changing the meteorology) could drive, for instance, a 68% increase in atmospheric sea salt concentration at the site of the Dome C ice core, which exhibits an approximate twofold glacial increase in sea salt flux. We also show how the sensitivity of this potential proxy decreases toward glacial sea ice extent—the basis of an explanation previously proposed for the lag observed between changes in sea salt flux and δD (an ice core proxy for air temperature) at glacial terminations. The data thereby permit simultaneous changes in sea ice extent and climate.