scholarly journals The multi-seasonal NO<sub>y</sub> budget in coastal Antarctica and its link with surface snow and ice core nitrate: results from the CHABLIS campaign

2007 ◽  
Vol 7 (2) ◽  
pp. 4127-4163 ◽  
Author(s):  
A. E. Jones ◽  
E. W. Wolff ◽  
D. Ames ◽  
S. J.-B. Bauguitte ◽  
K. C. Clemitshaw ◽  
...  

Abstract. Measurements of individual NOy components were carried out at Halley station in coastal Antarctica. The measurements were made as part of the CHABLIS campaign (Chemistry of the Antarctic Boundary Layer and the Interface with Snow) and cover over half a year, from austral winter 2004 through to austral summer 2005. They are the longest duration and most extensive NOy budget study carried out to date in polar regions. Results show clear dominance of organic NOy compounds (PAN and MeONO2) during the winter months, with low concentrations of inorganic NOy, but a reversal of this situation towards summer when the balance shifts in favour of inorganic NOy. Multi-seasonal measurements of surface snow nitrate correlate strongly with inorganic NOy species. One case study in August suggested that particulate nitrate was the dominant source of nitrate to the snowpack, but this was not the consistent picture throughout the measurement period. An analysis of NOx production rates showed that emissions of NOx from the snowpack dominate over gas-phase sources of "new NOx", suggesting that, for certain periods in the past, the flux of NOx into the boundary layer can be calculated from ice core nitrate data.

2011 ◽  
Vol 11 (17) ◽  
pp. 9271-9285 ◽  
Author(s):  
A. E. Jones ◽  
E. W. Wolff ◽  
D. Ames ◽  
S. J.-B. Bauguitte ◽  
K. C. Clemitshaw ◽  
...  

Abstract. Measurements of a suite of individual NOy components were carried out at Halley station in coastal Antarctica as part of the CHABLIS campaign (Chemistry of the Antarctic Boundary Layer and the Interface with Snow). Conincident measurements cover over half a year, from austral winter 2004 through to austral summer 2005. Results show clear dominance of organic NOy compounds (PAN and MeONO2) during the winter months, with low concentrations of inorganic NOy. During summer, concentrations of inorganic NOy compounds are considerably greater, while those of organic compounds, although lower than in winter, are nonetheless significant. The relative concentrations of the alkyl nitrates, as well as their seasonality, are consistent with an oceanic source. Multi-seasonal measurements of surface snow nitrate correlate strongly with inorganic NOy species (especially HNO3) rather than organic. One case study in August suggested that, on that occasion, particulate nitrate was the dominant source of nitrate to the snowpack, but this was not the consistent picture throughout the measurement period. An analysis of NOx production rates showed that emissions of NOx from the snowpack overwhelmingly dominate over gas-phase sources. This result suggests that, for certain periods in the past, the flux of NOx into the Antarctic boundary layer can be calculated from ice core nitrate data.


2008 ◽  
Vol 8 (1) ◽  
pp. 2657-2694 ◽  
Author(s):  
K. A. Read ◽  
A. C. Lewis ◽  
S. Bauguitte ◽  
A. M. Rankin ◽  
R. A. Salmon ◽  
...  

Abstract. In situ measurements of dimethyl sulphide (DMS) and methane sulphonic acid (MSA) were made at Halley Station, Antarctica (75°35´S, 26°19W) during February 2004–February 2005 as part of the CHABLIS (Chemistry of the Antarctic boundary layer and the interface with snow) project. DMS was present in the atmosphere at Halley all year (average 38.1±43 pptV) with a maximum monthly average value of 113.6±52 pptV in February 2004 coinciding temporally with a minimum in sea extent. Whilst seasonal variability and interannual variability can be attributed to a number of factors, short term variability appeared strongly dependent on air mass origin and trajectory pressure height. The MSA and derived non-sea salt sulphate (nss-SO42−) measurements showed no correlation with those of DMS (regression R2=0.039, and R2=0.001, respectively) in-line with the complexity of DMS fluxes, conflicting oxidation routes, transport of air masses and variable spatial coverage of both sea-ice and phytoplankton. MSA was generally low throughout the year, with an annual average of 42 ng m−3 (9.8±13.2 pptV), however MSA: nss-SO42− ratios were high implying a dominance of the addition oxidation route for DMS. Including BrO measurements into MSA production calculations demonstrated the significance of BrO on DMS oxidation within this region of the atmosphere in austral summer. Assuming an 80% yield of DMSO from the reaction of DMS+BrO, an atmospheric concentration of BrO equal to 3 pptV increased the calculated MSA production from DMS by a factor of 9 above that obtained when considering only reaction with the hydroxyl radical.


2008 ◽  
Vol 8 (11) ◽  
pp. 2985-2997 ◽  
Author(s):  
K. A. Read ◽  
A. C. Lewis ◽  
S. Bauguitte ◽  
A. M. Rankin ◽  
R. A. Salmon ◽  
...  

Abstract. In situ measurements of dimethyl sulphide (DMS) and methane sulphonic acid (MSA) were made at Halley Station, Antarctica (75°35' S, 26°19' W) during February 2004–February 2005 as part of the CHABLIS (Chemistry of the Antarctic Boundary Layer and the Interface with Snow) project. DMS was present in the atmosphere at Halley all year (average 38.1±43 pptV) with a maximum monthly average value of 113.6±52 pptV in February 2004 coinciding temporally with a minimum in sea extent. Whilst seasonal variability and interannual variability can be attributed to a number of factors, short term variability appeared strongly dependent on air mass origin and trajectory pressure height. The MSA and derived non-sea salt sulphate (nss-SO42−) measurements showed no correlation with those of DMS (regression R2=0.039, and R2=0.001 respectively) in-line with the complexity of DMS fluxes, alternative oxidation routes, transport of air masses and variable spatial coverage of both sea-ice and phytoplankton. MSA was generally low throughout the year, with an annual average of 42 ng m−3 (9.8±13.2 pptV), however MSA: nss-SO42− ratios were high implying a dominance of the addition oxidation route for DMS. Including BrO measurements into MSA production calculations demonstrated the significance of BrO on DMS oxidation within this region of the atmosphere in austral summer. Assuming an 80% yield of DMSO from the reaction of DMS+BrO, an atmospheric concentration of BrO equal to 3 pptV increased the calculated MSA production from DMS by a factor of 9 above that obtained when considering only reaction with the hydroxyl radical. These findings have significant atmospheric implications, but may also impact on the interpretation of ice cores which previously relied on the understanding of MSA and nss-SO42− chemistry to provide information on environmental conditions such as sea ice extent and the origins of sulphur within the ice.


2010 ◽  
Vol 10 (6) ◽  
pp. 15109-15165 ◽  
Author(s):  
W. J. Bloss ◽  
M. Camredon ◽  
J. D. Lee ◽  
D. E. Heard ◽  
J. M. C. Plane ◽  
...  

Abstract. A modelling study of radical chemistry in the coastal Antarctic boundary layer, based upon observations performed in the course of the CHABLIS (Chemistry of the Antarctic Boundary Layer and the Interface with Snow) campaign at Halley Research Station in coastal Antarctica during the austral summer 2004/2005, is described: a detailed zero-dimensional photochemical box model was used, employing inorganic and organic reaction schemes drawn from the Master Chemical Mechanism, with additional halogen (iodine and bromine) reactions added. The model was constrained to observations of long-lived chemical species, measured photolysis rates and meteorological parameters, and the simulated levels of HOx, NOx and XO compared with those observed. The model was able to replicate the mean levels and diurnal variation in the halogen oxides IO and BrO, and to reproduce NOx levels and speciation very well. The NOx source term implemented compared well with that directly measured in the course of the CHABLIS experiments. The model systematically overestimated OH and HO2 levels, likely a consequence of the combined effects of (a) estimated physical parameters and (b) uncertainties within the halogen, particularly iodine, chemical scheme. The principal sources of HOx radicals were the photolysis and bromine-initiated oxidation of HCHO, together with O(1D)+H2O. The main sinks for HOx were peroxy radical self- and cross-reactions, with the sum of all halogen-mediated HOx loss processes accounting for 40% of the total sink. Reactions with the halogen monoxides dominated CH3O2–HO2–OH interconversion, with associated local chemical ozone destruction in place of the ozone production which is associated with radical cycling driven by the analogous NO reactions. The analysis highlights the need for observations of physical parameters such as aerosol surface area and boundary layer structure to constrain such calculations, and the dependence of simulated radical levels and ozone loss rates upon a number of uncertain kinetic and photochemical parameters for iodine species.


2010 ◽  
Vol 10 (21) ◽  
pp. 10187-10209 ◽  
Author(s):  
W. J. Bloss ◽  
M. Camredon ◽  
J. D. Lee ◽  
D. E. Heard ◽  
J. M. C. Plane ◽  
...  

Abstract. A modelling study of radical chemistry in the coastal Antarctic boundary layer, based upon observations performed in the course of the CHABLIS (Chemistry of the Antarctic Boundary Layer and the Interface with Snow) campaign at Halley Research Station in coastal Antarctica during the austral summer 2004/2005, is described: a detailed zero-dimensional photochemical box model was used, employing inorganic and organic reaction schemes drawn from the Master Chemical Mechanism, with additional halogen (iodine and bromine) reactions added. The model was constrained to observations of long-lived chemical species, measured photolysis frequencies and meteorological parameters, and the simulated levels of HOx, NOx and XO compared with those observed. The model was able to replicate the mean levels and diurnal variation in the halogen oxides IO and BrO, and to reproduce NOx levels and speciation very well. The NOx source term implemented compared well with that directly measured in the course of the CHABLIS experiments. The model systematically overestimated OH and HO2 levels, likely a consequence of the combined effects of (a) estimated physical parameters and (b) uncertainties within the halogen, particularly iodine, chemical scheme. The principal sources of HOx radicals were the photolysis and bromine-initiated oxidation of HCHO, together with O(1D) + H2O. The main sinks for HOx were peroxy radical self- and cross-reactions, with the sum of all halogen-mediated HOx loss processes accounting for 40% of the total sink. Reactions with the halogen monoxides dominated CH3O2-HO2-OH interconversion, with associated local chemical ozone destruction in place of the ozone production which is associated with radical cycling driven by the analogous NO reactions. The analysis highlights the need for observations of physical parameters such as aerosol surface area and boundary layer structure to constrain such calculations, and the dependence of simulated radical levels and ozone loss rates upon a number of uncertain kinetic and photochemical parameters for iodine species.


2006 ◽  
Vol 33 (6) ◽  
Author(s):  
A. Virkkula ◽  
I. K. Koponen ◽  
K. Teinilä ◽  
R. Hillamo ◽  
V-M. Kerminen ◽  
...  

Tellus B ◽  
2007 ◽  
Vol 59 (1) ◽  
pp. 22-38 ◽  
Author(s):  
Katie A. Read ◽  
Alastair C. Lewis ◽  
Rhian A. Salmon ◽  
Anna E. Jones ◽  
Stéphane Bauguitte

2015 ◽  
Vol 15 (20) ◽  
pp. 12079-12113 ◽  
Author(s):  
J. Erbland ◽  
J. Savarino ◽  
S. Morin ◽  
J. L. France ◽  
M. M. Frey ◽  
...  

Abstract. Unraveling the modern budget of reactive nitrogen on the Antarctic Plateau is critical for the interpretation of ice-core records of nitrate. This requires accounting for nitrate recycling processes occurring in near-surface snow and the overlying atmospheric boundary layer. Not only concentration measurements but also isotopic ratios of nitrogen and oxygen in nitrate provide constraints on the processes at play. However, due to the large number of intertwined chemical and physical phenomena involved, numerical modeling is required to test hypotheses in a quantitative manner. Here we introduce the model TRANSITS (TRansfer of Atmospheric Nitrate Stable Isotopes To the Snow), a novel conceptual, multi-layer and one-dimensional model representing the impact of processes operating on nitrate at the air–snow interface on the East Antarctic Plateau, in terms of concentrations (mass fraction) and nitrogen (δ15N) and oxygen isotopic composition (17O excess, Δ17O) in nitrate. At the air–snow interface at Dome C (DC; 75° 06' S, 123° 19' E), the model reproduces well the values of δ15N in atmospheric and surface snow (skin layer) nitrate as well as in the δ15N profile in DC snow, including the observed extraordinary high positive values (around +300 ‰) below 2 cm. The model also captures the observed variability in nitrate mass fraction in the snow. While oxygen data are qualitatively reproduced at the air–snow interface at DC and in East Antarctica, the simulated Δ17O values underestimate the observed Δ17O values by several per mill. This is explained by the simplifications made in the description of the atmospheric cycling and oxidation of NO2 as well as by our lack of understanding of the NOx chemistry at Dome C. The model reproduces well the sensitivity of δ15N, Δ17O and the apparent fractionation constants (15&amp;varepsilon;app, 17Eapp) to the snow accumulation rate. Building on this development, we propose a framework for the interpretation of nitrate records measured from ice cores. Measurement of nitrate mass fractions and δ15N in the nitrate archived in an ice core may be used to derive information about past variations in the total ozone column and/or the primary inputs of nitrate above Antarctica as well as in nitrate trapping efficiency (defined as the ratio between the archived nitrate flux and the primary nitrate input flux). The Δ17O of nitrate could then be corrected from the impact of cage recombination effects associated with the photolysis of nitrate in snow. Past changes in the relative contributions of the Δ17O in the primary inputs of nitrate and the Δ17O in the locally cycled NO2 and that inherited from the additional O atom in the oxidation of NO2 could then be determined. Therefore, information about the past variations in the local and long-range processes operating on reactive nitrogen species could be obtained from ice cores collected in low-accumulation regions such as the Antarctic Plateau.


Author(s):  
Peter Convey

Antarctica originally formed part of the southern supercontinent, Gondwana, and its fossil record shows that the continent hosted cool temperate and even subtropical forests, dinosaurs, early mammals, and many other biota, despite lying at high southern paleolatitudes for over 100 My. The Antarctica of today is a continent of extremes, inspiring awe, trepidation, and superlatives from those privileged to experience it. It is certainly a forbidding place, more than twice the area of Australia, distant and isolated from other southern continents, with around 0.2 percent of its area ever exposed from permanent ice and snow and covered on average with ice more than 2 kilometers thick. In winter, the surface of an area of ocean of approximately the same size as the continent freezes around it, and throughout the year ice is one of the major drivers of physical and biological processes in the Southern Ocean. Antarctica is also distinct among the Earth’s continents, being the only one not to have ever had a natural human population, and only being discovered and explored over the last one to two centuries. Even now, the human population is limited to the temporary residents of national research stations (about five thousand in summer and one thousand in winter), augmented by thirty to forty thousand mostly ship-based tourist visitors in the austral summer. At least to human perception, the environments of the polar regions are challenging to life. Organisms that live on land in Antarctica today must survive chronic, highly variable and extreme environmental stresses, in particular low temperatures, desiccation, high winds, and a harsh radiation climate. At latitudes beyond the Antarctic Circle, extreme seasonality is driven by the sun remaining permanently below the horizon for up to several months during winter and, conversely, above the horizon in summer. In winter terrestrial habitats experience extremely low air temperatures, typically −40 to −60°C or lower (the lowest instrumentally recorded temperature on Earth is −89.2°C, at Vostok Station on the Antarctic polar plateau). As well as its extreme climate, parts of Antarctica, in particular the Antarctic Peninsula region, have been facing rates of regional climate change in recent decades that are the most rapid in the Southern Hemisphere, as well as the consequences of the anthropogenically caused stratospheric ozone hole. These provide both further challenges to the organisms native to the continent and its surrounding oceans, and a test-bed or proxy for understanding the consequences of change for organisms and ecosystems globally. Terrestrial ecosystems and biodiversity, the primary focus of this chapter, are generally depauperate, primarily comprised of cryptic and microscopic groups that are often overlooked except by specialists. Antarctic marine ecosystems, in contrast and despite also facing extreme seasonality and chronic exposure to near-freezing temperatures, can be highly diverse and comprise considerable biomass, possibly second only to tropical coral reefs.


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