Atmospheric nitrogen oxides (NO and NO2) at Dome C, East Antarctica, during the OPALE campaign

Mixing ratios of the atmospheric nitrogen oxides NO and NO2 were measured as part of the OPALE (Oxidant Production in Antarctic Lands & Export) campaign at Dome C, East Antarctica (75.1 degrees S, 123.3 degrees E, 3233 m), during December 2011 to January 2012. Profiles of NOx mixing ratios of the lower 100m of the atmosphere confirm that, in contrast to the South Pole, air chemistry at Dome C is strongly influenced by large diurnal cycles in solar irradiance and a sudden collapse of the atmospheric boundary layer in the early evening. Depth profiles of mixing ratios in firn air suggest that the upper snowpack at Dome C holds a significant reservoir of photolytically produced NO2 and is a sink of gas-phase ozone (O-3). First-time observations of bromine oxide (BrO) at Dome C show that mixing ratios of BrO near the ground are low, certainly less than 5 pptv, with higher levels in the free troposphere. Assuming steady state, observed mixing ratios of BrO and RO2 radicals are too low to explain the large NO2 : NO ratios found in ambient air, possibly indicating the existence of an unknown process contributing to the atmospheric chemistry of reactive nitrogen above the Antarctic Plateau. During 2011-2012, NOx mixing ratios and flux were larger than in 2009-2010, consistent with also larger surface O-3 mixing ratios resulting from increased net O-3 production. Large NOx mixing ratios at Dome C arise from a combination of continuous sunlight, shallow mixing height and significant NOx emissions by surface snow (F-NOx). During 23 December 2011-12 January 2012, median F-NOx was twice that during the same period in 20092010 due to significantly larger atmospheric turbulence and a slightly stronger snowpack source. A tripling of F-NOx in December 2011 was largely due to changes in snowpack source strength caused primarily by changes in NO3- concentrations in the snow skin layer, and only to a secondary order by decrease of total column O-3 and associated increase in NO3- photolysis rates. A source of uncertainty in model estimates of F-NOx is the quantum yield of NO3- photolysis in natural snow, which may change over time as the snow ages

Formaldehyde (HCHO) in air, snow and interstitial air at Concordia (East Antarctic plateau) in summer

During the 2011/12 and 2012/13 austral summers, HCHO was investigated for the first time in ambient air, snow, and interstitial air at the Concordia site, located near Dome C on the East Antarctic Plateau, by deploying an Aerolaser AL-4021 analyzer. Snow emission fluxes were estimated from vertical gradients of mixing ratios observed at 1 cm and 1 m above the snow surface as well as in interstitial air a few centimeters below the surface and in air just above the snowpack. Typical flux values range between 1 and 2 × 1012 molecules m−2 s−1 at night and 3 and 5 × 1012 molecules m−2 s−1 at noon. Shading experiments suggest that the photochemical HCHO production in the snowpack at Concordia remains negligible compared to temperature-driven air–snow exchanges. At 1 m above the snow surface, the observed mean mixing ratio of 130 pptv and its diurnal cycle characterized by a slight decrease around noon are quite well reproduced by 1-D simulations that include snow emissions and gas-phase methane oxidation chemistry. Simulations indicate that the gas-phase production from CH4 oxidation largely contributes (66%) to the observed HCHO mixing ratios. In addition, HCHO snow emissions account for ~ 30% at night and ~ 10% at noon to the observed HCHO levels

Characterization of the boundary layer at Dome C (East Antarctica) during the OPALE summer campaign

The regional climate model MAR was run for the region of Dome C located on the East Antarctic plateau, during Antarctic summer 2011–2012, in order to refine our understanding of meteorological conditions during the OPALE observation campaign. A very high vertical resolution is set up in the lower troposphere, with a grid spacing of roughly 2 m. Comparisons are made with observed temperatures and winds near the surface and from a 45 m high tower as well as sodar and radiation data. MAR is generally in very good agreement with the observations but sometimes underestimates cloud formation, leading to an underestimation of the simulated downward long-wave radiation. Absorbed short-wave radiation may also be slightly overestimated due to an underestimation of the snow albedo and this influences the surface energy budget and atmospheric turbulence. Nevertheless the model provides sufficiently reliable information that represent key parameters when discussing the representativeness of chemical measurements made nearby the ground surface during field campaigns conducted at the Concordia site located at Dome C (3233 m a.s.l.)

High resolution measurements of carbon monoxide along a late Holocene Greenland ice core: evidence for in situ production

We present high-resolution measurements of carbon monoxide (CO) concentrations from a shallow ice core of the North Greenland Eemian Ice Drilling project (NEEM-2011-S1). An optical-feedback cavity-enhanced absorption spectrometer (OF-CEAS) coupled to a continuous melter system performed continuous, online analysis during a four-week measurement campaign. This analytical setup generated stable measurements of CO concentrations with an external precision of 7.8 ppbv (1σ), based on repeated analyses of equivalent ice core sections. However, this first application of this measurement technique suffered from a poorly constrained procedural blank of 48 ± 25 ppbv and poor accuracy because an absolute calibration was not possible. The NEEM-2011-S1 CO record spans 1800 yr and the long-term trends within the most recent section of this record (i.e., post 1700 AD) resemble the existing discrete CO measurements from the Eurocore ice core. However, the CO concentration is highly variable (75–1327 ppbv range) throughout the ice core with high frequency (annual scale), high amplitude spikes characterizing the record. These CO signals are too abrupt and rapid to reflect atmospheric variability and their prevalence largely prevents interpretation of the record in terms of atmospheric CO variation. The abrupt CO spikes are likely the result of in situ production occurring within the ice itself, although the unlikely possibility of CO production driven by non-photolytic, fast kinetic processes within the continuous melter system cannot be excluded. We observe that 68% of the CO spikes are observed in ice layers enriched with pyrogenic aerosols. Such aerosols, originating from boreal biomass burning emissions, contain organic compounds, which may be oxidized or photodissociated to produce CO within the ice. However, the NEEM-2011-S1 record displays an increase of ~0.05 ppbv yr⁻¹ in baseline CO level prior to 1700 AD (129 m depth) and the concentration remains elevated, even for ice layers depleted in dissolved organic carbon (DOC). Thus, the processes driving the likely in situ production of CO within the NEEM ice may involve multiple, complex chemical pathways not all related to past fire history and require further investigation

Impact of subsurface crevassing on the depth–age relationship of high-Alpine ice cores extracted at Col du Dôme between 1994 and 2012

Three seasonally resolved ice core records covering the 20th century were extracted in 1994, 2004, and 2012 at a nearly identical location from the Col du Dôme (4250 m above sea level, m a.s.l.; Mont Blanc, French Alps) drill site. Here, we complete and combine chemical records of major ions and radiometric measurements of 3H and 210Pb obtained from these three cores with a 3D ice flow model of the Col du Dôme glacier to investigate in detail the origin of discontinuities observed in the depth–age relation of the ice cores drilled in 2004 and 2012. Taking advantage of the granitic bedrock at Col du Dôme, which makes the ice core 210Pb records sensitive to the presence of upstream crevasses, and the fact that the depth–age disturbances are observed at depths for which absolute time markers are available, we draw an overall picture of a dynamic crevasse formation. This can explain the non-disturbed depth–age relation of the ice core drilled in 1994 and the perturbations observed in those drilled in 2004 and 2012. Since crevasses are common at high-Alpine glacier sites, our study points to the important need for rigorous investigations of the depth–age scale and glaciological conditions upstream of drill sites before interpreting high-alpine ice core records in terms of atmospheric changes.</p

Factors controlling atmospheric DMS and its oxidation products (MSA and nssSO(4)(2-)) in the aerosol at Terra Nova Bay, Antarctica

This paper presents the results of simultaneous high time-resolution measurements of biogenic aerosol (methane sulfonic acid (MSA), non-sea salt sulfate nssSO(4)(2-)) with its gaseous precursor dimethylsulfide (DMS), performed at the Italian coastal base Mario Zucchelli Station (MZS) in Terra Nova Bay (MZS) during two summer campaigns (2018-2019 and 2019-2020). Data on atmospheric DMS concentration are scarce, especially in Antarctica. The DMS maximum at MZS occurs in December, one month earlier than at other Antarctic stations. The maximum of DMS concentration is connected with the phytoplanktonic senescent phase following the bloom of Phaeocystis antarctica that occurs in the polynya when sea ice opens up. The second plankton bloom occurs in January and, despite the high dimethylsufoniopropionate (DMSP) concentration in seawater, atmospheric DMS remains low, probably due to its fast biological turnover in seawater in this period. The intensity and timing of the DMS evolution during the two years suggest that only the portion of the polynya close to the sampling site produces a discernible effect on the measured DMS. The closeness to the DMS source area and the occurrence of air masses containing DMS and freshly formed oxidation products allow us to study the kinetic of biogenic aerosol formation and the reliable derivation of the branch ratio between MSA and nssSO(4)(2-) from DMS oxidation that is estimated to be 0.84 +/- 0.06. Conversely, for aged air masses with low DMS content, an enrichment of nssSO(4)(2-) with respect to MSA, is observed. We estimate that the mean contribution of freshly formed biogenic aerosol to PM10 is 17 % with a maximum of 56 %. The high contribution of biogenic aerosol to the total PM10 mass in summer in this area highlights the dominant role of the polynya on biogenic aerosol formation. Finally, due to the regional and year-to-year variability of DMS and related biogenic aerosol formation, we stress the need for long-term measurements of seawater and atmospheric DMS and biogenic aerosol along the Antarctic coast and in the Southern Ocean

Consistent histories of anthropogenic western European air pollution preserved in different Alpine ice cores

Individual high-Alpine ice cores have been proven to contain a well-preserved history of past anthropogenic air pollution in western Europe. The question of how representative one ice core is with respect to the reconstruction of atmospheric composition in the source region has not been addressed so far. Here, we present the first study systematically comparing longer-term ice-core records (1750–2015 CE) of various anthropogenic compounds, such as major inorganic aerosol constituents (NH4+, NO3-, SO42-), black carbon (BC), and trace species (Cd, F−, Pb). Depending on the data availability for the different air pollutants, up to five ice cores from four high-Alpine sites located in the European Alps analysed by different laboratories were considered. Whereas absolute concentration levels can partly differ depending on the prevailing seasonal distribution of accumulated precipitation, all seven investigated anthropogenic compounds are in excellent agreement between the various sites for their respective, species-dependent longer-term concentration trends. This is related to common source regions of air pollution impacting the four sites less than 100 km away including western European countries surrounding the Alps. For individual compounds, the Alpine ice-core composites developed in this study allowed us to precisely time the onset of pollution caused by industrialization in western Europe. Extensive emissions from coal combustion and agriculture lead to an exceeding of pre-industrial (1750–1850) concentration levels already at the end of the 19th century for BC, Pb, exSO42- (non-dust, non-sea salt SO42-), and NH4+, respectively. However, Cd, F−, and NO3- concentrations started surpassing pre-industrial values only in the 20th century, predominantly due to pollution from zinc and aluminium smelters and traffic. The observed maxima of BC, Cd, F−, Pb, and exSO42- concentrations in the 20th century and a significant decline afterwards clearly reveal the efficiency of air pollution control measures such as the desulfurization of coal, the introduction of filters and scrubbers in power plants and metal smelters, and the ban of leaded gasoline improving the air quality in western Europe. In contrast, NO3- and NH4+ concentration records show levels in the beginning of the 21th century which are unprecedented in the context of the past 250 years, indicating that the introduced abatement measures to reduce these pollutants were insufficient to have a major effect at high altitudes in western Europe. Only four ice-core composite records (BC, F−, Pb, exSO42-) of the seven investigated pollutants correspond well with modelled trends, suggesting inaccuracies of the emission estimates or an incomplete representation of chemical reaction mechanisms in the models for the other pollutants. Our results demonstrate that individual ice-core records from different sites in the European Alps generally provide a spatially representative signal of anthropogenic air pollution trends in western European countries.</p

High resolution measurements of carbon monoxide along a late Holocene Greenland ice core: evidence for in situ production

We present high-resolution measurements of carbon monoxide (CO) concentrations from a shallow ice core of the North Greenland Eemian Ice Drilling project (NEEM-2011-S1). An optical-feedback cavity-enhanced absorption spectrometer (OF-CEAS) coupled to a continuous melter system performed continuous, online analysis during a four-week measurement campaign. This analytical setup generated stable measurements of CO concentrations with an external precision of 7.8 ppbv (1σ), based on repeated analyses of equivalent ice core sections. However, this first application of this measurement technique suffered from a poorly constrained procedural blank of 48 ± 25 ppbv and poor accuracy because an absolute calibration was not possible. The NEEM-2011-S1 CO record spans 1800 yr and the long-term trends within the most recent section of this record (i.e., post 1700 AD) resemble the existing discrete CO measurements from the Eurocore ice core. However, the CO concentration is highly variable (75–1327 ppbv range) throughout the ice core with high frequency (annual scale), high amplitude spikes characterizing the record. These CO signals are too abrupt and rapid to reflect atmospheric variability and their prevalence largely prevents interpretation of the record in terms of atmospheric CO variation. The abrupt CO spikes are likely the result of in situ production occurring within the ice itself, although the unlikely possibility of CO production driven by non-photolytic, fast kinetic processes within the continuous melter system cannot be excluded. We observe that 68% of the CO spikes are observed in ice layers enriched with pyrogenic aerosols. Such aerosols, originating from boreal biomass burning emissions, contain organic compounds, which may be oxidized or photodissociated to produce CO within the ice. However, the NEEM-2011-S1 record displays an increase of ~0.05 ppbv yr−1 in baseline CO level prior to 1700 AD (129 m depth) and the concentration remains elevated, even for ice layers depleted in dissolved organic carbon (DOC). Thus, the processes driving the likely in situ production of CO within the NEEM ice may involve multiple, complex chemical pathways not all related to past fire history and require further investigation.This is the publisher’s final pdf. The published article is copyrighted by the author(s) and published by Copernicus Publications on behalf of the European Geosciences Union. The published article can be found at: http://www.climate-of-the-past.net/home.html

Characterizing Atmospheric Transport Pathways to Antarctica and the Remote Southern Ocean Using Radon-222

We discuss remote terrestrial influences on boundary layer air over the Southern Ocean and Antarctica, and the mechanisms by which they arise, using atmospheric radon observations as a proxy. Our primary motivation was to enhance the scientific community’s ability to understand and quantify the potential effects of pollution, nutrient or pollen transport from distant land masses to these remote, sparsely instrumented regions. Seasonal radon characteristics are discussed at 6 stations (Macquarie Island, King Sejong, Neumayer, Dumont d’Urville, Jang Bogo and Dome Concordia) using 1–4 years of continuous observations. Context is provided for differences observed between these sites by Southern Ocean radon transects between 45 and 67°S made by the Research Vessel Investigator. Synoptic transport of continental air within the marine boundary layer (MBL) dominated radon seasonal cycles in the mid-Southern Ocean site (Macquarie Island). MBL synoptic transport, tropospheric injection, and Antarctic outflow all contributed to the seasonal cycle at the sub-Antarctic site (King Sejong). Tropospheric subsidence and injection events delivered terrestrially influenced air to the Southern Ocean MBL in the vicinity of the circumpolar trough (or “Polar Front”). Katabatic outflow events from Antarctica were observed to modify trace gas and aerosol characteristics of the MBL 100–200 km off the coast. Radon seasonal cycles at coastal Antarctic sites were dominated by a combination of local radon sources in summer and subsidence of terrestrially influenced tropospheric air, whereas those on the Antarctic Plateau were primarily controlled by tropospheric subsidence. Separate characterization of long-term marine and katabatic flow air masses at Dumont d’Urville revealed monthly mean differences in summer of up to 5 ppbv in ozone and 0.3 ng m-3 in gaseous elemental mercury. These differences were largely attributed to chemical processes on the Antarctic Plateau. A comparison of our observations with some Antarctic radon simulations by global climate models over the past two decades indicated that: (i) some models overestimate synoptic transport to Antarctica in the MBL, (ii) the seasonality of the Antarctic ice sheet needs to be better represented in models, (iii) coastal Antarctic radon sources need to be taken into account, and (iv) the underestimation of radon in subsiding tropospheric air needs to be investigated

Convergence Without Hard Criteria: Does EU Soft Law Affect Domestic Unemployment Protection Schemes?

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