Variability of sulfate signal in ice core records based on five replicate cores

International audienceCurrent volcanic reconstructions based on ice core analysis have significantly improved over the past few decades by incorporating multiple-core analyses with a high temporal resolution from different parts of the polar regions into a composite common volcanic eruption record. Regional patterns of volcanic deposition are based on composite records, built from cores taken at both poles. However, in many cases only a single record at a given site is used for these reconstructions. This assumes that transport and regional meteorological patterns are the only source of the dispersion of the volcanic products. Here we evaluate the local-scale variability of a sulfate profile in a low-accumulation site (Dome C, Antarctica), in order to assess the representativeness of one core for such a reconstruction. We evaluate the variability with depth, statistical occurrence, and sulfate flux deposition variability of volcanic eruptions detected in five ice cores, drilled 1 m apart from each other. Local-scale variability, essentially attributed to snow drift and surface roughness at Dome C, can lead to a non-exhaustive record of volcanic events when a single core is used as the site reference , with a bulk probability of 30 % of missing volcanic events and close to 65 % uncertainty on one volcanic flux measurement (based on the standard deviation obtained from a five-core comparison). Averaging n records reduces the uncertainty of the deposited flux mean significantly (by a factor 1/ √ n); in the case of five cores, the uncertainty of the mean flux can therefore be reduced to 29 %

Air-snow transfer of nitrate on the East Antarctic plateau – Part 2: An isotopic model for the interpretation of deep ice-core records

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 modelling is required to test hypotheses in a~quantitative manner. Here we introduce the model "TRansfer of Atmospheric Nitrate Stable Isotopes To the Snow" (TRANSITS), 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 the 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 20 \unit{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 a~few~‰. This is explained by the simplifications made in the description of the atmospheric cycling and oxidation of NO2. The model reproduces well the sensitivity of δ15N, Δ17O and the apparent fractionation constants (15ϵapp, 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 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

An extraction method for nitrogen isotope measurement of ammonium in a low-concentration environment

Ammonia (NH3) participates in the nucleation and growth of aerosols and thus plays a major role in atmospheric transparency, pollution, health, and climate-related issues. Understanding its emission sources through nitrogen stable isotopes is therefore a major focus of current work to mitigate the adverse effects of aerosol formation. Since ice cores can preserve the past chemical composition of the atmosphere for centuries, they are a top tool of choice for understanding past NH3 emissions through ammonium (NH4+), the form of NH3 archived in ice. However, the remote or high-altitude sites where glaciers and ice sheets are typically localized have relatively low fluxes of atmospheric NH4+ deposition, which makes ice core samples very sensitive to laboratory NH3 contamination. As a result, accurate techniques for identifying and tracking NH3 emissions through concentration and isotopic measurements are highly sought to constrain uncertainties in NH3 emission inventories and atmospheric reactivity unknowns. Here, we describe a solid-phase extraction method for NH4+ samples of low concentration that limits external contamination and produces precise isotopic results. By limiting NH3atm exposure with a scavenging fume hood and concentrating the targeted NH4+ through ion exchange resin, we successfully achieve isotopic analysis of 50 nmol NH4+ samples with a 0.6 ‰ standard deviation. This extraction method is applied to an alpine glacier ice core from Col du Dôme, Mont Blanc, where we successfully demonstrate the analytical approach through the analysis of two replicate 8 m water equivalent ice cores representing 4 years of accumulation with a reproducibility of ±2.1 ‰. Applying this methodology to other ice cores in alpine and polar environments will open new opportunities for understanding past changes in NH3 emissions and atmospheric chemistry.</p

Snow optical properties at Dome C, (Concordia), Antarctica: implications for snow emissions and snow chemistry of reactive nitrogen

Measurements of e-folding depth, nadir reflectivity and stratigraphy of the snowpack around Concordia station (Dome C, 75.10 S, 123.31 E) were undertaken to determine wavelength dependent coefficients (350 nm to 550 nm) for light scattering and absorption and to calculate potential fluxes (depth-integrated production rates) of nitrogen dioxide (NO2) from the snowpack due to nitrate photolysis within the snowpack. The stratigraphy of the top 80 cm of Dome C snowpack generally consists of three main layers:- a surface of soft windpack (not ubiquitous), a hard windpack, and a hoar-like layer beneath the windpack(s). The e-folding depths are 10 cm for the two windpack layers and 20 cm for the hoar-like layer for solar radiation at a wavelength of 400 nm; about a factor 2–4 larger than previous model estimates for South Pole. The absorption cross-section due to impurities in each snowpack layer are consistent with a combination of absorption due to black carbon and HULIS (HUmic LIke Substances), with amounts of 1–2 ng g−1 of black carbon for the surface snow layers. Depth-integrated photochemical production rates of NO2 in the Dome C snowpack were calculated as 5.3×1012 moleculesm−2 s−1, 2.3×1012 moleculesm−2 s−1 and 8×1011 moleculesm−2 s−1 for clear skies and solar zenith angles of 60, 70 and 80 respectively using the TUV-snow radiative-transfer model. Depending upon the snowpack stratigraphy, a minimum of 85% of the NO2 may originate from the top 20 cm of the Dome C snowpack. It is found that on a multi-annual time-scale photolysis can remove up to 80% of nitrate from surface snow, confirming independent isotopic evidence that photolysis is an important driver of nitrate loss occurring in the EAIS (East Antarctic Ice Sheet) snowpack. However, the model cannot completely account for the total observed nitrate loss of 90–95% or the shape of the observed nitrate concentration depth profile. A more complete model will need to include also physical processes such as evaporation, re-deposition or diffusion between the quasi-liquid layer on snow grains and firn air to account for the discrepancies

Air–snow transfer of nitrate on the East Antarctic Plateau - Part 1: Isotopic evidence for a photolytically driven dynamic equilibrium in summer

Here we report the measurement of the comprehensive isotopic composition (δ15N, Δ17O and δ18O) of nitrate at the air–snow interface at Dome C, Antarctica (DC, 75°06' S, 123°19' E), and in snow pits along a transect across the East Antarctic Ice Sheet (EAIS) between 66° S and 78° S. In most of the snow pits, nitrate loss (either by physical release or UV photolysis of nitrate) is observed and fractionation constants associated are calculated. Nitrate collected from snow pits on the plateau (snow accumulation rate below 50 kg m−2 a−1) displays average fractionation constants of (−59±10) ‰, (+2.0±1.0) ‰ and (+8.7±2.4)‰ for δ15N, Δ17O and δ18O, respectively. In contrast, snow pits sampled on the coast show distinct isotopic signatures with average fractionation constants of (−16±14) ‰, (−0.2±1.5) ‰ and (+3.1±5.8) ‰, for δ15N, Δ17O and δ18O, respectively. Our observations corroborate that photolysis (associated with a 15N / 14N fractionation constant of the order of –48 ‰ according to Frey et al. (2009) is the dominant nitrate loss process on the East Antarctic Plateau, while on the coast the loss is less pronounced and could involve both physical release and photochemical processes. Year-round isotopic measurements at DC show a~close relationship between the Δ17O of atmospheric nitrate and Δ17O of nitrate in skin layer snow, suggesting a photolytically driven isotopic equilibrium imposed by nitrate recycling at this interface. Atmospheric nitrate deposition may lead to fractionation of the nitrogen isotopes and explain the almost constant shift of the order of 25 ‰ between the δ15N values in the atmospheric and skin layer nitrate at DC. Asymptotic δ15N(NO3−) values calculated for each snow pit are found to be correlated with the inverse of the snow accumulation rate (ln(δ15N as. + 1) = (5.76±0.47) ċ (kg m−2 a−1/ A) + (0.01±0.02)), confirming the strong relationship between the snow accumulation rate and the degree of isotopic fractionation, consistent with previous observations by Freyer et al. (1996). Asymptotic Δ17O(NO3−) values on the plateau are smaller than the values found in the skin layer most likely due to oxygen isotope exchange between the nitrate photoproducts and water molecules from the surrounding ice. However, the apparent fractionation in Δ17O is small, thus allowing the preservation of a portion of the atmospheric signal

Photolysis imprint in the nitrate stable isotope signal in snow and atmosphere of East Antarctica and implications for reactive nitrogen cycling

The nitrogen (delta N-15) and triple oxygen (delta O-17 and delta O-18) isotopic composition of nitrate (NO3-) was measured year-round in the atmosphere and snow pits at Dome C, Antarctica (DC, 75.1 degrees S, 123.3 degrees E), and in surface snow on a transect between DC and the coast. Comparison to the isotopic signal in atmospheric NO3- shows that snow NO3- is significantly enriched in delta N-15 by > 200 parts per thousand and depleted in delta O-18 by < 40 parts per thousand. Post-depositional fractionation in delta O-17(NO3-) is small, potentially allowing reconstruction of past shifts in tropospheric oxidation pathways from ice cores. Assuming a Rayleigh-type process we find fractionation constants epsilon of -60 +/- 15 parts per thousand, 8 +/- 2 parts per thousand and 1 +/- 1 parts per thousand, for delta N-15, delta O-18 and delta O-17, respectively. A photolysis model yields an upper limit for the photolytic fractionation constant (15)epsilon of delta N-15, consistent with lab and field measurements, and demonstrates a high sensitivity of (15)epsilon to the incident actinic flux spectrum. The photolytic (15)epsilon is process-specific and therefore applies to any snow covered location. Previously published (15)epsilon values are not representative for conditions at the Earth surface, but apply only to the UV lamp used in the reported experiment (Blunier et al., 2005; Jacobi et al., 2006). Depletion of oxygen stable isotopes is attributed to photolysis followed by isotopic exchange with water and hydroxyl radicals. Conversely, N-15 enrichment of the NO3- fraction in the snow implies N-15 depletion of emissions. Indeed, delta N-15 in atmospheric NO3- shows a strong decrease from background levels (4 +/- 7 parts per thousand) to -35 parts per thousand in spring followed by recovery during summer, consistent with significant snowpack emissions of reactive nitrogen. Field and lab evidence therefore suggest that photolysis is an important process driving fractionation and associated NO3- loss from snow. The delta O-17 signature confirms previous coastal measurements that the peak of atmospheric NO3- in spring is of stratospheric origin. After sunrise photolysis drives then redistribution of NO3- from the snowpack photic zone to the atmosphere and a snow surface skin layer, thereby concentrating NO3- at the surface. Little NO3- appears to be exported off the EAIS plateau, still snow emissions from as far as 600 km inland can contribute to the coastal NO3- budget

Variability of sulfate signal in ice core records based on five replicate cores

Current volcanic reconstructions based on ice core analysis have significantly improved over the past few decades by incorporating multiple-core analyses with a high temporal resolution from different parts of the polar regions into a composite common volcanic eruption record. Regional patterns of volcanic deposition are based on composite records, built from cores taken at both poles. However, in many cases only a single record at a given site is used for these reconstructions. This assumes that transport and regional meteorological patterns are the only source of the dispersion of the volcanic products. Here we evaluate the local-scale variability of a sulfate profile in a low-accumulation site (Dome C, Antarctica), in order to assess the representativeness of one core for such a reconstruction. We evaluate the variability with depth, statistical occurrence, and sulfate flux deposition variability of volcanic eruptions detected in five ice cores, drilled 1 m apart from each other. Local-scale variability, essentially attributed to snow drift and surface roughness at Dome C, can lead to a non-exhaustive record of volcanic events when a single core is used as the site reference, with a bulk probability of 30 % of missing volcanic events and close to 65 % uncertainty on one volcanic flux measurement (based on the standard deviation obtained from a five-core comparison). Averaging <i>n</i> records reduces the uncertainty of the deposited flux mean significantly (by a factor 1∕ <mo form="infix">√</mo> <i>n</i>); in the case of five cores, the uncertainty of the mean flux can therefore be reduced to 29 %

Snow optical properties at Dome C, Antarctica - Implications for snow emissions and snow chemistry of reactive nitrogen

Measurements of e-folding depth, nadir reflectivity and stratigraphy of the snowpack around Concordia station (Dome C, 75.10° S, 123.31° E) were undertaken and used to determine wavelength dependent coefficients (350 nm to 550 nm) for light scattering and absorption and to calculate potential fluxes of nitrogen dioxide (NO) from the snowpack due to nitrate photolysis within the snowpack. The stratigraphy of the top 80 cm of Dome C snowpack generally consists of three main layers: a surface of soft windpack (not ubiquitous), a hard windpack and a hoar-like layer beneath the windpack(s). The e-folding depths are ∼10 cm for the two windpack layers and ∼20 cm for the hoar-like layer for solar radiation at a wavelength of 400 nm, about a factor 2-4 larger than previous model estimates for South Pole. Depth integrated photochemical reaction rates of nitrate photolysis in the Dome C snowpack were calculated to give molecular fluxes of NO of 5.3×10 molecules m s, 2.3×10 molecules m s and 8×10 molecules m s for solar zenith angles of 60°, 70° and 80° respectively for clear sky conditions using the TUV-snow radiative-transfer model. Depending upon the snowpack stratigraphy, a minimum of 85% of the NO originates from within the top 20 cm of the Dome C snowpack. It is found that on a multi-annual scale, nitrate photolysis can remove up to 80% of nitrate from surface snow, confirming independent isotopic evidence that photolysis is an important driver of nitrate loss occurring in the EAIS snowpack. However, the model cannot account for the total observed nitrate loss of 90-95% or the shape of the observed nitrate depth profile. A more complete model will need to include also physical processes such as evaporation, re-deposition or diffusion between the quasi-liquid layer on snow grains and firn air to account for the discrepancies. © 2011 Author(s)

Isotopic approach for sources deconvolution of atmospheric NH4 NO3

During events of particle pollution, especially at springtime, ammonium nitrate (NH4NO3) often displays the strongest increase in concentration, totaling almost half of the mass concentration of the particle mass load. This often leads to exceed the 50 μg m-3 daily threshold imposed by the European regulation on air quality to inform the public. The continental scale of such pollution events poses severe threat to human health and decreases significantly the quality of our environment. It is therefore the uppermost importance to identify the reason and sources leading to the formation of the ammonium nitrate particles. In this context, the INACS program was set up to investigate the potential of using the stable isotopes of nitrogen and oxygen to discriminate the factors responsible for the formation of NH4NO3 particles. The deconvolution of the potential sources of this particulate matter, a secondary particle species formed by the acid-base interaction between HNO3 and NH3, is particularly difficult to trace through "traditional" analytical chemistry methods. We used the well-established denitrifier bacteria method developed (eg. Kaiser et al., 2007 and references therein) to determine the nitrogen and triple oxygen isotopic composition of NO3 - (further details in Morin et al. 2008, 2009). For NH4 +, the azide method developed by Liu et al. (2014) is used to determine its nitrogen isotopic composition. Figure 1 shows the chemical pattern of two pollution events that occurred in 2013-2014. While the winter event can reasonably be attributed to the oil-fired and wood-burning heating applications, the springtime event shows a clearly different pattern with the majority of the increase of mass concentration due to the formation of ammonium nitrate..