Abstract. 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.

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Long-term observations of the reactive chemical composition of the tropical marine boundary layer (MBL) are rare, despite its crucial role for the chemical stability of the atmosphere. Recent observations of reactive bromine species in the tropical MBL showed unexpectedly high levels that could potentially have an impact on the ozone budget. Uncertainties in the ozone budget are amplified by our poor understanding of the fate of NO x (= NO + NO 2 ), particularly the importance of nighttime chemical NO x sinks. Here, we present year-round observations of the multiisotopic composition of atmospheric nitrate in the tropical MBL at the Cape Verde Atmospheric Observatory. We show that the observed oxygen isotope ratios of nitrate are compatible with nitrate formation chemistry, which includes the BrNO 3 sink at a level of ca. 20 ± 10% of nitrate formation pathways. The results also suggest that the N 2 O 5 pathway is a negligible NO x sink in this environment. Observations further indicate a possible link between the NO 2 /NO x ratio and the nitrogen isotopic content of nitrate in this low NO x environment, possibly reflecting the seasonal change in the photochemical equilibrium among NO x species. This study demonstrates the relevance of using the stable isotopes of oxygen and nitrogen of atmospheric nitrate in association with concentration measurements to identify and constrain chemical processes occurring in the MBL.monitoring | oxidation | tropic | bromine chemistry | aerosols T he tropical marine lower troposphere is one of the most photochemically active compartments of the global atmosphere. The year-round high solar radiation, temperature, and humidity render this region the second largest contributor to methane removal via the OH sink (1). A large proportion of tropospheric ozone loss also occurs in the tropical marine boundary layer (MBL), where the concentrations of precursors, such as NO x (= NO + NO 2 ) and volatile organic carbons (VOCs) (2), are generally too low to keep the ozone production rate above its destruction rate. The destruction of ozone is further highlighted by the recently discovered role of halogen chemistry at low latitudes (3), which is known to destroy ozone catalytically (4). The subtle oxidation chemistry coupling NO x , halogens, and VOCs with ozone production and destruction in the MBL is still not fully understood, as demonstrated by the historically overlooked bromine chemistry (3) or the role of heterogeneous N 2 O 5 hydrolysis as a NO x sink (5, 6).Being the end product of the NO x /O 3 /VOC interaction, atmospheric nitrate is particularly well suited to probe such chemistry, especially through its stable isotope composition (7). Indeed, isotopic measurements have proven to be instrumental in identifying and quantifying sources, processes affecting the formation of atmospheric nitrate [particulate NO 3 − plus gas-phase nitric acid (HNO 3 ); hereafter defined as NO 3 − ], and the role of its precursors (i.e., the complex chemical interactions between NO x , halogens, and ozone...

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International audienceStable isotope ratios of nitrate preserved in deep ice cores are expected to provide unique and valuable information regarding paleoatmospheric processes. However, due to the post-depositional loss of nitrate in snow, this information may be erased or significantly modified by physical or photochemical processes before preservation in ice. We investigated the role of solar UV photolysis in the post-depositional modification of nitrate mass and stable isotope ratios at Dome C, Antarctica, during the austral summer of 2011/2012. Two 30 cm snow pits were filled with homogenized drifted snow from the vicinity of the base. One of these pits was covered with a plexiglass plate that transmits solar UV radiation, while the other was covered with a different plexiglass plate having a low UV transmittance. Samples were then collected from each pit at a 2–5 cm depth resolution and a 10-day frequency. At the end of the season, a comparable nitrate mass loss was observed in both pits for the top-level samples (0–7 cm) attributed to mixing with the surrounding snow. After excluding samples impacted by the mixing process, we derived an average apparent nitrogen isotopic fractionation (15εapp) of −67.8 ± 12 ‰ for the snow nitrate exposed to solar UV using the nitrate stable isotope ratios and concentration measurements. For the control samples in which solar UV was blocked, an apparent average 15εapp value of −12.0 ± 1.7 ‰ was derived. This difference strongly suggests that solar UV photolysis plays a dominant role in driving the isotopic fractionation of nitrate in snow. We have estimated a purely photolytic nitrogen isotopic fractionation (15εphoto) of −55.8 ± 12.0 ‰ from the difference in the derived apparent isotopic fractionations of the two experimental fields, as both pits were exposed to similar physical processes except exposure to solar UV. This value is in close agreement with the 15εphoto value of −47.9 ± 6.8 ‰ derived in a laboratory experiment simulated for Dome C conditions (Berhanu et al., 2014). We have also observed an insensitivity of 15 ε with depth in the snowpack under the given experimental setup. This is due to the uniform attenuation of incoming solar UV by snow, as 15ε is strongly dependent on the spectral distribution of the incoming light flux. Together with earlier work, the results presented here represent a strong body of evidence that solar UV photolysis is the most relevant post-depositional process modifying the stable isotope ratios of snow nitrate at low-accumulation sites, where many deep ice cores are drilled. Nevertheless, model-ing the loss of nitrate in snow is still required before a robust interpretation of ice core records can be provided

The nitrite-coated filter technique is a sufficiently robust, field-deployable method for the determination of the triple-oxygen isotopic composition of tropospheric O(3). Further ambient measurements will undoubtedly lead to an improved quantitative view of natural Δ(17)O(O(3)) variation and transfer in the atmosphere.

[1] Here we present measurements of the size-resolved concentration and isotopic composition of atmospheric nitrate (NO 3 À ) collected during a cruise in coastal California. Significant differences in air mass origin and atmospheric chemistry were observed in the two main regions of this cruise (South and Central Coast) with corresponding differences in NO 3 À concentration and isotope ratios. Measurements of the N, which had an average value of (0.0 ± 3.2)‰, the observed diurnality suggests a combined effect of isotopic exchange between gas-phase precursors and variability in reactive nitrogen sources. These findings represent a significant advance in our understanding of the isotope dynamics of nitrate and its precursor molecules, with potentially important implications for air quality modeling.

Abstract. Variations in the stable oxygen isotope composition of atmospheric nitrate act as novel tools for studying oxidative processes taking place in the troposphere. They provide both qualitative and quantitative constraints on the pathways determining the fate of atmospheric nitrogen oxides (NO + NO2 = NOx). The unique and distinctive 17O excess (Δ17O = δ17O − 0.52 × δ18O) of ozone, which is transferred to NOx via oxidation, is a particularly useful isotopic fingerprint in studies of NOx transformations. Constraining the propagation of 17O excess within the NOx cycle is critical in polar areas, where there exists the possibility of extending atmospheric investigations to the glacial–interglacial timescale using deep ice core records of nitrate. Here we present measurements of the comprehensive isotopic composition of atmospheric nitrate collected at Dome C (East Antarctic Plateau) during the austral summer of 2011/2012. Nitrate isotope analysis has been here combined for the first time with key precursors involved in nitrate production (NOx, O3, OH, HO2, RO2, etc.) and direct observations of the transferrable Δ17O of surface ozone, which was measured at Dome C throughout 2012 using our recently developed analytical approach. Assuming that nitrate is mainly produced in Antarctica in summer through the OH + NO2 pathway and using concurrent measurements of OH and NO2, we calculated a Δ17O signature for nitrate on the order of (21–22 ± 3) ‰. These values are lower than the measured values that ranged between 27 and 31 ‰. This discrepancy between expected and observed Δ17O(NO3−) values suggests the existence of an unknown process that contributes significantly to the atmospheric nitrate budget over this East Antarctic region. However, systematic errors or false isotopic balance transfer functions are not totally excluded.