Measurement of the 17O‐excess (Δ17O) of tropospheric ozone using a nitrite‐coated filter

Vicars, W. C.; Bhattacharya, S. K.; Erbland, Joseph; Savarino, Joël

doi:10.1002/rcm.6218

Cited by 57 publications

(46 citation statements)

References 62 publications

(203 reference statements)

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“…There are also significant differences in the NO 3 À in the snow and atmosphere at Summit in 2010 and 2011, which can be enlightening on their own. First, it is clear that BrO is not having an influence on NO 3 À formation at [Johnston and Thiemens, 1997;Vicars et al, 2012]). In 2010, the δ 18 O-NO 3 À in the atmosphere has an average value of 54‰, while in 2011 it is 91‰.…”

Section: Local Chemistry At Summitmentioning

confidence: 99%

Analysis of nitrate in the snow and atmosphere at Summit, Greenland: Chemistry and transport

et al. 2016

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International audienceAs a major sink of atmospheric nitrogen oxides (NO_x= NO + NO₂), nitrate (NO₃^-) in polar snow can reflect the long-range transport of NO_x and related species (e.g., PAN). On the other hand, because NO₃^- in snow can be photolyzed, potentially producing gas-phase NO_x locally, NO₃^- in snow (and thus, ice) may reflect local processes. Here we investigate the relationship between local atmospheric composition at Summit, Greenland (72°35’N, 38°25’W) and the isotopic composition of NO₃^- to determine the degree to which local processes influence atmospheric and snow NO₃^-. Based on snow and atmospheric observations during May-June 2010 and 2011, we find no connection between the local atmospheric concentrations of a suite of gases (BrO, NO, NO_y, HNO₃ and nitrite (NO₂^-)) and the NO₃^- isotopic composition or concentration in snow. This suggests that 1) the snow NO₃^- at Summit is primarily derived from long-range transport and 2) this NO₃^- is largely preserved in the snow. Additionally, three isotopically distinct NO₃^- sources were found to be contributing to the NO₃^- in the snow at Summit during both 2010 and 2011. Through the complete isotopic composition of NO₃^-, we suggest that these sources are local anthropogenic particulate NO₃^- from station activities (δ¹⁵N = 16‰, Δ¹⁷O = 4‰ and δ¹⁸O = 23‰), NO₃^- formed from mid-latitude NO_x (δ¹⁵N = -10‰, Δ¹⁷O = 29‰, δ¹⁸O = 78‰) and a NO₃^- source that is possibly influenced or derived from stratospheric ozone NO₃^- (δ¹⁵N = 5‰, Δ¹⁷O = 39‰, δ¹⁸O = 100‰)

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Section: Local Chemistry At Summitmentioning

confidence: 99%

Analysis of nitrate in the snow and atmosphere at Summit, Greenland: Chemistry and transport

et al. 2016

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“…18 O values are difficult to measure, so they can only be inferred based on assumptions (+23.9 ‰; Fang et al, 2011;Guha et al, 2017 Generally, the winter to summer isotopic differences are thought to be due to the high oxygen isotopic values of N2O5 due to interaction with O3 (Johnston and Thiemens, 1997;Michalski et al, 2003;Morin et al, 2008;Vicars et al, 2012) and low values of OH in isotopic equilibrium with atmospheric H2O (Dubey et al, 1997). According to Table 5, these two reaction pathways produce nitrates via R4-R7-R8 with 2/3 O from NO2, 1/6 O from O3 and 1/6 O from H2O, and nitrates via R6 with 2 10 out of 3 O atoms coming from NO2 and 1 added O from OH (e.g., Michalski et al, 2003).…”

mentioning

confidence: 99%

The Δ17O and δ18O values of simultaneously collected atmospheric nitrates from anthropogenic sources – Implications for polluted air masses

Savard

Cole

Vet

et al. 2018

Preprint

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“…It should also be noted that the Δ 17 O used for ozone has no impact on this estimation because all 17 O-excess transfer mechanisms scale identically with this parameter (15), thus conserving the Δ 17 O seasonality. Nevertheless, in this study, we used Δ 17 O(O 3 ) measured in the vicinity of the CVAO, applying our unique analytical approach (37), and thus did not adjust this variable to match the observed Δ 17 O, in contrast to previous studies (7,12,13,18 (Fig. 2), the CTM largely favored its daytime chemistry (i.e., NO 2 + OH), placing too much emphasis on the N 2 O 5 hydrolysis and not enough on the NO 3 pathways.…”

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confidence: 99%

Isotopic composition of atmospheric nitrate in a tropical marine boundary layer

Savarino

Morin

Erbland

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

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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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Measurement of the ¹⁷O‐excess (Δ¹⁷O) of tropospheric ozone using a nitrite‐coated filter

Cited by 57 publications

References 62 publications

Analysis of nitrate in the snow and atmosphere at Summit, Greenland: Chemistry and transport

Analysis of nitrate in the snow and atmosphere at Summit, Greenland: Chemistry and transport

The Δ<sup>17</sup>O and δ<sup>18</sup>O values of simultaneously collected atmospheric nitrates from anthropogenic sources – Implications for polluted air masses

Isotopic composition of atmospheric nitrate in a tropical marine boundary layer

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Measurement of the 17O‐excess (Δ17O) of tropospheric ozone using a nitrite‐coated filter

Cited by 57 publications

References 62 publications

Analysis of nitrate in the snow and atmosphere at Summit, Greenland: Chemistry and transport

Analysis of nitrate in the snow and atmosphere at Summit, Greenland: Chemistry and transport

The Δ&lt;sup&gt;17&lt;/sup&gt;O and δ&lt;sup&gt;18&lt;/sup&gt;O values of simultaneously collected atmospheric nitrates from anthropogenic sources – Implications for polluted air masses

Isotopic composition of atmospheric nitrate in a tropical marine boundary layer

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Measurement of the ¹⁷O‐excess (Δ¹⁷O) of tropospheric ozone using a nitrite‐coated filter

The Δ<sup>17</sup>O and δ<sup>18</sup>O values of simultaneously collected atmospheric nitrates from anthropogenic sources – Implications for polluted air masses