Isotopic composition of passively collected nitrogen dioxide emissions: Vehicle, soil and livestock source signatures

Felix, J. David; Elliott, Emily M.

doi:10.1016/j.atmosenv.2014.04.005

Cited by 183 publications

(147 citation statements)

References 46 publications

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“…5c and 5d). All the observed values of δ 15 N-NO 3 − fall within the previously reported atmospheric δ 15 N-NO 3 − ranges in land (Elliott et al, 2009;Fang et al, 2011;Felix and Elliott, 2014) and in marine boundary layer (Altieri et al, 2013;Gobel et al, 2013;Hastings et al, 2003;Morin et al, 2009;Savarino et al, 2013). The mass-weighted mean aerosol δ 15 N-NO 3 − in 2014 (+1.6‰ in the ECSs, -1.1‰ for dust aerosol and -2.6‰ for background aerosol sampled in the NWPO) were similar to those in 2015 (+1.9‰ in the ECSs, -3.8‰…”

supporting

confidence: 69%

Sources of reactive nitrogen in marine aerosol over the Northwest Pacific Ocean in spring

Li¹,

Kao²,

Bao³

et al. 2017

Preprint

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supporting

confidence: 69%

Sources of reactive nitrogen in marine aerosol over the Northwest Pacific Ocean in spring

Li¹,

Kao²,

Bao³

et al. 2017

Preprint

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“…This method of NO x collection for isotopic analysis is unique among existing methods (e.g., passive samplers 6,17 and sulfuric acid and hydrogen peroxide solution 8 ) in that it has been laboratory-and field-verified with respect to field applicability, reproducibility, sample solution stability, and efficiency of collection under a range of field conditions. This novel method is unique in its capabilities to actively collect NO x in field environments for isotopic analysis at ambient concentrations at a 30-120 min time resolution.…”

Section: Discussionmentioning

confidence: 99%

“…In addition to methodological issues 4,17 , a variety of different types of air sampling may also contribute to differences in the reported ranges for isotope values associated with the same source. For example, isotopic signatures associated with vehicle emissions of NO x have been suggested based on collections at near-road sites 5 , in traffic tunnels 6 , and directly from the tailpipes of vehicles 7,8 . Furthermore, previous methods have time resolutions of 24 h at best, and significant changes in ambient NO x concentrations are observed on hourly (or shorter) timescales , is further validated through the demonstration of its collection efficiency under changing NO x and meteorological conditions in the field, the test of solution stability and ammonia interferences, and the substantiation of its reproducibility in urban environments.…”

Section: Introductionmentioning

confidence: 99%

Automated, High-resolution Mobile Collection System for the Nitrogen Isotopic Analysis of NO<sub>x</sub>

Wojtal

Miller

O'Conner

et al. 2016

JoVE

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Nitrogen oxides (NO x = NO + NO 2 ) are a family of atmospheric trace gases that have great impact on the environment. NO x concentrations directly influence the oxidizing capacity of the atmosphere through interactions with ozone and hydroxyl radicals. The main sink of NO x is the formation and deposition of nitric acid, a component of acid rain and a bioavailable nutrient. NO x is emitted from a mixture of natural and anthropogenic sources, which vary in space and time. The collocation of multiple sources and the short lifetime of NO x make it challenging to quantitatively constrain the influence of different emission sources and their impacts on the environment. Nitrogen isotopes of NO x have been suggested to vary amongst different sources, representing a potentially powerful tool to understand the sources and transport of NO x . However, previous methods of collecting atmospheric NO x integrate over long (week to month) time spans and are not validated for the efficient collection of NO x in relevant, diverse field conditions. We report on a new, highly efficient field-based system that collects atmospheric NO x for isotope analysis at a time resolution between 30 min and 2 hr. This method collects gaseous NO x in solution as nitrate with 100% efficiency under a variety of conditions. Protocols are presented for collecting air in urban settings under both stationary and mobile conditions. We detail the advantages and limitations of the method and demonstrate its application in the field. Data from several deployments are shown to 1) evaluate field-based collection efficiency by comparisons with in situ NO x concentration measurements, 2) test the stability of stored solutions before processing, 3) quantify in situ reproducibility in a variety of urban settings, and 4) demonstrate the range of N isotopes of NO x detected in ambient urban air and on heavily traveled roadways.

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“…The isotopic signatures of NO x sources and their relationship with the δ 15 N of NO − 3 are poorly constrained (e.g., Fibiger et al, 2014), particularly in the Southern Hemisphere. For example, the δ 15 N of NO x from vehicle emissions in South Africa were consistently negative (Heaton, 1990) while the δ 15 N of NO x from vehicle emissions found in Switzerland was mostly positive (Ammann et al, 1999), and a recent study in the US suggests very positive values associated with vehicle emissions (Felix and Elliott, 2014). Natural, biogenic soil emissions have not been directly quantified, but fertilized soils in a laboratory study emitted NO x with very low δ 15 N (from −48.9 to −19.9 ‰) (Li and Wang, 2008), and lightning-sourced NO x is expected to be near 0 ‰.…”

Section: Seasonal Shifts In No −mentioning

confidence: 99%

Investigation of post-depositional processing of nitrate in East Antarctic snow: isotopic constraints on photolytic loss, re-oxidation, and source inputs

et al. 2015

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Abstract. Snowpits along a traverse from coastal East Antarctica to the summit of the ice sheet (Dome Argus) are used to investigate the post-depositional processing of nitrate (NO − 3 ) in snow. Seven snowpits from sites with accumulation rates between 24 and 172 kg m −2 a −1 were sampled to depths of 150 to 300 cm. At sites from the continental interior (low accumulation, < 55 kg m −2 a −1 ), nitrate mass fraction is generally > 200 ng g −1 in surface snow and decreases quickly with depth to < 50 ng g −1 . Considerably increasing values of δ 15 N of nitrate are also observed (16-461 ‰ vs. air N 2 ), particularly in the top 20 cm, which is consistent with predicted fractionation constants for the photolysis of nitrate. The δ 18 O of nitrate (17-84 ‰ vs. VSMOW (Vienna Standard Mean Ocean Water)), on the other hand, decreases with increasing δ 15 N, suggestive of secondary formation of nitrate in situ (following photolysis) with a low δ 18 O source. Previous studies have suggested that δ 15 N and δ 18 O of nitrate at deeper snow depths should be predictable based upon an exponential change derived near the surface. At deeper depths sampled in this study, however, the relationship between nitrate mass fraction and δ 18 O changes, with increasing δ 18 O of nitrate observed between 100 and 200 cm. Predicting the impact of post-depositional loss, and therefore changes in the isotopes with depth, is highly sensitive to the depth interval over which an exponential change is assumed. In the snowpits collected closer to the coast (accumulation > 91 kg m −2 a −1 ), there are no obvious trends detected with depth and instead seasonality in nitrate mass fraction and isotopic composition is found. In comparison to the interior sites, the coastal pits are lower in δ 15 N (−15-71 ‰ vs. air N 2 ) and higher in δ 18 O of nitrate (53-111 ‰ vs. VSMOW). The relationships found amongst mass fraction, δ 15 N, δ 18 O and 17 O ( 17 O = δ 17 O-0.52 × δ 18 O) of nitrate cannot be explained by local post-depositional processes alone, and are instead interpreted in the context of a primary atmospheric signal. Consistent with other Antarctic observational and modeling studies, the isotopic results are suggestive of an important influence of stratospheric ozone chemistry on nitrate formation during the cold season and a mix of tropospheric sources and chemistry during the warm season. Overall, the findings in this study speak to the sensitivity of nitrate isotopic composition to post-depositional processing and highlight the strength of combined use of the nitrogen and oxygen isotopes for a mechanistic understanding of this processing.

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Isotopic composition of passively collected nitrogen dioxide emissions: Vehicle, soil and livestock source signatures

Cited by 183 publications

References 46 publications

Sources of reactive nitrogen in marine aerosol over the Northwest Pacific Ocean in spring

Sources of reactive nitrogen in marine aerosol over the Northwest Pacific Ocean in spring

Automated, High-resolution Mobile Collection System for the Nitrogen Isotopic Analysis of NO<sub>x</sub>

Investigation of post-depositional processing of nitrate in East Antarctic snow: isotopic constraints on photolytic loss, re-oxidation, and source inputs

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