Collection of NO and NO2 for Isotopic Analysis of NOx Emissions

Fibiger, D. L.; Hastings, Meredith G.; Lew, Audrey F.; Peltier, Richard E.

doi:10.1021/ac502968e

Cited by 49 publications

(128 citation statements)

References 22 publications

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“…NOTE: Purchase premade solutions because they tend to contain lower "blank" NO 3 -concentrations than other forms. 4 1. Prepare 10 M NaOH.…”

Section: Solution Preparationmentioning

confidence: 99%

“…The original method 4 suggests that this must be done within 24 hr of sample collection. Below are results that suggest that the samples can be stored for up to seven days prior to reduction.…”

Section: Sample Reductionmentioning

confidence: 99%

“…Stable isotopes may be useful as a way to better track the spatial patterns and temporal trends of sources and the chemistry of NO x and NO 3 -in the environment and to add new constraints on atmospheric models 3 . To date, the isotopic signatures associated with different NO x sources remain highly uncertain, particularly because of large uncertainties associated with previous methods 4 .…”

Section: Introductionmentioning

confidence: 99%

“…Fibiger et al found that previously used methods often varied greatly in terms of their efficiency in capturing NO x , with changes in conditions greatly influencing field collection (e.g., temperature, humidity, flow rates, age of solution) 4 . The inefficient uptake of previous NO and NO 2 capture methods could lead to fractionations.…”

Section: Introductionmentioning

confidence: 99%

“…For example, higher rates of oxidation for 14 N relative to 15 N could yield low biases in δ 15 N-NO x that are not representative of atmospheric values. 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 .…”

Section: Introductionmentioning

confidence: 99%

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Automated, High-resolution Mobile Collection System for the Nitrogen Isotopic Analysis of NOx

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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“…NOTE: Purchase premade solutions because they tend to contain lower "blank" NO 3 -concentrations than other forms. 4 1. Prepare 10 M NaOH.…”

Section: Solution Preparationmentioning

confidence: 99%

Section: Sample Reductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Automated, High-resolution Mobile Collection System for the Nitrogen Isotopic Analysis of NOx

Wojtal

Miller

O'Conner

et al. 2016

JoVE

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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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The anthropogenic perturbation of the marine nitrogen cycle by atmospheric deposition: Nitrogen cycle feedbacks and the ¹⁵N Haber‐Bosch effect

Yang

Gruber

2016

Global Biogeochemical Cycles

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Over the last 100 years, anthropogenic emissions have led to a strong increase of atmospheric nitrogen deposition over the ocean, yet the resulting impacts and feedbacks are neither well understood nor quantified. To this end, we run a suite of simulations with the ocean component of the Community Earth System Model v1.2 forced with five scenarios of nitrogen deposition over the period from 1850 through 2100, while keeping all other forcings unchanged. Even though global oceanic net primary production increases little in response to this fertilization, the higher export and the resulting expansion of the oxygen minimum zones cause an increase in pelagic and benthic denitrification and burial by about 5%. In addition, the enhanced availability of fixed nitrogen in the surface ocean reduces global ocean N2 fixation by more than 10%. Despite the compensating effects through these negative feedbacks that eliminate by the year 2000 about 60% of the deposited nitrogen, the anthropogenic nitrogen input forced the upper ocean N budget into an imbalance of between 9 and 22 Tg N yr−1 depending on the deposition scenario. The excess nitrogen accumulates to highly detectable levels and causes in most areas a distinct negative trend in the δ15N of the oceanic fixed nitrogen pools—a trend we refer to as the 15N Haber‐Bosch effect. Changes in surface nitrate utilization and the nitrogen feedbacks induce further changes in the δ15N of NO3−, making it a good but complex recorder of the overall impact of the changes in atmospheric deposition.

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Collection of NO and NO₂ for Isotopic Analysis of NO_x Emissions

Cited by 49 publications

References 22 publications

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

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

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

The anthropogenic perturbation of the marine nitrogen cycle by atmospheric deposition: Nitrogen cycle feedbacks and the ¹⁵N Haber‐Bosch effect

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Collection of NO and NO2 for Isotopic Analysis of NOx Emissions

Cited by 49 publications

References 22 publications

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

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

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

The anthropogenic perturbation of the marine nitrogen cycle by atmospheric deposition: Nitrogen cycle feedbacks and the 15N Haber‐Bosch effect

Contact Info

Product

Resources

About

Collection of NO and NO₂ for Isotopic Analysis of NO_x Emissions

The anthropogenic perturbation of the marine nitrogen cycle by atmospheric deposition: Nitrogen cycle feedbacks and the ¹⁵N Haber‐Bosch effect