δ¹⁵N-stable isotope analysis of NH_x: An overview on analytical measurements, source sampling and its source apportionment

Abstract

• Challenges in sampling of NH₃ sources for d¹⁵N analysis are highlighted.

• Uncertainties in the isotope-based source apportionment of NH₃ and NH₄⁺ are outlined.

• Characterizing dynamic isotopic fractionation may reduce uncertainties of NH_x science.

Agricultural sources and non-agricultural emissions contribute to gaseous ammonia (NH₃) that plays a vital role in severe haze formation. Qualitative and quantitative contributions of these sources to ambient PM_2.5 (particulate matter with an aerodynamic equivalent diameter below 2.5 µm) concentrations remains uncertain. Stable nitrogen isotopic composition (δ¹⁵N) of NH₃ and NH₄⁺ (δ¹⁵N(NH₃) and δ¹⁵N(NH₄⁺), respectively) can yield valuable information about its sources and associated processes. This review provides an overview of the recent progress in analytical techniques for δ¹⁵N(NH₃) and δ¹⁵N(NH₄⁺) measurement, sampling of atmospheric NH₃ and NH₄⁺ in the ambient air and their sources signature (e.g., agricultural vs. fossil fuel), and isotope-based source apportionment of NH₃ in urban atmosphere. This study highlights that collecting sample that are fully representative of emission sources remains a challenge in fingerprinting δ¹⁵N(NH₃) values of NH₃ emission sources. Furthermore, isotopic fractionation during NH₃ gas-to-particle conversion under varying ambient field conditions (e.g., relative humidity, particle pH, temperature) remains unclear, which indicates more field and laboratory studies to validate theoretically predicted isotopic fractionation are required. Thus, this study concludes that lack of refined δ¹⁵N(NH₃) fingerprints and full understanding of isotopic fractionation during aerosol formation in a laboratory and field conditions is a limitation for isotope-based source apportionment of NH₃. More experimental work (in chamber studies) and theoretical estimations in combinations of field verification are necessary in characterizing isotopic fractionation under various environmental and atmospheric neutralization conditions, which would help to better interpret isotopic data and our understanding on NH_x (NH₃ + NH₄⁺) dynamics in the atmosphere.

Graphical abstract

Keywords

Aerosol ammonium / Atmospheric gaseous ammonia / Isotope fingerprinting / Isotope-based source apportionment / Ammonia gas-to-particle conversion

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