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The NO3 center dot-driven nighttime aging of brown carbon (BrC) is known to greatly impact its atmospheric radiative forcing. However, the impact of oxidation by NO3 center dot on the optical properties of BrC in atmospheric waters as well as the associated reaction mechanism remain unclear. In this work, we found that the optical variation of BrC proxies under environmentally relevant NO3 center dot exposure depends strongly on their sources, with enhanced light absorptivity for biomass-burning BrC but bleaching for urban aerosols and humic substances. High-resolution mass spectrometry using FT-ICR MS shows that oxidation by NO3 center dot leads to the formation of light-absorbing species (e.g., nitrated organics) for biomass-burning BrC while destroying electron donors (e.g., phenols) within charge transfer complexes in urban aerosols and humic substances, as evidenced by transient absorption spectroscopy and NaBH4 reduction experiments as well. Moreover, we found that the measured rate constants between NO3 center dot with real BrCs (k = (1.8 +/- 0.6) x 10(7) M(C)(-1)s(-1), expressed as moles of carbon) are much higher than those of individual model organic carbon (OC), suggesting the reaction with OCs may be a previously ill-quantified important sink of NO3 center dot in atmospheric waters. This work provides insights into the kinetics and molecular transformation of BrC during the oxidation by NO3 center dot, facilitating further evaluation of BrC's climatic effects and atmospheric NO3 center dot levels.

期刊论文 2024-02-06 DOI: 10.1021/acs.est.3c08726 ISSN: 0013-936X

Leaching of nitrate (NO3 (-))-a reactive nitrogen form with impacts on ecosystem health-increases during the non-growing season (NGS) of agricultural soils under cold climates. Cover crops are effective at reducing NGS NO3 (-) leaching, but this benefit may be altered with less snow cover inducing more soil freezing under warmer winters. Our objective was to quantify the effect of winter warming on NO3 (-) leaching from cover crops for a loamy sand (LS) and a silt loam (SIL) soil. This research was conducted over 2 years in Ontario, Canada, using 18 high-precision weighing lysimeters designed to study ecosystem services from agricultural soils. Infra-red heaters were used to simulate warming in lysimeters under a wheat-corn-soybean rotation planted with a cover crop mixture with (+H) and without heating (-H). Nitrate leaching determination used NO3 (-) concentration at 90 cm (discrete sampling) and high temporal resolution drainage volume measurements. Data were analyzed for fall, overwinter, spring-thaw, post-planting, and total period (i.e., November 1 to June 30 of 2017/2018 and 2018/2019). Warming significantly affected soil temperature and soil water content-an effect that was similar for both years. As expected, experimental units under + H presented warmer soils at 5 and 10 cm, along with higher soil water content in liquid form than -H lysimeters, which translated into higher drainage values for + H than -H, especially during the overwinter period. NO3 (-) concentrations at 90 cm were only affected by winter heating for the LS soil. The drainage and NO3 (-) concentrations exhibited high spatial variation, which likely reduced the sensitivity to detect significant differences. Thus, although absolute differences in NO3 (-) leaching between LS vs. SIL and +H (LS) vs. -H (LS) were large, only a trend occurred for higher leaching in LS in 2018/2019. Our research demonstrated that soil heating can influence overwinter drainage (for LS and SIL soils) and NO3 (-) concentration at 90 cm in the LS soil-important NO3 (-) leaching controlling factors. However, contrary to our initial hypothesis, the heating regime adopted in our study did not promote colder soils during the winter. We suggest different heating regimes such as intermittent heating to simulate extreme weather freeze/thaw events as a future research topic.

期刊论文 2022-08-31 DOI: 10.3389/fenvs.2022.897221

Glacier melting exports a large amount of nitrate to downstream aquatic ecosystems. Glacial lakes and glacier-fed rivers in proglacial environments serve as primary recipients and distributors of glacier-derived nitrate (NO3-), yet little is known regarding the sources and cycling of nitrate in these water bodies. To address this knowledge gap, we conducted a comprehensive analysis of nitrate isotopes (delta15NNO3, delta18ONO3, and Delta17ONO3) in waters from the glacial lake and river of the Rongbuk Glacier-fed Basin (RGB) in the mountain Everest region. The concentrations of NO3- were low (0.43 +/- 0.10 mg/L), similar to or even lower than those observed in glacial lakes and glacier-fed rivers in other high mountain regions, suggesting minimal anthropogenic influence. The NO3- concentration decreases upon entering the glacial lake due to sedimentation, and it increases gradually from upstream to downstream in the river as a soil source is introduced. The analysis of Delta17ONO3 revealed a substantial contribution of unprocessed atmospheric nitrate, ranging from 34.29 to 56.43%. Denitrification and nitrification processes were found to be insignificant in the proglacial water of RGB. Our study highlights the critical role of glacial lakes in capturing and redistributing glacier-derived NO3- and emphasizes the need for further investigations on NO3- transformation in the fast-changing proglacial environment over the Tibetan Plateau and other high mountain regions.

期刊论文 2020-01-01 DOI: http://dx.doi.org/10.1021/acs.est.3c06419 ISSN: 0013-936X
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