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Title: Sensitivity of nitrate concentration‐discharge patterns to soil nitrate distribution and drainage properties in the vertical dimension
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Author(s) / Creator(s):
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Date Published:
Journal Name:
Hydrological Processes
Page Range / eLocation ID:
2477 to 2493
Medium: X
Sponsoring Org:
National Science Foundation
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  1. Polyolefinic monoterpenes represent a potentially important but understudied source of organic nitrates (ONs) and secondary organic aerosol (SOA) following oxidation due to their high reactivity and propensity for multi-stage chemistry. Recent modeling work suggests that the oxidation of polyolefinic γ-terpinene can be the dominant source of nighttime ON in a mixed forest environment. However, the ON yields, aerosol partitioning behavior, and SOA yields from γ-terpinene oxidation by the nitrate radical (NO3), an important nighttime oxidant, have not been determined experimentally. In this work, we present a comprehensive experimental investigation of the total (gas + particle) ON, hydroxy nitrate, and SOA yields following γ-terpinene oxidation by NO3. Under dry conditions, the hydroxy nitrate yield  =  4(+1/−3) %, total ON yield  =  14(+3/−2) %, and SOA yield  ≤  10 % under atmospherically relevant particle mass loadings, similar to those for α-pinene + NO3. Using a chemical box model, we show that the measured concentrations of NO2 and γ-terpinene hydroxy nitrates can be reliably simulated from α-pinene + NO3 chemistry. This suggests that NO3 addition to either of the two internal double bonds of γ-terpinene primarily decomposes forming a relatively volatile keto-aldehyde, reconciling the small SOA yield observed here and for other internal olefinic terpenes. Based on aerosol partitioning analysis and identification of speciated particle-phase ON applying high-resolution liquid chromatography–mass spectrometry, we estimate that a significant fraction of the particle-phase ON has the hydroxy nitrate moiety. This work greatly contributes to our understanding of ON and SOA formation from polyolefin monoterpene oxidation, which could be important in the northern continental US and the Midwest, where polyolefinic monoterpene emissions are greatest. 
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  2. Abstract

    Sensors that use ultraviolet (UV) light absorption to measure nitrate in seawater at in situ temperatures require a correction to the calibration coefficients if the calibration and sample temperatures are not identical. This is mostly due to the bromide molecule, which absorbs more UV light as temperature increases. The current correction applied to in situ ultraviolet spectrophotometer (ISUS) and submersible ultraviolet nitrate analyzer (SUNA) nitrate sensors generally follows Sakamoto et al. (2009, Limnol. Oceanogr. Methods 7, 132–143). For waters warmer than the calibration temperature, this correction model can lead to a 1–2 μmol kg−1positive bias in nitrate concentration. Here we present an updated correction model, which reduces this small but noticeable bias by at least 50%. This improved model is based on additional laboratory data and describes the temperature correction as an exponential function of wavelength and temperature difference from the calibration temperature. It is a better fit to the experimental data than the current model and the improvement is validated using two populations of nitrate profiles from Biogeochemical Argo floats navigating through tropical waters. One population is from floats equipped with ISUS sensors while the other arises from floats with SUNA sensors on board. Although this model can be applied to both ISUS and SUNA nitrate sensors, it should not be used for OPUS UV nitrate sensors at this time. This new approach is similar to that used for OPUS sensors (Nehir et al., 2021, Front. Mar. Sci. 8, 663800) with differing model coefficients. This difference suggests that there is an instrumental component to the temperature correction or that there are slight differences in experimental methodologies.

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  3. null (Ed.)
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