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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Sensitivity of nitrate concentration‐discharge patterns to soil nitrate distribution and drainage properties in the vertical dimension
- Award ID(s):
- 1831937
- NSF-PAR ID:
- 10195802
- Date Published:
- Journal Name:
- Hydrological Processes
- Volume:
- 34
- Issue:
- 11
- ISSN:
- 0885-6087
- Page Range / eLocation ID:
- 2477 to 2493
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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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
μ mol 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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Abstract. We present a novel photolytic source of gas-phase NO3 suitable for use in atmospheric chemistry studies that has several advantages over traditional sources that utilize NO2 + O3 reactions and/or thermal dissociation of dinitrogen pentoxide (N2O5). The method generates NO3 via irradiation of aerated aqueous solutions of ceric ammonium nitrate (CAN, (NH4)2Ce(NO3)6) and nitric acid (HNO3) or sodium nitrate (NaNO3). We present experimental and model characterization of the NO3 formation potential of irradiated CAN / HNO3 and CAN / NaNO3 mixtures containing [CAN] = 10−3 to 1.0 M, [HNO3] = 1.0 to 6.0 M, [NaNO3] = 1.0 to 4.8 M, photon fluxes (I) ranging from 6.9 × 1014 to 1.0 × 1016 photons cm−2 s−1, and irradiation wavelengths ranging from 254 to 421 nm. NO3 mixing ratios ranging from parts per billion to parts per million by volume were achieved using this method. At the CAN solubility limit, maximum [NO3] was achieved using [HNO3] ≈ 3.0 to 6.0 M and UVA radiation (λmax = 369 nm) in CAN / HNO3 mixtures or [NaNO3] ≥ 1.0 M and UVC radiation (λmax = 254 nm) in CAN / NaNO3 mixtures. Other reactive nitrogen (NO2, N2O4, N2O5, N2O6, HNO2, HNO3, HNO4) and reactive oxygen (HO2, H2O2) species obtained from the irradiation of ceric nitrate mixtures were measured using a NOx analyzer and an iodide-adduct high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS). To assess the applicability of the method for studies of NO3-initiated oxidative aging processes, we generated and measured the chemical composition of oxygenated volatile organic compounds (OVOCs) and secondary organic aerosol (SOA) from the β-pinene + NO3 reaction using a Filter Inlet for Gases and AEROsols (FIGAERO) coupled to the HR-ToF-CIMS.
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1002/hyp.13742
