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1. Nitrate chemistry in the northeast US – Part 1: Nitrogen isotope seasonality tracks nitrate formation chemistry

   https://doi.org/10.5194/acp-23-4185-2023  

   Bekker, Claire; Walters, Wendell W; Murray, Lee T; Hastings, Meredith G (January 2023, Atmospheric Chemistry and Physics)

   Abstract. Despite significant precursor emission reductions in theUS over recent decades, atmospheric nitrate deposition remains an importantterrestrial stressor. Here, we utilized statistical air mass back trajectoryanalysis and nitrogen stable isotope deltas (δ(15N)) toinvestigate atmospheric nitrate spatiotemporal trends in the northeastern USfrom samples collected at three US EPA Clean Air Status and Trends Network(CASTNET) sites from December 2016–2018. For the considered sites, similarseasonal patterns in nitric acid (HNO3) and particulate nitrate(pNO3) concentrations were observed with spatial differences attributedto nitrogen oxide (NOx) emission densities in source contributingregions that were typically ≤ 1000 km. Significant spatiotemporalδ(15N) variabilities in HNO3 and pNO3 were observedwith higher values during winter relative to summer, like previous reportsfrom CASTNET samples collected in the early 2000s for our study region. Inthe early 2000s, δ(15N) of atmospheric nitrate in the northeastUS had been suggested to be driven by NOx emissions; however, we didnot find significant spatiotemporal changes in the modeled NOxemissions by sector and fuel type or δ(15N, NOx) for thesource regions of the CASTNET sites. Instead, the seasonal and spatialdifferences in the observed δ(15N) of atmospheric nitrate weredriven by nitrate formation pathways (i.e., homogeneous reactions ofNO2 oxidation via hydroxyl radical or heterogeneous reactions ofdinitrogen pentoxide on wetted aerosol surfaces) and their associatedδ(15N) fractionation. Under the field conditions of lowNOx relative to O3 concentrations and when δ(15N,NOx) emission sources do not have significant variability, wedemonstrate that δ(15N) of atmospheric nitrate can be a robusttracer for diagnosing nitrate formation. 

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2. Tracking Photo-Oxidation Reactions of Aquatic Organic Matter Using Triple Oxygen Isotopes

   https://doi.org/10.1021/acsearthspacechem.5c00057  

   Crocker, Daniel R; Sutherland, Kevin M; Freudenberg, Benjamin; Alonso, Kimberly; Pearson, Ann; Ward, Collin P; Johnston, David T (June 2025, ACS Earth and Space Chemistry)

   The three-isotope system of oxygen (16O, 17O, 18O) is a powerful tool to study environmental oxidation chemistry and cycling of oxygen-bearing species (e.g., sulfates, nitrates, carbonates, etc.). Despite its evident utility, little work has focused onextending the triple oxygen isotope (Δ’17O) tool to oxygen contained in organic matter (OM). This is largely due to methodological challenges with isolating OM-bound oxygen and preparing it for isotopic analysis. Herein, we report on a newly developed method for high-precision Δ’17O measurements of OM (Δ’17O precision of 0.020‰) and apply this technique to investigate partial photochemical oxidation of Suwannee River natural OM in air-equilibrated aquatic samples. Through this, we reveal that the oxygen isotope evolution of the Suwannee OM supports a model whereby OM partial photo-oxidation proceeds via one or more reactive oxygen intermediates. Our measurements further highlight the potential of triple oxygen isotope analyses on OM-bound oxygen to fingerprint OM oxidation pathways, redox chemistry, and source and synthesis reactions. 

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3. Sources and Pathways of Formation of Recalcitrant and Residual Phosphorus in an Agricultural Soil

   https://doi.org/10.3390/soilsystems2030045  

   Joshi, Sunendra; Li, Wei; Bowden, Mark; Jaisi, Deb (September 2018, Soil Systems)

   Phosphorus (P) is an essential nutrient for sustaining life and agricultural production. Transformation of readily available P into forms that are unavailable to plants adds costs to P replenishment, which eventually translates into lower agronomic benefits and potential loss of soil P into runoff may degrade water quality. Therefore, understanding the sources and pathways of the formation of residual P pools in soils is useful information needed for the development of any technological or management efforts to minimize or inhibit the formation of such P pool and thus maximize availability to plants. In this research, we paired phosphate oxygen isotope ratios (δ18OP) with solid-state 31P NMR and quantitative XRD techniques along with general soil chemistry methods to identify the precipitation pathways of acid-extracted inorganic P (Pi) pools in an agricultural soil. Based on the comparison of isotope values of 0.5 mol L−1 NaOH-Pi, 1 mol L−1 HCl-Pi, and 10 mol L−1 HNO3-Pi pools and correlations of associated elements (Ca, Fe, and Al) in these pools, the HNO3-Pi pool appears most likely to be transformed from the NaOH-Pi pool. A narrow range of isotope values of acid-Pi pools in shallow (tilling depth) and below (where physical mixing is absent) is intriguing but likely suggests leaching of particle-bound P in deeper soils. Overall, these findings provide an improved understanding of the sources, transport, and transformation of acid-Pi pools in agricultural soils and further insights into the buildup of legacy P in soils. 

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4. Triple oxygen isotope evidence for a hot Archean ocean

   https://doi.org/10.1130/G50230.1  

   McGunnigle, J.P.; Cano, E.J.; Sharp, Z.D.; Muehlenbachs, K.; Cole, D.; Hardman, M.F.; Stachel, T.; Pearson, D.G. (May 2022, Geology)

   Triple oxygen isotope (δ17O and δ18O) values of high- and low-temperature altered oceanic crust and products of basalt alteration experiments were measured to better constrain ocean isotope compositions in deep time. The data define an array of δ18O and Δ′17O (Δ′17O=δ′17O – λRL × δ′18O + γ) values from mantle values toward 1‰ and –0.01‰, respectively, with a λ of ~0.523. The altered oceanic crust data were used to construct a model for estimating δ18O-Δ′17O values of the ancient oceans if the continental weathering flux (FCW) and/or hydrothermal oceanic crust alteration flux (FHT) changed through time. A maximum lowering of 7‰ and 4‰, respectively, is achieved in the most extreme cases. The δ18O value of the ocean cannot be raised by more than 1.1‰. Eclogites from the Roberts Victor kimberlite (South Africa), with a protolith age of 3.1 Ga, have δ18O-Δ′17O values that precisely overlap with those of the modern altered oceanic crust, suggesting that the Archean oceans had similar isotope values as today. Published triple isotope data for Archean cherts show that all samples have been altered to some degree and suggest an Archean ocean surface temperature of ~70–100 °C. An ocean as light as –2‰ is still consistent with our eclogite data and reduce our temperature estimates by 10 °C. 

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5. Technical note: Gas-phase nitrate radical generation via irradiation of aerated ceric ammonium nitrate mixtures

   https://doi.org/10.5194/acp-23-13869-2023  

   Lambe, Andrew T.; Bai, Bin; Takeuchi, Masayuki; Orwat, Nicole; Zimmerman, Paul M.; Alton, Mitchell W.; Ng, Nga L.; Freedman, Andrew; Claflin, Megan S.; Gentner, Drew R.; et al (November 2023, Atmospheric Chemistry and Physics)

   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. 

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