Abstract Ammonia (NH3) from animal feeding operations (AFOs) is an important source of reactive nitrogen in the US, but despite its ramifications for air quality and ecosystem health, its near‐source evolution remains understudied. To this end, Phase I of the Transport and Transformation of Ammonia (TRANS2Am) field campaign was conducted in the northeastern Colorado Front Range in summer 2021 and characterized atmospheric composition downwind of AFOs during 10 research flights. Airborne measurements of NH3, nitric acid (HNO3), and a suite of water‐soluble aerosol species collected onboard the University of Wyoming King Air research aircraft present an opportunity to investigate the sensitivity of particulate matter (PM) formation to AFO emissions. We couple the observations with thermodynamic modeling to predict the seasonality of ammonium nitrate (NH4NO3) formation. We find that during TRANS2Am northeastern Colorado is consistently in the NH3‐rich and HNO3‐limited NH4NO3formation regime. Further investigation using the Extended Aerosol Inorganics Model reveals that summertime temperatures (mean: 23°C) of northeastern Colorado, especially near the surface, inhibit NH4NO3formation despite high NH3concentrations (max: ≤114 ppbv). Finally, we model spring/autumn and winter conditions to explore the seasonality of NH4NO3formation and find that cooler temperatures could support substantially more NH4NO3formation. Whereas NH4NO3only exceeds 1 μg m−3∼10% of the time in summer, modeled NH4NO3would exceed 1 μg m−361% (88%) of the time in spring/autumn (winter), with a 10°C (20°C) temperature decrease relative to the campaign.
more »
« less
Summertime Airborne Measurements of Ammonia Emissions From Cattle Feedlots and Dairies in Northeastern Colorado
Abstract Phase One of the Transportation and Transformation of Ammonia (TRANS2Am) field campaign took place in northeastern Colorado during the summer of 2021. One of the goals of TRANS2Am was to measure ammonia (NH3) emissions from cattle feedlots and dairies. Most of these animal husbandry facilities are co‐located within oil and gas development, an important source of methane (CH4) and ethane (C2H6) in the region. Phase One of TRANS2Am included 12 near‐source research flights. We present estimates of NH3emissions ratios with respect to CH4(NH3EmR), with and without correction of CH4from oil and gas, for 29 feedlots and dairies in the region. The data shows larger emissions ratios than previously reported in the literature with a large range of values (i.e., 0.1–2.6 ppbv ppbv−1). Facilities housing cattle and dairy had a mean (std) of 1.20 (0.63) and 0.29 (0.08) ppbv ppbv−1, respectively. We also found that only 15% of the total ammonia (NHx) is in the particle phase (i.e., ) near major sources during the warm summertime months. We examined the evolution of NH3in one plume that was sampled at different distances and altitudes up to 25 km downwind and estimated the NH3lifetime against deposition and partitioning to the particle phase to be 87–120 min. Finally, we calculated estimates of NH3emission rates from four optimally sampled facilities. These ranged from 4 to 29 g NH3 · h−1 · hd−1.
more »
« less
- Award ID(s):
- 2020127
- PAR ID:
- 10548341
- Publisher / Repository:
- American Geophysical Union
- Date Published:
- Journal Name:
- Journal of Geophysical Research: Atmospheres
- Volume:
- 128
- Issue:
- 23
- ISSN:
- 2169-897X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Ruddlesden–Popper perovskites (RPPs) are promising materials for optoelectronic devices. While iodide‐based RPPs are well‐studied, the crystallization of mixed‐halide RPPs remains less explored. Understanding the factors affecting their formation and crystallization are vital for optimizing morphology, phase purity, and orientation, which directly impact device performance. Here, we investigate the crystallization and properties of mixed‐halide RPPs (PEA)2FAn−1Pbn(Br1/3I2/3)3n + 1(PEA = C6H5(CH2)2NH3+and FA = CH(NH2)2+) (n = 1, 5, 10) using DMSO ((CH3)2SO) or NMP (OC4H6NCH3) as cosolvents and MACl (MA = CH3NH3+) as an additive. For the first time, the presence of planar defects in RPPs is directly observed by in situ grazing‐incidence wide‐angle X‐ray scattering (GIWAXS) and confirmed through the simulation of the patterns that matched the experimental. GIWAXS data also reveals that DMSO promotes higher crystallinity and vertical orientation, while MACl enhances crystal quality but increases halide segregation, shown here by nano X‐ray fluorescence (nano‐XRF) experiments. For low‐n RPPs, orientation is crucial for solar cell efficiency, but its impact decreases with increasing n. Our findings provide insights into optimizing mixed‐halide RPPs, guiding strategies to improve crystallization, phase control, and orientation for better performance not only in solar cells but also in other potential optoelectronic devices.more » « less
-
Beryllium ammonia complexes Be(NH 3 ) 4 are known to bear two diffuse electrons in the periphery of a Be(NH 3 ) 4 2+ skeleton. The replacement of one ammonia with a methyl group forms CH 3 Be(NH 3 ) 3 with one peripheral electron, which is shown to maintain the hydrogenic-type shell model observed for Li(NH 3 ) 4 . Two CH 3 Be(NH 3 ) 3 monomers are together linked by aliphatic chains to form strongly bound beryllium ammonia complexes, (NH 3 ) 3 Be(CH 2 ) n Be(NH 3 ) 3 , n = 1–6, with one electron around each beryllium ammonia center. In the case of a linear carbon chain, this system can be seen as the analog of two hydrogen atoms approaching each other at specific distances (determined by n). We show that the two electrons occupy diffuse s-type orbitals and can couple exactly as in H 2 in either a triplet or singlet state. For long hydrocarbon chains, the singlet is an open-shell singlet nearly degenerate with the triplet spin state, which transforms to a closed-shell singlet for n = 1 imitating the σ-covalent bond of H 2 . The biradical character of the system is analyzed, and the singlet–triplet splitting is estimated as a function of n based on multi-reference calculations. Finally, we consider the case of bent hydrocarbon chains, which allows the closer proximity of the two diffuse electrons for larger chains and the formation of a direct covalent bond between the two diffuse electrons, which happens for two Li(NH 3 ) 4 complexes converting the open-shell to closed-shell singlets. The energy cost for bending the hydrocarbon chain is nearly compensated by the formation of the weak covalent bond rendering bent and linear structures nearly isoenergetic.more » « less
-
The reactive partitioning of cis and trans β-IEPOX was investigated on hydrated inorganic seed particles, without the addition of acids. No organic aerosol (OA) formation was observed on dry ammonium sulfate (AS); however, prompt and efficient OA growth was observed for the cis and trans β-IEPOX on AS seeds at liquid water contents of 40–75% of the total particle mass. OA formation from IEPOX is a kinetically limited process, thus the OA growth continues if there is a reservoir of gas-phase IEPOX. There appears to be no differences, within error, in the OA growth or composition attributable to the cis / trans isomeric structures. Reactive uptake of IEPOX onto hydrated AS seeds with added base (NaOH) also produced high OA loadings, suggesting the pH dependence for OA formation from IEPOX is weak for AS particles. No OA formation, after particle drying, was observed on seed particles where Na+ was substituted for NH4+. The Henry's Law partitioning of IEPOX was measured on NaCl particles (ionic strength ~9 M) to be 3 × 107 M atm−1 (−50 / +100%). A small quantity of OA was produced when NH4+ was present in the particles, but the chloride (Cl-) anion was substituted for sulfate (SO42-), possibly suggesting differences in nucleophilic strength of the anions. Online time-of-flight aerosol mass spectrometry and offline filter analysis provide evidence of oxygenated hydrocarbons, organosulfates, and amines in the particle organic composition. The results are consistent with weak correlations between IEPOX-derived OA and particle acidity or liquid water observed in field studies, as the chemical system is nucleophile-limited and not limited in water or catalyst activity.more » « less
-
ABSTRACT 8‐oxoguanosine (OG) is a common form of DNA damage and is itself more susceptible to further oxidative transformations. The oxidized OG derivatives can covalently bond with nucleophilic amino acid residues, contributing to DNA–protein crosslinks (DPCs). Previous research in this context focused on the reactivity of the two‐electron oxidized OG intermediate, 2‐amino‐7,9‐dihydro‐purine‐6,8‐dione (OGOX), toward nucleophilic addition. In contrast, the role of one‐electron oxidized OG radical cations (OG•+) remains unexplored. Herein, we investigate a model system using 9‐methyl‐8‐oxoguanine radical cation (9MOG•+) as an analogue of OG nucleoside and CH3NH2as a mimic for the lysineε‐amine. The reaction of 9MOG•+with methylamine was measured across a range of kinetic energy in the gas phase by guided‐ion‐beam mass spectrometry. Density functional theory (DFT) and DLPNO‐CCSD(T) quantum chemistry computations were performed to elucidate reaction pathways and structures. Our results reveal that at low reaction energies, DPCs occur through direct nucleophilic addition, yielding C2‐+NH2CH3[9MOG]•and C4‐+NH2CH3[9MOG]•. At high energies, DPCs become possible between protonated [9MOG+H]+and•CH2NH2/•NHCH3generated from hydrogen abstraction. This work provides insights into the distinct roles of one‐ versus two‐electron oxidized OG species in DPC formation, expanding knowledge of OG lesions and their biological consequences.more » « less
An official website of the United States government

