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Emerging contaminants (EC) distributed on surfaces in the environment can be oxidized by gas phase species (top–down) or by oxidants generated by the underlying substrate (bottom–up). One class of EC is the neonicotinoid (NN) pesticides that are widely distributed in air, water, and on plant and soil surfaces as well as on airborne dust and building materials. This study investigates the OH oxidation of the systemic NN pesticide acetamiprid (ACM) at room temperature. ACM on particles and as thin films on solid substrates were oxidized by OH radicals either from the gas phase or from an underlying TiO2or NaNO2substrate, and for comparison, in the aqueous phase. The site of OH attack is both the secondary >CH2group as well as the primary –CH3group attached to the tertiary amine nitrogen, with the latter dominating. In the case of top–down oxidation of ACM by gas phase OH radicals, addition to the –CN group also occurs. Major products are carbonyls and alcohols, but in the presence of sufficient water, their hydrolyzed products dominate. Kinetics measurements show ACM is more reactive toward gas phase OH radicals than other NN nitroguanidines, with an atmospheric lifetime of a few days. Bottom–up oxidation of ACM on TiO2exposed to sunlight outdoors (temperatures were above 30 °C) was also shown to occur and is likely to be competitive with top–down oxidation. These findings highlight the different potential oxidation processes for EC and provide key data for assessing their environmental fates and toxicologies.
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Pathways to Detection of Strongly-Bound Inorganic Species: The Vibrational and Rotational Spectral Data of AlH2OH, HMgOH, AlH2NH2, and HMgNH2
Small, inorganic hydrides are likely hiding in plain sight, waiting to be detected toward various astronomical objects. AlH 2 OH can form in the gas phase via a downhill pathway, and the present, high-level quantum chemical study shows that this molecule exhibits bright infrared features for anharmonic fundamentals in regions above and below that associated with polycyclic aromatic hydrocarbons. AlH 2 OH along with HMgOH, HMgNH 2 , and AlH 2 NH 2 are also polar with AlH 2 OH having a 1.22 D dipole moment. AlH 2 OH and likely HMgOH have nearly unhindered motion of the hydroxyl group but are still strongly bonded. This could assist in gas phase synthesis, where aluminum oxide and magnesium oxide minerals likely begin their formation stages with AlH 2 OH and HMgOH. This work provides the spectral data necessary to classify these molecules such that observations as to the buildup of nanoclusters from small molecules can possibly be confirmed.
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- Award ID(s):
- 1757220
- PAR ID:
- 10335954
- Date Published:
- Journal Name:
- Frontiers in Astronomy and Space Sciences
- Volume:
- 8
- ISSN:
- 2296-987X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3389/fspas.2021.643348
