skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: Top–down versus bottom–up oxidation of a neonicotinoid pesticide by OH radicals
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.  more » « less
Award ID(s):
2303948 2011967
PAR ID:
10499111
Author(s) / Creator(s):
; ; ; ;
Publisher / Repository:
National Academy of Sciences
Date Published:
Journal Name:
Proceedings of the National Academy of Sciences
Volume:
121
Issue:
7
ISSN:
0027-8424
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; ; ; ; ; ; ; ; et al (, Global Biogeochemical Cycles)
    Abstract Large stocks of soil carbon (C) and nitrogen (N) in northern permafrost soils are vulnerable to remobilization under climate change. However, there are large uncertainties in present‐day greenhouse gas (GHG) budgets. We compare bottom‐up (data‐driven upscaling and process‐based models) and top‐down (atmospheric inversion models) budgets of carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O) as well as lateral fluxes of C and N across the region over 2000–2020. Bottom‐up approaches estimate higher land‐to‐atmosphere fluxes for all GHGs. Both bottom‐up and top‐down approaches show a sink of CO2in natural ecosystems (bottom‐up: −29 (−709, 455), top‐down: −587 (−862, −312) Tg CO2‐C yr−1) and sources of CH4(bottom‐up: 38 (22, 53), top‐down: 15 (11, 18) Tg CH4‐C yr−1) and N2O (bottom‐up: 0.7 (0.1, 1.3), top‐down: 0.09 (−0.19, 0.37) Tg N2O‐N yr−1). The combined global warming potential of all three gases (GWP‐100) cannot be distinguished from neutral. Over shorter timescales (GWP‐20), the region is a net GHG source because CH4dominates the total forcing. The net CO2sink in Boreal forests and wetlands is largely offset by fires and inland water CO2emissions as well as CH4emissions from wetlands and inland waters, with a smaller contribution from N2O emissions. Priorities for future research include the representation of inland waters in process‐based models and the compilation of process‐model ensembles for CH4and N2O. Discrepancies between bottom‐up and top‐down methods call for analyses of how prior flux ensembles impact inversion budgets, more and well‐distributed in situ GHG measurements and improved resolution in upscaling techniques. 
    more » « less
  2. ; ; ; ; ; ; ; ; (, Environmental Science: Atmospheres)
    Neonicotinoids (NNs) are commonly found throughout the environment on surfaces such as seeds, soil, vegetation, and blowing dust particles. However, there is a paucity of data on the kinetics and oxidation products formed on contact with the atmosphere which limits understanding of their potentially far-reaching impacts. In this study, in situ attenuated total reflectance (ATR) FTIR spectroscopy was used to investigate the OH oxidation of thin films of three solid NNs, imidacloprid (IMD), dinotefuran (DNF) and clothianidin (CLD) at 295 ± 3 K. The experimentally measured reaction probabilities based on initial rates of NN loss are (1.6 ± 0.8) × 10 −2 for IMD, (1.5 ± 0.6) × 10 −2 for DNF and (0.9 ± 0.2) × 10 −2 for CLD (±1 σ ), suggesting initial NN lifetimes with respect to OH of 10–17 days. The kinetics were interpreted using a multiphase kinetics model, KM-SUB, which showed that the OH uptake and reaction occurred primarily in the surface layer. Products identified by mass spectrometry included carbonyl-, alcohol- and olefin-containing species formed via hydrogen abstraction from aliphatic C–H groups. Additionally, carbonyl-containing desnitro and urea derivative products were observed from secondary reactions of the initially formed photodegradation products. Reaction with OH will contribute to NN loss both during the day as well as at night when there are non-photolytic sources of this radical. Thus, OH reactions with both the parent neonicotinoid and its photodegradation products should be considered in assessing their environmental impacts. 
    more » « less
  3. ; (, Atmospheric chemistry and physics discussion)
    The daytime oxidation of biogenic hydrocarbons is attributed to both OH radicals and O3, while nighttime chemistry is dominated by the reaction with O3 and NO3 radicals. Here, the diurnal pattern of Secondary Organic Aerosol (SOA) originating from biogenic hydrocarbons was intensively evaluated under varying environmental conditions (temperature, humidity, sunlight intensity, NOx levels, and seed conditions) by using the UNIfied Partitioning Aerosol phase Reaction (UNIPAR) model, which comprises multiphase gas-particle partitioning and in-particle chemistry. The oxidized products of three different hydrocarbons (isoprene, α-pinene, and β-caryophyllene) were predicted by using near explicit gas mechanisms for four different oxidation paths (OH, O3, NO3, and O(3P)) during day and night. The gas mechanisms implemented the Master Chemical Mechanism (MCM v3.3.1), the reactions that formed low volatility products via peroxy radical (RO2) autoxidation, and self- and cross-reactions of nitrate-origin RO2. In the model, oxygenated products were then classified into volatility-reactivity base lumping species, which were dynamically constructed under varying NOx levels and aging scales. To increase feasibility, the UNIPAR model that equipped mathematical equations for stoichiometric coefficients and physicochemical parameters of lumping species was integrated with the SAPRC gas mechanism. The predictability of the UNIPAR model was demonstrated by simulating chamber-generated SOA data under varying environments day and night. Overall, the SOA simulation decoupled to each oxidation path indicated that the nighttime isoprene SOA formation was dominated by the NO3-driven oxidation, regardless of NOx levels. However, the oxidation path to produce the nighttime α-pinene SOA gradually transited from the NO3-initiated reaction to ozonolysis as NOx levels decreased. For daytime SOA formation, both isoprene and α-pinene were dominated by the OH-radical initiated oxidation. The contribution of the O(3P) path to all biogenic SOA formation was negligible in daytime. Sunlight during daytime promotes the decomposition of oxidized products via photolysis and thus, reduces SOA yields. Nighttime α-pinene SOA yields were significantly higher than daytime SOA yields, although the nighttime α-pinene SOA yields gradually decreased with decreasing NOx levels. For isoprene, nighttime chemistry yielded higher SOA mass than daytime at the higher NOx level (isoprene/NOx > 5 ppbC/ppb). The daytime isoprene oxidation at the low NOx level formed epoxy-diols that significantly contributed SOA formation via heterogeneous chemistry. For isoprene and α-pinene, daytime SOA yields gradually increased with decreasing NOx levels. The daytime SOA produced more highly oxidized multifunctional products and thus, it was generally more sensitive to the aqueous reactions than the nighttime SOA. β-Caryophyllene, which rapidly oxidized and produced SOA with high yields, showed a relatively small variation in SOA yields from changes in environmental conditions (i.e., NOx levels, seed conditions, and diurnal pattern), and its SOA formation was mainly attributed to ozonolysis day and night. To mimic the nighttime α-pinene SOA formation under the polluted urban atmosphere, α-pinene SOA formation was simulated in the presence of gasoline fuel. The simulation suggested the growth of α-pinene SOA in the presence of gasoline fuel gas by the enhancement of the ozonolysis path under the excess amount of ozone, which is typical in urban air. We concluded that the oxidation of the biogenic hydrocarbon with O3 or NO3 radicals is a source to produce a sizable amount of nocturnal SOA, despite of the low emission at night. 
    more » « less
  4. ; ; ; ; ; ; (, Nature Communications)
    Abstract Aldehydes are ubiquitous in star-forming regions and carbonaceous chondrites, serving as essential intermediates in metabolic pathways and molecular mass growth processes to vital biomolecules necessary for the origins of life. However, their interstellar formation mechanisms have remained largely elusive. Here, we unveil the formation of lactaldehyde (CH3CH(OH)CHO) by barrierless recombination of formyl (HĊO) and 1-hydroxyethyl (CH3ĊHOH) radicals in interstellar ice analogs composed of carbon monoxide (CO) and ethanol (CH3CH2OH). Lactaldehyde and its isomers 3-hydroxypropanal (HOCH2CH2CHO), ethyl formate (CH3CH2OCHO), and 1,3-propenediol (HOCH2CHCHOH) are identified in the gas phase utilizing isomer-selective photoionization reflectron time-of-flight mass spectrometry and isotopic substitution studies. These findings reveal fundamental formation pathways for complex, biologically relevant aldehydes through non-equilibrium reactions in interstellar environments. Once synthesized, lactaldehyde can act as a key precursor to critical biomolecules such as sugars, sugar acids, and amino acids in deep space. 
    more » « less
  5. ; ; ; ; ; (, The Journal of Chemical Physics)
    Infrared (IR) action spectroscopy is utilized to characterize carbon-centered hydroperoxy-cyclohexyl radicals (·QOOH) transiently formed in cyclohexane oxidation. The oxidation pathway leads to three nearly degenerate ·QOOH isomers, β-, γ-, and δ-QOOH, which are generated in the laboratory by H-atom abstraction from the corresponding ring sites of the cyclohexyl hydroperoxide (CHHP) precursor. The IR spectral features of jet-cooled and stabilized ·QOOH radicals are observed from 3590 to 7010 cm−1 (∼10–20 kcal mol−1) at energies in the vicinity of the transition state (TS) barrier leading to OH radicals that are detected by ultraviolet laser-induced fluorescence. The experimental approach affords selective detection of β-QOOH, arising from its significantly lower TS barrier to OH products compared to γ and δ isomers, which results in rapid unimolecular decay and near unity branching to OH products. The observed IR spectrum of β-QOOH includes fundamental and overtone OH stretch transitions, overtone CH stretch transitions, and combination bands involving OH or CH stretch with lower frequency modes. The assignment of β-QOOH spectral features is guided by anharmonic frequencies and intensities computed using second-order vibrational perturbation theory. The overtone OH stretch (2νOH) of β-QOOH is shifted only a few wavenumbers from that observed for the CHHP precursor, yet they are readily distinguished by their prompt vs slow dissociation rates to OH products. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email