Products of the Gas-Phase OH and NO<sub>3</sub> Radical-Initiated Reactions of Naphthalene

Sasaki, Jennifer C.; Aschmann, Sara M.; Kwok, Eric S. C.; Atkinson, Roger; Arey, Janet

doi:10.1021/es9701523

Cited by 185 publications

(232 citation statements)

References 24 publications

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“…Then, Product II a can be converted into Product III a via further reaction with the NO 3 radicals of which the formation mechanism may be similar to that of naphthalene with NO 3 radicals. 37 Figure 5B shows the three pathways for the reaction of PM particles with NO 3 radicals. The first pathway is the transformation of the carbamate group into a hydroxyl group resulting in the formation of Product I a .…”

Section: Resultsmentioning

confidence: 99%

Heterogeneous Reactions of Pirimiphos-Methyl and Pirimicarb with NO₃ Radicals

et al. 2012

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Pirimiphos-methyl (PMM) and pirimicarb (PM) are two typical N,N-dialkyl substituted pyrimidine pesticides. The heterogeneous reactions of suspended PMM and PM particles with NO 3 radicals are investigated using an online aerosol time-of-flight mass spectrometer and a real-time atmospheric gas analysis mass spectrometer. Three products for PMM and five products for PM are observed and assigned with the aid of GC/MS. Phosphoric acid 2-diethylamino-6-methyl-4-pyrimidinyl dimethyl ester and 2-(dimethylamino)-5,6-dimethyl-4-hydroxy-pyrimidine are the main reaction products observed for PMM and PM, respectively. The effective rate constants for the reactions of PMM and PM particles with NO 3 radicals are (9.9 ± 0.3) × 10 −12 and (7.5 ± 0.3) × 10 −13 cm 3 molecule −1 s −1 , respectively, obtained using a mixed-phase relative rate method. Geometries and energies of transition states (TS) and intermediates (IM) are obtained by DFT calculation to elucidate the detailed mechanism of the PS group oxidation into the PO group for PMM. The theoretical studies present the reasonable intermediates including the S-oxide and the diradical (IM1 a and IM2 a ). The mechanism explanation may provide useful information for understanding the degradation mechanism of organothionophosphorus compounds in the environment.

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Section: Resultsmentioning

confidence: 99%

Heterogeneous Reactions of Pirimiphos-Methyl and Pirimicarb with NO₃ Radicals

et al. 2012

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“…1.3 315 ± 33 10.4 ± 0.8 3.8 ± 0.9 467 ± 93 7.5 ± 0.5 a Calculated from first-order decay of naphthalene (k OH = 2.2 × 10 −11 molec −1 cm −3 , Sasaki et al, 1997); relative standard deviation of fit was typically less than ±1 %. b Uncertainty based on ±10 % relative standard deviation of PTR-MS calibration for naphthalene.…”

Section: R D Mcwhinney Et Al: Redox Activity Of Naphthalene Soamentioning

confidence: 99%

“…They may also be produced as secondary products of polycyclic aromatic hydrocarbon (PAH) oxidation. Naphthalene (Bunce et al, 1997;Chan et al, 2009;Kautzman et al, 2010;Lee and Lane, 2009;Sasaki et al, 1997), phenanthrene (Lee and Lane, 2010;Wang et al, 2007), and anthracene (Kwamena et al, 2006) all generate their corresponding quinone species (naphthoquinone, phenanthrenequinone, and anthraquinone, respectively) via reaction with gas-phase oxidants. Formation of these species from PAH precursors in the atmosphere could increase the redox activity of ambient particles during photochemical aging in locations with PAH emission sources.…”

Section: Introductionmentioning

confidence: 99%

Naphthalene SOA: redox activity and naphthoquinone gas–particle partitioning

2013

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Abstract. Chamber secondary organic aerosol (SOA) from low-NO x photooxidation of naphthalene by hydroxyl radical was examined with respect to its redox cycling behaviour using the dithiothreitol (DTT) assay. Naphthalene SOA was highly redox-active, consuming DTT at an average rate of 118 ± 14 pmol per minute per µg of SOA material. Measured particle-phase masses of the major previously identified redox active products, 1,2-and 1,4-naphthoquinone, accounted for only 21 ± 3 % of the observed redox cycling activity. The redox-active 5-hydroxy-1,4-naphthoquinone was identified as a new minor product of naphthalene oxidation, and including this species in redox activity predictions increased the predicted DTT reactivity to 30 ± 5 % of observations. These results suggest that there are substantial unidentified redox-active SOA constituents beyond the small quinones that may be important toxic components of these particles. A gas-to-SOA particle partitioning coefficient was calculated to be (7.0 ± 2.5) × 10 −4 m 3 µg −1 for 1,4-naphthoquinone at 25 • C. This value suggests that under typical warm conditions, 1,4-naphthoquinone is unlikely to contribute strongly to redox behaviour of ambient particles, although further work is needed to determine the potential impact under conditions such as low temperatures where partitioning to the particle is more favourable. Also, higher order oxidation products that likely account for a substantial fraction of the redox cycling capability of the naphthalene SOA are likely to partition much more strongly to the particle phase.

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“…While naphthalene itself is not carcinogenic, it is the most abundant PAH in polluted urban areas (Arey et al, 1989) and leads to formation of mutagenic nitronaphthalenes by OH and NO 3 -initiated reactions (Sasaki et al, 1997). The main sources of naphthalene in the urban atmosphere are motor vehicle exhaust and residential heating; the predominant sink is its reaction with OH, leading to lifetimes of naphthalene typically shorter than one day (Atkinson and Arey, 1994).…”

Section: Introductionmentioning

confidence: 99%

Measuring atmospheric naphthalene with laser-induced fluorescence

et al. 2004

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Abstract.A new method for measuring gas-phase naphthalene in the atmosphere is based on laser-induced fluorescence at low pressure. The fluorescence spectrum of naphthalene near 308 nm was identified. Naphthalene fluorescence quenching by N 2 , O 2 and H 2 O was investigated in the laboratory. No significant quenching was found for H 2 O with mixing ratio up to 2.5%. The quenching rate of naphthalene fluorescence is (1.98±0.18) ×10 −11 cm 3 molecule −1 s −1 for N 2 , and (2.48±0.08)×10 −10 cm 3 molecule −1 s −1 for O 2 at 297 K. Instrument calibrations were performed with a range of naphthalene mixing ratios between 5 and 80 parts per billion by volume (ppbv, 10 −9 ). In the current instrument configuration, the detection limit is estimated to be about 20 parts per trillion by volume (pptv, 10 −12 ) with 2σ confidence and a 1-min integration time. Measurements of atmospheric naphthalene in three cities, Nashville, TN, Houston, TX, and New York City, NY, are presented. Good correlation between naphthalene and major anthropogenic pollutants is found.

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Products of the Gas-Phase OH and NO₃ Radical-Initiated Reactions of Naphthalene

Cited by 185 publications

References 24 publications

Heterogeneous Reactions of Pirimiphos-Methyl and Pirimicarb with NO₃ Radicals

Heterogeneous Reactions of Pirimiphos-Methyl and Pirimicarb with NO₃ Radicals

Naphthalene SOA: redox activity and naphthoquinone gas–particle partitioning

Measuring atmospheric naphthalene with laser-induced fluorescence

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Products of the Gas-Phase OH and NO3 Radical-Initiated Reactions of Naphthalene

Cited by 185 publications

References 24 publications

Heterogeneous Reactions of Pirimiphos-Methyl and Pirimicarb with NO3 Radicals

Heterogeneous Reactions of Pirimiphos-Methyl and Pirimicarb with NO3 Radicals

Naphthalene SOA: redox activity and naphthoquinone gas–particle partitioning

Measuring atmospheric naphthalene with laser-induced fluorescence

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Product

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Products of the Gas-Phase OH and NO₃ Radical-Initiated Reactions of Naphthalene

Heterogeneous Reactions of Pirimiphos-Methyl and Pirimicarb with NO₃ Radicals

Heterogeneous Reactions of Pirimiphos-Methyl and Pirimicarb with NO₃ Radicals