Flash Photolysis of 2,4,6-Trinitrotoluene Solutions

Suryanarayanan, K.; Capellos, C.

doi:10.21236/ad0755109

Cited by 2 publications

(5 citation statements)

References 3 publications

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“…(9) or the expected behavior using apparent quantum yield as a proxy for k as shown in Figure 3A. Suryanarayanan and Capellos (1974) photolyzed TNT in methanol solutions under acidic conditions at various concentrations of LiCl and found that the rate of reaction did decrease as LiCl increased in a manner that followed eq. (9).…”

Section: Impact Of Seawater and Salinity On Photolysis Ratesmentioning

confidence: 81%

“…which is followed by its ionization in polar solvents to form a TNT anion. This TNT anion is likely the one that reacted with hydrogen ions in the work of Suryanarayanan and Capellos (1974) and exhibited the behavior of the primary salt effect. In the current study, the higher pH would minimize the reaction given in eq.…”

Section: Impact Of Seawater and Salinity On Photolysis Ratesmentioning

confidence: 98%

“…as was used by Suryanarayanan and Capellos (1974). In this equation, k is the rate constant, A is a constant, Z a and Z b are the charges of the reacting ions,  is the ionic strength, and k o is the rate constant at infinite dilution.…”

Section: Impact Of Seawater and Salinity On Photolysis Ratesmentioning

confidence: 99%

“…An increased hydrogen ion concentration (lower pH) was found to lower the photolysis rate of TNT, 2,6-DNT, and 2,4-DNT in ultrapure water, but not change TNT photolysis rates in pond water (pH decrease from 8.0 to 4.0), and slightly increase 2,4-DNT and 2,6-DNT photolysis rates in seawater (pH decrease from 8.1 to 6.4) (Burlinson et al, 1979;Mabey et al, 1982, Luning Prak et al, 2013. The complex interplay of hydrogen ion and other ions in photolysis is demonstrated by the result that addition of lithium chloride to TNT solutions reduced its photolysis rate under acidic conditions in methanol (Suryanarayanan and Capellos, 1974). In contrast, the addition of sodium chloride to water around pH 7 increased 2,4-DNT photolysis rates for a 4% solution with no additional rate increases for 8% and 15% solutions (Mihas et al, 2007).…”

Section: Introductionmentioning

confidence: 99%

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Photolysis of 2,4,6-trinitrotoluene in seawater and estuary water: Impact of pH, temperature, salinity, and dissolved organic matter

Prak

Breuer

Rios

et al. 2017

Marine Pollution Bulletin

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The influence of salinity, pH, temperature, and dissolved organic matter on the photolysis rate of 2,4,6-trinitrotoluene (TNT) in marine, estuary, and laboratory-prepared waters was studied using a Suntest CPS+® solar simulator equipped with optical filters. TNT degradation rates were determined using HPLC analysis, and products were identified using LC/MS. Minimal or no TNT photolysis occurred under a 395-nm long pass filter, but under a 295-nm filter, first-order TNT degradation rate constants and apparent quantum yields increased with increasing salinity in both natural and artificial seawater. TNT rate constants increased slightly with increasing temperature (10 to 32°C) but did not change significantly with pH (6.4 to 8.1). The addition of dissolved organic matter (up to 5mg/L) to ultrapure water, artificial seawater, and natural seawater increased the TNT photolysis rate constant. Products formed by TNT photolysis in natural seawater were determined to be 2,4,6-trinitrobenzaldehyde, 1,3,5-trinitrobenzene, 2,4,6-trinitrobenzoic acid, and 2-amino-4,6-dinitrobenzoic acid.

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Section: Impact Of Seawater and Salinity On Photolysis Ratesmentioning

confidence: 81%

Section: Impact Of Seawater and Salinity On Photolysis Ratesmentioning

confidence: 98%

Section: Impact Of Seawater and Salinity On Photolysis Ratesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Photolysis of 2,4,6-trinitrotoluene in seawater and estuary water: Impact of pH, temperature, salinity, and dissolved organic matter

Prak

Breuer

Rios

et al. 2017

Marine Pollution Bulletin

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“…Nitrosation reactions have been implicated in formation of several of the photodegradation products identified by Burlinson and Kaplan [21, 34–36]. As an initial photoproduct of TNT in aqueous solution, the excited 1,2,6-trinitrobenzyl anion [55] intermediate can undergo nitrosation to 1,2,6-trinitrobenzaldoxime [35], which in turn can undergo a Beckmann fragmentation to 1,2,6-trinitrobenzonitrile or a cyclization-dehydration reaction to 4,6-dinitro-1,2-benzisoxazole (Fig 1). Benzaldoximes are susceptible to both photochemical and nonphotochemical Beckmann rearrangements to primary amides (Fig 1) [56–58].…”

Section: Introductionmentioning

confidence: 99%

13C and 15N NMR identification of product compound classes from aqueous and solid phase photodegradation of 2,4,6-trinitrotoluene

Thorn

2019

PLoS ONE

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Photolysis is one of the main transformation pathways for 2,4,6-trinitrotoluene (TNT) released into the environment. Upon exposure to sunlight, TNT is known to undergo both oxidation and reduction reactions with release of nitrite, nitrate, and ammonium ions, followed by condensation reactions of the oxidation and reduction products. In this study, compound classes of transformation products from the aqueous and solid phase photodegradation of 2,4,6-trinitrotoluene (TNT) have been identified by liquid and solid state 13C and 15N NMR. Aqueous phase experiments were performed on saturated solutions of T15NT in deionized water, natural pond water (pH = 8.3, DOC = 3.0 mg/L), pH 8.0 buffer solution, and in the presence of Suwannee River Natural Organic Matter (SRNOM; pH = 3.7), using a Pyrex-filtered medium pressure mercury lamp. Natural sunlight irradiations were performed on TNT in the solid phase and dissolved in the pond water. In deionized water, carboxylic acid, aldehyde, aromatic amine, primary amide, azoxy, nitrosophenol, and azo compounds were formed. 15N NMR spectra exhibited major peaks centered at 128 to 138 ppm, which are in the range of phenylhydroxylamine and secondary amide nitrogens. The secondary amides are proposed to represent benzanilides, which would arise from photochemical rearrangement of nitrones formed from the condensation of benzaldehyde and phenylhydroxylamine derivatives of TNT. The same compound classes were formed from sunlight irradiation of TNT in the solid phase. Whereas carboxylic acids, aldehydes, aromatic amines, phenylhydroxylamines, and amides were also formed from irradiation of TNT in pond water and in pH 8 buffer solution, azoxy and azo compound formation was inhibited. Solid state 15N NMR spectra of photolysates from the lamp irradiation of unlabeled 2,6-dinitrotoluene in deionized water also demonstrated the formation of aromatic amine, phenylhydroxylamine/ 2° amide, azoxy, and azo nitrogens.

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Flash Photolysis of 2,4,6-Trinitrotoluene Solutions

Cited by 2 publications

References 3 publications

Photolysis of 2,4,6-trinitrotoluene in seawater and estuary water: Impact of pH, temperature, salinity, and dissolved organic matter

Photolysis of 2,4,6-trinitrotoluene in seawater and estuary water: Impact of pH, temperature, salinity, and dissolved organic matter

13C and 15N NMR identification of product compound classes from aqueous and solid phase photodegradation of 2,4,6-trinitrotoluene

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