Characterization of formaldehyde and formaldehyde-releasing preservatives by combined reversed-phase cation-exchange high-performance liquid chromatography with postcolumn derivatization using Nash's reagent

Summers, W. R.

doi:10.1021/ac00213a010

Cited by 24 publications

(11 citation statements)

References 24 publications

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“…The reactions were stopped by the addition of TFA (0.5%) to avoid further conversion of formaldehyde to formic acid by alcohol oxidase. Formaldehyde was then derivatized with 2,4-pentanedione for 15 min at 58°C in the presence of ammonium acetate and glacial acetic acid as described by Summers (22). The derivative was analyzed by HPLC as indicated below.…”

Section: Methodsmentioning

confidence: 99%

Aerobic Biodegradation of 2,4-Dinitroanisole by Nocardioides sp. Strain JS1661

Fida

Palamuru

Pandey

et al. 2014

Appl Environ Microbiol

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DNAN (2,4-dinitroanisole) is one of the insensitive nitroaromatic ingredients increasingly used as a replacement for 2,4,6-trinitrotoluene (TNT) in munitions. DNAN or its metabolites can be toxic to earthworms, bacteria, algae, and plants (1, 2). Therefore, the release of DNAN to the environment could pose ecological and health risks. There is little information about the environmental behavior of DNAN (2), and no bacteria capable of complete biodegradation have been reported.The initial reaction in the biotransformation of DNAN by bacteria and in abiotic transformation with zero valent iron is the reduction of the nitro group in the ortho position to yield 2-amino-4-nitroanisole (3-5). Under anoxic conditions, DNAN is biotransformed to toxic metabolites such as diaminoanisole (3,(5)(6)(7)(8). A Bacillus strain was reported to transform DNAN slowly under aerobic conditions to 2-amino-4-nitroanisole as a predominant dead-end product (4). A recent investigation revealed substantial aerobic biodegradation of DNAN by enrichment cultures derived from activated sludge, but the responsible bacteria were not isolated (9). During alkaline hydrolysis, DNAN is converted to 2,4-dinitrophenolate via an unstable hydride-Meisenheimer complex (10). Phototransformation of DNAN resulted in 2-hydroxy-4-nitroanisole and 2,4-dinitrophenol (2,4-DNP) as major and minor products, respectively (5, 11). The pathway of 2,4-DNP biodegradation under aerobic conditions is well-known, and the genes involved have been characterized for Rhodococcus erythropolis and Nocardia (12, 13). A Rhodococcus sp. has been reported to degrade 4-nitroanisole by a pathway involving removal of the methyl group and subsequent degradation of the resulting 4-nitrophenol via 4-nitrocatechol and 1,2,4-trihydroxybenzene (14). Biotransformation of DNAN to 2,4-DNP has been reported in mammals (15).We isolated bacteria able to grow on DNAN as the sole carbon source under aerobic conditions and elucidated the catabolic pathway. An initial O-demethylation catalyzed by a hydrolase was followed by degradation of the resultant 2,4-dinitrophenol by a pathway involving formation of a hydride-Meisenheimer complex (16,17). MATERIALS AND METHODSIsolation of DNAN-degrading bacteria. An activated sludge sample from Holston Army Ammunition Plant was inoculated (20% [vol/vol]) into 1/4-strength minimal salts medium (MSB) (18) (pH 6.5) containing 2,4-dinitroanisole (DNAN) (100 M), and the suspension was incubated at 30°C with shaking. Following the disappearance of DNAN as monitored by high-performance liquid chromatography (HPLC) (see below), samples (20% [vol/vol]) were repeatedly transferred into fresh medium and then spread on MSB agar (1.5%) plates containing DNAN (100 M). Individual colonies that appeared after 4 days of incubation were tested for the ability to degrade DNAN in carbon-and nitrogen-free MSB. Isolates that used DNAN as the sole source of carbon, nitrogen, and energy were selected for further study. 16S rRNA gene analysis was used for identification of the strains...

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Section: Methodsmentioning

confidence: 99%

Aerobic Biodegradation of 2,4-Dinitroanisole by Nocardioides sp. Strain JS1661

Fida

Palamuru

Pandey

et al. 2014

Appl Environ Microbiol

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“…The injection volume for all samples was 10 μl, and the wavelength for the UV detector was 254 nm. Concentrations of formaldehyde were determined using HPLC through derivatization with Nash's reagent (0.02 M of 2,4‐pentanedione and 2 M of ammonium acetate, pH 6) [45]. One milliliter of aqueous formaldehyde sample was derivatized with 1 ml of Nash's reagent for 1 h at 60°C in a water bath (Precision, Winchester, VA, USA).…”

Section: Methodsmentioning

confidence: 99%

Reductive transformation of hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine, octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine, and methylenedinitramine with elemental iron

Daniel

Kim

et al. 2005

Enviro Toxic and Chemistry

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Reductive (pre)treatment with elemental iron is a potentially useful method for degrading nitramine explosives in water and soil. In the present study, we examined the kinetics, products, and mechanisms of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) degradation with elemental iron. Both RDX and HMX were transformed with iron to formaldehyde, NH4+, N2O, and soluble products. The yields of formaldehyde were relatively constant (71% +/- 5%), whereas the yields of NH4+ and N2O varied, depending on the nitramine and the mechanism. The reactions most likely were controlled by a surface process rather than by external mass transfer. Methylenedinitramine (MDNA) was an intermediate of both RDX and HMX and was transformed quantitatively to formaldehyde with iron. However, product distributions and kinetic modeling results suggest that MDNA represented a minor reaction path and accounted for only 30% of the RDX reacted and 14% of the formaldehyde produced. Additional experiments showed that RDX reduction with elemental iron could be mediated by graphite and Fe2+ sorbed to magnetite, as demonstrated previously for nitroaromatics and nitrate esters. Methylenedinitramine was degraded primarily through reduction in the presence of elemental iron, because its hydrolysis was slow compared to its reactions with elemental iron and surface-bound Fe2+. Our results show that in a cast iron-water system, RDX may be transformed via multiple mechanisms involving different reaction paths and reaction sites.

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“…[8] Common derivatization agents for the determination of formaldehyde in various matrices include chromotropic acid, [16][17][18][19] pentafluorophenylhydrazine, [20][21][22] O-(pentafluorobenzyl)hydroxylamine, [5,6,23,24] 2,4dinitrophenylhydrazine (DNPH), [14,17,[25][26][27][28][29][30] and acetylacetone (as 4-amino-3-penten-2-one). [14,17,[31][32][33][34][35] 2,4-Dinitrophenylhydrazine is perhaps the most commonly used derivatization reagent for the analysis of formaldehyde in PCPs. [30,36] High-performance liquid chromatography (HPLC) with UV-absorbance detection is often employed for the detection of DNPH derivatives, [14,25,[28][29][30][37][38][39] although HPLC mass spectrometric methods are also used.…”

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confidence: 99%

“…[14] Most applications of the acetylacetone method use direct detection by absorbance at ≈ 410 nm, [14,17,30,32,35] although some HPLC-absorbance/fluorescence methods have been reported. [33,34,36] However, spectrophotometric methods suffer from non-specificity and matrix interferences even when HPLC is employed. HPLC with tandem mass spectrometry (MS/MS) allows for the development of compound-specific methods and the use of mass-labeled internal standards compensates for matrix effects.…”

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confidence: 99%

“…Due to its small and polar nature, formaldehyde is typically derivatized before analysis . Common derivatization agents for the determination of formaldehyde in various matrices include chromotropic acid, pentafluorophenylhydrazine, O ‐(pentafluorobenzyl)hydroxylamine, 2,4‐dinitrophenylhydrazine (DNPH), and acetylacetone (as 4‐amino‐3‐penten‐2‐one) …”

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