Optimization for biodegradation of 2,4,6-trinitrotoluene (TNT) by Pseudomonas putida

In this study, a strain of Pseudomonas putida KP-T202, isolated from the soil in a contaminated site, degraded 2,4,6-trinitrotoluene (TNT). In order to make this biodegradation process commercially feasible and reduce biodegradation time, optimal environmental factors are determined. At an initial concentration of 100 mg/l, TNT was totally degraded within 15 h under aerobic conditions. The optimal conditions for the biodegradation of TNT were found to be 30 degrees C, pH 7, 1% corn steep liquor (CSL), 0.025% NH,CI and 0.1% Tween 80; the reaction rate constant was 0.348 h(-1) These environmental conditions can be used to improve the efficiency of large-scale reactors for the treatment of TNT-contaminated wastewater and soil. In addition, the intermediates were identified as 2-amino-4,6-dinitrotoluene, 4-amino-2,6-dinitrotoluene, 2,4-dinitrotoluene and 2,6-dinitrotoluene.     

Kinetics of the alkaline hydrolysis of important nitroaromatic co-contaminants of 2,4,6-trinitrotoluene in highly contaminated soils

Until this day, large amounts of TNT and related nitroaromatic compounds are found in soils. To obtain basic data for alkaline hydrolysis of these compounds as a novel remediation technology for contaminated soils, we investigated two soils (HTNT2, ELBP2) from two former ammunition plants in Germany. Hydrolysis was performed at pH 11 and pH 12 by addition of Ca(OH)2. During treatment at pH 12 the TNT content dropped to almost zero, and the content of the aminodinitrotoluenes (2A-4,6DNT, 4A-2,6DNT) and the 2,4-dinitrotoluene (2,4-DNT) decreased by about 75% (only HTNT2) and 63%, respectively. The experimental data were described using a pseudo-first-order kinetic. Furthermore, an increase of 2,6-DNT and trinitrobenzene (TNB) as well as in one case also of TNT was initially noted in addition to hydrolysis, leading temporarily to an increase of their total amounts of up to 147%, 986%, and 122%, respectively. The results demonstrate that alkaline hydrolysis is difficult when nitroaromatics except TNT represent the major contaminants. However, regarding 2,6-DNT and TNB higher reduction rates than calculated were actually achieved by alkaline hydrolysis. In the case that TNT is the only contaminant or if it is accompanied by certain lower concentrated nitroaromatics alkaline hydrolysis is a valuable remediation technology, especially for soils that are highly contaminated.     

N-15 NMR study of the immobilization of 2,4- and 2,6-dinitrotoluene in aerobic compost

Large-scale aerobic windrow composting has been used to bioremediate washout lagoon soils contaminated with the explosives TNT (2,4,6-trinitrotoluene) and RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) at several sites within the United States. We previously used 15N NMR to investigate the reduction and binding of T15NT in aerobic bench-scale reactors simulating the conditions of windrow composting. These studies have been extended to 2,4-dinitrotoluene (2,4DNT) and 2,6-dinitrotoluene (2,6DNT), which, as impurities in TNT, are usually presentwherever soils have been contaminated with TNT. Liquid-state 15N NMR analyses of laboratory reactions between 4-methyl-3-nitroaniline-15N, the major monoamine reduction product of 2,4DNT, and the Elliot soil humic acid, both in the presence and absence of horseradish peroxidase, indicated that the amine underwent covalent binding with quinone and other carbonyl groups in the soil humic acid to form both heterocyclic and non-heterocyclic condensation products. Liquid-state 15N NMR analyses of the methanol extracts of 20 day aerobic bench-scale composts of 2,4-di-15N-nitrotoluene and 2,6-di-15N-nitrotoluene revealed the presence of nitrite and monoamine, but not diamine, reduction products, indicating the occurrence of both dioxygenase enzyme and reductive degradation pathways. Solid-state CP/MAS 15N NMR analyses of the whole composts, however, suggested that reduction to monoamines followed by covalent binding of the amines to organic matter was the predominant pathway.     

Metabolism of [14C]-2,4,6-trinitrotoluene in tobacco cell suspension cultures

The metabolism of 2,4,6-trinitrotoluene (TNT) was investigated in tobacco cell suspension cultures amended with [14C]-TNT. Five metabolites were purified and characterized. Temporal evolution of metabolites was monitored during a 120 h incubation period. Metabolites structure was identified by acid and enzymatic hydrolysis, followed by electrospray ionization mass spectrometry and 1H and 13C NMR spectroscopy analyses. The majority of metabolites were conjugates formed by glycose conjugation on the hydroxylamine group of either 2-hydroxylamino-4,6-dinitrotoluene (2-HADNT) or 4-hydroxylamino-2,6-dinitrotoluene (4-HADNT), which led to monoglycoside then to diglycoside. Various diglycosides were observed with gentiobioside or sophoroside formation. Bound residues represented a small fraction (<10% of initial 14C) irrespective of the interval after TNT amendment. Free ADNT was detected only in the medium. This study highlights the central role played by HADNT in the TNT metabolic pathway in tobacco cell suspension culture, and the key role of these compounds and of glycosyltransferases in TNT phytoremediation processes.     

Graphite-mediated reduction of 2,4-dinitrotoluene with elemental iron

The mechanism and pathway through which 2,4-dinitrotoluene (DNT) is reduced with elemental iron were investigated through batch experiments performed utilizing the same iron surface area, with high-purity iron powder and Master Builders scrap iron. In addition to different kinetics and adsorption patterns, the distribution of two intermediates, 4-amino-2-nitrotoluene (4A2NT) and 2-amino-4-nitrotoluene (2A4NT), contrasted sharply. This suggests that different mechanisms are involved in DNT reduction with pure iron and scrap iron. We hypothesized that exposed graphite in scrap iron transferred reductants from iron to adsorbed nitroaromatic molecules. This hypothesis was supported by an experiment conducted using two-compartment dialysis cells in which ONT and pure iron powder were separated by a graphite sheet. Results indicate that graphite-mediated, indirect reduction of DNT occurred primarily through reduction of the ortho nitro group to form 2A4NT, whereas DNT reduction at the iron (hydr/oxide) surface occurred via para nitro reduction to give 4A2NT. Based on pH and product analysis, atomic hydrogen probably accounted for most of the reducing equivalents that passed through the graphite, reacting with adsorbed DNT mainly through ortho nitro reduction. In contrast, electron was a minor fraction of the reducing equivalents, reducing DNT mainly through para nitro reduction. The implications of graphite as a reaction site and conductor of electron and atomic hydrogen are discussed with respect to treatment processes involving iron.     

15N NMR investigation of the covalent binding of reduced TNT amines to soil humic acid,model compounds,and lignocellulose

The five major reductive degradation products of TNT-4ADNT (4-amino-2,6-dinitrotoluene), 2ADNT (2-amino-4,6-dinitrotoluene), 2,4DANT (2,4-diamino-6-nitrotoluene), 2,6DANT (2,6-diamino-4-nitrotoluene), and TAT (2,4,6-triaminotoluene)-labeled with 15N in the amine positions, were reacted with the IHSS soil humic acid and analyzed by 15N NMR spectrometry. In the absence of catalysts, all five amines underwent nucleophilic addition reactions with quinone and other carbonyl groups in the soil humic acid to form both heterocyclic and nonheterocyclic condensation products. Imine formation via 1,2-addition of the amines to quinone groups in the soil humic acid was significant with the diamines and TAT but not the monoamines. Horseradish peroxidase (HRP) catalyzed an increase in the incorporation of all five amines into the humic acid. In the case of the diamines and TAT, HRP also shifted the binding away from heterocyclic condensation product toward imine formation. A comparison of quantitative liquid phase with solid-state CP/MAS 15N NMR indicated that the CP experiment underestimated imine and heterocyclic nitrogens in humic acid, even with contact times optimal for observation of these nitrogens. Covalent binding of the mono- and diamines to 4-methylcatechol, the HRP catalyzed condensation of 4ADNT and 2,4DANT to coniferyl alcohol, and the binding of 2,4DANT to lignocellulose with and without birnessite were also examined.     

Enhanced degradation of 2,4,6-trinitrotoluene (TNT) in a soil column planted with Indian mallow (Abutilon avicennae)

Phytoremediation of soil contaminated with 2,4,6-trinitrotoluene (TNT) was studied by growing Indian mallow (Abutilon avicennae) in a soil column reactor with 2 kg of TNT contaminated soil (120 mgTNT/kg) in the top and 18 kg of uncontaminated soil in the bottom. After 50 d, TNT remaining in the column with Indian mallow was 23.2% of the initial TNT, while 48.1% of the initial TNT remained in the column without Indian mallow. In the TNT contaminated column, the growth of Indian mallow decreased by 32.4% in roots and 34.3% in shoots on a dry weight basis, respectively, compared to the uncontaminated column. However, critical symptoms such as chlorosis and leaf loss were not observed. Of the 76.8% of the TNT that disappeared in the planted column, less than 0.2% of initial TNT was recovered in the shoot and root extracts of Indian mallow. TNT transformation products in plants include unidentified polar intermediates and aminodinitrotoluenes. The results showed that planting Indian mallow in TNT contaminated soil enhanced TNT reduction both by stimulating microbial activity that enhances microbial TNT transformation, and by direct uptake and phytotransformation of TNT.     

Synthesis of octabrominated diphenyl ethers from aminodiphenyl ethers

Polybrominated diphenyl ethers (PBDEs) are additive brominated flame retardants (BFRs), which have become widespread pollutants in abiotic and biotic environments including man. Tetra- to hexaBDEs and decaBDE are the most common environmental PBDE contaminants. Congeners of octabromodiphenyl ethers (octaBDEs) originate from used industrial OctaBDE mixtures and from transformation products of the high-volume industrial BFR mixture "DecaBDE", which most exclusively consists of perbrominated diphenyl ether (BDE-209). The objective of the present work was to develop methods for the synthesis of authentic octaBDE congeners in order to make them available as standards for analytical, toxicological, and stability studies, as well as studies concerning physical-chemical properties. The syntheses of six octaBDEs, 2,2',3,3',4,4',5,5'-octabromodiphenyl ether (BDE-194), 2,2',3,3',4,4',5,6'-octabromodiphenyl ether (BDE-196), 2,2',3,3',4,5,5',6-octabromodiphenyl ether (BDE-198), 2,2',3,3',4,5',6,6'-octabromodiphenyl ether (BDE-201), 2,2',3,3',5,5',6,6'-octabromodiphenyl ether (BDE-202), and 2,2',3,4,4',5,6,6'-octabromdipheny ether (BDE-204), are described, of which BDE-204 was prepared via two different pathways. Syntheses of BDE-198, BDE-201, BDE-202, and BDE-204 are based on octabromination of mono- or diaminodiphenyl ethers followed by diazotization and reduction of the amino group(s). BDE-194 and BDE-196 were prepared by bromination of 3,3',4,4',5,5'-hexabromodiphenyl ether (BDE-169) and 2,3,3',4,4',5',6-heptabromodiphenyl ether (BDE-191), respectively, and BDE-169 and BDE-191 were prepared from 4,4'-diaminodiphenyl ether and 3,4'-diamiodiphenyl ether, respectively. The synthesized PBDE congeners are described by 1H NMR, 13C NMR, electron ionization mass spectra, and their melting points.     

Reactivity of partially reduced arylhydroxylamine and nitrosoarene metabolites of 2,4,6-trinitrotoluene (TNT) toward biomass and humic acids

Sequential anaerobic/aerobic treatment of 2,4,6-trinitrotoluene (TNT) generally results in the incorporation of residues into biomass and natural organic matter fractions of a system. To better understand the potential contribution of hydroxylamine and nitroso moieties in these reactions, studies were conducted using model systems taking advantage of the biocatalytic-activity of Clostridium acetobutylicum that does not produce aminated TNT derivatives. To evaluate binding to biomass only, systems containing cell-free extracts of C. acetobutylicum and molecular hydrogen as a reductant were employed. At the end of treatment, mass balance studies showed that 10% of the total 14C was associated with an insoluble protein-containing precipitate that could not be extracted with organic solvents. Model reactions were conducted between a mixture of 2,4-dihydroxylamino-6-nitrotoluene (DHA6NT) and 4-hydroxylamino-2,6-dinitrotoluene (4HADNT) and 1-thioglycerol to test the involvement of the nitroso-thiol reaction in binding to biomass. It was demonstrated that DHA6NT formed a new and relatively polar product with 1-thioglycerol only in the presence of oxygen. The oxygen requirement confirmed that the nitroso functionality was responsible for the binding reaction. The reactivity of arylhydroxylamino and nitrosoarene functionalities toward International Humic Substance Society (IHSS) peat humic acid was evaluated under anaerobic and aerobic conditions, respectively. 4HADNT showed no appreciable reactivity toward peat humic acid. Conversely, the nitrosoarene compound, nitrosobenzene, showed rapid reactivity with peat humic acid (50% removal in 48 h). When tested with two other humic acids (selected on the basis of their protein content), it became apparent that the proteinaceous fraction was responsible at least in part for the nitrosoarene's removal from solution. Furthermore, the pretreatment of the humic acids with a selective thiol derivatizing agent had a considerable effect on their ability to react with nitrosobenzene. Finally, molecular modeling tools were used to compare the electrophilic characteristics of potential nitroso intermediates forming from the oxidation of arylhydroxylamino metabolites of TNT. Molecular modeling analysis demonstrated that the more reduced TNT derivative containing nitroso groups were more likely to react with nucleophiles in humic substances than the less reduced nitroso intermediates.     

Soil column evaluation of factors controlling biodegradation of DNT in the vadose zone

High concentrations of 2,4-dinitrotoluene (2,4-DNT) and 2,6-dinitrotoluene (2,6-DNT) are present in vadose zone soils at many facilities where explosives manufacturing has taken place. Both DNT isomers can be biodegraded under aerobic conditions, but rates of intrinsic biodegradation observed in vadose zone soils are not appreciable. Studies presented herein demonstrate that nutrient limitations control the onset of rapid 2,4-DNT biodegradation in such soils. In column studies conducted at field capacity, high levels of 2,4-DNT biodegradation were rapidly stimulated by the addition of a complete mineral medium but not by bicarbonate-buffered distilled deionized water or by phosphate-amended tap water. Biodegradation of 2,6-DNT was not observed under any conditions. Microcosm studies using a DNT-degrading culture from column effluent suggest that, after the onset of 2,4-DNT degradation, nitrite evolution will eventually control the extent of degradation achieved by two mechanisms. First, high levels of nitrite (40 mM) were found to strongly inhibit 2,4-DNT degradation. Second, nitrite production reduces the solution pH, and at pH levels below 6.0, 2,4-DNT degradation slows rapidly. Under conditions evaluated in laboratory-scale studies, 2,4-DNT biodegradation enhanced the rate of contaminant loss from the vadose zone by a factor of 10 when compared to the washout due to leaching.     

Characterization of aromatic compound sorptive interactions with black carbon (charcoal) assisted by graphite as a model

Molecular interactions controlling the sorption of pollutants to environmental black carbons (soot, charcoal) are not well-resolved. Sorption of a series of aromatic compounds was studied to wood charcoal and nonporous graphite powder as a model adsorbent. Issues of concern were the possible involvement of pi-pi electron donor-acceptor (EDA) interactions of electron-poor and electron-rich solutes with the graphene (polycyclic aromatic) surface and size exclusion effects. Sorption of pi-acceptors, benzonitrile (BNTL), 4-nitrotoluene (MNT), 2,4-dinitrotoluene (DNT), and 2,4,6-trinitrotoluene (TNT), and to a lesser extent pi-donor solutes, naphthalene (NAPH) and phenanthrene (PHEN), was greater than predicted by hydrophobic driving forces in accord with their acceptor or donor strength. Hydrophobic effects were estimated using a concentration-dependent free energy relationship between adsorption and partitioning into an inert solvent (n-hexadecane or benzene) for a non-donor/non-acceptor calibration set (benzene and chlorinated and methylated benzenes). Molecular complexation between acceptors and model graphene donors, NAPH, PHEN, and pyrene (PYR), in chloroform and benzene was tracked by ring-current induced upfield shifts in the 1H NMR spectrum and by charge-transfer bands in the UV/visible spectrum. The EDA component of graphite-water adsorption for the acceptors correlated with the NMR-determined complexation constant with the model donors in chloroform, which, in turn, correlated with pi-acceptor strength (TNT > DNT > MNT > BNTL) and pi-donor strength (PYR > PHEN > NAPH). Charcoal-graphite isotherms calculated from charcoal-water and graphite-water isotherms indicated molecular sieving effects on charcoal for tetrasubstituted benzenes (tetramethylbenzenes and TNT) and some trisubstituted benzenes (1,3,5-trichlorobenzene, possibly DNT). When steric effects are taken into account, the order in adsorption among acceptors was qualitatively similar for graphite and charcoal. The results suggest pi-pi EDA interactions of the acceptors-and possibly donors, although the calibration set may underestimate the hydrophobic effect for fused ring systems-with both graphite and charcoal surfaces. For graphite, it is postulated that pi-acceptors interact with electron-rich regions of the basal plane near edges and defects and that pi-donors interact with electron-depleted regions further away. A similar mechanism may operate on the charcoal but would be modified by the (mostly) electron-withdrawing effects of 0 functionality on the edges of graphene sheets.     

Mechanisms of dioxin formation from the high-temperature oxidation of 2-chlorophenol

The homogeneous, gas-phase oxidative thermal degradation of 2-chlorophenol was studied in a 1 cm i.d., fused silica flow reactor at a concentration of 88 ppm, reaction time of 2.0 s, over a temperature range of 300 to 1000 degrees C. Observed products in order of yield were as follows: 4,6-dichlorodibenzofuran (4,6-DCDF) > dibenzo-p-dioxin (DD) > 1-monochlorodibenzo-p-dioxin (1-MCDD), 4-chlorodibenzofuran (4-MCDF), dibenzofuran (DF), naphthalene, chloronaphthalene, 2,4-dichlorophenol, 2,6-dichlorophenol, phenol, chlorobenzene, and benzene. In contrast to pyrolysis, 4,6-DCDF is the major product rather than DD, and 1-MCDD and naphthalene are formed at temperatures as low as 400 degrees C. Under oxidative conditions, .OH and Cl. are the major carriers, which favors 4,6-DCDF formation over DD or 1-MCDD through abstraction of H. through diketo- and ether- intermediates. It is proposed that below 500 degrees C, unimolecular tautomerization/HCI elimination and CO elimination/isomerization reactions result in the formation of 1-MCDD and naphthalene, respectively.     

Determination of benzotriazole and benzophenone UV filters in sediment and sewage sludge

Benzophenones and benzotriazoles are widely used as ultraviolet (UV) light filters and stabilizers in cosmetics, skin creams, and body lotions and as corrosion inhibitors in building materials, automobile components, and automotive antifreeze cooling systems. Benzophenones and benzotriazoles have been reported to occur in the environment. Some of these UV filters have been reported to possess significant estrogenic activity. Despite this, very few studies have examined their occurrence and profiles in the environment. In this work, we determined five benzophenone-type UV filters and two benzotriazole-type corrosion inhibitors, namely, 2-hydroxy-4-methoxybenzophenone (2OH-4MeO-BP), 2,4-dihydroxybenzophenone (2,4OH-BP), 2,2'-dihydroxy-4-methoxybenzophenone (2,2'OH-4MeO-BP), 2,2',4,4'-tetrahydroxybenzophenone (2,2',4,4'OH-BP), 4-hydroxybenzophenone (4OH-BP), 1H-benzotriazole (1H-BT), and 5-methyl-1H-benzotriazole (5Me-1H-BT), in sediment and sewage sludge samples, using liquid-liquid extraction and liquid chromatography-tandem mass spectrometry (LC-MS/MS). In addition, four benzotriazole-type UV stabilizers, namely, 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole (UV-326), 2,4-di-t-butyl-6-(5-chloro-2H-benzotriazole-2-yl) phenol (UV-327), 2-(2H-benzotriazole-2yl)-4,6-di-t-pentylphenol (UV-328), and 2-(5-t-butyl-2-hydroxyphenyl) benzotriazole (TBHPBT) were determined by gas chromatography (GC)-mass spectrometry (MS). The limits of quantitation (LOQ) were in the ranges of 0.06-0.33 ng g?1 dry weight (dw) and 0.1-1.65 ng g?1 dw for sediment and sludge samples, respectively. Recoveries of target compounds spiked into sample matrices and passed through the entire analytical procedure ranged from 70% to 116% (RSD: 3.32-13.8%) and from 82% to 106% (RSD: 2.89-8.09%) for the compounds analyzed by LC-MS/MS and GC-MS, respectively. The methods were applied to the analysis of sediment samples from the Songhua, Saginaw, and Detroit Rivers; the sum concentrations of target compounds were 3.29-9.93, 5.81-22.5, and 190-389 ng g?1 dw, respectively. Five sludge samples collected from five wastewater treatment plants in northeastern China contained the sum concentrations of target compounds in the range of 104-6370 ng g?1 dw. The concentration of UV-328 in sludge was the highest (mean: 1300 ng g?1 dw) among the target compounds. To our knowledge, this is the first work to report the occurrence of 2OH-4MeO-BP, 2,4OH-BP, 2,2'OH-4MeO-BP, 2,2',4,4'OH-BP, and 4OH-BP in sediment and sludge samples.     

Structures and pesticidal activities of derivatives of dinitrophenols. IX. Effects of substitution of dinitrophenols with C4 to C13 alpha-branched alkyl groups and of esterification on the eradication of apple mildew

The eradication of apple mildew caused by Podosphaera leucotricha (Ell. and Everh.) Salm. with 2-(C₄ to C₁₃ α-branched alkyl)-4,6-dinitrophenols and 4-(C₄ to C₁₃ α-branched alkyl)-2,6-dinitrophenols was examined. 4-(1-Ethylbutyl)- and most 4-(C₇ to C₁₂ α-branched alkyl)-2,6-dinitrophenols were significantly more active than their 2-alkyl-4,6-dinitrophenol analogues. Compounds containing 4-C₁₃ alkyls did not show significant activity. Activity generally increased as the α-alkyl branch lengthened. Methyl carbonates did not show lower activity than the parent phenols, but esterification of 4-(C₁₂ or C₁₃ α-branched alkyl)-2,6-dinitrophenols to ethyl carbonates or crotonates gave compounds with reduced activity. Methyl-, ethyl- or isopropyl-carbonates and crotonates of 4-(1-ethylhexyl)-2,6-dinitrophenol had much higher activity than the corresponding esters of the 4-(1-methylheptyl) isomer or of 2-(1-ethyl-hexyl)-4,6-dinitrophenol. Compounds containing long ester chains (C₇ or C₈) had less activity than 4-(1-ethylhexyl)-2,6-dinitrophenol. O-Methylation produced compounds with less activity than the parent 4-(1-ethylhexyl)- and 4-(1-propyl-pentyl)-2,6-dinitrophenols.     

Structures and pesticidal activities of derivatives of dinitrophenols. 8. Effects of substitution with C5 to C13-s-alkyl groups and of esterification on the acaricidal activity of dinitrophenols

38 methyl-, 37 ethyl- and 19 other alkyl-carbonates, 37 crotonates, 10 acrylates and 17 other esters, and 15 methyl ethers of 2-(C₅ to C₁₃-s-alkyl)-4,6-dinitro- and 4-(C₄ t4 to C₁₃-s-alkyl)-2,6-dinitrophenols were synthesised, and their activities against Tetranychus telarius (greenhouse red spider mite) were investigated. 2-s-Alkyl-4,6-dinitrophenols and esters were more active than their 4-s-alkyl-2,6-dinitro- analogues, acaricidal activity remaining high with the 4,6-dinitrophenols up to 2-(C₁₁-s-alkyl). Generally compactness of the 2-s-alkyl group aided activity. Methyl ethers had very low activity. Esters of 2-(C₃ to C₇-s-alkyl)-4,6-dinitrophenols were more acaricidal than the parent phenols, but the reverse was the case with C₈ to C₁₃-s-alkyl compounds. Crotonates and other esters were generally less active than methyl carbonates. The methyl carbonates of 2-(1-ethylhexyl)- and 2-(1-propylpentyl)-4,6-dinitrophenols were found to be of particular economic interest as acaricides.     

Structures and pesticidal activities of derivatives of dinitrophenols. XI. Effects of substitution of dinitrophenols with C3 to C13 alpha-branched alkyl groups and of esterification on the eradication of cucumber mildew

The eradication of cucumber mildew caused by Sphaerotheca fuliginea (Schlecht. ex Fr.) Poll. with 2-(C₄ to C₁₃ α-branched alkyl)-4,6-dinitrophenols and 4-(C₄ to C₁₃ α-branched alkyl)-2,6-dinitrophenols was examined. 2-(C₈ to C₁₃ α-Branched alkyl)-4,6-dinitrophenols were highly active, but O-methylation produced compounds with no activity. 4-(C₇ to C₁₀ and several C₁₁ to C₁₃ α-branched alkyl)-2,6-dinitro-phenols gave a significant degree of eradication. 2-(C₆ to C₁₃ α-Branched alkyl)-4,6-dinitrophenols were significantly more active than their 4-alkyl-2,6-dinitrophenol analogues. Esterification of C₄ to C₇ α-branched alkyl dinitrophenols to methyl- or ethyl- carbonates or crotonates gave compounds with enhanced activity. Generally, the methyl- or ethyl- carbonates or 2-C₈-alkyl-4,6-dinitrophenols were as active as the parent phenols, but the higher alkyl carbonates or crotonates had lower activity. Esterification of 2-(C₉ to C₁₃ α-branched alkyl)-4,6-dinitrophenols to ethyl carbonates and crotonates gave compounds with reduced activity.     

Sequential electrolytic oxidation and reduction of aqueous phase energetic compounds

Contamination of soils and groundwater with energetic compounds has been documented at many former ammunition manufacturing plants and ranges. Recent research at Colorado State University (CSU) has demonstrated the potential utility of electrolytic degradation of organic compounds using an electrolytic permeable reactive barrier (e-barrier). In principle, an electrolytic approach to degrade aqueous energetic compounds such as hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) or 2,4,6-trinitrotoluene (TNT) can overcome limitations of management strategies that involve solely oxidation or reduction, through sequential oxidation-reduction or reduction-oxidation. The objective of this proof-of-concept research was to evaluate transformation of aqueous phase RDX and TNT in flow-through electrolytic reactors. Laboratory experiments were conducted using six identical column reactors containing porous media and expanded titanium-mixed-metal-oxide electrodes. Three columns tested TNT transformation and three tested RDXtransformation. Electrode sequence was varied between columns and one column for each contaminant acted as a no-voltage control. Over 97% of TNT and 93% of RDX was transformed in the reactors under sequential oxidation-reduction. Significant accumulation of known degradation intermediates was not observed under sequential oxidation-reduction. Removal of approximately 90% of TNT and 40% of RDX was observed under sequential reduction-oxidation. Power requirements on the order of 3 W/m2 were measured during the experiment. This suggests that an in-situ electrolytic approach may be cost-practical for managing groundwater contaminated with explosive compounds.     

Mechanisms of dioxin formation from the high-temperature pyrolysis of 2-bromophenol

Brominated hydrocarbons are the most commonly used flame retardants. Materials containing brominated hydrocarbons are frequently disposed in municipal and hazardous waste incinerators as well as being subjected to thermal reaction in accidental fires. This results in the potential for formation of brominated dioxins and other hazardous combustion byproducts. In contrast to chlorinated hydrocarbons, the reactions of brominated hydrocarbons have been studied only minimally. As a model brominated hydrocarbon that may form brominated dioxins, we studied the homogeneous, gas-phase pyrolytic thermal degradation of 2-bromophenol in a 1-cm i.d., fused-silica flow reactor at a concentration of 90 ppm, with a reaction time of 2.0 s, and over a temperature range of 300 to 1000 degrees C. Observed products included dibenzo-p-dioxin (DD), 1-monobromodibenzo-p-dioxin (1-MBDD), 4-monobromodibenzofuran (4-MBDF), dibenzofuran (DF), naphthalene, bromonaphthalene, 2,4- and 2,6-dibromophenol, phenol, bromobenzene, and benzene. These results are compared and contrasted with previous results reported for 2-chlorophenol. At temperatures lower than 700 degrees C, formation of 2-bromophenoxyl radical, which decomposes through CO elimination to form a bromocyclopentadienyl radical, forms naphthalene and 2-bromonaphthalene through radical recombination/rearrangement reactions. However, unlike the results for 2-chlorophenol, where naphthalene is the major product, DD becomes the major product for the pyrolysis of 2-bromophenol. The formation of DD and 1-MBDD are attributed to radical-radical reactions involving 2-bromophenoxyl radical with the carbon- (bromine) centered radical and the carbon- (hydrogen) centered radical mesomers of 2-bromophenoxyl radical, respectively. The potential product, 4,6-dibromodibenzofuran (4,6-DBDF) for which the analogous product, 4,6-dichlorodibenzofuran (4,6 DCDF), was observed in the oxidation of 2-chlorophenol, was not detected. This is attributed to the pyrolytic conditions of our experiments (e.g., shorter reaction times and higher temperatures) that favor reaction intermediates that form DD and 1-MBDD.     

Structures and pesticidal activities of derivatives of dinitrophenols. X. Effects of substitution od dinitrophenols with C3 to C13 alpha-branched alkyl groups and of esterification on the eradication of barley mildew

The studies of the eradication of barley mildew due to Erysiphe graminis Mérat with alkyldinitrophenols reported earlier¹ were continued. The degree of eradication was highest with 4-(C₉ α-branched alkyl)-2,6-dinitrophenols. 4-Alkyl-2,6-dinitrophenols containing a heptyl or higher alkyl branch were significantly less active, and compounds containing the C₁₂ or C₁₃ alkyls were not active since the most compact of the C₁₂ α-branched alkyls is 1-pentylheptyl. 2-(1-Methylheptyl)- and 2-(1-propylpentyl)-4,6-dinitrophenols had high activity, but their esters showed reduced activity. Esterification of 4-(α-branched alkyl)-2,6-dinitrophenols to methyl carbonates did not affect the activity shown by the compounds, but when certain 4-C₁₀ and C₁₁ alkyl-2,6-dinitrophenols were esterified to ethyl carbonates the activity of the products was reduced. Also activity was diminished by conversion of some 4-C₉ and C₁₀ alkyl-2,6-dinitrophenols to crotonates. Whereas the methyl- and ethyl- carbonates of 4-(1-ethylhexyl)-2,6-dinitrophenol gave consistently high degrees of eradication of barley mildew, the performance of the crotonate of this phenol was not consistent. Lower aliphatic esters of the active C₈-alkyl phenols were themselves active. Esterification of 4-(1-ethylhexyl)-2,6-dinitrophenol to the benzoate, isopropyl carbonate or S-methyl thiolocarbonate gave compounds with substantially reduced activity. 2-t-Butyl-4,6-dinitrophenyl or 4-t-butyl- or t-octyl-2,6-dinitrophenyl esters gave little or no significant eradication.