Biodegradation of RDX within soil-water slurries using a combination of differing redox incubation conditions

Biodegradation of 14C-tagged hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) was studied in aerobic, anaerobic, and anaerobic/aerobic slurries to identify the conditions maximizing RDX-mineralization in Cornhusker Army Ammunition Plant (CAAP, NE) groundwater. Supplementation with phosphate and adequate quantities of acetate caused 25% mineralization of RDX in 3 weeks by microorganisms native to CAAP. Under anaerobic conditions, the same supplementation resulted in 20% mineralization in 3 weeks and 30% mineralization in 6 weeks. The highest degree of mineralization (50%) was obtained under aerobic conditions when the contaminated groundwater was augmented with a consortium of three microbes isolated from another RDX contaminated soil (Hastings, NE) in addition to supplemented with phosphate and acetic acid. Use of complex organic sources (potato or corn starch) slowed down the rates of mineralization under anaerobic conditions, but rapid mineralization ensued as soon as the aerobic conditions were created. Final RDX concentrations in aqueous phase were below detection limit under most conditions. Assimilation of RDX by the cells was negligible.     

Secondary electrospray ionization-ion mobility spectrometry for explosive vapor detection

The unique capability of secondary electrospray ionization (SESI) as a nonradioactive ionization source to detect analytes in both liquid and gaseous samples was evaluated using aqueous solutions of three common military explosives: cyclo-1,3,5-trimethylene-2,4,6-trinitramine (RDX), nitroglycerin (NG) and pentaerythritol tetranitrate (PETN). The adducts formed between the compounds and their respective dissociation product, RDX.NO(2)(-), NG.NO(3)(-), and PETN.NO(3)(-), gave the most intense signal for the individual compound but were more sensitive to temperature than other species. These autoadducts were identified as RDX.NO(2)(-), NG.NO(3)(-), and PETN.NO(3)(-) and had maximum signal intensity at 137, 100, and 125 degrees C, respectively. The reduced mobility values of the three compounds were constant over the temperature range from 75 to 225 degrees C. The signal-to-noise ratios for RDX, NG, and PETN at 50 mg L(-1) in methanol-water were 340, 270, and 170, respectively, with a nominal noise of 8 +/- 2 pA. In addition to the investigation of autoadduct formation, the concept of doping the ionization source with nonvolatile adduct-forming agents was investigated and described for the first time. The SESI-IMS detection limit for RDX was 116 microg L(-1) in the presence of a traditional volatile chloride dopant and 5.30 microg L(-1) in the presence of a nonvolatile nitrate dopant. In addition to a lower detection limit, the nitrate dopant also produced a greater response sensitivity and a higher limit of linearity than did the traditional volatile chloride dopant.     

Kinetics of RDX degradation by zero-valent iron (ZVI)

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is a common groundwater contaminant at military facilities. The current research has been conducted to evaluate the use of zero-valent iron (ZVI) for the remediation of water contaminated with RDX. RDX was found to degrade rapidly in the presence of ZVI. The observed first-order kinetic constant for RDX reduction follows an enzymatic-like kinetic model with respect to the ZVI concentration. At low ZVI concentrations, RDX reduction follows pseudo first order kinetics with respect to ZVI concentration; while at high ZVI concentrations the RDX reduction is zero-order. Nitroso compounds (MNX, DNX, and TNX), nitrate, nitrite and nitrous oxide were identified as the main by-products for the RDX reduction by ZVI. The nitroso compounds were found to undergo reduction by ZVI.     

Detoxification of PAX-21 ammunitions wastewater by zero-valent iron for microbial reduction of perchlorate

US Army and the Department of Defense (DoD) facilities generate perchlorate (ClO₄⁻) from munitions manufacturing and demilitarization processes. Ammonium perchlorate is one of the main constituents in Army's new main charge melt-pour energetic, PAX-21. In addition to ammonium perchlorate, hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and 2,4-dinitroanisole (DNAN) are the major constituents of PAX-21. In order to evaluate microbial perchlorate reduction as a practical option for the treatment of perchlorate in PAX-21 wastewater, we conducted biodegradation experiments using glucose as the primary sources of electrons and carbon. Batch experiments showed that negligible perchlorate was removed in microbial reactors containing PAX-21 wastewater while control bottles containing seed bacteria and glucose rapidly and completely removed perchlorate. These results suggested that the constituents in PAX-21 wastewater may be toxic to perchlorate reducing bacteria. A series of batch toxicity test was conducted to identify the toxic constituents in PAX-21 and DNAN was identified as the primary toxicant responsible for inhibiting the activity of perchlorate reducing bacteria. It was hypothesized that pretreatment of PAX-21 by zero-valent iron granules will transform toxic constituents in PAX-21 wastewater to non-toxic products. We observed complete reduction of DNAN to 2,4-diaminoanisole (DAAN) and RDX to formaldehyde in abiotic iron reduction study. After a 3-day acclimation period, perchlorate in iron-treated PAX-21 wastewater was rapidly decreased to an undetectable level in 2 days. This result demonstrated that iron treatment not only removed energetic compounds but also eliminated the toxic constituents that inhibited the subsequent microbial process.     

Relationships between acute toxicities of para nitrophenol (p-NP) and nitrobenzene (NB) to Daphnia magna and Photobacterium phosphoreum: physicochemical properties and metabolites under anaerobic/aerobic sequentials

In this study, the acute toxicities of nitrobenzene (NB) and para nitrophenol (p-NP) were investigated in a high rate sequential anaerobic migrating blanket (AMBR)/aerobic completely stirred tank reactor (CSTR) using Microtox and Daphnia magna tests. After sequential anaerobic and aerobic treatments, the inhibitions in the Microtox bacteria decreased from an initial 78.10-48.20% and 4.00%, respectively, in wastewater containing 40.00 mg/L p-NP. The inhibitions of the influent wastewater containing 60.00 mg/L NB decreased from 72.10% to 45.30% and to 4.00% after anaerobic and aerobic treatment, respectively. The acute toxicity removals were 94% and 93% in the effluent of the whole sequential system, for p-NP and NB, respectively. The acute toxicity in the influent was dependent on the parent NB and p-NP concentrations and ons their physicochemical properties such as hydrophobicity, octanol/water partition coefficient and vapour density for both Microtox bacteria and Daphnia magna while the toxicity in the effluent of the anaerobic reactor was strongly dependent on the metabolites of p-NP (p-amino phenol, phenol, NH(4)-N) and NB (aniline) for Microtox test. This effluent was not toxic to Daphnia magna.     

氧化木薯淀粉与丙烯酸丁酯/醋酸乙烯酯的接枝共聚反应研究

以过硫酸铵为引发剂,以氧化后的木薯淀粉为接枝骨架,制备了氧化淀粉-丙烯酸丁酯-醋酸乙烯酯接枝共聚物.考察了氧化剂浓度对黏度及引发剂浓度、单体浓度、反应温度和反应时间对接枝率、接枝效率的影响.实验结果表明,在氧化剂浓度为0.04mol/L,引发剂浓度为9×10-3mol/L,单体浓度为1.0mol/L,反应温度为65℃,反应3h时,反应体系的接枝率和接枝效率较高.通过红外光谱对接枝共聚物进行了结构表征.     

Preparation of explosive nanoparticles in a porous chromium(III) oxide matrix: a first attempt to control the reactivity of explosives

This paper reports the first attempt to control the combustion and the detonation properties of a high explosive through its structure. A porous chromium(III) oxide matrix produced by the combustion of ammonium dichromate was infiltrated by hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). The structure of the Cr(2)O(3) matrix was studied by both scanning and transmission electron microscopy (SEM, TEM); the Cr(2)O(3)/RDX nanocomposites were characterized by nitrogen adsorption. A mathematical model based on these techniques was used to demonstrate that the Cr(2)O(3) matrix encloses and stabilizes RDX particles at the nanoscale. The decomposition process of the nanocomposites was investigated by atomic force microscopy (AFM). The reactivity and sensitivity of the nanocomposites were studied by impact and friction tests, differential scanning calorimetry (DSC), time-resolved cinematography and detonation experiments, and were correlated with their structure. The size of RDX nanoparticles and their distribution in the Cr(2)O(3) matrix have an important influence on their reactivity. The reactive properties of nanostructured RDX differ significantly from those of classical micron-sized RDX. For instance, the melting point disappears and the decomposition temperature is significantly lowered. The quantization of the explosive particles in the Cr(2)O(3) matrix decreases the sensitivity to mechanical stress and allows controlling the decomposition mode-i.e.?combustion versus detonation.     

Preparation and characterization of GA/RDX nanostructured energetic composites

Graphene aerogel (GA) with nano-porous structure was assembled through the formation of physical cross-links between graphene sheets by a facile sol–gel method and supercritical CO ₂ drying process. Then hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) was added and trapped in the nano-porous three-dimensional networks of GA to obtain a novel GA/RDX nanostructured energetic composite. The composition, morphology and structure of the obtained GA/RDX nanostructured energetic composite were characterized by elemental analysis, scanning electron microscopy, nitrogen sorption tests and X-ray diffraction. Moreover, the thermal decomposition characteristic was investigated by thermogravimetry and differential scanning calorimetry. The results showed that GA could be a perfect aerogel matrix for the fabrication of GA/RDX nanostructured energetic composite due to its unique nano-porous structure and attributes. It was also demonstrated that RDX homogeneously disperses in the as-prepared GA/RDX nanostructured energetic composite at nanometric scale. GA showed promising catalytic effects for the thermal decomposition of RDX. After incorporating with GA, the decomposition of RDX was obviously accelerated.     

Fluorescence quenching as an indirect detection method for nitrated explosives

A novel approach based on fluorescence quenching is presented for the analysis of nitrated explosives. Seventeen common explosives and their degradation products are shown to be potent quenchers of pyrene, having Stern-Volmer constants that generally increase with the degree of nitration. Aromatic explosives such as 2,4,6-trinitrotoluene (2,4,6-TNT) are more effective quenchers than aliphatic or nitramine explosives. In addition, nitroaromatic explosives are found to have unique interactions with pyrene that lead to a wavelength dependence of their Stern-Volmer constants. This phenomenon allows for their differentiation from other nitrated explosives. The fluorescence quenching method is then applied to the determination of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazine(HMX), 2,4,6-TNT, nitromethane, and ammonium nitrate in various commercial explosive samples. The samples are separated by capillary liquid chromatography with post-column addition of the pyrene solution and detection by laser-induced fluorescence. The indirect fluorescence quenching method shows increased sensitivity and selectivity over traditional UV-visible absorbance as well as the ability to detect a wider range of organic and inorganic nitrated compounds.     

Thermal reactivity of some nitro- and nitroso-compounds derived from 1,3,5,7-tetraazabicyclo[3.3.1]nonane at contamination by ammonium nitrate

Thermal reactivity of 3,7-dinitro-1,3,5,7-tetraazabicyclo[3.3.1]nonane (DPT), 3,7-dinitroso-1,3,5,7-tetraazabicyclo[3.3.1]nonane (DNPT), 1,3,5-trinitroso-1,3,5-triazinane (TMTA or R-salt), 1,3,5-trinitro-1,3,5-triazinane (hexogen or RDX), 1,5-diacetyl-3,7-dinitro-1,3,5,7-tetrazocane (DADN), alpha-modification of the 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (octogen or HMX) and of their mixtures with 2wt.% of ammonium nitrate (AN) has been examined by means of non-isothermal differential thermal analysis. The resulting data were analyzed according to the Kissinger method. The reactivity was expressed as the E(a)R(-1) slopes of the Kissinger relationship. A relatively high reactivity has been found with mixtures of DPT and DNPT with AN. Electronic charges q(N) at nitrogen atoms in molecules of the compounds studied were calculated by means of ab initio DFT B3LYP/6-31G** method. The relationships were confirmed between the slopes E(a)R(-1) and the q(N) values for the nitrogen atoms primarily undergoing reaction. On the basis of these relationships it is stated that the destabilizing effect of AN is due to acidolytic attack of nitric acid (resulting from dissociation of ammonium nitrate) at the nitrogen atoms with the most negative q(N) values in the molecules of the compounds studied.     

Reductive transformation of 2,4,6-trinitrotoluene, hexahydro-1,3,5-trinitro-1,3,5-triazine, and nitroglycerin by pyrite and magnetite

Reductive transformation of 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and nitroglycerin (NG) by pyrite (FeS(2)) and magnetite (Fe(3)O(4)) was investigated to determine the role of Fe(II)-bearing minerals on the fate of toxic explosives in Fe/S-rich natural environment. Results from batch experiments showed that 65% of TNT and 45% of RDX were transformed from solution in the presence of pyrite under pH 7.4 buffered conditions within 32 days. Without a buffered solution, transformation of TNT and RDX decreased. NG was continuously and rapidly transformed by pyrite under both conditions. Complete removal of NG was achieved in 32 days under buffered conditions. NH(4)(+) was identified as a reduction product for RDX and NG in the pyrite-water system. Reductive transformation of RDX and NG by magnetite was slower than that by pyrite. The results suggest that abiotic transformation of the explosives by pyrite and magnetite may be considered when determining the fate of explosives in Fe/S-rich subsurface environments.     

Trace analysis of ethanol, MTBE, and related oxygenate compounds in water using solid-phase microextraction and gas chromatography/mass spectrometry

Solid-phase microextraction (SPME) and gas chromatography/mass spectrometry have been combined for trace-level determination of very polar compounds in water, including the widely used gasoline oxygenates ethanol and methyl tert-butyl ether (MTBE). A relatively simple extraction method using a divinylbenzene/Carboxen/poly(dimethylsiloxane) SPME fiber was optimized for the routine analysis of ethanol and MTBE in groundwater and reagent water. A sodium chloride concentration of 25% (w/w) combined with an extraction time of 25 min provided the greatest sensitivity while maintaining analytical efficiency. Replicate analyses in fortified reagent and groundwater spiked with microgram per liter concentrations of ethanol and MTBE indicate quantitative and reproducible recovery of these and related oxygenate compounds. Method detection limits were 15 microg L(-1) for ethanol, 1.8 microg L(-1) for tert-butyl alcohol, 0.038 microg L(-1) for tert-amyl methyl ether, 0.025 microg L(-1) for ethyl-tert-butyl ether, and 0.008 microg L(-1) for MTBE.     

Calculations of bond dissociation energies and dipole moments in energetic materials using density-functional methods

We compare the effectiveness of six exchange/correlation functional combinations (Becke/Lee, Yang and Parr; Becke-3/Lee, Yang and Parr; Becke/Perdew-Wang 91; Becke-3/Perdew-Wang 91; Becke/Perdew 86; Becke-3/Perdew 86) for computing C-N, O-O and N-NO2 dissociation energies and dipole moments of five compounds. The studied compounds are hexabydro-1,3,5-trinitro-1,3,5-triazine (RDX), dimethylnitramine, cyanogen, nitromethane and ozone. The Becke-3/Perdew 86 in conjunction with 6-31G** is found to give the best results, although for the dipole moments of RDX, there is a slightly difference that B3P86/6-31G** is less reliable than B3P86/6-31+G**.     

Evaluation of a TiO2 photocatalysis treatment on nitrophenols and nitramines contaminated plant wastewaters by solid-phase extraction coupled with ESI HPLC–MS

Nitration reactions of aromatic compounds are commonly involved in different industrial processes for pharmaceutical, pesticide or military uses. For many years, most of the manufacturing sites used lagooning systems to treat their process effluents. In view of a photocatalytic degradation assay, the wastewater of a lagoon was investigated by using HPLC coupled with mass spectrometry. The wastewater was highly concentrated in RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) and two herbicides Dinoterb (2-tert-butyl-4,6-dinitrophenol) and Dinoseb (2-sec-butyl-4,6-dinitrophenol). First of all, an analytical method using solid-phase extraction (SPE) combined with HPLC ESI MS/MS was put in work for identification and titration of RDX, HMX and the two dinitrophenols in a complex natural matrix. Then, the UV/TiO₂ treatment was investigated for pollutants removal. Dinitrophenolic compounds were significantly degraded after a 8-h-exposition of the wastewater/TiO₂ suspension, whereas RDX and HMX were poorly affected.     

Linker-assisted immunoassay and liquid chromatography/mass spectrometry for the analysis of glyphosate

A novel, sensitive, linker-assisted enzyme-linked immunosorbent assay (L'ELISA) was compared to on-line solid-phase extraction (SPE) with high-performance liquid chromatography/mass spectrometry (HPLC/MS) for the analysis of glyphosate in surface water and groundwater samples. The L'ELISA used succinic anhydride to derivatize glyphosate, which mimics the epitotic attachment of glyphosate to horseradish peroxidase hapten. Thus, L'ELISA recognized the derivatized glyphosate more effectively (detection limit of 0.1 microg/L) and with increased sensitivity (10-100 times) over conventional ELISA and showed the potential for other applications. The precision and accuracy of L'ELISA then was compared with on-line SPE/HPLC/MS, which detected glyphosate and its degradate derivatized with 9-fluorenylmethyl chloroformate using negative-ion electrospray (detection limit 0.1 microg/ L, relative standard deviation +/- 15%). Derivatization efficiency and matrix effects were minimized by adding an isotope-labeled glyphosate (2-13C15N). The accuracy of L'EUSA gave a false positive rate of 18% between 0.1 and 1.0 microg/L and a false positive rate of only 1% above 1.0 microg/L The relative standard deviation was +/- 20%. The correlation of L'ELISA and HPLC/MS for 66 surface water and groundwater samples was 0.97 with a slope of 1.28, with many detections of glyphosate and its degradate in surface water but not in groundwater.     

Development of a portable immunoextraction-reversed-phase liquid chromatography system for field studies of herbicide residues

A portable system based on immunoextraction and reversed-phase HPLC was developed for the field analysis of herbicides in groundwater and surface water. Atrazine, simazine, and cyanazine were used as model analytes for this work. These were measured in water by using three coupled columns: an anti-atrazine antibody column for the selective extraction of these analytes, a reversed-phase precolumn for their reconcentration, and a reversed-phase analytical column for their separation. Various factors were considered in the optimization of this system, including the binding properties of the immunoextraction column, the effect of flow rate on the performance of each column, the selection of sample volume, and the choice of mobile phases for the RPLC columns. A typical analysis with this system allowed the injection of one sample every 7.5 min and provided results for all three of the tested herbicides in less than 10 min. In the analysis of atrazine alone, samples could be injected every 4 min and results were obtained within 8 min. There was good correlation between this technique and a comparable benchtop system. The lower limits of detection for the given analytes were approximately 0.2-0.25 microg/L, with a linear range that extended to 20 microg/L and a dynamic range that went up to at least 100 microg/L. The use of this technique in the field was demonstrated through applications that involved the development of time and location profiles for triazine herbicides in environmental samples.     

淀粉与丙烯酸乙酯接枝共聚物的合成与表征

以硝酸铈铵(CAN)为引发剂,研究了丙烯酸乙酯(EA)与玉米淀粉接枝共聚体系的自由基引发反应规律.实验结果得到较佳的反应条件为:单体浓度1.4939mol/L,引发剂浓度0.0293mol/L,AGU浓度1.1075mol/L,硝酸浓度0.02 mol/L,反应温度50℃,反应时间3h.在以上的反应条件下,转化率(C)可达98.64％,接枝率(G)可达34.92％,接枝效率(GE)可达74.55％.通过对接枝共聚产物的红外分析、核磁共振波谱分析、DSC分析及电镜扫描分析对产物进行了表征.结果表明,EA与淀粉发生了接枝共聚反应.     

Anammox bacteria with attached-growth media for nitrogen removal in wastewater

In side-by-side tests with high nitrogen wastewaters (483–1096 mg N/L), it was shown that an attached-growth media system more effectively removed nitrogen than did a suspended-growth system. The attached-growth system better handled the high nitrogen loading concentrations as calculated by the specific annamox activities (SAA) of the two systems. Moreover, the attached-growth medium was able to retain the anammox culture within the system. Based on these results, attached-growth was chosen for additional investigation of the effect of acetate in short- and long-term studies. In a short-term experiment, acetate concentrations of 0.25 and 0.5 mM did not affect the anammox bacteria activity. However, in a long-term experiment, the addition of acetate at 0.25 mM decreased the ammonium oxidation rate. The results from this study suggest that attached-growth systems show more promise for use in the field than suspended-growth systems.     

The fate and transport of RDX, HMX, TNT and DNT in the volcanic soils of Hawaii: a laboratory and modeling study

The adsorption and degradation behavior of RDX, HMX, TNT and DNT and the impact of pH, ionic strength and dissolved organic matter on sorption were examined for two volcanic soils of a former military training area on Hawaii Island, Hawaii, USA. The transport of these chemicals in the soil was also studied in small packed columns and simulated using a water-flow and solute-transport model, HYDRUS_1D. The results show that HMX and RDX are both significantly more mobile than TNT and DNT. The adsorbability of the four chemicals was ranked as: RDXRDX>DNT>TNT. No significant trend was observed for the effect of ionic strength, pH and dissolved organic carbon (DOC) on the adsorption of explosive compounds within the concentrations and pH ranges evaluated. The simulation results show that TNT and DNT would not leach beyond a depth of 30cm soil profile whereas a significant amount of HMX and RDX would pass the 30cm depth. It seems that the risk for contamination of groundwater is much higher for both HMX and RDX than for DNT and TNT as the substratum in this area consists of highly permeable lavas.     

Application of rhamnolipid and surfactin for enhanced diesel biodegradation--effects of pH and ammonium addition

This study investigated the effects of pH and ammonium concentrations on the potential application of two biosurfactants, surfactin (SF) and rhamnolipid (RL), for enhanced diesel biodegradation with a series of bench-scale experiments. In general, compared to the experiments without biosurfactant addition, adding RL or SF to diesel-water systems at concentrations above their critical micelle concentration (CMC) values benefited diesel emulsification, and therefore enhanced diesel biodegradation. The effects of pH on RL or SF-enhanced biodegradation of diesel were in good agreement with the trends of emulsion index values for RL or SF addition, respectively, under different pH conditions, suggesting that enhanced diesel emulsification by RL or SF addition promoted biodegradation of diesel. In diesel-water systems with 50mg/L of RL addition, an optimum pH condition for microbial growth and diesel biodegradation was found to be at a pH 7.2, while decreasing pH to 5.2 or increasing it to 8.4 reduced those parameters considerably. For the cases where 40 mg/L of SF was added, the enhancing ability shared a general trend with that observed for adding 50mg/L of RL as the pH increased from 5.2 to 7.2. Further increase of pH to 8.4, however, did not seem to negatively influence biodegradation and biomass growth. With respect to the effects of ammonium concentration on diesel biodegradation in diesel-water systems with 50mg/L of RL addition, an optimum ammonium addition for microbial growth and diesel biodegradation was found between 200 and 300 mg-N/L, but a dramatic decrease in growth and biodegradation occurred at ammonium addition up to 450 mg-N/L. For the cases where 40 mg/L of SF was added, an increase of ammonium addition from 50 to 200mg-N/L substantially increased microbial growth and biodegradation of diesel. Further increase of ammonium concentration to 450 mg-N/L, however, did not further improve diesel biodegradation.