Evaluation of bioremediation methods for the treatment of soil contaminated with explosives in Louisiana Army Ammunition Plant, Minden, Louisiana

Two bioremediation methods, namely, soil slurry reactor and land farming technique were evaluated for the treatment of soil contaminated with explosives in Louisiana Army Ammunition Plant, Minden, Louisiana. The soil had a high concentration of 2,4,6-trinitrotoluene (TNT) of 10,000 mg/kg of soil and medium level contamination of RDX 1900 mg/kg and HMX 900 mg/kg of soil. The results indicated that soil slurry reactor under co-metabolic condition with molasses as co-substrate removed TNT more efficiently than land farming method. TNT removal efficiency was 99% in soil slurry reactor compared to 82% in land farming after 182 days. HMX and RDX were also removed from the soil in both methods, but the removal efficiency was low. The radiolabeled study showed that soil microbes mineralize TNT. The mass-balance of TNT indicated 23.5% of TNT was mineralized to CO(2), 22.6% was converted to biomass, and 52.3% was converted to various TNT intermediates in the soil slurry reactor. Both methods maintained high bacterial population fairly well. The results of this bench-scale study are promising with regard to transferring the technology to full-scale application at this site.     

Composition of explosives by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Commercial explosives are complex mixtures that contain not only the active explosive agent(s) but also a host of other organic and inorganic compounds. The ultrahigh mass resolving power (m/delta m50% >200,000) and mass accuracy (<1 ppm) of electrospray ionization Fourier transform ion cyclotron resonance (ESI FTICR) mass spectrometry allow for definitive identification of various species in TNT, RDX, and HMX. We are thereby able to correct prior misassignments of the elemental compositions of the most abundant negative ions from electrospray of RDX and HMX. Although the (known) active agents of many explosives may be identified by low-resolution MS or MS/MS, it is the other characteristic components (indigenous or artificial additives) whose presence and elemental composition can potentially identify the source of the product. ESI FTICR mass spectrometry of smokeless powder, TNT, and Powermite resolves and identifies numerous nonactive ingredients, many of which are recovered in a postblast residue. In contrast, the residue recovered from an explosion of military C4 yielded several species derived from RDX but virtually none from other ingredients.     

Ionization parameters of some nitro compounds on the surface of alkali metal oxide bronze

The efficiency and activation energy of the selective ionization of some nitro compounds (TNT, HMX, RDX, etc.) on the surface of sodium-vanadium oxide bronze under atmospheric conditions have been evaluated for the first time.     

Desorption electrospray ionization of explosives on surfaces: sensitivity and selectivity enhancement by reactive desorption electrospray ionization

Desorption electrospray ionization (DESI), an ambient mass spectrometry technique, is used for trace detection of the explosives trinitrohexahydro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), 2,4,6-trinitrotoluene (TNT), Pentaerythritol tetranitrate (PETN), and their plastic compositions (Composition C-4, Semtex-H, Detasheet) directly from a wide variety of surfaces (metal, plastic, paper, polymer) without sample preparation or pretreatment. Analysis of the explosives is performed under ambient conditions from virtually any surface in very short times (<5 s) including confirmatory tandem mass spectrometry (MS/MS) experiments, while retaining the sensitivity and specificity that mass spectrometry offers. Increased selectivity is obtained both by MS/MS and by performing additional experiments in which additives are included in the spray solvent. These reactive DESI experiments (reactions accompanying desorption) produce such ions as the chloride and trifluoroacetate adducts of RDX and HMX or the Meisenheimer complex of TNT. Desorption atmospheric pressure chemical ionization, a variant of DESI that uses gas-phase ions generated by atmospheric pressure corona discharges of toluene or other organic compounds, provides evidence for a heterogeneous-phase (gaseous ion/absorbed analyte) charge-transfer mechanism of DESI ionization in the case of explosives. Plastic explosives on surfaces were analyzed directly as fingerprints, without sample preparation, to test DESI as a possible method for in situ detection of explosives-contaminated surfaces. DESI also allowed detection of explosives in complex matrixes, including lubricants, household cleaners, vinegar, and diesel fuel. Absolute limits of detection for the neat explosives were subnanogram in all cases and subpicogram in the case of TNT. The DESI response was linear over 3 orders of magnitude for TNT. Quantification of RDX on paper gave a precision (RSD) of 2.3%. Pure water could be used as the spray solution for DESI, and it showed ionization efficiencies for RDX in the negative ion mode similar to that given by methanol/water. DESI represents a simple and rapid way to detect explosives in situ with high sensitivity and specificity and is especially useful when they are present in complex mixtures or in trace amounts on ordinary environmental surfaces.     

Identification of explosives with two-dimensional ultraviolet resonance Raman spectroscopy

The first two-dimensional (2D) resonance Raman spectra of TNT, RDX, HMX, and PETN are measured with an instrument that sequentially and rapidly switches between laser wavelengths, illuminating these explosives with forty wavelengths between 210 nm and 280 nm. Two-dimensional spectra reflect variations in resonance Raman scatter with illumination wavelength, adding information not available from single or few one-dimensional spectra, thereby increasing the number of variables available for use in identification, which is especially useful in environments with contaminants and interferents. We have recently shown that 2D resonance Raman spectra can identify bacteria. Thus, a single device that identifies the presence of explosives, bacteria, and other chemicals in complex backgrounds may be feasible.     

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.     

TNT 对 RDX 热分解行为影响的研究

针对部分黑梯炸药的 DSC 曲线无 RDX 熔化峰的情况,通过分析不同升温速率下单质 RDX 的 DSC 曲线,确定有利于黑梯炸药 DSC 曲线出现 RDX 熔化峰的测试条件。并将 TNT 和 RDX 以质量比为3︰7和4︰6的比例溶解在丙酮中,重结晶制成黑梯炸药,用 DSC 对其进行热分析,通过改变 DSC 测试条件出现了 RDX 的熔化峰。分析认为,部分 RDX 在熔融 TNT 中溶解后,液相 RDX 以自催化的方式分解,分解峰左移,峰温降低,对熔化峰进行了掩盖。对样品的热分解动力学和热力学参数进行计算和对比之后发现,黑梯炸药的活化能比 RDX 增加了6.02％,热爆炸临界温度提高了2.08℃,热力学参数发生了变化,说明 TNT 和 RDX 通过氢键相互作用,提高了RDX 的热稳定性, RDX 的使用安全性有一定改善。     

Detection of explosives and related compounds by low-temperature plasma ambient ionization mass spectrometry

Detection of explosives is important for public safety. A recently developed low-temperature plasma (LTP) probe for desorption and ionization of samples in the ambient environment ( Anal. Chem. 2008 , 80 , 9097 ) is applied in a comprehensive evaluation of analytical performance for rapid detection of 13 explosives and explosives-related compounds. The selected chemicals [pentaerythritol tetranitrate (PETN), trinitrotoluene (TNT), cyclo-1,3,5-trimethylenetrinitramine (RDX), tetryl, cyclo-1,3,5,7-tetramethylenetetranitrate (HMX), hexamethylene triperoxide diamine (HMTD), 2,4-dinitrotoluene, 1,3-dinitrobenzene, 1,3,5-trinitrobenzene, 2-amino-4,6-dinitrotoluene, 4-amino-2,6-dinitrotoluene, 2,6-dinitrotoluene, and 4-nitrotoluene) were tested at levels in the range 1 pg-10 ng. Most showed remarkable sensitivity in the negative-ion mode, yielding limits of detection in the low picogram range, particularly when analyzed from a glass substrate heated to 120 °C. Ions typically formed from these molecules (M) by LTP include [M + NO(2)](-), [M](-), and [M - NO(2)](-). The LTP-mass spectrometry methodology displayed a linear signal response over three orders of magnitude of analyte amount for the studied explosives. In addition, the effects of synthetic matrices and different types of surfaces were evaluated. The data obtained demonstrate that LTP-MS allows detection of ultratrace amounts of explosives and confirmation of their identity. Tandem mass spectrometry (MS/MS) was used to confirm the presence of selected explosives at low levels; for example, TNT was confirmed at absolute levels as low as 0.6 pg. Linearity and intra- and interday precision were also evaluated, yielding results that demonstrate the potential usefulness and ruggedness of LTP-MS for the detection of explosives of different classes. The use of ion/molecule reactions to form adducts with particular explosives such as RDX and HMX was shown to enhance the selectivity and specificity. This was accomplished by merging the discharge gas with an appropriate reagent headspace vapor (e.g., from a 0.2% trifluoracetic acid solution).     

基于分子动力学的DNAN基熔铸炸药结合能和热分解反应性能研究

采用Compass力场对DNAN基熔铸炸药的结合能、溶度参数进行分子动力学模拟。计算结果表明:DNAN/RDX混合体系的溶度参数大于DNAN/HMX混合体系的溶度参数;当RDX团簇和HMX团簇的直径均大于15×10^-10 m时,DNAN/RDX混合体系的结合能远大于DNAN/HMX混合体系的结合能。基于ReaxFF-lg力场的分子动力学计算方法,对目标温度为2 000~3 500 K时DNAN/RDX混合炸药的热分解反应进行研究。结果表明:DNAN分子和RDX分子在高温下的初始分解反应路径均会受到影响;除了两种组分的硝基官能团发生脱落形成硝基官能团的初始反应路径不会受到影响之外,DNAN分子生成CH₂O碎片、RDX分子生成HONO和C₃H₃N₃碎片的反应路径均会受到抑制。     

Comparison of visible and near-infrared Raman cross-sections of explosives in solution and in the solid state

Raman cross-sections of explosives in solution and in the solid state have been measured using visible and near-infrared excitation via secondary calibration. These measurements are valuable for both fundamental scientific purposes and applications in the standoff detection of explosives. The explosive compounds RDX, HMX, TNT, 2,4-DNT, 2,6-DNT, and ammonium nitrate were measured using discrete excitation wavelengths ranging from 532 nm to 785 nm. A comparison of the spectral features and cross-sections between the solid state and solution was performed. Comparison is also made to cross-sections measured with deep ultraviolet excitation.     

Anaerobic treatment of pinkwater in a fluidized bed reactor containing GAC

Pinkwater is generated during the handling and demilitarization of conventional explosives. This listed hazardous waste contains dissolved trinitrotoluene (TNT) and cyclo trimethylene trinitramine (RDX), as well as some by-products. It represents the largest quantity of hazardous waste generated by the operations support command, and its treatment produces a by-product hazardous waste--spent granular activated carbon (GAC).Anaerobic treatment in a fluidized bed reactor (FBR) containing GAC is an emerging technology for organic compounds resistant to aerobic biological treatment. Bench scale batch studies using an anaerobic consortium of bacteria fed ethanol as the sole electron donor demonstrated the transformation of TNT to triaminotoluene (TAT), which then degrades to undetectable end products. RDX is sequentially degraded to nitroso-, dinitroso-, trinitroso- and hydroxylaminodinitroso-RDX before the triazine ring is presumably cleaved, forming methanol and formaldehyde as major end products. The bacterial members of the anaerobic consortia are typically found in sludge digesters at municipal or industrial wastewater treatment plants.The results of a pilot scale evaluation of this process that was conducted at McAlester Army Ammunition Plant (MCAAP, OK) over a 1 year period are reported in this paper. The pilot test experienced wide fluctuations in influent concentrations, representative of true field conditions. The FBR was a 20 in. (51 cm) diameter column with an overall height of 15 ft (4.9 m) and a bed of GAC occupying 11 ft (3.4m). Water was recirculated through the column continuously at 30 gpm (114 l/min) to keep the GAC fluidized, and pinkwater for treatment was pumped into the recirculation line. Several flowrates were evaluated to determine the proper mass loading rate (mass of TNT and RDX per reactor volume per time, kg/m(3) per day) which the reactor could handle while meeting the discharge limitations. Based on the tests performed, a 1 gpm (3.785 l/min) rate in the 188 gal (710 l) volume of the fluidized GAC bed was determined to consistently meet the discharge requirements.This information was used to develop a cost estimate for a system capable of treating the total effluent currently produced at MCAAP. The cost of installing and operating this system was compared to the cost of GAC adsorption for MCAAP at current pinkwater generation rates. The GAC-FBR system had an annual operating cost of approximately US$ 19K, compared to US$ 71 K annually for GAC adsorption. When including the amortization of the capital equipment required for the GAC-FBR, the payback period for installation of this new process was estimated at 3.7 years.     

Recovery of nitrotoluenes in wastewater by solvent extraction

Toluene extraction was utilized to recover 2,4-dinitrotoluene (DNT), 2,6-DNT, and 2,4,6-trinitrotoluene (TNT) from wastewater of toluene nitration process. The batch-wise experiments were performed to elucidate the influence of various operating variables on the extracting behavior, including extracting temperature, volume ratios of solvent versus wastewater, agitation time, acidity of wastewater, and extraction stages. It was found that recovery of total organic compounds (TOC) was significantly elevated with increasing extraction temperature. Besides, high volume ratio of toluene/wastewater (2.0) and wastewater acidified to lower pH value enhanced the recovery percentage of TOC, in which extractable tendency was as follows: 2,6-DNT>2,4-DNT>2,4,6-TNT. It is worth noting that the nitrotoluenes in wastewater would be almost completely recovered using three sequential stages toluene extraction at the agitation time of 12min and pH 3.0. It is apparent that this established method is promising for the treatment of wastewater from toluene nitration processed industrially.     

Effect of food-grade surfactant on bioremediation of explosives-contaminated soil

The use of native soil bacteria to biodegrade explosives-contaminated soil under co-metabolic conditions has been demonstrated. The addition of food-grade surfactants could improve the process by enhancing the rates of explosives desorption from soil, thereby increasing the bioavailability of explosives for microbial degradation. The objective of this study was to decrease residence time in the slurry reactor, thereby increasing output and reducing clean-up costs. In this study, Tween 80 (monooleate), served not only as a surfactant but also as the carbon substrate for the soil microorganisms. Four 2l soil slurry reactors were operated in batch mode with soil containing 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). The results indicated that TNT and RDX were removed in all reactors except the control (no added carbon source). The reactor enriched with surfactant and molasses performed better than reactors with either molasses or surfactant alone. The TNT and its metabolite, 4-amino-2,6-dinitrotoluene were removed faster in the reactor with surfactant plus molasses (35 days) than in the reactor with molasses alone as carbon source (45 days). A radiolabeling study of the mass balance of TNT in the slurry reactors showed substantial mineralization of TNT to CO2.     

合成超级高能量密度材料途径的探索

高能炸药的发展可以看做经TNT,RDX,HMX三个阶段,而现在进入以CL-20为标志的第四个阶段,CL-20的能量密度增益也仅大于HMX约10%;文章举出了量子化学家们对可能的超级高能量密度材料八氮杂立方烷性能所做的引人注目的计算结果,并强调新的氮同素异形体将是最有希望的超级高能量密度材料。最近在质谱谱线中发现了N＋５,Christe制得了N＋５的盐。 关于聚合氮Nn,n为一个很大的数字,N原子均以共价键相结合而成为三维的网状结构,它是最值得重视的,有可能成为下一世纪威力最大的超级高级量密度材料。     

Development of adsorptive removal process for treatment of explosives contaminated wastewater using activated carbon

The adsorption characteristics of nitro-organics such as trinitro-toluene (TNT), dinitro-toluene (DNT) and nitrobenzene (NB) on granular activated carbon (GAC) were studied to understand their dynamic adsorption behaviour for dilute aqueous solutions. A model was developed to predict the dynamics of the adsorption process and the effect of various design and operating parameters on adsorption characteristics. The model predictions would provide inputs to design of bench scale and pilot plant scale experiments.Section 2 of the paper describes the assumptions, predictions, development of the model and its validation with experimental data generated during bench scale and pilot plant trials. Section 3 presents the breakthrough characteristics obtained by conducting experimental runs for GAC of different surface areas from 650 to 1500 m(2)/g, hydraulic loading rates (HLR) ranging between 12 and 24 m(3)/h/m(2), feed concentrations from 50 to 130 mg/l and bed heights between 300 and 1000 mm for TNT, DNT and NB solutions. The effect of these independent parameters on the breakthrough time, adsorption capacity and the minimum concentration achieved in the effluent was studied and the results obtained are presented in this paper. These indicate that the adsorption capacity goes though a maximum when studied as a function of HLR and feed concentration. The adsorption capacity per unit surface area also shows a maximum around 1000 m(2)/g. The minimum bed height required for meeting environmental effluent discharge limit of 1 ppm was experimentally found to be about 800 mm. These results compare well with the predictions based on the model developed for column adsorption process. Data from these experimental runs and the model predictions have been used to optimise various parameters for the design of a pilot plant unit with 200 l per hour capacity.     

RDX和HMX混合物中HMX的分离研究

根据HMX和RDX在不同溶剂中的溶解机理的差异,选用两种代表性物质对RDX和HMX混合物进行分离研究,确立以N,N-二甲基甲酰胺(DMF)为溶剂的分离RDX和HMX混合物的最佳工艺条件。最佳工艺条件为物料比14,溶解温度95～100℃,解离剂为水,解离温度90℃,解离时间2 h。运用高效液相色谱(HPLC)对分离得到的HMX进行了纯度测定,HMX纯度可达98%;通过偏光显微镜观察显示分离得到的HMX为β-晶型。分离得到的HMX在民用混合炸药中得到了再利用,可以替代直接生产的HMX。     

Aqueous solubility and alkaline hydrolysis of the novel high explosive hexanitrohexaazaisowurtzitane (CL-20)

The recently developed polycyclic nitramine CL-20 is considered as a possible replacement for the monocyclic nitramines RDX and HMX. The present study reports aqueous solubility data for CL-20, as well as the kinetic parameters for its alkaline hydrolysis with sodium hydroxide below and above its solubility limits. Aqueous solubility of CL-20 was measured in the temperature range of 4–69 °C and the data were fitted to a generalized solubility model. Alkaline hydrolysis experiments were conducted at 15, 20, 30 and 40 °C, with hydroxide concentrations ranging from 0.25 to 300 mM. Like RDX and HMX, alkaline hydrolysis of CL-20 follows second-order kinetics. CL-20 alkaline hydrolysis was found to proceed at a significantly faster rate than RDX. The temperature dependency of the second-order rate constants was evaluated using the Arrhenius model. The activation energy for CL-20 was found to be within close range of the activation energies reported for RDX and HMX.     

RDX和HMX机械刺激临界反应阈值试验研究

为了研究RDX和HMX在机械刺激下的临界反应阈值以及丙酮重结晶工艺对它们的影响，采用BAM撞击感度仪和摩擦感度仪测试了不同温度条件下的临界撞击能量和临界摩擦力。结果显示，80、60、40 ℃和25 ℃下，RDX的临界撞击能量分别为5.0、7.5、7.5、7.5 J，HMX的分别为4.0、4.0、5.0、5.0 J；RDX的临界摩擦力分别为120、120、128、144 N，HMX的分别为108、108、108、120 N。丙酮重结晶后，RDX在25 ℃的临界撞击能量和临界摩擦力分别为5.0 J、128 N；HMX在80、60、40 ℃和25 ℃下的临界撞击能量均为7.5 J，临界摩擦力分别为108、108、120、128 N。撞击感度和摩擦感度的结果表明:在25~80 ℃范围内，RDX和HMX的机械感度随着温度的提高呈下降趋势，重结晶工艺对RDX和HMX的机械感度存在着一定的影响。     

RDX基复合物静电喷雾法制备及性能研究

采用静电喷雾技术制备了以氟橡胶(F2604)、聚乙烯醇缩丁醛(PVB)及三硝基甲苯(TNT)为包覆材料的黑索今(RDX)基复合颗粒,对所制备的复合颗粒进行扫描电镜(SEM)、傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)和差示扫描量热仪(DSC)分析,得到超细包覆粒子的包覆效果及其热分解特性。结果表明:F2604/RDX与PVB/RDX复合颗粒为形貌规整、粒径均一的球形颗粒,而TNT/RDX复合颗粒为不规则多面体;F2604/RDX、PVB/RDX与TNT/RDX复合颗粒的红外吸收峰和X射线衍射峰位置与RDX一致;PVB/RDX复合物活化能最低,为137.059 k J/mol。     

非线性偏最小二乘法在混合炸药体系液相色谱中的应用

本文着重讨论了非线性偏最小二乘法(简称NLPLS)在混合炸药体系定量分析领域里的应用。以HMT、RDX、Tetryl、TNT等常用炸药为对象,对炸药的高效液相色谱分析中所遇到的复杂体系如谱峰严重重叠体系、待分析物含量相对悬殊体系等进行了研究。结果表明,本方法对混合炸药体系的液相色谱分析数据具有较强的处理能力,对完全重叠色谱的解析置信度取95％,误差小于5％。为解决这类炸药的液相色谱定量分析问题增添了另一条途径。