Degradation of explosives-related compounds using nickel catalysts

We report the ability of nickel-based catalysts to degrade explosives compounds in aqueous solution. Several nickel catalysts completely degraded the explosives, although rates varied. Nearly all of the organic explosive compounds tested, including 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), were rapidly degraded to below detection limits by a powdered nickel on an alumina-silicate support (Aldrich nickel catalyst). Perchlorate degradation was minimal (<25%). Degradation of TNT by Aldrich nickel catalyst resulted in apparent first-order kinetics. Significant gaseous 14C was released and collected in an alkaline solution (most likely carbon dioxide) from [14C]RDX and [14C]HMX, indicating heterocyclic ring cleavage. Significant gaseous 14C was not produced from [14C]TNT, but spectrophotometric evidence indicated loss of aromaticity. Degradation occurred in low ionic strength solutions, groundwater, and from pH 3 to pH 9. Degradation of TNT, RDX, and HMX was maintained in flow-through columns of Aldrich nickel catalyst mixed with sand down to a hydraulic retention time of 4h. These data indicate that nickel-based catalysts may be an effective means for remediation of energetics-contaminated groundwater.     

Anaerobic biotransformation of explosives in aquifer slurries amended with ethanol and propylene glycol

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), and 2,4,6-trinitrotoluene (TNT) are explosives that are frequently found as environmental contaminants on military installations. Hydrogen has been shown to support the anaerobic transformation of these explosives. We investigated ethanol and propylene glycol as electron donors for providing syntrophically produced H2 for stimulating the anaerobic biodegradation of explosives in contaminated soil. The study was conducted using anoxic microcosms constructed with slurries of the contaminated soil and groundwater. The addition of 5mM ethanol and propylene glycol enhanced the biodegradation of RDX and HMX relative to the control bottles. Ethanol was depleted within about 20 days, resulting in the transient formation of hydrogen, acetate, and methane. The hydrogen headspace concentration increased from 8 ppm to 1838 ppm before decreasing to background concentrations. Propylene glycol was completely degraded after 15 days, forming hydrogen, propionate, and acetate as end-products. The hydrogen headspace concentrations increased from 56 ppm to 628 ppm before decreasing to background concentrations. No methane formation was observed during the incubation period of 48 days. Our findings indicate the addition of ethanol and propylene to the aquifer slurries increased the hydrogen concentrations and enhanced the biotransformation of RDX and HMX in the explosive-contaminated soil.     

亚甲基蓝表面修饰纳米TiO2降解造纸废水动力学

以亚甲基蓝(MB)作为表面修饰剂,采用简单的化学吸附法制备亚甲基蓝表面修饰的纳米TiO2光催化剂(TiO2-MB)。经表面修饰后,TiO2-MB光催化剂波长响应范围红移至可见光区575 nm处。探讨了光催化剂量、光照时间和溶液pH值对TiO2-MB光催化降解造纸废水的影响;研究了纳米TiO2-MB对造纸废水的暗吸附规律和光降解性能。结果表明:纳米TiO2-MB对造纸废水的吸附规律都较好地符合Langmuir和Freundlich吸附等温模型,属于吸热反应;光催化降解动力学符合Langmuir-Hinshelwood动力学模型。在160 W高压汞灯光照80 min,3.0 g/L纳米TiO2-MB光催化降解pH=2.0的造纸废水(COD:2 069.8 mg/L),COD去除率可达94.7%,处理效果远高于避光条件下。光催化剂经8次使用仍具有较高的催化活性。     

电生成Fenton试剂光催化降解孔雀石绿的研究

为了提高染料废水的处理效果,采用电生成Fenton试剂光催化氧化系统对孔雀石绿模拟印染废水进行了降解研究,通过与无光照时的对比实验发现:光照能明显加快电生成Fenton试剂对孔雀石绿印染废水的降解脱色速率,20 min内脱色率达到98%以上,40 min内COD去除率达到80%以上,同时通过红外光谱、紫外-可见光谱等手段研究了光照与电生成Fenton试剂的协同作用,初步探讨了电生成Fenton试剂光催化降解孔雀石绿印染废水的反应机理,很好地实现了光催化与电化学氧化降解技术的联合应用。     

Dissolution rates of three high explosive compounds: TNT,RDX, and HMX

Incidental exposure to high explosive compounds can cause subtle health effects to which a population could be more susceptible than injury by detonation. Proper source characterization is a key requirement in the conduct of risk assessments. For nonvolatile solid explosives, dissolution is one of the primary mechanisms that controls fate and transport, resulting in exposure to these compounds remote from their source. To date, information describing dissolution rates of high explosives has been sparse. The objective of this study was to determine the dissolution rates of three high explosive compounds, 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), in dilute aqueous solutions as a function of temperature, surface area, and energy input. To determine each variable's impact on dissolution rate, experiments were performed where one variable was changed while the other two were held constant. TNT demonstrated the fastest dissolution rate followed by HMX and then RDX. Dissolution rate correlation equations were developed for each explosive compound incorporating the three aforementioned variables, independently, and collectively in one correlation equation.     

The role of ferrous ion in Fenton and photo-Fenton processes for the degradation of phenol

The efficiency of different Fenton-related oxidative processes such as Fenton, solar-Fenton and UV-Fenton were examined using phenol as a model compound in simulated and industrial wastewater. A batch study was conducted to optimize parameters like pH, hydrogen peroxide concentration and ferrous ion concentration governing the Fenton process. At optimum conditions, different Fenton-related processes were compared for the degradation of phenol. Increased degradation and mineralisation efficiency were observed in photo-Fenton processes as compared to conventional Fenton process. The maximum mineralising efficiency for phenol with Fenton, solar and UV-Fenton processes were 41%, 96% and 97% respectively. In Fenton process, carboxylic acids like acetic acid and oxalic acid were formed as end products during the degradation of phenol while in photo-Fenton processes, both these ions were identified during the early stages of phenol degradation and were oxidized almost completely at 120 min of the reaction time. In photo-Fenton processes (solar and UV light) complete degradation were observed with 0.4 mM of Fe2+ catalyst as compared to 0.8 mM of Fe2+ in conventional Fenton process. In Fenton and solar-Fenton processes, an iron reusability study was performed to minimize the amount of iron used in treatment process. The efficacy of Fenton and solar-Fenton processes was applied to effluent from phenol resin-manufacturing unit for the removal and mineralisation of phenol.     

不同态二氧化钛处理模拟印染废水的研究

以普通载玻片为基底材料,负载态和悬浮态的纳米二氧化钛/普通二氧化钛被用于处理甲基红模拟印染废水,实验结果表明:纳米二氧化钛的脱色效果明显优于普通的二氧化钛,适当增加负载量和处理时间,负载态的处理效果与悬浮态相当。首次提出了由光源决定的纳米光催化活性激发理论,解释了不同光源辐照时脱色率变化曲线差异的问题,并发现纳米TiO2光催化氧化模拟印染废水的脱色反应,主要由吸附过程控制的表面反应机理;150 mL模拟印染废水中,加入3块纳米TiO2负载量1 mg/cm2的普通载玻片,3~5 mL ClO2或H2O2,紫外光照60 min后,脱色率达到99.2%。     

沼渣生物炭基Fenton催化剂的制备及其高效降解吡虫啉农药废水的研究

以废弃物沼渣和含铁剩余污泥为原料,采用一步热解法制备沼渣生物炭基Fenton催化剂(以下简称催化剂),构建了非均相Fenton反应体系处理含吡虫啉模拟废水,考察了H2 O2和催化剂用量对吡虫啉去除率的影响.结果表明,非均相Fenton反应体系中,H2 O2最佳投加量为0.50 g/L,催化剂最佳投加量为1.00 g/L...     

纳米生态建筑涂料光催化降解甲醛的研究

以掺加纳米TiO2制备的光催化建筑涂料为催化剂,研究了在紫外光照条件下对气态甲醛的催化降解,并探讨了纳米催化剂晶型、用量和吸附量对光催化降解甲醛的影响。实验结果表明,锐钛型纳米TiO2具有较高的光催化降解甲醛的活性,1h甲醛的降解率可达到70％左右,产物主要为二氧化碳和水;光催化降解甲醛受到涂膜上吸附量的较大影响;该涂料对甲醛的光催化降解反应表现出一级动力学速率规律,且具有良好的线性关系。     

LiFePO4非均相Fenton法处理亚甲基蓝染料的研究

采用水热法制备出LiFePO4催化剂,通过电子显微镜(SEM)、X射线衍射(XRD)和傅立叶红外光谱(FTIR)对其进行表征,并将其作为非均相Fenton催化剂处理亚甲基蓝(MB)染料溶液。实验结果表明,在催化剂用量为4 g/L,H2O2浓度为0.04 mol/L,pH值为3,温度为50℃,反应时间为60 min的条件下,浓度为500 mg/L的亚甲基蓝脱色率达99%。根据实验结果,讨论了LiFePO4作为非均相Fenton催化剂对亚甲基蓝的降解机理。     

Photocatalytic degradation of lignin using Pt/TiO2 as the catalyst

Photocatalytic degradation of lignin was studied with the use of catalysts TiO(2) and Pt/TiO(2). The influence of several experimental parameters, i.e. pH, catalyst dosage and illumination on lignin degradation was investigated. The results showed that application of UV irradiation alone has almost no effect on the reduction of dissolved organic carbon (DOC) and American Dye Manufacture Institute value (ADMI). However, the addition of TiO(2) and Pt/TiO(2) reduced the original DOC (251 mg l(-1)) by more than 40% within 30 min of treatment and the reaction can be simulated with pseudo-first order kinetics. Rapid degradation of lignin was observed in acidic solution using either TiO(2) or Pt/TiO(2) as the catalyst compared to high pH cases. The content of Pt in the Pt/TiO(2) catalyst is 1%. In addition, too much catalyst addition has not increased the DOC and ADMI reduction proportionally. The investigation also indicated that the photocatalytic degradation rates could be enhanced 1-6 times faster after doping TiO(2) with Pt in different pH cases. A modified Nernst type model was adopted to simulate the decoloring process using TiO(2) and Pt/TiO(2) based on the profiles of oxidation reduction potential during the photocatalytic reaction. The developed equation can be used to predict the color removal efficiency of lignin wastewater by the photocatalytic process.     

Dissolution kinetics of sub-millimeter Composition B detonation residues: role of particle size and particle wetting

The dissolution of the 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) from microscale particles (<250 μm) of the explosive formulation Composition B was examined and compared to dissolution from macroscopic particles (>0.5 mm). The dissolution of explosives from detonation soot was also examined. The measured mass transfer coefficients for the microscale particles were one to two orders of magnitude greater than the macroscopic particles. When normalized to particle surface area, mass transfer coefficients of microscale and macroscale particles were similar, indicating that the bulk dissolution processes were similar throughout the examined size range. However, an inverse relationship was observed between the particle diameter and the RDX:TNT mass transfer rate coefficient ratio for dry-attritted particles, which suggests that RDX may be more readily dissolved (relative to TNT) in microscale particles compared to macroscale particles. Aqueous weathering of larger Composition B residues generated particles that possessed mass transfer coefficients that were on the order of 5- to 20-fold higher than dry-attritted particles of all sizes, even when normalized to particle surface area. These aqueous weathered particles also possessed a fourfold lower absolute zeta-potential than dry-attritted particles, which is indicative that they were less hydrophobic (and hence, more wettable) than dry-attritted particles. The increased wettability of these particles provides a plausible explanation for the observed enhanced dissolution. The wetting history and the processes by which particles are produced (e.g., dry physical attrition vs. aqueous weathering) of Composition B residues should be considered when calculating mass transfer rates for fate and transport modeling.     

Degradation of ampicillin antibiotic in aqueous solution by ZnO/polyaniline nanocomposite as photocatalyst under sunlight irradiation

PURPOSE AND METHOD: ZnO/polyaniline nanocomposite in core-shell structure was prepared by the synthesis and adsorption of polyaniline chains on the structure of ZnO nanoparticles. Fourier transform infrared and ultraviolet-visible (UV-Vis) spectroscopy, X-ray diffraction patterns, field emission scanning electron microscopy, and transmission electron microscopy were used to characterize the composition and structure of the nanocomposite. The nanocomposite was used as an active photocatalyst for photodegradation and removal of ampicillin in aqueous solution. RESULTS: UV-Vis spectroscopy studies showed that ZnO/polyaniline nanocomposite absorbs visible light irradiation as well as ultraviolet spectrum, and therefore, it can be photoactivated under visible and ultraviolet lights. The photocatalytic activity of ZnO/polyaniline nanocomposite in degradation of ampicillin molecules in aqueous solution under natural sunlight irradiation was evaluated and compared with that of ZnO nanoparticles and pristine polyaniline. The ZnO/polyaniline core-shell nanocomposite exhibited higher photocatalytic activity compared to ZnO nanoparticles and pristine polyaniline. The effect of operating conditions (pH, ZnO/polyaniline nanocomposite dosage, and ampicillin concentration) in the photocatalytic degradation of ampicillin using ZnO/polyaniline nanocomposite was investigated. The optimum conditions for maximum efficiency of ampicillin degradation under 120 min sunlight irradiation were found as 10 mg L(-1) dosage of ZnO/polyaniline nanocomposite, ampicillin concentration of 4.5 mg L(-1), and solution pH?=?5. Under optimum operating conditions, degradation efficiency was reached to 41% after 120 min of exposure to the sunlight irradiation.     

Sequential biodegradation of TNT,RDX and HMX in a mixture

We describe TNT's inhibition of RDX and HMX anaerobic degradation in contaminated soil containing indigenous microbial populations. Biodegradation of RDX or HMX alone was markedly faster than their degradation in a mixture with TNT, implying biodegradation inhibition by the latter. The delay caused by the presence of TNT continued even after its disappearance and was linked to the presence of its intermediate, tetranitroazoxytoluene. PCR–DGGE analysis of cultures derived from the soil indicated a clear reduction in microbial biomass and diversity with increasing TNT concentration. At high-TNT concentrations (30 and 90 mg/L), only a single band, related to Clostridium nitrophenolicum, was observed after 3 days of incubation. We propose that the mechanism of TNT inhibition involves a cytotoxic effect on the RDX- and HMX-degrading microbial population. TNT inhibition in the top active soil can therefore initiate rapid transport of RDX and HMX to the less active subsurface and groundwater.     

Remediation of RDX- and HMX-contaminated groundwater using organic mulch permeable reactive barriers

Organic mulch is a complex organic material that is typically populated with its own consortium of microorganisms. The organisms in mulch breakdown complex organics to soluble carbon, which can then be used by these and other microorganisms as an electron donor for treating RDX and HMX via reductive pathways. A bench-scale treatability study with organic mulch was conducted for the treatment of RDX- and HMX-contaminated groundwater obtained from a plume at the Pueblo Chemical Depot (PCD) in Pueblo, Colorado. The site-specific cleanup criteria of 0.55 ppb RDX and 602 ppb HMX were used as the logical goals of the study. Column flow-through tests were run to steady-state at the average site seepage velocity, using a 70%:30% (vol.:vol.) mulch:pea gravel packing to approach the formation's permeability. Significant results included: (1) Complete removal of 90 ppb influent RDX and 8 ppb influent HMX in steady-state mulch column effluent; (2) pseudo-first-order steady-state kinetic rate constant, k, of 0.20 to 0.27 h(-1) based on RDX data, using triplicate parallel column runs; (3) accumulation of reduced RDX intermediates in the steady-state column effluent at less than 2% of the influent RDX mass; (4) no binding of RDX to the column fill material; and (5) no leaching of RDX, HMX or reduction intermediates from the column fill material. The results of the bench-scale study will be used to design and implement a pilot-scale organic mulch/pea gravel permeable reactive barrier (PRB) at the site.     

LiFePO_4非均相Fenton法处理亚甲基蓝染料的研究

采用水热法制备出LiFePO4催化剂,通过电子显微镜（SEM）、X射线衍射（XRD）和傅立叶红外光谱（FTIR）对其进行表征,并将其作为非均相Fenton催化剂处理亚甲基蓝（MB）染料溶液。实验结果表明,在催化剂用量为4 g/L,H2O2浓度为0.04 mol/L,pH值为3,温度为50℃,反应时间为60 min的条件下,浓度为500 mg/L的亚甲基蓝脱色率达99%。根据实验结果,讨论了LiFePO4作为非均相Fenton催化剂对亚甲基蓝的降解机理。     

Fe/Ce/沸石负载型类芬顿催化剂制备及其特性

采用柠檬酸盐溶胶-凝胶法制备了Fe/Ce/沸石负载型芬顿催化剂,通过透射电镜(TEM)和X射线衍射(XRD)对其进行表征,并将其作为非均相类芬顿催化剂处理孔雀石绿染料溶液。研究表明,通过掺杂Ce,可提高催化剂颗粒分散度和催化剂表面的氧气含量,进而提高催化活性。在催化剂投加量3.0 g/L,H2O2投加量67 mg/L,pH=8.0的条件下,反应30 min后,浓度为150 mg/L的孔雀石绿溶液脱色率可达97.3%。     

Chronic toxicity of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) in soil determined using the earthworm (Eisenia andrei) reproduction test

The sublethal and chronic effects of the environmental contaminant and explosive octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) in artificial soil were assessed using the earthworm (Eisenia andrei). Based on various reproduction parameters (total and hatched number of cocoons, number of juveniles and their biomass), fecundity was reduced at the different concentrations of HMX tested (from 280.0 +/- 12.3 to 2502.9 +/- 230.0 mg kg-1 dry soil) in spiked artificial soil (LOEC: 280.0 +/- 12.3 mg kg-1 dry soil). The growth of adult E. andrei was also reduced at the different concentrations tested, though no mortality occurred, even at the highest tested concentrations. The number of juveniles produced was correlated with the number of total and hatched cocoons, and the biomass of juveniles was correlated with the number of cocoons. Pooled results of these and earlier studies on explosives (TNT, RDX) using the E. andrei reproduction test confirm that effects of HMX on cocoon production are indicative of some reproductive consequences (number of juvenile and their biomass), whereas adult growth, in general, does not correlate strongly with change in reproduction capacity.     

Solar TiO2-assisted photocatalytic degradation of IGCC power station effluents using a Fresnel lens

The heterogeneous TiO2 assisted photocatalytic degradation of wastewater from a thermoelectric power station under concentrated solar light irradiation using a Fresnel lens has been studied. The efficiency of photocatalytic degradation was determined from the analysis of cyanide and formate removal. Firstly, the influence of the initial concentration of H2O2 and TiO2 on the degradation kinetics of cyanides and formates was studied based on a factorial experimental design. Experimental kinetic constants were fitted using neural networks. Results showed that the photocatalytic process was effective for cyanides destruction (mainly following a molecular mechanism), whereas most of formates (degraded mainly via a radical path) remained unaffected. Finally, to improve formates degradation, the effect of lowering pH on their degradation rate was evaluated after complete cyanide destruction. The photooxidation efficiency of formates reaches a maximum at pH around 5-6. Above pH 6, formate anion is subjected to electrostatic repulsion with the negative surface of TiO2. At pH<4.5, formate adsorption and photon absorption are reduced due to some catalyst agglomeration.     

Oxidation of TNT by photo-Fenton process

A series of photo-Fenton reactions have been performed for the degradation of 2,4,6-trinitrotoluene (TNT) in a 4.2-l reactor. The degradation reaction rate of TNT followed a pseudo-first-order behavior; and the rate constants for 2.4mW cm(-2)UV only, 2.4mW cm(-2)UV/H(2)O(2), Fenton, photo-Fenton (2.4mW cm(-2)) and photo-Fenton (4.7mW cm(-2)) were 0.002min(-1), 0.007min(-1), 0.014min(-1), 0.025min(-1) and 0.037min(-1), respectively. Increasing the intensity of UV light, and the concentrations of ferrous ions and hydrogen peroxide promoted the oxidation rate under the experimental conditions in this study. The weighting factor (f), the Fe(II)-promoted efficiency (r) and the promoted-UV light efficiency (p) were calculated to clarify their effects on the TNT oxidation. Moreover, the inhibition effect of hydroxyl radical was also observed in both Fenton and photo-Fenton oxidation when the concentration of Fe(II) were higher than 2.88mM. Solid phase micro-extraction was first applied to the separation of the organic byproducts from TNT oxidation. GC/MS was employed to identify the byproducts during the Fenton and photo-Fenton oxidation of TNT. These compounds were clarified as 1,3,5-trinitrobenzene, 1-methyl-2,4-dinitrobenzene 2,5-dinitrobenzoic acid and 1,3-dinitrobenzene. By these byproducts, the mechanisms of the methyl group oxidation, decarboxylation, aromatic ring breakage, and hydrolysis can be recognized and demonstrated. The pathway of TNT oxidation by photo-Fenton process was also proposed in this study.