超声强化混凝去除蓝藻实验研究

研究了超声波对藻类的混凝去除强化,证明超声波可以快速、高效地提高藻类混凝去除效率,减少混凝剂用量.在混凝剂投加量为0.8 mg/L时,5 s超声处理,藻类去除效果比对照样好30%.同样,藻类去除率都为92%时,5 s超声预处理可以将混凝剂投加量降低至1/3.超声预处理时间对强化混凝效果有很大的影响,在实验条件下,1～5 s的超声处理均可产生满意的结果,1 s为最优、最经济时间,而预处理超过30 s反而降低混凝效果.低频下不同处理频率对超声强化混凝效果影响不大,在80 kHz的频率下,最佳功率为50 W.最佳pH值在8～9范围内.     

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.     

Studies on plant-mediated fate of the explosives RDX and HMX

The fate of the explosives RDX and HMX on exposure to plants was investigated in 'natural' aquatic systems of Myriophyllum aquaticum for 16 days, and in axenic hairy root cultures of Catharanthus roseus for > or = 9 weeks. Exposure levels were: HMX, 5 mg/l; and RDX, approximately 8 mg/l. Exposure outcomes observed include: HMX, no transformation by aquatic plants, and minimal biological activity by axenic roots; and RDX, removal by both plant systems. In the case of RDX exposure to axenic roots, since 14C-RDX was included, removal was confirmed by the accumulation of 14C-label in the biomass. The intracellular 14C-label in these RDX studies was detected in two forms: intact RDX and bound unknown(s).     

Leaching of bisphenol A (BPA) from polycarbonate plastic to water containing amino acids and its degradation by radical oxygen species

In this study, (1) the change in the concentration of bisphenol A (BPA) leached from polycarbonate plastic (PCP) tube to water samples containing phosphate, sodium barbital, glycine, methionine or albumin at 37 degrees C as a function of time, and (2) the degradation rate of BPA leached from PCP tube to amino acid solutions in the presence of radical oxygen species (ROS) were investigated. The BPA leaching velocity (BPA-LV) from PCP tube to 50 mM glycine at pH 6 or 7 was twice that to control water, and the leaching was enhanced above pH 8. At pH 11, BPA-LV was significantly higher in 50 mM glycine and methionine solutions than in 50 mM NaOH. These results indicate that basic pH and amino acids contained in water could accelerate BPA leaching. The BPA-LV in phosphate buffer was different from the BPA-LVs in other buffers (barbital and glycine) at the same pH. BPA leached to the glycine or methionine solutions at pH 11 was degraded time dependently in a similar manner as the control water in the presence of ROS. The degradation of leached BPA was inhibited in the glycine solution, but was accelerated in the methionine solution. However, degradation of BPA added to freshly prepared methionine was inhibited in a similar manner to BPA in glycine. BPA degradation could be influenced by some kinds of amino acids, but glycine and methionine might be involved in BPA degradation in different ways.     

Photocatalytic Treatment of RDX Wastewater with Nano-Sized Titanium Dioxide (5 pp)

Background, Aim and Scope The polynitramines, hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), are important military explosives and regulated toxic hazardous compounds. Production, testing and use of the compounds has resulted in numerous acres of contaminated soils and groundwater near many munitions facilities. Economical and efficient methods for treatment of wastewater and cleanup of soils or groundwater containing RDX and HMX are needed. This study focuses on the photocatalytic treatment of RDX wastewater with nano-sized titanium dioxide (nano-TiO2) under simulated sunlight, whose intensity and wavelength are similar to that of the real sunlight in Xi'an at noon. The objective is to determine the potential for RDX destruction with nano-TiO2 in aqueous solution. Materials and Methods: An activated carbon fiber (ACF) cloth-loaded with nano-TiO2 was put into the RDX containing solution, and the concentration of RDX was measured (by HPLC–UV) at regular time intervals under simulated sunlight. Results: The RDX degradation percentage of the photocatalytic process is higher than that of Fenton oxidation before 80 min, equivalent after 80 min, and it reaches 95% or above after 120 min. The nano-TiO2 catalyst can be used repeatedly. Discussion: The photocatalytic degradation kinetics of RDX under simulated sunlight can be described by a first-order reaction kinetics equation. The possible degradation mechanism of RDX was presented and the degradation performance was compared with that of biological method. Conclusions: It was demonstrated that the degradation of RDX wastewater is very effective with nano-TiO2 as the photocatalytic catalyst under simulated sunlight. The efficiency of the nano-TiO2 catalyst for RDX degradation under simulated sunlight is nearly identical to that of Fenton oxidation. Recommendations and Perspectives: To date, a number of catalysts show poor absorption and utilization of sunlight, and still need ultraviolet light irradiation during wastewater degradation. The nano-TiO2 used in the described experiments features very good degradation of RDX under simulated sunlight, and the manufacturing costs are rather low (around 10 Euro/m2). Moreover, the degradation efficiency is higher compared to that of the biological method. This method exhibits great potential for practical applications owing to its easiness and low cost. If it can be applied extensively, the efficiency of wastewater treatment will be enhanced greatly.     

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.     

Drip-feed bioreactor for the treatment of concentrated wastes with minimal dilution

Avoiding substrate inhibition is a significant challenge in designing biological treatment systems for concentrated or toxic wastes. Substrate inhibition is commonly avoided by diluting the waste before treatment, however, dilution of a waste before treatment is not always feasible. In the case of radioactive mixed wastes and chemical warfare materiel (CWM), dilution presents regulatory and safety concerns. In this study, we investigated a "drip-feed" reactor configuration as an alternative approach for the biological treatment of concentrated waste streams with minimal dilution and complete containment. In the drip-feed reactor undiluted waste is slowly fed to biomass in a reactor at a rate sufficient to maintain activity, but at a low enough rate so that bacterial degradation maintains the reactor concentration below the toxic threshold. The reactor has no effluent, but rather fills as the undiluted waste is fed to the reactor, which has the advantage of preventing the release of hazardous material into the environment during treatment. Volatile releases are prevented with the use of condensers. The drip-feed bioreactor configuration was tested under aerobic conditions, at 25 degrees C, using a 10% acetonitrile feed solution. The treatment of acetonitrile to less than 0.1 mg l(-1) was achieved with a dilution factor of only 3.4. The acetonitrile degradation reaction was pH sensitive, where the optimal pH range for the biodegradation process was approximately between 6.5 and 7.1 and the biodegradation rate declined precipitously above pH 7.2. The applicability of the drip-feed reactor configuration to the treatment of mixed wastes and CWM is discussed.     

Geochemical and microbiological processes contributing to the transformation of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in contaminated aquifer material

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is a potential human carcinogen, and its contamination of subsurface environments is a significant threat to public health. This study investigated abiotic and biological degradation of RDX in contaminated aquifer material. Anoxic batch systems were started with and without pre-aeration of aquifer material to distinguish initial biological RDX reduction from abiotic RDX reduction. Aerating the sediment eliminated chemical reductants in the native aquifer sediment, primarily Fe(II) sorbed to mineral surfaces. RDX (50 μM) was completely reduced and transformed to ring cleavage products when excess concentrations (2 mM) of acetate or lactate were provided as the electron donor for aerated sediment. RDX was reduced concurrently with Fe(III) when acetate was provided, while RDX, Fe(III), and sulfate were reduced simultaneously with lactate amendment. Betaproteobacteria were the dominant microorganisms associated with RDX and Fe(III)/sulfate reduction. In particular, Rhodoferax spp. increased from 21% to 35% and from 28% to 60% after biostimulation by acetate and lactate, respectively. Rarefaction analyses demonstrated that microbial diversity decreased in electron-donor-amended systems with active RDX degradation. Although significant amounts of Fe(III) and/or sulfate were reduced after biostimulation, solid-phase reactive minerals such as magnetite or ferrous sulfides were not observed, suggesting that RDX reduction in the aquifer sediment is due to Fe(II) adsorbed to solid surfaces as a result of Fe(III)-reducing microbial activity. These results suggest that both biotic and abiotic processes play an important role in RDX reduction under in situ conditions.     

碱性条件促进太湖蓝藻厌氧发酵产挥发性脂肪酸

采用批式研究实验,考察了酸性(pH 5)、中性(pH 7)和碱性(pH 9)条件下,太湖蓝藻厌氧发酵产挥发性脂肪酸(volatile fatty acids,VFAs)过程中的产酸指标,酸分布及蓝藻有机成分降解的效果。结果表明,pH为9时VFAs产率最高,为0.274 g VFAs/g VS,VS降解率达到51.91%。蓝藻有机成分中蛋白质、碳水化合物、脂类降解率也在pH为9时达到最高,分别为53.2%、30%和40.6%。实验对蓝藻产酸效果与其他固废产酸效果进行了比较,比较结果说明,太湖蓝藻作为厌氧发酵原料生产挥发性脂肪酸具有可行性。     

Age dependent acute oral toxicity of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and two anaerobic N-nitroso metabolites in deer mice (Peromyscus maniculatus)

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) transforms anaerobically into N-nitroso compounds: hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine (MNX), hexahydro-1,3-dinitroso-5-nitro-1,3,5-triazine (DNX), and hexahydro-1,3,5-trinitroso-1,3,5-triazine (TNX). Exposure to these N-nitroso metabolites may occur in areas contaminated with explosives, as anaerobic degradation occurs via some bacteria and is one remediation strategy used for RDX. Few papers report acute oral toxicity and none have evaluated age dependent toxicity of RDX or its N-nitroso metabolites. Median lethal dose (LD₅₀) was determined in deer mice (Peromyscus maniculatus) of three age classifications 21 d, 50 d, and 200 d for RDX, MNX, and TNX using the US EPA up-and-down procedure (UDP). Hexahydro-1,3,5-trinitro-1,3,5-triazine and N-nitroso metabolites caused similar overt signs of toxicity. Median lethal dose for 21 d deer mice were 136, 181, and 338 mg/kg for RDX, MNX, and TNX, respectively. Median lethal dose for 50 d deer mice were 319, 575, and 338 mg/kg for RDX, MNX, and TNX, respectively. Median lethal dose for 200 d deer mice were 158, 542, and 999 mg/kg for RDX, MNX, and TNX, respectively. These data suggest that RDX is the most potent compound tested, and age dependent toxicity may exist for all compounds and could play a role in RDX and RDX N-nitroso metabolite ecological risk evaluation of terrestrial wildlife at RDX contaminated sites.     

Photochemical transformations of tetrabromobisphenol A and related phenols in water

A method was developed for studies of the phototransformation at UV irradiation of aqueous solutions of tetrabromobisphenol A (TBBPA), tribromobisphenol A (TriBBPA), tetrachlorobisphenol A (TCBPA), 2,4-dichlorophenol at various pHs as well as 2-chlorophenol, 2-bromophenol, 3,4-dichlorophenol and bisphenol A at pH 11. The absorbance spectra of the compounds and the emission spectra of the light-source were determined and used to calculate disappearance quantum yields of the photochemical reactions that were taking place. No major differences between the disappearance quantum yields of TBBPA and TCBPA were observed at pH 10, while the disappearance quantum yield of TriBBPA was approximately two times higher. The rate of decomposition of TBBPA was six times higher at pH 8 than at pH 6. Identification of the degradation products of TBBPA and TriBBPA, by GC-MS analysis and by comparison to synthesised reference compounds, indicated that TBBPA and TriBBPA decompose via different mechanisms. Three isopropylphenol derivatives; 4-isopropyl-2,6-dibromophenol, 4-isopropylene-2,6-dibromophenol and 4-(2-hydroxyisopropyl)-2,6-dibromophenol, were identified as major degradation products of TBBPA while the major degradation product of TriBBPA was tentatively identified as 2-(2,4-cyclopentadienyl)-2-(3,5-dibromo-4-hydroxyphenyl)propane.     

粉煤灰和电石渣对聚丙烯塑料裂解的影响研究

研究了粉煤灰和电石渣对聚丙烯塑料裂解的影响,讨论了加入量对裂解速度和裂解产物的影响.结果表明:粉煤灰和电石渣都使裂解产物中的轻质部分(汽油和裂解气)增加、重油降低;粉煤灰比电石渣更能加快反应的进行,而且加入量越多,反应越快,需时越短;粉煤灰比电石渣对聚丙烯塑料的裂解具有明显的催化促进效果.     

Determination of pentachlorophenol (PCP) in waste wood--method comparison by a collaborative trial

Two independently developed and validated procedures for the determination of pentachlorophenol (PCP) in waste wood were compared by means of a collaborative trial. Both methods foresee quantification of PCP by gas chromatography (GC-ECD) after acetylation and differ with regard to the use of methanol or toluene/sulphuric acid, respectively, as solvent in the sonication extraction step. Test samples with established analyte homogeneity were prepared from a ground "real life" starting material. A total of 23 participating laboratories with experience in wood preservative analysis were instructed to apply both methods to three levels of content in the range of 0.5-20 mg PCP/kg. In case of the toluene/sulphuric acid extraction, lower recoveries and higher interlaboratory dispersion of results at the higher PCP contents were observed. Seen against the background of the Horwitz equation a reproducibility standard deviation of approximately 19% for the methanol extraction at the 4.5 mg/kg level meets the requirement for a sound analytical method. Thus, the sonication extraction procedure with methanol has been annexed as a reference method to the German waste wood regulation.     

Differences in herbicide adsorption on soil using several soil ph modification techniques

Abstract

Effects of soil pH on weak acid and weak base herbicide adsorption by soil are often determined by modifying soil pH in the laboratory. Modification of soil pH with acidic or basic amendments such as HCl or NaOH can cause changes in the soil‐solution system that may affect pesticide adsorption. The partition coefficients (K_d) for atrazine and dicamba by Waukegan, Piano, and Walla Walla silt loam soils stabilized in the field at different pH levels were compared to the K_d obtained when the soil pH was adjusted with acidic or basic amendments before herbicide addition. NaOH addition to raise soil pH generally increased the soluble soil organic carbon (SSOC) concentration in solution compared to field soils at the same pH and to soil treated with Ca(OH)₂. NaOH decreased the soil solution ionic strength slightly. Acidifying soils increased the soil solution ionic strength, when compared to field soils at the same pH and had no effect on SSOC concentration. Dicamba adsorption to soil was minimal (K_d < 0.22) and not influenced by soil pH in the range of 4.1 to 6.0; adsorption by laboratory amended soils in some cases underestimated adsorption compared to nonamended soils. Atrazine adsorption increased with decreased pH in all soils, and was overestimated slightly by several laboratory treatments to reduce pH compared to adsorption by field soils. Treatments to raise the pH did not affect atrazine adsorption. Overall, herbicide adsorption differences due to pH modification were small (<30%), and were not affected by soil solution ionic strength, saturating cation, or SSOC concentration in solution.     

苦土和氧化镁处理氮磷废水的对比研究

分别采用苦土、纯氧化镁为沉淀剂对模拟高浓度氮磷废水(N/P=0.8)进行了脱氮除磷研究,比较了沉淀剂投加量、pH对2种沉淀剂处理氮磷废水的影响,对沉淀产物进行XRD分析,并进行了经济效益比较。结果表明,pH是影响2种沉淀剂处理氮磷废水的主要因素,随着pH的增加,脱氮除磷效果提高,在平衡pH为9～10之间时氮磷处理效果最佳,pH继续增加,由于磷酸镁沉淀的形成使得氨氮去除率降低。此外,处理相同的废水,苦土的最佳投加量要大于纯氧化镁,但是经济效益比较结果表明,以苦土为沉淀剂处理氮磷废水可大大降低处理成本。     

Sonochemical decomposition of natural polyphenolic compound (condensed tannin)

Sonochemical treatment of grape condensed tannin was studied with the aim to destroy phenolic constituents, using ultrasonic frequency of 20 kHz in the presence and in the absence of hydrogen peroxide (H2O2), as an oxidative agent. Various pH, H2O2 concentration and temperature combinations were used in order to investigate the role of these parameters in the studied process. In order to estimate the effect of ultrasound, similar experiments were conducted in terms of pH, H2O2 concentration and temperature conditions, but without sonication. In all cases the presence of H2O2 was resulted in considerably higher removal of total phenolics (TP). It was observed that pH and temperature present also a significant effect on TP removal in the presence of H2O2, both with and without sonication. Under similar experimental conditions higher reaction rates, concerning TP removal, were obtained in the presence of ultrasonic irradiation, than in its absence.     

Halide salts accelerate degradation of high explosives by zerovalent iron

Zerovalent iron (Fe(0), ZVI) has drawn great interest as an inexpensive and effective material to promote the degradation of environmental contaminants. A focus of ZVI research is to increase degradation kinetics and overcome passivation for long-term remediation. Halide ions promote corrosion, which can increase and sustain ZVI reactivity. Adding chloride or bromide salts with Fe(0) (1% w/v) greatly enhanced TNT, RDX, and HMX degradation rates in aqueous solution. Adding Cl or Br salts after 24h also restored ZVI reactivity, resulting in complete degradation within 8h. These observations may be attributed to removal of the passivating oxide layer and pitting corrosion of the iron. While the relative increase in degradation rate by Cl(-) and Br(-) was similar, TNT degraded faster than RDX and HMX. HMX was most difficult to remove using ZVI alone but ZVI remained effective after five HMX reseeding cycles when Br(-) was present in solution.     

Dynamic and equilibrium studies of the RDX removal from soil using CMC-coated zerovalent iron nanoparticles

Rapid chemical degradation of toxic RDX explosive in soil can be accomplished using zerovalent nanoiron suspension stabilized in dilute carboxymethyl cellulose solution (CMC-ZVINs). The effect of operating conditions (redox-potential, Fe/RDX molar ratio) was studied on batchwise removal of RDX in contaminated soil. While anaerobic conditions resulted in 98% RDX removal in 3 h, only slightly over 60% RDX removal could be attained under aerobic conditions. The molar ratio did not have any influence on the intermediate and final RDX degradation products (methylenedinitramine, nitroso derivative, N₂, N₂O, NO₂^?), however, their distribution changed. Dynamic studies were conducted using a flow-through short column packed with RDX-contaminated soil and fed with CMC-ZVINs. The column was operated at two interstitial velocities (2.2 and 1.6 cm min^?1), resulting in the 76.6% and 95% removal of the initial RDX soil contamination load (60 mg kg^?1), respectively. While the column operating conditions could be further optimized, 95% of the RDX initially present in the contaminated soil packed in the column was degraded when flushed with a CMC-ZVINs suspension in this work.     

Biodegradation of nonylphenol in sewage sludge

We investigated the effects of various factors on the aerobic degradation of nonylphenol (NP) in sewage sludge. NP (5 mg/kg) degradation rate constants (k₁) calculated were 0.148 and 0.224 day⁻¹ for the batch experiment and the bioreactor experiment, respectively, and half-lives (t_1/2) were 4.7 and 3.1 days, respectively. The optimal pH value for NP degradation in sludge was 7.0 and the degradation rate was enhanced when the temperature was increased and when yeast extract (5 mg/l) and surfactants such as brij 30 or brij 35 (55 or 91 μM) were added. The addition of aluminum sulfate (200 mg/l) and hydrogen peroxide (1 mg/l) inhibited NP degradation within 28 days of incubation. Of the microorganism strains isolated from the sludge samples, we found that strain CT7 (identified as Bacillus sphaericus) manifested the best degrading ability.     

Anaerobic treatment of army ammunition production wastewater containing perchlorate and RDX

Perchlorate is an oxidizer that has been routinely used in solid rocket motors by the Department of Defense and National Aeronautics and Space Administration. Royal Demolition Explosive (RDX) is a major component of military high explosives and is used in a wide variety of munitions. Perchlorate bearing wastewater typically results from production of solid rocket motors, while RDX is transferred to Army industrial wastewaters during load, assemble and pack operations for new munitions, and hot water or steam washout for disposal and deactivation of old munitions (commonly referred to as demilitarization, or simply demil). Biological degradation in Anaerobic Fluidized Bed Reactors (AFBR), has been shown to be an effective method for the removal of both perchlorate and RDX in contaminated wastewater. The focus of this study was to determine the effectiveness of removal of perchlorate and RDX, individually and when co-mingled, using ethanol as an electron donor under steady state conditions. Three AFBRs were used to assess the effectiveness of this process in treating the wastewater. The performance of the bioreactors was monitored relative to perchlorate, RDX, and chemical oxygen demand removal effectiveness. The experimental results demonstrated that the biodegradation of perchlorate and RDX was more effective in bioreactors receiving the single contaminant than in the bioreactor where both contaminants were fed.